Science.gov

Sample records for intermolecular systems formed

  1. Intermolecular interactions and solvent diffusion in ordered nanostructures formed by self-assembly of block copolymers

    NASA Astrophysics Data System (ADS)

    Gu, Zhiyong

    Hydrogels formed by Poloxamer poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers find various pharmaceutical and biomedical applications. A variety of ordered structures can be exhibited by Poloxamer block copolymers in selective solvents such as water, for example, micellar cubic phase, hexagonal phase, lamellar phase, etc. We are interested in the thermodynamic and transport properties of water in such hydrogels that have an ordered (lyotropic liquid crystalline) structure. We have investigated the time evolution of water loss from Poloxamer gel films under a driving force of known water vapor pressure in the air in contact with the film. The experimental data on the drying process have been fitted to the diffusion equation for water in the film, under a boundary condition that includes the water concentration in the gel at infinite time; the water diffusion coefficient and other parameters have thus been obtained. The water chemical potential and osmotic pressure in the gel have been obtained from osmotic stress measurements. The osmotic pressure (force), together with data on the corresponding lyotropic liquid crystal spacing (distance) that we obtained from Small Angle X-Ray Scattering (SAXS) measurements, have been analyzed to provide information on the prevailing intermolecular (inter-assembly) forces in the gel. The forces in the gel reveal interactions that occur at two levels, that of the PEO coil and that of the PEO segment.

  2. Permutationally invariant fitting of intermolecular potential energy surfaces: A case study of the Ne-C2H2 system

    NASA Astrophysics Data System (ADS)

    Li, Jun; Guo, Hua

    2015-12-01

    The permutation invariant polynomial-neural network (PIP-NN) approach is extended to fit intermolecular potential energy surfaces (PESs). Specifically, three PESs were constructed for the Ne-C2H2 system. PES1 is a full nine-dimensional PIP-NN PES directly fitted to ˜42 000 ab initio points calculated at the level of CCSD(T)-F12a/cc-pCVTZ-F12, while the other two consist of the six-dimensional PES for C2H2 [H. Han, A. Li, and H. Guo, J. Chem. Phys. 141, 244312 (2014)] and an intermolecular PES represented in either the PIP (PES2) or PIP-NN (PES3) form. The comparison of fitting errors and their distributions, one-dimensional cuts and two-dimensional contour plots of the PESs, as well as classical trajectory collisional energy transfer dynamics calculations shows that the three PESs are very similar. We conclude that full-dimensional PESs for non-covalent interacting molecular systems can be constructed efficiently and accurately by the PIP-NN approach for both the constituent molecules and intermolecular parts.

  3. A functional fragment of Tau forms fibers without the need for an intermolecular cysteine bridge

    SciTech Connect

    Huvent, Isabelle; Kamah, Amina; Cantrelle, François-Xavier; Barois, Nicolas; Slomianny, Christian; Smet-Nocca, Caroline; Landrieu, Isabelle; Lippens, Guy

    2014-03-07

    Highlights: • A functional fragment of Tau forms bundled ribbon-like fibrils. • Nucleation of its fibril formation is faster than for full-length Tau. • In contrast to full-length Tau, without cysteines, the fragment still forms fibers. - Abstract: We study the aggregation of a fragment of the neuronal protein Tau that contains part of the proline rich domain and of the microtubule binding repeats. When incubated at 37 °C with heparin, the fragment readily forms fibers as witnessed by Thioflavin T fluorescence. Electron microscopy and NMR spectroscopy show bundled ribbon like structures with most residues rigidly incorporated in the fibril. Without its cysteines, this fragment still forms fibers of a similar morphology, but with lesser Thioflavin T binding sites and more mobility for the C-terminal residues.

  4. Calculation of the absolute thermodynamic properties of association of host-guest systems from the intermolecular potential of mean force.

    PubMed

    Ghoufi, Aziz; Malfreyt, Patrice

    2006-12-14

    The authors report calculations of the intermolecular potential of mean force (PMF) in the case of the host-guest interaction. The host-guest system is defined by a water soluble calixarene and a cation. With an organic cation such as the tetramethylammonium cation, the calixarene forms an insertion complex, whereas with the Lanthane cation, the supramolecular assembly is an outer-sphere complex. The authors apply a modified free energy perturbation method and the force constraint technique to establish the PMF profiles as a function of the separation distance between the host and guest. They use the PMF profile for the calculation of the absolute thermodynamic properties of association that they compare to the experimental values previously determined. They finish by giving some structural features of the insertion and outer-sphere complexes at the Gibbs free energy minimum. PMID:17176145

  5. Low-valent niobium-catalyzed intermolecular [2 + 2 + 2] cycloaddition of tert-butylacetylene and arylnitriles to form 2,3,6-trisubstituted pyridine derivatives.

    PubMed

    Satoh, Yasushi; Obora, Yasushi

    2013-08-01

    A catalytic system based on low-valent niobium has been developed, consisting of NbCl5, Zn, and an alkoxysilane. This combination has been shown to be an efficient catalyst for the synthesis of pyridine derivatives from the intermolecular cycloaddition of alkynes and nitriles via a niobacyclopentadiene intermediate. PMID:23848456

  6. Desensitization of metastable intermolecular composites

    DOEpatents

    Busse, James R.; Dye, Robert C.; Foley, Timothy J.; Higa, Kelvin T.; Jorgensen, Betty S.; Sanders, Victor E.; Son, Steven F.

    2011-04-26

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  7. Ground state analytical ab initio intermolecular potential for the Cl{sub 2}-water system

    SciTech Connect

    Hormain, Laureline; Monnerville, Maurice Toubin, Céline; Duflot, Denis; Pouilly, Brigitte; Briquez, Stéphane; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón

    2015-04-14

    The chlorine/water interface is of crucial importance in the context of atmospheric chemistry. Modeling the structure and dynamics at this interface requires an accurate description of the interaction potential energy surfaces. We propose here an analytical intermolecular potential that reproduces the interaction between the Cl{sub 2} molecule and a water molecule. Our functional form is fitted to a set of high level ab initio data using the coupled-cluster single double (triple)/aug-cc-p-VTZ level of electronic structure theory for the Cl{sub 2} − H{sub 2}O complex. The potential fitted to reproduce the three minima structures of 1:1 complex is validated by the comparison of ab initio results of Cl{sub 2} interacting with an increasing number of water molecules. Finally, the model potential is used to study the physisorption of Cl{sub 2} on a perfectly ordered hexagonal ice slab. The calculated adsorption energy, in the range 0.27 eV, shows a good agreement with previous experimental results.

  8. Effect of donor orientation on ultrafast intermolecular electron transfer in coumarin-amine systems.

    PubMed

    Singh, P K; Nath, S; Bhasikuttan, A C; Kumbhakar, M; Mohanty, J; Sarkar, S K; Mukherjee, T; Pal, H

    2008-09-21

    Effect of donor amine orientation on nondiffusive ultrafast intermolecular electron transfer (ET) reactions in coumarin-amine systems has been investigated using femtosecond fluorescence upconversion measurements. Intermolecular ET from different aromatic and aliphatic amines used as donor solvents to the excited coumarin-151 (C151) acceptor occurs with ultrafast rates such that the shortest fluorescence lifetime component (tau(1)) is the measure of the fastest ET rate (tau(1)=tau(ET) (fast)=(k(ET) (fast))(-1)), assigned to the C151-amine contact pairs in which amine donors are properly oriented with respect to C151 to maximize the acceptor-donor electronic coupling (V(el)). It is interestingly observed that as the amine solvents are diluted by suitable diluents (either keeping solvent dielectric constant similar or with increasing dielectric constant), the tau(1) remains almost in the similar range as long as the amine dilution does not cross a certain critical limit, which in terms of the amine mole fraction (x(A)) is found to be approximately 0.4 for aromatic amines and approximately 0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the tau(1) values are seen to increase very sharply. The large difference in the critical x(A) values involving aromatic and aliphatic amine donors has been rationalized in terms of the largely different orientational restrictions for the ET reactions as imposed by the aliphatic (n-type) and aromatic (pi-type) nature of the amine donors [A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008)]. Since the highest occupied molecular orbital (HOMO) of the n-type aliphatic amines is mostly centralized at the amino nitrogen, only some specific orientations of these amines with respect to the close-contact acceptor dye [also of pi-character; A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008) and E. W. Castner et al., J. Phys. Chem. A 104, 2869 (2000)] can give suitable V(el) and thus

  9. Universal scaling of potential energy functions describing intermolecular interactions. I. Foundations and scalable forms of new generalized Mie, Lennard-Jones, Morse, and Buckingham exponential-6 potentials

    SciTech Connect

    Xantheas, Sotiris S.; Werhahn, Jasper C.

    2014-08-14

    Based on the formulation of the analytical expression of the potential V(r) describing intermolecular interactions in terms of the dimensionless variables r*=r/rm and !*=V/!, where rm is the separation at the minimum and ! the well depth, we propose more generalized scalable forms for the commonly used Lennard-Jones, Mie, Morse and Buckingham exponential-6 potential energy functions (PEFs). These new generalized forms have an additional parameter from and revert to the original ones for some choice of that parameter. In this respect, the original forms can be considered as special cases of the more general forms that are introduced. We also propose a scalable, but nonrevertible to the original one, 4-parameter extended Morse potential.

  10. Studies on the stability and intermolecular interactions of cellulose and polylactide systems using molecular modeling

    NASA Astrophysics Data System (ADS)

    Karst, David T.

    The stability and intermolecular interactions of cellulose and polylactide (PLA) systems were studied using molecular modeling. This work explains how grafting various groups onto cellulose increases hydrolysis of the glycosidic linkages of cellulose. A substituent increases hydrolysis of cellulose by serving as an anchor to the end of the cleaved cellulose to which it is bonded, making it less mobile, and allowing it to have stronger interactions than those in pure hydrolyzed cellulose. Hydrolysis increases with the size of the substituent. Molecules sorbed but not grafted to cellulose do not increase hydrolysis. Hydrolysis mainly occurs at glucoses bonded to the substituent. A substituent on the sixth carbon position of cellulose increases hydrolysis to a greater extent than does one on the second or third carbon position. The effect of blending poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) and the effect of various arrangements of L-lactide and D-lactide in poly(L-lactide-co-D-lactide) on the resistance of polylactide (PLA) to hydrolysis has been explained. Among the homopolymer blends, the 50/50 PLLA/PDLA blend has the greatest resistance to hydrolysis due to its having stronger hydrogen-bonding and van der Waals forces than pure PLLA or PDLA. The change in potential energy for hydrolysis decreases linearly with increasing % PLLA or % PDLA from 0 to 50%. Among the copolymers containing a given percentage of L-lactide and D-lactide, those containing longer blocks of L-lactide and D-lactide have greater resistance to hydrolysis compared to those with shorter blocks or random copolymers because copolymers with longer blocks are more stable before hydrolysis compared to the other copolymers. Among the copolymers with long blocks of L- and D-lactide, those containing 50% L-lactide have a greater resistance to hydrolysis compared to the copolymers with 26% or 74% L-lactide. Blends or copolymers that are mirror images of each other have the same resistance to

  11. Intermolecular Hydrogen Bonds Formed Between Amino Acid Molecules in Aqueous Solution Investigated by Temperature-jump Nanosecond Time-resolved Transient Mid-IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ye, Man-ping; Li, Heng; Zhang, Qing-li; Weng, Yu-xiang; Qiu, Xiang-gang

    2007-08-01

    Carboxyl (COO-) vibrational modes of two amino acids histidine and glycine in D2O solution were investigated by temperature-dependent FTIR spectroscopy and temperature-jump nanosecond time-resolved IR difference absorbance spectroscopy. The results show that hydrogen bonds are formed between amino acid molecules as well as between the amino acid molecule and the solvent molecules. The asymmetric vibrational frequency of COO- around 1600-1610 cm-1 is blue shifted when raising temperature, indicating that the strength of the hydrogen bonds becomes weaker at higher temperature. Two bleaching peaks at 1604 and 1612 cm-1 were observed for histidine in response to a temperature jump from 10 °C to 20 °C. The lower vibrational frequency at 1604 cm-1 is assigned to the chain COO- group which forms the intermolecular hydrogen bond with NH3+ group, while the higher frequency at 1612 cm-1 is assigned to the end COO- group forming hydrogen bonds with the solvent molecules. This is because that the hydrogen bonds in the former are expected to be stronger than the latter. In addition the intensities of these two bleaching peaks are almost the same. In contrast, only the lower frequency at 1604 cm-1 bleaching peak has been observed for glycine. The fact indicates that histidine molecules form a dimer-like intermolecular chain while glycine forms a relatively longer chain in the solution. The rising phase of the IR absorption kinetics in response to the temperature-jump detected at 1604 cm-1 for histidine is about 30+/-10 ns, within the resolution limit of our instrument, indicating that breaking or weakening the hydrogen bond is a very fast process.

  12. Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host-Guest Systems.

    PubMed

    Zhang, Dawei; Chatelet, Bastien; Serrano, Eloisa; Perraud, Olivier; Dutasta, Jean-Pierre; Robert, Vincent; Martinez, Alexandre

    2015-10-01

    The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation-π and anion-π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron-poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion-pair recognition. Wavefunction calculations highlight how short- and long-range interactions interfere in this recognition process, suggesting that a disruption of anion-π interactions can occur in the presence of a co-bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. PMID:26401973

  13. Shell forming system

    NASA Technical Reports Server (NTRS)

    Kendall, Jr., James M. (Inventor); Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor)

    1987-01-01

    An apparatus is provided for forming gas-filled spheres of metal, glass or other material, which produces spheres (12) of uniform size and wall thickness in a relatively simple system. The system includes concentric nozzles, including an inner nozzle (18) through which gas flows and and an outer nozzle (20), which jointly define an annular passageway (50) through which a liquid flows. The flow rates are adjusted so that the gas flows at greater velocity than does the liquid, out of their respective nozzles, e.g. three times as great, in order to produce an extrusion (30) which undergoes axisymmetric oscillations resulting in the pinch off into hollow spheres with very uniform spacing. The system is useful not only where gas-filled spheres are required, but also is useful to accurately control the dispensing of solid, liquid, or gaseous materials.

  14. Methyl group dynamics in paracetamol and acetanilide: probing the static properties of intermolecular hydrogen bonds formed by peptide groups

    NASA Astrophysics Data System (ADS)

    Johnson, M. R.; Prager, M.; Grimm, H.; Neumann, M. A.; Kearley, G. J.; Wilson, C. C.

    1999-06-01

    Measurements of tunnelling and librational excitations for the methyl group in paracetamol and tunnelling excitations for the methyl group in acetanilide are reported. In both cases, results are compared with molecular mechanics calculations, based on the measured low temperature crystal structures, which follow an established recipe. Agreement between calculated and measured methyl group observables is not as good as expected and this is attributed to the presence of comprehensive hydrogen bond networks formed by the peptide groups. Good agreement is obtained with a periodic quantum chemistry calculation which uses density functional methods, these calculations confirming the validity of the one-dimensional rotational model used and the crystal structures. A correction to the Coulomb contribution to the rotational potential in the established recipe using semi-emipircal quantum chemistry methods, which accommodates the modified charge distribution due to the hydrogen bonds, is investigated.

  15. Desensitization and recovery of metastable intermolecular composites

    DOEpatents

    Busse, James R.; Dye, Robert C.; Foley, Timothy J.; Higa, Kelvin T.; Jorgensen, Betty S.; Sanders, Victor E.; Son, Steven F.

    2010-09-07

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  16. An approach to the origin of self-replicating system. I - Intermolecular interactions

    NASA Technical Reports Server (NTRS)

    Macelroy, R. D.; Coeckelenbergh, Y.; Rein, R.

    1978-01-01

    The present paper deals with the characteristics and potentialities of a recently developed computer-based molecular modeling system. Some characteristics of current coding systems are examined and are extrapolated to the apparent requirements of primitive prebiological coding systems.

  17. Forming different planetary systems

    NASA Astrophysics Data System (ADS)

    Zhou, Ji-Lin; Xie, Ji-Wei; Liu, Hui-Gen; Zhang, Hui; Sun, Yi-Sui

    2012-08-01

    With the increasing number of detected exoplanet samples, the statistical properties of planetary systems have become much clearer. In this review, we summarize the major statistical results that have been revealed mainly by radial velocity and transiting observations, and try to interpret them within the scope of the classical core-accretion scenario of planet formation, especially in the formation of different orbital architectures for planetary systems around main sequence stars. Based on the different possible formation routes for different planet systems, we tentatively classify them into three major catalogs: hot Jupiter systems, standard systems and distant giant planet systems. The standard system can be further categorized into three sub-types under different circumstances: solar-like systems, hot Super-Earth systems, and subgiant planet systems. We also review the theory of planet detection and formation in binary systems as well as planets in star clusters.

  18. Shell forming system

    NASA Technical Reports Server (NTRS)

    Kendall, Jr., James M. (Inventor); Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor)

    1990-01-01

    Hollow shells of high uniformity are formed by emitting liquid through an outer nozzle and gas through an inner nozzle, to form a hollow extrusion, by flowing the gas at a velocity between about 1.3 and 10 times the liquid velocity. The natural breakup rate of the extrusion can be increased to decrease shell size by applying periodic perturbations to one of the materials prior to exiting the nozzles, to a nozzle, or to the extrusion.

  19. Canonical forms for nonlinear systems

    NASA Technical Reports Server (NTRS)

    Su, R.; Hunt, L. R.; Meyer, G.

    1983-01-01

    Necessary and sufficient conditions for transforming a nonlinear system to a controllable linear system have been established, and this theory has been applied to the automatic flight control of aircraft. These transformations show that the nonlinearities in a system are often not intrinsic, but are the result of unfortunate choices of coordinates in both state and control variables. Given a nonlinear system (that may not be transformable to a linear system), we construct a canonical form in which much of the nonlinearity is removed from the system. If a system is not transformable to a linear one, then the obstructions to the transformation are obvious in canonical form. If the system can be transformed (it is called a linear equivalent), then the canonical form is a usual one for a controllable linear system. Thus our theory of canonical forms generalizes the earlier transformation (to linear systems) results. Our canonical form is not unique, except up to solutions of certain partial differential equations we discuss. In fact, the important aspect of this paper is the constructive procedure we introduce to reach the canonical form. As is the case in many areas of mathematics, it is often easier to work with the canonical form than in arbitrary coordinate variables.

  20. Morphology and the Strength of Intermolecular Contact in Protein Crystals

    NASA Technical Reports Server (NTRS)

    Matsuura, Yoshiki; Chernov, Alexander A.

    2002-01-01

    The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

  1. Spin radical enhanced magnetocapacitance effect in intermolecular excited states.

    PubMed

    Zang, Huidong; Wang, Jianguo; Li, Mingxing; He, Lei; Liu, Zitong; Zhang, Deqing; Hu, Bin

    2013-11-14

    This article reports the magnetocapacitance effect (MFC) based on both pristine polymer MEH-PPV and its composite system doped with spin radicals (6R-BDTSCSB). We observed that a photoexcitation leads to a significant positive MFC in the pristine MEH-PPV. Moreover, we found that a low doping of spin radicals in polymer MEH-PPV causes a significant change on the MFC signal: an amplitude increase and a line-shape narrowing under light illumination at room temperature. However, no MFC signal was observed under dark conditions in either the pristine MEH-PPV or the radical-doped MEH-PPV. Furthermore, the magnitude increase and line-shape narrowing caused by the doped spin radicals are very similar to the phenomena induced by increasing the photoexcitation intensity. Our studies suggest that the MFC is essentially originated from the intermolecular excited states, namely, intermolecular electron-hole pairs, generated by a photoexcitation in the MEH-PPV. More importantly, by comparing the effects of spin radicals and electrically polar molecules on the MFC magnitude and line shape, we concluded that the doped spin radicals can have the spin interaction with intermolecular excited states and consequently affect the internal spin-exchange interaction within intermolecular excited states in the development of MFC. Clearly, our experimental results indicate that dispersing spin radicals forms a convenient method to enhance the magnetocapacitance effect in organic semiconducting materials. PMID:24144347

  2. Substrate system for spray forming

    DOEpatents

    Chu, Men G.; Chernicoff, William P.

    2002-01-01

    A substrate system for receiving a deposit of sprayed metal droplets including a movable outer substrate on which the sprayed metal droplets are deposited. The substrate system also includes an inner substrate disposed adjacent the outer substrate where the sprayed metal droplets are deposited on the outer substrate. The inner substrate includes zones of differing thermal conductivity to resist substrate layer porosity and to resist formation of large grains and coarse constituent particles in a bulk layer of the metal droplets which have accumulated on the outer substrate. A spray forming apparatus and associated method of spray forming a molten metal to form a metal product using the substrate system of the invention is also provided.

  3. Substrate system for spray forming

    DOEpatents

    Chu, Men G.; Chernicoff, William P.

    2000-01-01

    A substrate system for receiving a deposit of sprayed metal droplets including a movable outer substrate on which the sprayed metal droplets are deposited. The substrate system also includes an inner substrate disposed adjacent the outer substrate where the sprayed metal droplets are deposited on the outer substrate. The inner substrate includes zones of differing thermal conductivity to resist substrate layer porosity and to resist formation of large grains and coarse constituent particles in a bulk layer of the metal droplets which have accumulated on the outer substrate. A spray forming apparatus and associated method of spray forming a molten metal to form a metal product using the substrate system of the invention is also provided.

  4. Centrosymmetric resonance-assisted intermolecular hydrogen bonding chains in the enol form of β-diketone: Crystal structure and theoretical study.

    PubMed

    Franca, Eduardo F; Guilardi, Silvana; Paixão, Drielly A; Teixeira, Róbson R; Pereira, Wagner L; Ellena, Javier A

    2016-07-01

    Isobenzofuran-1(3H)-ones (phtalides) are heterocycles that present a benzene ring fused to a γ-lactone functionality. This structural motif is found in several natural and synthetic compounds that present relevant biological activities. In the present investigation, the 3-(2-hydroxy-4,4-dimethyl-6-oxocyclohexen-1-yl)isobenzofuran-1(3H)-one was characterized by single-crystal X-ray analysis. In the crystal structure, there are two molecules per asymmetric unit. One of them exhibits resonance assisted hydrogen bonds (RAHBs). Semi-empirical and DFT calculations were performed to obtain electronic structure and π-delocalization parameters, in order to better understand the energy stabilization of RAHBs in the crystal packing of the studied molecule. The structural parameters showed good agreement between theoretical and experimental data. The theoretical investigation revealed that the RAHBs stabilization energy is directly related to the electronic delocalization of the enol form fragment. In addition, RAHBs significantly affected the HOMO and charge distribution around the conjugated system. PMID:27410224

  5. Intermolecular perturbation theory

    NASA Astrophysics Data System (ADS)

    Hayes, I. C.; Hurst, G. J. B.; Stone, A. J.

    The new intermolecular perturbation theory described in the preceding papers is applied to some van der Waals molecules. HeBe is used as a test case, and the perturbation method converges well at interatomic distances down to about 4 a0, giving results in excellent agreement with supermolecule calculations. ArHF and ArHCl have been studied using large basis sets, and the results agree well with experimental data. The ArHX configuration is favoured over the ArXH configuration mainly because of larger polarization and charge-transfer contributions. In NeH2 the equilibrium geometry is determined by a delicate balance between opposing effects; with a double-zeta-polarization basis the correct configuration is predicted.

  6. Mapping intermolecular bonding in C60

    PubMed Central

    Sundqvist, Bertil

    2014-01-01

    The formation of intermolecular bonds in C60 has been investigated in detail at pressures below 2.2 GPa and up to 750 K. Fullerene samples were heated in a temperature gradient to obtain data on the formation of dimers and low-dimensional polymers along isobars. Intermolecular bonding was analyzed ex situ by Raman scattering, using both intramolecular modes and intermolecular stretching modes. Semi-quantitative reaction maps are given for the formation of dimers and chains. The activation energy for dimer formation decreases by 0.2 meV pm−1 when intermolecular distances decrease and dimer formation is noticeably affected by the rotational state of molecules. Above 400–450 K larger oligomers are formed; below 1.4 GPa most of these are disordered, with small domains of linear chains, but above this the appearance of stretching modes indicates the existence of ordered one-dimensional polymers. At the highest pressures and temperatures two-dimensional polymers are also observed. PMID:25145952

  7. The structure of a tetrameric α-carbonic anhydrase from Thermovibrio ammonificans reveals a core formed around intermolecular disulfides that contribute to its thermostability.

    PubMed

    James, Paul; Isupov, Michail N; Sayer, Christopher; Saneei, Vahid; Berg, Svein; Lioliou, Maria; Kotlar, Hans Kristian; Littlechild, Jennifer A

    2014-10-01

    Carbonic anhydrase enzymes catalyse the reversible hydration of carbon dioxide to bicarbonate. A thermophilic Thermovibrio ammonificans α-carbonic anhydrase (TaCA) has been expressed in Escherichia coli and structurally and biochemically characterized. The crystal structure of TaCA has been determined in its native form and in two complexes with bound inhibitors. The tetrameric enzyme is stabilized by a unique core in the centre of the molecule formed by two intersubunit disulfides and a single lysine residue from each monomer that is involved in intersubunit ionic interactions. The structure of this core protects the intersubunit disulfides from reduction, whereas the conserved intrasubunit disulfides are not formed in the reducing environment of the E. coli host cytosol. When oxidized to mimic the environment of the periplasmic space, TaCA has increased thermostability, retaining 90% activity after incubation at 70°C for 1 h, making it a good candidate for industrial carbon-dioxide capture. The reduction of all TaCA cysteines resulted in dissociation of the tetrameric molecule into monomers with lower activity and reduced thermostability. Unlike other characterized α-carbonic anhydrases, TaCA does not display esterase activity towards p-nitrophenyl acetate, which appears to result from the increased rigidity of its protein scaffold. PMID:25286845

  8. Intermolecular shielding from molecular magnetic susceptibility. A new view of intermolecular ring current effects.

    PubMed

    Facelli, Julio C

    2006-03-01

    This paper presents calculations of the NICS (nuclear independent chemical shieldings) in a rectangular grid surrounding the molecules of benzene, naphthalene and coronene. Using the relationship between calculated NICS and the induced magnetic field, the calculated NICS are used to predict intermolecular effects due to molecular magnetic susceptibility or ring current effects. As expected from approximate ring current models, these intermolecular shielding effects are concentrated along the direction perpendicular to the molecular plane and they approach asymptotically to a dipolar functional dependence, i.e. (1-3 cos(2)theta)/r(3)). The deviations from the dipolar functional form require that the calculations of these intermolecular effects be done using a suitable interpolation scheme of the NICS calculated on the grid. The analysis of the NICS tensor components shows that these intermolecular shielding effects should be primarily expected on shielding components of the neighboring molecules nuclei, which are perpendicular to the molecular plane of the aromatic compound generating the induced field. The analysis of the calculated NICS along the series benzene, naphthalene and coronene shows that these intermolecular effects increase monotonically with the number of aromatic rings. PMID:16477673

  9. System for forming janus particles

    DOEpatents

    Hong, Liang; Jiang, Shan; Granick, Steve

    2011-01-25

    The invention is a method of forming Janus particles, that includes forming an emulsion that contains initial particles, a first liquid, and a second liquid; solidifying the first liquid to form a solid that contains at least a portion of the initial particles on a surface of the solid; and treating the exposed particle sides with a first surface modifying agent, to form the Janus particles. Each of the initial particles on the surface has an exposed particle side and a blocked particle side.

  10. White polymer light-emitting electrochemical cells using emission from exciplexes with long intermolecular distances formed between polyfluorene and π-conjugated amine molecules

    NASA Astrophysics Data System (ADS)

    Nishikitani, Y.; Takeuchi, H.; Nishide, H.; Uchida, S.; Yazaki, S.; Nishimura, S.

    2015-12-01

    The authors present white polymer light-emitting electrochemical cells (PLECs) fabricated with polymer blend films of poly(9,9-di-n-dodecylfluorenyl-2,7-diyl) (PFD) and π-conjugated triphenylamine molecules. The PLECs have bulk heterojunction structures composed of van der Waals interfaces between the PFD segments and the amine molecules. White-light electroluminescence (EL) can be achieved via light-mixing of the blue exciton emission from PFD and long-wavelength exciplex emission from excited complexes consisting of PFD segments (acceptors (As)) and the amine molecules (donors (Ds)). Precise control of the distances between the PFD and the amine molecules, affected through proper choice of the concentrations of PFD, amine molecules, and polymeric solid electrolytes, is critical to realizing white emission. White PLECs can be fabricated with PFD and amine molecules whose highest occupied molecular orbital (HOMO) levels range from -5.3 eV to -5.0 eV. Meanwhile, PLECs fabricated with amine molecules whose HOMO levels are lower than -5.6 eV cannot produce exciplex emission. The distances between the PFD and amine molecules of the exciplexes appear to be larger than 0.4 nm. These experimental data are explained by perturbation theory using the charge-transfer state ( A - D + ), the locally excited state ( A * D ), which is assumed to be the locally excited acceptor state in which there is no interaction with the donor molecule; and the energy gap between the HOMO levels of the PFD and the amine molecules. Color-stable white PLECs were fabricated using 4,4',4″-tris[N-(2-naphthyl)-N-phenylamino]-triphenylamine, which has a HOMO level of -5.2 eV, as the amine molecule, and the color stability of the device is a function of the fact that PFD forms exciplexes with these molecules.

  11. A canonical form for nonlinear systems

    NASA Technical Reports Server (NTRS)

    Su, R.; Hunt, L. R.

    1986-01-01

    The concepts of transformation and canonical form have been used in analyzing linear systems. These ideas are extended to nonlinear systems. A coordinate system and a corresponding canonical form are developed for general nonlinear control systems. Their usefulness is demonstrated by showing that every feedback linearizable system becomes a system with only feedback paths in the canonical form. For control design involving a nonlinear system, one approach is to put the system in its canonical form and approximate by that part having only feedback paths.

  12. Frontier orbital symmetry control of intermolecular electron transfer

    SciTech Connect

    Stevens, B.

    1990-11-01

    Research continued on the study of intermolecular electron transfer. This report discusses the following topics: fluorescence quenching by electron transfer and the modification of quenching dynamics by solvent properties and net free energy change; transient absorption measurements following selective excitation of 1:1 EDA complex isomers; selective quenching of dual fluorescence from linked EDA systems; electron-transfer sensitized cycloreversion of rubrene endoperoxide; and vibronic modification of adiabatic requirements for intermolecular electron transfer. (CBS)

  13. Intermolecular electrostatic energies using density fitting

    PubMed Central

    Cisneros, G. Andrés; Piquemal, Jean-Philip; Darden, Thomas A.

    2009-01-01

    A method is presented to calculate the electron-electron and nuclear-electron intermolecular Coulomb interaction energy between two molecules by separately fitting the unperturbed molecular electron density of each monomer. This method is based on the variational Coulomb fitting method which relies on the expansion of the ab initio molecular electron density in site-centered auxiliary basis sets. By expanding the electron density of each monomer in this way the integral expressions for the intermolecular electrostatic calculations are simplified, lowering the operation count as well as the memory usage. Furthermore, this method allows the calculation of intermolecular Coulomb interactions with any level of theory from which a one-electron density matrix can be obtained. Our implementation is initially tested by calculating molecular properties with the density fitting method using three different auxiliary basis sets and comparing them to results obtained from ab initio calculations. These properties include dipoles for a series of molecules, as well as the molecular electrostatic potential and electric field for water. Subsequently, the intermolecular electrostatic energy is tested by calculating ten stationary points on the water dimer potential-energy surface. Results are presented for electron densities obtained at four different levels of theory using two different basis sets, fitted with three auxiliary basis sets. Additionally, a one-dimensional electrostatic energy surface scan is performed for four different systems (H2O dimer, Mg2+–H2O, Cu+–H2O, and n-methyl-formamide dimer). Our results show a very good agreement with ab initio calculations for all properties as well as interaction energies. PMID:16095348

  14. Evaluation of Questions in General Chemistry Textbooks According to the Form of the Questions and the Question-Answer Relationship (QAR): The Case of Intra-and Intermolecular Chemical Bonding

    ERIC Educational Resources Information Center

    Pappa, Eleni T.; Tsaparlis, Georgios

    2011-01-01

    One way of checking to what extent instructional textbooks achieve their aim is to evaluate the questions they contain. In this work, we analyze the questions that are included in the chapters on chemical bonding of ten general chemistry textbooks. We study separately the questions on intra- and on intermolecular bonding, with the former…

  15. Studies on intermolecular interaction on binary mixtures of methyl orange-water system: excess molar functions of ultrasonic parameters at different concentrations and at different temperatures.

    PubMed

    Thanuja, B; Kanagam, Charles; Sreedevi, S

    2011-11-01

    Density (ρ), viscosity (η) and ultrasonic velocity (u) of binary mixtures of methyl orange and water were measured at different concentrations and at different temperatures; several useful parameters such as excess volume, excess velocity, and excess adiabatic compressibility have been calculated. These parameters are used to explain the nature of intermolecular interactions taking place in the binary mixture. The above study is helpful in understanding the dye/solvent interaction at different concentration and temperatures. PMID:21596612

  16. Plasma formed ion beam projection lithography system

    SciTech Connect

    Leung, Ka-Ngo; Lee, Yung-Hee Yvette; Ngo, Vinh; Zahir, Nastaran

    2002-01-01

    A plasma-formed ion-beam projection lithography (IPL) system eliminates the acceleration stage between the ion source and stencil mask of a conventional IPL system. Instead a much thicker mask is used as a beam forming or extraction electrode, positioned next to the plasma in the ion source. Thus the entire beam forming electrode or mask is illuminated uniformly with the source plasma. The extracted beam passes through an acceleration and reduction stage onto the resist coated wafer. Low energy ions, about 30 eV, pass through the mask, minimizing heating, scattering, and sputtering.

  17. Cross linking molecular systems to form ultrathin dielectric layers

    NASA Astrophysics Data System (ADS)

    Feng, Danqin

    Dehydrogenation leads to cross linking of polymer or polymer like formation in very different systems: self-assembled monolayers and in closo -carboranes leading to the formation of semiconducting and dielectric boron carbide. We find evidence of intermolecular interactions for a self-assembled monolayer (SAM) formed from a large molecular adsorbate, [1,1';4',1"-terphenyl]-4,4"-dimethanethiol, from the dispersion of the molecular orbitals with changing the wave vector k and from the changes with temperature. With the formation self assembled molecular (SAM) layer, the molecular orbitals hybridize to electronic bands, with indications of significant band dispersion of the unoccupied molecular orbitals. Although organic adsorbates and thin films are generally regarded as "soft" materials, the effective Debye temperature, indicative of the dynamic motion of the lattice normal to the surface, can be very high, e.g. in the multilayer film formed from [1,1'-biphenyl]-4,4'-dimethanethiol (BPDMT). Depending on molecular orientation, the effective Debye temperature can be comparable to that of graphite due to the 'stiffness' of the benzene rings, but follows the expected Debye-Waller behavior for the core level photoemission intensities with temperature. This is not always the case. We find that a monomolecular film formed from [1,1';4',1"-terphenyl]-4,4"-dimethanethiol deviates from Debye-Waller temperature behavior and is likely caused by temperature dependent changes in molecular orientation. We also find evidence for the increase in dielectric character with polymerization (cross-linking) in spite of the decrease in the HOMO-LUMO gap upon irradiation of TPDMT. The changes in the HOMO-LUMO gap, with cross-linking, are roughly consistent with the band dispersion. The decomposition and cross-linking processes are also accompanied by changes in molecular orientation. The energetics of the three isomeric carborane cage compounds [ closo-1,2-orthocarborane, closo-1

  18. Intermolecular interactions in rifabutin—2-hydroxypropyl-β-cyclodextrin—water solutions

    NASA Astrophysics Data System (ADS)

    Anshakova, A. V.; Yermolenko, Yu. V.; Konyukhov, V. Yu.; Polshakov, V. I.; Maksimenko, O. O.; Gelperina, S. E.

    2015-05-01

    The possibility of a intermolecular complex rifabutin (RB)-2-hydroxypropyl-β-cyclodextrin (HP-β-CD) formed as a result of the interaction of the piperidine fragment of the RB molecule and the hydrophobic cavity of the HP-β-CD molecule was found. The stability constant of the intermolecular complex was determined.

  19. Slab edge insulating form system and methods

    DOEpatents

    Lee, Brain E.; Barsun, Stephan K.; Bourne, Richard C.; Hoeschele, Marc A.; Springer, David A.

    2009-10-06

    A method of forming an insulated concrete foundation is provided comprising constructing a foundation frame, the frame comprising an insulating form having an opening, inserting a pocket former into the opening; placing concrete inside the foundation frame; and removing the pocket former after the placed concrete has set, wherein the concrete forms a pocket in the placed concrete that is accessible through the opening. The method may further comprise sealing the opening by placing a sealing plug or sealing material in the opening. A system for forming an insulated concrete foundation is provided comprising a plurality of interconnected insulating forms, the insulating forms having a rigid outer member protecting and encasing an insulating material, and at least one gripping lip extending outwardly from the outer member to provide a pest barrier. At least one insulating form has an opening into which a removable pocket former is inserted. The system may also provide a tension anchor positioned in the pocket former and a tendon connected to the tension anchor.

  20. Dancing Crystals: A Dramatic Illustration of Intermolecular Forces

    ERIC Educational Resources Information Center

    Mundell, Donald W.

    2007-01-01

    Crystals of naphthalene form on the surface of an acetone solution and dance about in an animated fashion illustrating surface tension, crystallization, and intermolecular forces. Additional experiments reveal the properties of the solution. Flows within the solutions can be visualized by various means. Previous demonstrations of surface motion…

  1. Intermolecular Silacarbonyl Ylide Cycloadditions: A Direct Pathway to Oxasilacyclopentenes

    PubMed Central

    Bourque, Laura E.; Woerpel, K. A.

    2009-01-01

    Silacarbonyl ylides, generated by metal-catalyzed silylene transfer to carbonyls, participate in formal intermolecular 1,3-dipolar cycloaddition reactions with carbonyl compounds and alkynes to form dioxasilacyclopentane acetals and oxasilacyclopentenes in an efficient, one-step process. PMID:18922005

  2. Plastic instability in omega forming alloy systems

    NASA Astrophysics Data System (ADS)

    Banerjee, S.

    2006-11-01

    The plastic flow behaviour of two ω forming systems namely ordered Nb-40Ti-15Al and metastable Zr-Nb alloys has been studied over a range of strain rate and temperature to establish the domain of serrated flow or Protevin-Le Chatelier (PLC) effect. The observed features of serrated flow in these alloys are strikingly similar to that observed during PLC effect of solid solution alloys. Samples deformed in the serrated flow regime have been studied at different levels of magnification using light, scanning electron and transmission electron microscopy. A very characteristic feature of deformation in these alloys has been the presence precipitate free channels, microbands and deformation bands. The proposed mechanism of serrated flow involves creation of soft channels formed by shearing of ω-particles and dynamic restoration of ω-particles within the soft channel resulting in pinning of dislocation. It appears that this is the characteristic feature of deformation of ω forming system exhibiting PLC effect.

  3. Maximizing Singlet Fission by Intermolecular Packing.

    PubMed

    Wang, Linjun; Olivier, Yoann; Prezhdo, Oleg V; Beljonne, David

    2014-10-01

    A novel nonadiabatic molecular dynamics scheme is applied to study the singlet fission (SF) process in pentacene dimers as a function of longitudinal and lateral displacements of the molecular backbones. Detailed two-dimensional mappings of both instantaneous and long-term triplet yields are obtained, characterizing the advantageous and unfavorable stacking arrangements, which can be achieved by chemical substitutions to the bare pentacene molecule. We show that the SF rate can be increased by more than an order of magnitude through tuning the intermolecular packing, most notably when going from cofacial to the slipped stacked arrangements encountered in some pentacene derivatives. The simulations indicate that the SF process is driven by thermal electron-phonon fluctuations at ambient and high temperatures, expected in solar cell applications. Although charge-transfer states are key to construct continuous channels for SF, a large charge-transfer character of the photoexcited state is found to be not essential for efficient SF. The reported time domain study mimics directly numerous laser experiments and provides novel guidelines for designing efficient photovoltaic systems exploiting the SF process with optimum intermolecular packing. PMID:26278443

  4. Forming the Solar System from Pebbles

    NASA Astrophysics Data System (ADS)

    Kretke, Katherine A.; Levison, H. F.

    2015-12-01

    In recent years, theories surrounding the formation of small-bodies and planets have been undergoing a radical shift. Particles with stopping times comparable to their orbital times, often called "pebbles" (although they range from sub-centimeter to meter sizes), interact with gaseous protoplanetary disks in very special ways. This allows them to be not only be concentrated, allowing them to gravitationally collapse and directly produce the planetesimal building blocks of planetary systems, but also later be efficiently accreted on to these planetesimals, rapidly producing larger planets. Here we present simulations using the planet formation code LIPAD, which can follow the dynamical evolution of planetary system all the way from pebbles and planetesimals to mature planetary systems. We show how pebble accretion can explain the observed structure of our Solar System, by forming a system of giant planets, ice giants, and a system of terrestrial planets; even providing an explanation the for the low mass of Mars and of the Asteroid Belt.

  5. Reducing quasilinear systems to block triangular form

    SciTech Connect

    Tunitsky, Dmitry V

    2013-03-31

    The paper is concerned with systems of n quasilinear partial differential equations of the first order with 2 independent variables. Using a geometric formalism for such equations, which goes back to Riemann, it is possible to assign a field of linear operators on an appropriate vector bundle to this type of quasilinear system. Several tests for a quasilinear system to be reducible to triangular or block triangular form are obtained in terms of this field; they supplement well known results on diagonalization and block diagonalization due to Haantjes and Bogoyavlenskij. Bibliography: 10 titles.

  6. Identification and measurement of intermolecular interaction in polyester/polystyrene blends by FTIR-photoacoustic spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fourier transform infrared photoacoustic spectrometry was used to reveal and identify n-p type intermolecular interaction formed in plastic comprising binary blends of polystyrene and a biodegradable polymer, either polylactic acid, polycaprolactone or poly(tetramethyleneadipate-co-terephthalate)....

  7. Correlation functions for glass-forming systems

    PubMed

    Jacobs

    2000-07-01

    We present a simple, linear, partial-differential equation for the density-density correlation function in a glass-forming system. The equation is written down on the basis of fundamental and general considerations of linearity, symmetry, stability, thermodynamic irreversibility and consistency with the equation of continuity (i.e. , conservation of matter). The dynamical properties of the solutions show a change in behavior characteristic of the liquid-glass transition as a function of one of the parameters (temperature). The equation can be shown to lead to the simplest mode-coupling theory of glasses and provides a partial justification of this simplest theory. It provides also a method for calculating the space dependence of the correlation functions not available otherwise. The results suggest certain differences in behavior between glassy solids and glass-forming liquids which may be accessible to experiment. A brief discussion is presented of how the method can be applied to other systems such as sandpiles and vortex glasses in type II superconductors. PMID:11088609

  8. Determination of Multidimensional Intermolecular Potential Energy Surfaces

    NASA Astrophysics Data System (ADS)

    Cohen, Ronald Carl

    High resolution spectroscopy of the low frequency van der Waals vibrations (also referred to as Vibration -Rotation-Tunneling (VRT) spectroscopy) in weakly bound complexes provides the means to probe intermolecular forces with unprecedented detail and precision. We present an overview of the experimental information on intermolecular forces and intermolecular dynamics which has been obtained by far infrared VRT spectroscopy of 18 complexes. We then turn to a detailed examination of the Ar-H_2O complex, a simple prototype for the study of intermolecular forces. The measurement and analysis of 9 VRT bands is described. These data are first used to obtain a qualitative description of the intermolecular potential energy surface (IPS). A new simple and efficient method for calculating the eigenvalues of the multidimensional intermolecular dynamics on the IPS has been developed. This algorithm (an adaptation of the Collocation Method) was then used in a direct fit to obtain an accurate and detailed description of the intermolecular forces acting within the Ar-H_2O complex.

  9. Pressure Modulation of Backbone Conformation and Intermolecular Distance of Conjugated Polymers Toward Understanding the Dynamism of π-Figuration of their Conjugated System.

    PubMed

    Noguchi, Yuki; Saeki, Akinori; Fujiwara, Takenori; Yamanaka, Sho; Kumano, Masataka; Sakurai, Tsuneaki; Matsuyama, Naoto; Nakano, Motohiro; Hirao, Naohisa; Ohishi, Yasuo; Seki, Shu

    2015-06-18

    Continuous tuning of the backbone conformation and interchain distance of a π-conjugated polymer is an essential prerequisite to unveil the inherent electrical and optical features of organic electronics. To this end, applying pressure in a hydrostatic medium or diamond anvil cell is a facile approach without the need for side-chain synthetic engineering. We report the development of high-pressure, time-resolved microwave conductivity (HP-TRMC) and evaluation of transient photoconductivity in the regioregular poly(3-hexylthiophene) (P3HT) film and its bulk heterojunction blend with methanofullerene (PCBM). X-ray diffraction experiments under high pressure were performed to detail the pressure dependence of π-stacking and interlamellar distances in P3HT crystallites and PCBM aggregates. The HP-TRMC results were further correlated with high-pressure Raman spectroscopy and density functional theory calculation. The increased HP-TRMC conductivity of P3HT under pressure was found to be relevant to the planarity of the backbone conformation and intramolecular hole mobility. The effects of pressure on the backbone planarity are estimated to be ∼0.3 kJ mol(-1) based on the compressibility derived from the X-ray diffraction under high pressure, suggesting the high enough energy to cause modulation of the planarity in terms of the Landau-de Gennes free energy of isolated P3HT chains as 0.23 kJ mol(-1). In contrast, the P3HT:PCBM blend showed a simple decrease in photoconductivity irrespective of the identical compressive behavior of P3HT. A mechanistic insight into the interplay of intra- and intermolecular mobilities is a key to tailoring the dynamic π-figuration associated with electrical properties, which may lead to the use of HP-TRMC for exploring divergent π-conjugated materials at the desired molecular arrangement and conformation. PMID:25563063

  10. Kinetic theory for flows of nonhomogeneous rodlike liquid crystalline polymers with a nonlocal intermolecular potential.

    PubMed

    Wang, Qi; E, Weinan; Liu, Chun; Zhang, Pingwen

    2002-05-01

    The Doi kinetic theory for flows of homogeneous, rodlike liquid crystalline polymers (LCPs) is extended to model flows of nonhomogeneous, rodlike LCPs through a nonlocal (long-range) intermolecular potential. The theory features (i) a nonlocal, anisotropic, effective intermolecular potential in an integral form that is consistent with the chemical potential, (ii) short-range elasticity as well as long-range isotropic and anisotropic elasticity, (iii) a closed-form stress expression accounting for the nonlocal molecular interaction, and (iv) an extra elastic body force exclusively associated with the integral form of the intermolecular potential. With the effective intermolecular potential, the theory is proven to be well posed in that it warrants a positive entropy production and thereby the second law of thermodynamics. Approximate theories are obtained by gradient expansions of the number density function in the free energy density. PMID:12059561

  11. Mechanism of Intermolecular Electron Transfer in Bionanostructures

    NASA Astrophysics Data System (ADS)

    Gruodis, A.; Galikova, N.; Šarka, K.; Saulė, R.; Batiuškaitė, D.; Saulis, G.

    Hepatocellular carcinoma (HCC) is one of the most common malignant tumors worldwide. Most patients are inoperable and hepatoma cells are resistant to conventional chemotherapies. Thus, the development of novel therapies for HCC treatment is of paramount importance. Amongst different alimentary factors, vitamin C and vitamin K3 In the present work, it has been shown that the treatment of mouse hepatoma MH-22A cells by vitamin C and vitamin K3 at the ratio of 100:1 greatly enhanced their cytotoxicity. When cells were subjected to vitamin C at 200 μM or to vitamin K3 at 2 μM separately, their viability reduced by only about 10%. However, when vitamins C and K3 were combined at the same concentrations, they killed more than 90% of cells. To elucidate the mechanism of the synergistic cytotoxicity of the C&K3 mixture, theoretical quantum-chemical analysis of the dynamics of intermolecular electron transfer (IET) processes within the complexes containing C (five forms) and K3 (one form) has been carried out. Optimization of the ground state complex geometry has been provided by means of GAUSSIAN03 package. Simulation of the IET has been carried out using NUVOLA package, in the framework of molecular orbitals (MO). The rate of IET has been calculated using Fermi Golden rule. The results of simulations allow us to create the preliminary model of the reaction pathway.

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

    DOE PAGESBeta

    Bai, Yang; He, Hui-Min; Li, Ying; Zhou, Zhong-Jun; Wang, Jia-Jun; Wu, Di; Chen, Wei; Gu, Feng-Long; Sumpter, Bobby G.; Huang, Jingsong

    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 (H2O)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

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

    SciTech Connect

    Bai, Yang; He, Hui-Min; Li, Ying; Zhou, Zhong-Jun; Wang, Jia-Jun; Wu, Di; Chen, Wei; Gu, Feng-Long; Sumpter, Bobby G.; Huang, Jingsong

    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, 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 (H2O)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.

  14. Intermolecular domain docking in the hairpin ribozyme

    PubMed Central

    Sumita, Minako; White, Neil A.; Julien, Kristine R.; Hoogstraten, Charles G.

    2013-01-01

    The hairpin ribozyme is a prototype small, self-cleaving RNA motif. It exists naturally as a four-way RNA junction containing two internal loops on adjoining arms. These two loops interact in a cation-driven docking step prior to chemical catalysis to form a tightly integrated structure, with dramatic changes occurring in the conformation of each loop upon docking. We investigate the thermodynamics and kinetics of the docking process using constructs in which loop A and loop B reside on separate molecules. Using a novel CD difference assay to isolate the effects of metal ions linked to domain docking, we find the intermolecular docking process to be driven by sub-millimolar concentrations of the exchange-inert Co(NH3)63+. RNA self-cleavage requires binding of lower-affinity ions with greater apparent cooperativity than the docking process itself, implying that, even in the absence of direct coordination to RNA, metal ions play a catalytic role in hairpin ribozyme function beyond simply driving loop-loop docking. Surface plasmon resonance assays reveal remarkably slow molecular association, given the relatively tight loop-loop interaction. This observation is consistent with a “double conformational capture” model in which only collisions between loop A and loop B molecules that are simultaneously in minor, docking-competent conformations are productive for binding. PMID:23324606

  15. 46 CFR 108.474 - Aqueous film forming foam systems.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 4 2014-10-01 2014-10-01 false Aqueous film forming foam systems. 108.474 Section 108... DESIGN AND EQUIPMENT Fire Extinguishing Systems Foam Extinguishing Systems § 108.474 Aqueous film forming foam systems. Aqueous film forming foam systems may be installed if approved by the Commandant....

  16. 46 CFR 108.474 - Aqueous film forming foam systems.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 4 2013-10-01 2013-10-01 false Aqueous film forming foam systems. 108.474 Section 108... DESIGN AND EQUIPMENT Fire Extinguishing Systems Foam Extinguishing Systems § 108.474 Aqueous film forming foam systems. Aqueous film forming foam systems may be installed if approved by the Commandant....

  17. 46 CFR 108.474 - Aqueous film forming foam systems.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 4 2012-10-01 2012-10-01 false Aqueous film forming foam systems. 108.474 Section 108... DESIGN AND EQUIPMENT Fire Extinguishing Systems Foam Extinguishing Systems § 108.474 Aqueous film forming foam systems. Aqueous film forming foam systems may be installed if approved by the Commandant....

  18. 46 CFR 108.474 - Aqueous film forming foam systems.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 4 2011-10-01 2011-10-01 false Aqueous film forming foam systems. 108.474 Section 108... DESIGN AND EQUIPMENT Fire Extinguishing Systems Foam Extinguishing Systems § 108.474 Aqueous film forming foam systems. Aqueous film forming foam systems may be installed if approved by the Commandant....

  19. 46 CFR 108.474 - Aqueous film forming foam systems.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 4 2010-10-01 2010-10-01 false Aqueous film forming foam systems. 108.474 Section 108... DESIGN AND EQUIPMENT Fire Extinguishing Systems Foam Extinguishing Systems § 108.474 Aqueous film forming foam systems. Aqueous film forming foam systems may be installed if approved by the Commandant....

  20. Quantitative tomographic imaging of intermolecular FRET in small animals

    PubMed Central

    Venugopal, Vivek; Chen, Jin; Barroso, Margarida; Intes, Xavier

    2012-01-01

    Forster resonance energy transfer (FRET) is a nonradiative transfer of energy between two fluorescent molecules (a donor and an acceptor) in nanometer range proximity. FRET imaging methods have been applied to proteomic studies and drug discovery applications based on intermolecular FRET efficiency measurements and stoichiometric measurements of FRET interaction as quantitative parameters of interest. Importantly, FRET provides information about biomolecular interactions at a molecular level, well beyond the diffraction limits of standard microscopy techniques. The application of FRET to small animal imaging will allow biomedical researchers to investigate physiological processes occurring at nanometer range in vivo as well as in situ. In this work a new method for the quantitative reconstruction of FRET measurements in small animals, incorporating a full-field tomographic acquisition system with a Monte Carlo based hierarchical reconstruction scheme, is described and validated in murine models. Our main objective is to estimate the relative concentration of two forms of donor species, i.e., a donor molecule involved in FRETing to an acceptor close by and a nonFRETing donor molecule. PMID:23243567

  1. Calculations of helical twisting powers from intermolecular torques.

    PubMed

    Earl, David J; Wilson, Mark R

    2004-05-22

    We present a Monte Carlo molecular simulation method that calculates the helical twisting power of a chiral molecule by sampling intermolecular torques. The approach is applied to an achiral nematic liquid crystalline system, composed of Gay-Berne particles, that is doped with chiral molecules. Calculations are presented for six chiral dopant molecules and the results show a good correlation with the sign and magnitude of experimentally determined helical twisting powers. PMID:15267981

  2. Femtosecond Fourier-transform spectroscopy of low-frequency intermolecular motions in weakly interacting liquids

    SciTech Connect

    Castner, E.W. Jr.; Chang, Y.J.; Melinger, J.S.; McMorrow, D.

    1993-07-01

    Recent work on the subject of solvation dynamics has concentrated on understanding the ultrafast dynamics of intermolecular interactions in strongly interacting, polar, and hydrogen-bonding solvents. In general, investigations into the effects of solvation dynamics on chemical reactions have concentrated on the highly polar liquids because it is in these solvents that the largest spectroscopic changes with solvent relaxation are observed. In these very polar liquids, however, the intermolecular dynamics are very complex, consisting of contributions from reorientational diffusion, inertially limited rotations, intermolecular vibrations involving both reorientational (librational) and translational degrees of freedom, and interaction-induced collisional effects. The role of collisional interaction-induced effects in shaping the intermolecular dynamics of molecular liquids has been a subject of considerable discussion. Molecular dynamics simulations have suggested that collisional effects can have a significant role in shaping the femtosecond dynamics and nonlinear-optical properties of molecular liquids. However, for anisotropic molecules, it is difficult to separate experimentally the collisional effects from other phenomena. In this paper the authors examine the intermolecular dynamics of the weakly interacting liquid carbon tetrachloride (CCl{sub 4}). Because carbon tetrachloride is a spherical top molecule (belonging to the T{sub d} point group), its intermolecular light-scattering spectrum is purely interaction-induced. By studying this purely collision-induced feature in CCl{sub 4}, the authors hope to gain insight on the lowest-frequency intermolecular vibrational behavior of more complex systems.

  3. Fluorescence photoactivation by intermolecular proton transfer.

    PubMed

    Swaminathan, Subramani; Petriella, Marco; Deniz, Erhan; Cusido, Janet; Baker, James D; Bossi, Mariano L; Raymo, Françisco M

    2012-10-11

    We designed a strategy to activate fluorescence under the influence of optical stimulations based on the intermolecular transfer of protons. Specifically, the illumination of a 2-nitrobenzyl derivative at an activating wavelength is accompanied by the release of hydrogen bromide. In turn, the photogenerated acid encourages the opening of an oxazine ring embedded within a halochromic compound. This structural transformation extends the conjugation of an adjacent coumarin fluorophore and enables its absorption at an appropriate excitation wavelength. Indeed, this bimolecular system offers the opportunity to activate fluorescence in liquid solutions, within rigid matrixes and inside micellar assemblies, relying on the interplay of activating and exciting beams. Furthermore, this strategy permits the permanent imprinting of fluorescent patterns on polymer films, the monitoring of proton diffusion within such materials in real time on a millisecond time scale, and the acquisition of images with spatial resolution at the nanometer level. Thus, our operating principles for fluorescence activation can eventually lead to the development of valuable photoswitchable probes for imaging applications and versatile mechanisms for the investigation of proton transport. PMID:22994311

  4. Covalent intermolecular interaction of the nitric oxide dimer (NO)2

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Zheng, Gui-Li; Lv, Gang; Geng, Yi-Zhao; Ji, Qing

    2015-09-01

    Covalent bonds arise from the overlap of the electronic clouds in the internucleus region, which is a pure quantum effect and cannot be obtained in any classical way. If the intermolecular interaction is of covalent character, the result from direct applications of classical simulation methods to the molecular system would be questionable. Here, we analyze the special intermolecular interaction between two NO molecules based on quantum chemical calculation. This weak intermolecular interaction, which is of covalent character, is responsible for the formation of the NO dimer, (NO)2, in its most stable conformation, a cis conformation. The natural bond orbital (NBO) analysis gives an intuitive illustration of the formation of the dimer bonding and antibonding orbitals concomitant with the breaking of the π bonds with bond order 0.5 of the monomers. The dimer bonding is counteracted by partially filling the antibonding dimer orbital and the repulsion between those fully or nearly fully occupied nonbonding dimer orbitals that make the dimer binding rather weak. The direct molecular mechanics (MM) calculation with the UFF force fields predicts a trans conformation as the most stable state, which contradicts the result of quantum mechanics (QM). The lesson from the investigation of this special system is that for the case where intermolecular interaction is of covalent character, a specific modification of the force fields of the molecular simulation method is necessary. Project supported by the National Natural Science Foundation of China (Grant Nos. 90403007 and 10975044), the Key Subject Construction Project of Hebei Provincial Universities, China, the Research Project of Hebei Education Department, China (Grant Nos. Z2012067 and Z2011133), the National Natural Science Foundation of China (Grant No. 11147103), and the Open Project Program of State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, China (Grant No. Y5

  5. Intermolecular Vibrations of Hydrophobic Amino Acids

    NASA Astrophysics Data System (ADS)

    Williams, Michael Roy Casselman

    Hydrophobic amino acids interact with their chemical environment through a combination of electrostatic, hydrogen bonding, dipole, induced dipole, and dispersion forces. These interactions all have their own characteristic energy scale and distance dependence. The low-frequency (0.1-5 THz, 5-150 cm-1) vibrational modes of amino acids in the solid state are a direct indicator of the interactions between the molecules, which include interactions between an amino acid functional group and its surroundings. This information is central to understanding the dynamics and morphology of proteins. The alpha-carbon is a chiral center for all of the hydrophobic amino acids, meaning that they exist in two forms, traditionally referred to as L- and D-enantiomers. This nomenclature indicates which direction the molecule rotates plane-polarized visible light (levorotory and dextrorotory). Chiral a-amino acids in proteins are exclusively the L-variety In the solid state, the crystal lattice of the pure L-enantiomer is the mirror image of the D-enantiomer crystal lattice. These solids are energetically identical. Enantiomers also have identical spectroscopic properties except when the measurement is polarization sensitive. A mixture of equal amounts D- and L-amino acid enantiomers can crystallize into a racemic (DL-) structure that is different from that of the pure enantiomers. Whether a solution of both enantiomers will crystallize into a racemic form or spontaneously resolve into a mixture of separate D- and L-crystals largely depends on the interactions between molecules available in the various possible configurations. This is an active area of research. Low-frequency vibrations with intermolecular character are very sensitive to changes in lattice geometry, and consequently the vibrational spectra of racemic crystals are usually quite distinct from the spectra of the crystals of the corresponding pure enantiomers in the far-infrared (far-IR). THz time-domain spectroscopy (THz

  6. Separation of intra- and intermolecular contributions to the PELDOR signal

    NASA Astrophysics Data System (ADS)

    Schöps, Philipp; Plackmeyer, Jörn; Marko, Andriy

    2016-08-01

    Pulsed Electron-electron Double Resonance (PELDOR) is commonly used to measure distances between native paramagnetic centers or spin labels attached to complex biological macromolecules. In PELDOR the energies of electron magnetic dipolar interactions are measured by analyzing the oscillation frequencies of the recorded time resolved signal. Since PELDOR is an ensemble method, the detected signal contains contributions from intramolecular, as well as intermolecular electron spin interactions. The intramolecular part of the signal contains the information about the structure of the studied molecules, thus it is very important to accurately separate intra- and intermolecular contributions to the total signal. This separation can become ambiguous, when the length of the PELDOR signal is not much longer than twice the oscillation period of the signal. In this work we suggest a modulation depth scaling method, which can use short PELDOR signals in order to extract the intermolecular contribution. Using synthetic data we demonstrate the advantages of the new approach and analyze its stability with regard to signal noise. The method was also successfully tested on experimental data of three systems measured at Q-Band frequencies, two model compounds in deuterated and protonated solvents and one biological sample, namely BetP. The application of the new method with an assigned value of the signal modulation depth enables us to determine the interspin distances in all cases. This is especially interesting for the model compound with an interspin distance of 5.2 nm in the protonated solvent and the biological sample, since an accurate separation of the intra- and intermolecular PELDOR signal contributions would be difficult with the standard approach in those cases.

  7. Separation of intra- and intermolecular contributions to the PELDOR signal.

    PubMed

    Schöps, Philipp; Plackmeyer, Jörn; Marko, Andriy

    2016-08-01

    Pulsed Electron-electron Double Resonance (PELDOR) is commonly used to measure distances between native paramagnetic centers or spin labels attached to complex biological macromolecules. In PELDOR the energies of electron magnetic dipolar interactions are measured by analyzing the oscillation frequencies of the recorded time resolved signal. Since PELDOR is an ensemble method, the detected signal contains contributions from intramolecular, as well as intermolecular electron spin interactions. The intramolecular part of the signal contains the information about the structure of the studied molecules, thus it is very important to accurately separate intra- and intermolecular contributions to the total signal. This separation can become ambiguous, when the length of the PELDOR signal is not much longer than twice the oscillation period of the signal. In this work we suggest a modulation depth scaling method, which can use short PELDOR signals in order to extract the intermolecular contribution. Using synthetic data we demonstrate the advantages of the new approach and analyze its stability with regard to signal noise. The method was also successfully tested on experimental data of three systems measured at Q-Band frequencies, two model compounds in deuterated and protonated solvents and one biological sample, namely BetP. The application of the new method with an assigned value of the signal modulation depth enables us to determine the interspin distances in all cases. This is especially interesting for the model compound with an interspin distance of 5.2nm in the protonated solvent and the biological sample, since an accurate separation of the intra- and intermolecular PELDOR signal contributions would be difficult with the standard approach in those cases. PMID:27243966

  8. Competing intramolecular vs. intermolecular hydrogen bonds in solution.

    PubMed

    Nagy, Peter I

    2014-01-01

    A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. PMID:25353178

  9. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    PubMed Central

    Nagy, Peter I.

    2014-01-01

    A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. PMID:25353178

  10. Estimation of intermolecular interactions in polymer networks

    SciTech Connect

    Subrananian, P.R.; Galiatsatos, V.

    1993-12-31

    Strain-birefringence measurements have been used to estimate intermolecular interactions in polymer networks. The intensity of the interaction has been quantified through a theoretical scheme recently proposed by Erman. The results show that these interactions diminish with decreasing molecular weight between cross-links and decreasing cross-link functionality.

  11. An improved intermolecular potential for sulfur hexafluoride

    SciTech Connect

    Aziz, R.A.; Slaman, M.J. ); Taylor, W.L.; Hurly, J.J. Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221 )

    1991-01-15

    Second virial coefficient data and viscosity were used to evaluate effective isotropic intermolecular potential functions proposed in the literature for sulfur hexafluoride. It was found that none of the potentials could predict the properties simultaneously. We have constructed a Morse--Morse--Spline--van der Waals (MMSV) potential which satisfactorily correlates second virial coefficient and viscosity data at the same time.

  12. Vibrational nano-spectroscopic imaging correlating structure with intermolecular coupling and dynamics

    PubMed Central

    Pollard, Benjamin; Muller, Eric A.; Hinrichs, Karsten; Raschke, Markus B.

    2014-01-01

    Molecular self-assembly, the function of biomembranes and the performance of organic solar cells rely on nanoscale molecular interactions. Understanding and control of such materials have been impeded by difficulties in imaging their properties with the desired nanometre spatial resolution, attomolar sensitivity and intermolecular spectroscopic specificity. Here we implement vibrational scattering-scanning near-field optical microscopy with high spectral precision to investigate the structure–function relationship in nano-phase separated block copolymers. A vibrational resonance is used as a sensitive reporter of the local chemical environment and we image, with few nanometre spatial resolution and 0.2 cm−1 spectral precision, solvatochromic Stark shifts and line broadening correlated with molecular-scale morphologies. We discriminate local variations in electric fields between nano-domains with quantitative agreement with dielectric continuum models. This ability to directly resolve nanoscale morphology and associated intermolecular interactions can form a basis for the systematic control of functionality in multicomponent soft matter systems. PMID:24721995

  13. Co-operative intermolecular kinetics of 2-oxoglutarate dependent dioxygenases may be essential for system-level regulation of plant cell physiology

    PubMed Central

    Kundu, Siddhartha

    2015-01-01

    Can the stimulus-driven synergistic association of 2-oxoglutarate dependent dioxygenases be influenced by the kinetic parameters of binding and catalysis?In this manuscript, I posit that these indices are necessary and specific for a particular stimulus, and are key determinants of a dynamic clustering that may function to mitigate the effects of this trigger. The protein(s)/sequence(s) that comprise this group are representative of all major kingdoms of life, and catalyze a generic hydroxylation, which is, in most cases accompanied by a specialized conversion of the substrate molecule. Iron is an essential co-factor for this transformation and the response to waning levels is systemic, and mandates the simultaneous participation of molecular sensors, transporters, and signal transducers. Here, I present a proof-of-concept model, that an evolving molecular network of 2OG-dependent enzymes can maintain iron homeostasis in the cytosol of root hair cells of members of the family Gramineae by actuating a non-reductive compensatory chelation by the phytosiderophores. Regression models of empirically available kinetic data (iron and alpha-ketoglutarate) were formulated, analyzed, and compared. The results, when viewed in context of the superfamily responding as a unit, suggest that members can indeed, work together to accomplish system-level function. This is achieved by the establishment of transient metabolic conduits, wherein the flux is dictated by kinetic compatibility of the participating enzymes. The approach adopted, i.e., predictive mathematical modeling, is integral to the hypothesis-driven acquisition of experimental data points and, in association with suitable visualization aids may be utilized for exploring complex plant biochemical systems. PMID:26236316

  14. System and method for incremental forming

    SciTech Connect

    Beltran, Michael; Cao, Jian; Roth, John T.

    2015-12-29

    A system includes a frame configured to hold a workpiece and first and second tool positioning assemblies configured to be opposed to each other on opposite sides of the workpiece. The first and second tool positioning assemblies each include a toolholder configured to secure a tool to the tool positioning assembly, a first axis assembly, a second axis assembly, and a third axis assembly. The first, second, and third axis assemblies are each configured to articulate the toolholder along a respective axis. Each axis assembly includes first and second guides extending generally parallel to the corresponding axis and disposed on opposing sides of the toolholder with respect to the corresponding axis. Each axis assembly includes first and second carriages articulable along the first and second guides of the axis assembly, respectively, in the direction of the corresponding axis.

  15. Cutting tool form compensation system and method

    DOEpatents

    Barkman, W.E.; Babelay, E.F. Jr.; Klages, E.J.

    1993-10-19

    A compensation system for a computer-controlled machining apparatus having a controller and including a cutting tool and a workpiece holder which are movable relative to one another along a preprogrammed path during a machining operation utilizes a camera and a vision computer for gathering information at a preselected stage of a machining operation relating to the actual shape and size of the cutting edge of the cutting tool and for altering the preprogrammed path in accordance with detected variations between the actual size and shape of the cutting edge and an assumed size and shape of the cutting edge. The camera obtains an image of the cutting tool against a background so that the cutting tool and background possess contrasting light intensities, and the vision computer utilizes the contrasting light intensities of the image to locate points therein which correspond to points along the actual cutting edge. Following a series of computations involving the determining of a tool center from the points identified along the tool edge, the results of the computations are fed to the controller where the preprogrammed path is altered as aforedescribed. 9 figures.

  16. Cutting tool form compensaton system and method

    DOEpatents

    Barkman, William E.; Babelay, Jr., Edwin F.; Klages, Edward J.

    1993-01-01

    A compensation system for a computer-controlled machining apparatus having a controller and including a cutting tool and a workpiece holder which are movable relative to one another along a preprogrammed path during a machining operation utilizes a camera and a vision computer for gathering information at a preselected stage of a machining operation relating to the actual shape and size of the cutting edge of the cutting tool and for altering the preprogrammed path in accordance with detected variations between the actual size and shape of the cutting edge and an assumed size and shape of the cutting edge. The camera obtains an image of the cutting tool against a background so that the cutting tool and background possess contrasting light intensities, and the vision computer utilizes the contrasting light intensities of the image to locate points therein which correspond to points along the actual cutting edge. Following a series of computations involving the determining of a tool center from the points identified along the tool edge, the results of the computations are fed to the controller where the preprogrammed path is altered as aforedescribed.

  17. Rorschach Form Quality in Two Editions of Exner's Comprehensive System.

    ERIC Educational Resources Information Center

    Barley, William D.; And Others

    Form level is a major element in the scoring and interpretation of Rorschach responses. Exner's 1974 text and 1976 comprehensive system workbook provided helpful norms and scoring conventions for determining form quality, but its 1985 revision appeared to lead to generally lower levels of form quality. To examine this clinical impression, the…

  18. Single-molecule magnets ``without'' intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Wernsdorfer, W.; Vergnani, L.; Rodriguez-Douton, M. J.; Cornia, A.; Neugebauer, P.; Barra, A. L.; Sorace, L.; Sessoli, R.

    2012-02-01

    Intermolecular magnetic interactions (dipole-dipole and exchange) affect strongly the magnetic relaxation of crystals of single-molecule magnets (SMMs), especially at low temperature, where quantum tunneling of the magnetization (QTM) dominates. This leads to complex many-body problems [l]. Measurements on magnetically diluted samples are desirable to clearly sort out the behaviour of magnetically-isolated SMMs and to reveal, by comparison, the effect of intermolecular interactions. Here, we diluted a Fe4 SMM into a diamagnetic crystal lattice, affording arrays of independent and iso-oriented magnetic units. We found that the resonant tunnel transitions are much sharper, the tunneling efficiency changes significantly, and two-body QTM transitions disappear. These changes have been rationalized on the basis of a dipolar shuffling mechanism and of transverse dipolar fields, whose effect has been analyzed using a multispin model. Our findings directly prove the impact of intermolecular magnetic couplings on the SMM behaviour and disclose the magnetic response of truly-isolated giant spins in a diamagnetic crystalline environment.[4pt] [1] W. Wernsdorfer, at al, PRL 82, 3903 (1999); PRL 89, 197201 (2002); Nature 416, 406 (2002); IS Tupitsyn, PCE Stamp, NV Prokof'ev, PRB 69, 132406 (2004).

  19. Evidence of pressure induced intermolecular proton transfer via mutarotation: the case of supercooled d-fructose.

    PubMed

    Cecotka, Adam; Tripathy, Satya N; Paluch, Marian

    2015-07-15

    This paper describes a systematic investigation on the role of pressure in mutarotation kinetics of supercooled d-fructose using dielectric spectroscopy. The structural relaxation time acts as a suitable dynamical observable to monitor the mutarotation process that enables the construction of the kinetic curves. The reaction kinetic shapes have been analyzed using the Avrami model. At low temperature, sigmoidal kinetic curves are noted, which correspond to the high concentration of furanosidic forms. The magnitude of activation energy of the process significantly decreases with increasing pressure and is comparable to the solvated systems at 100 MPa. A potential connection between cooperative motion and the origin of intermolecular proton transfer via mutarotation at elevated pressure is also discussed. These experimental observations have fundamental significance on theoretical explanation of the mechanism involving mutarotation in sugars. PMID:26144525

  20. An isotopic mass effect on the intermolecular potential

    NASA Astrophysics Data System (ADS)

    Herman, Michael F.; Currier, Robert P.; Clegg, Samuel M.

    2015-10-01

    The impact of isotopic variation on the electronic energy and intermolecular potentials is often suppressed when calculating isotopologue thermodynamics. Intramolecular potential energy surfaces for distinct isotopologues are in fact equivalent under the Born-Oppenheimer approximation, which is sometimes used to imply that the intermolecular interactions are independent of isotopic mass. In this communication, the intermolecular dipole-dipole interaction between hetero-nuclear diatomic molecules is considered. It is shown that the intermolecular potential contains mass-dependent terms even though each nucleus moves on a Born-Oppenheimer surface. The analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologue thermodynamics.

  1. Computing free energy hypersurfaces for anisotropic intermolecular associations.

    PubMed

    Strümpfer, Johan; Naidoo, Kevin J

    2010-01-30

    We previously used an adaptive reaction coordinate force biasing method for calculating the free energy of conformation (Naidoo and Brady, J Am Chem Soc 1999, 121, 2244) and chemical reactions (Rajamani et al., J Comput Chem 2003, 24, 1775) amongst others. Here, we describe a generalized version able to produce free energies in multiple dimensions, descriptively named the free energies from adaptive reaction coordinate forces method. To illustrate it, we describe how we calculate a multidimensional intermolecular orientational free energy, which can be used to investigate complex systems such as protein conformation and liquids. This multidimensional intermolecular free energy W(r, theta(1), theta(2), phi) provides a measure of orientationally dependent interactions that are appropriate for applications in systems that inherently have molecular anisotropic features. It is a highly informative free energy volume, which can be used to parameterize key terms such as the Gay-Berne intermolecular potential in coarse grain simulations. To demonstrate the value of the information gained from the W(r, theta(1), theta(2), phi) hypersurfaces we calculated them for TIP3P, TIP4P, and TIP5P dimer water models in vacuum. A comparison with a commonly used one-dimensional distance free energy profile is made to illustrate the significant increase in configurational information. The W(r) plots show little difference between the three models while the W(r, theta(1), theta(2), phi) hypersurfaces reveal the underlying energetic reasons why these potentials reproduce tetrahedrality in the condensed phase so differently from each. PMID:19462397

  2. Bile salt–induced intermolecular disulfide bond formation activates Vibrio cholerae virulence

    PubMed Central

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

    2013-01-01

    To be successful pathogens, bacteria must often restrict the expression of virulence genes to host environments. This requires a physical or chemical marker of the host environment as well as a cognate bacterial system for sensing the presence of a host to appropriately time the activation of virulence. However, there have been remarkably few such signal–sensor pairs identified, and the molecular mechanisms for host-sensing are virtually unknown. By directly applying a reporter strain of Vibrio cholerae, the causative agent of cholera, to a thin layer chromatography (TLC) plate containing mouse intestinal extracts, we found two host signals that activate virulence gene transcription. One of these was revealed to be the bile salt taurocholate. We then show that a set of bile salts cause dimerization of the transmembrane transcription factor TcpP by inducing intermolecular disulfide bonds between cysteine (C)-207 residues in its periplasmic domain. Various genetic and biochemical analyses led us to propose a model in which the other cysteine in the periplasmic domain, C218, forms an inhibitory intramolecular disulfide bond with C207 that must be isomerized to form the active C207–C207 intermolecular bond. We then found bile salt–dependent effects of these cysteine mutations on survival in vivo, correlating to our in vitro model. Our results are a demonstration of a mechanism for direct activation of the V. cholerae virulence cascade by a host signal molecule. They further provide a paradigm for recognition of the host environment in pathogenic bacteria through periplasmic cysteine oxidation. PMID:23341592

  3. Orthogonal canonical forms for second-order systems

    NASA Technical Reports Server (NTRS)

    Williams, Trevor; Laub, Alan

    1989-01-01

    The authors prove that a linear second-order system with arbitrary damping cannot be reduced to Hessenberg-triangular form by means of orthogonal transformations, while this reduction is always possible for the modal damping commonly assumed for models of flexible structures. The type of canonical form obtainable by means of orthogonal transformations acting on a second-order system is heavily dependent on the type of damping considered. If the damping matrix is merely positive semi-definite symmetric, it is generally not possible to obtain a reduction to Hessenberg-triangular form, while this reduction is trivial for zero or Rayleigh damping. If damping is modal, however, as is commonly assumed in structural models, the reduction exists and is nontrivial. Furthermore, reduction to triangular second-order Schur form is always possible for such damping: this canonical form appears likely to have applications to second-order system theory.

  4. Further Reductions of Normal Forms for Dynamical Systems

    NASA Astrophysics Data System (ADS)

    Chen, Guoting; Della Dora, Jean

    2000-09-01

    We propose in this paper a method for obtaining a significant refinement of normal forms for dynamical systems or vector fields, with concrete and interesting applications. We use lower order nonlinear terms in the normal form for the simplifications of higher order terms. Our approach is applicable for both the non nilpotent and the nilpotent cases. For dynamical systems of dimensions 2 and 3 we give an algorithm that leads to interesting finite order normal forms which are optimal (or unique) with respect to equivalence by formal near identity transformations. We can compute at the same time a formal diffeormorphism that realizes the normalization. Comparisons with other methods are given for several examples.

  5. Cooling system optimization analysis for hot forming processes

    NASA Astrophysics Data System (ADS)

    Ghoo, Bonyoung; Umezu, Yasuyoshi; Watanabe, Yuko

    2013-12-01

    Hot forming technology was developed to produce automotive panels having ultra-high tensile stress over 1500MPa. The elevated temperature corresponds with decreased flow stress and increased ductility. Furthermore, hot forming products have almost zero springback amounts. This advanced forming technology accelerates the needs for numerical simulations coupling with thermal-mechanical formulations. In the present study, 3-dimensional finite element analyses for hot forming processes are conducted using JSTAMP/NV and LS-DYNA considering cooling system. Special attention is paid to the optimization of cooling system using thermo-mechanical finite element analysis through the influence of various cooling parameters. The presented work shows an adequate cooling system functions and microstructural phase transformation material model together with a proper set of numerical parameters can give both efficient and accurate design insight in hot forming manufacturing process. JSTAMP/NV and LS-DYNA can become a robust combination set for complex hot forming analysis which needs thermo-mechanical and microstructural material modeling and various process modeling. The use of the new JSTAMP/NV function for multishot manufacturing process is shown good capabilities in cooling system evaluation. And the use of the advanced LS-DYNA microstructural phase transformation model is shown good evaluation results in martensite amount and Vickers hardness after quenching.

  6. A New Sheet Metal Forming System Based on Incremental Punching

    NASA Astrophysics Data System (ADS)

    Luo, Yuanxin

    Stamping is one of the most commonly used manufacturing processes. Everyday, millions of parts are formed by this process. The conventional stamping is to form a part in one or several operations with a press machine and a set/sets of dies. It is very efficient but is not cost effective for small batch production parts and prototypes as the dies are expensive and time consuming to make. Recently, with the increasing demands for low-volume and customer-made products, a die-less forming method, Incremental Sheet Metal Forming (ISMF), has become one of the leading R&D topics in the industry. ISMF uses a small generic tool to apply a sequence of operations along the given path to deform the sheet incrementally. These small deformations accumulate to form the final shape of the part. As a result, different parts can be made by the same setup. Despite of some 30 years of research and development, however, ISMF technology is still premature for industrial applications due to the following reasons: The accuracy of the part is limited; the surface roughness is poor; and the productivity is low. This motivates the presented research. In this research, a new incremental forming system based on incremental punching is designed and built. The system consists of a 3-axes CNC platform, a high speed hydraulic cylinder with a hemispherical forming tool, and a PC-based CNC control system. The hydraulic system provides the forming force to deform the sheet metal with constant stokes, while the CNC system positions the part. When forming a part, the forming tool punches the sheet metal along the given contour of the part punch by punch; when one layer of the part is completed, the forming tool moves down to the next layer; and the process is finished till all layers are completed. The CNC control system works with standard NC code, and hence, is easy to use. In order to ensure the desirable performance of the machine, dynamic analysis of the machine is necessary. The analysis is

  7. Molecular and ionic diffusion in aqueous - deep eutectic solvent mixtures: probing inter-molecular interactions using PFG NMR.

    PubMed

    D'Agostino, Carmine; Gladden, Lynn F; Mantle, Mick D; Abbott, Andrew P; Ahmed, Essa I; Al-Murshedi, Azhar Y M; Harris, Robert C

    2015-06-21

    Pulsed field gradient (PFG) NMR has been used to probe self-diffusion of molecular and ionic species in aqueous mixtures of choline chloride (ChCl) based deep eutectic solvents (DESs), in order to elucidate the effect of water on motion and inter-molecular interactions between the different species in the mixtures, namely the Ch(+) cation and hydrogen bond donor (HBD). The results reveal an interesting and complex behaviour of such mixtures at a molecular level. In general, it is observed that the hydroxyl protons ((1)H) of Ch(+) and the hydrogen bond donor have diffusion coefficients significantly different from those measured for their parent molecules when water is added. This indicates a clear and significant change in inter-molecular interactions. In aqueous Ethaline, the hydroxyl species of Ch(+) and HBD show a stronger interaction with water as water is added to the system. In the case of Glyceline, water has little effect on both hydroxyl proton diffusion of Ch(+) and HBD. In Reline, it is likely that water allows the formation of small amounts of ammonium hydroxide. The most surprising observation is from the self-diffusion of water, which is considerably higher that expected from a homogeneous liquid. This leads to the conclusion that Reline and Glyceline form mixtures that are inhomogeneous at a microscopic level despite the hydrophilicity of the salt and HBD. This work shows that PFG NMR is a powerful tool to elucidate both molecular dynamics and inter-molecular interactions in complex liquid mixtures, such as the aqueous DES mixtures. PMID:25994171

  8. Enhanced Two-Stage Reactive Polymer Network Forming Systems

    PubMed Central

    Nair, Devatha P.; Cramer, Neil B.; McBride, Matthew K.; Gaipa, John C.; Shandas, Robin; Bowman, Christopher N.

    2012-01-01

    In this study, we develop thiol/acrylate two-stage reactive network forming polymer systems that exhibit two distinct and orthogonal stages of curing. Using a thiol-acrylate system with excess acrylate functional groups, a first stage polymer network is formed via a 1 to 1 stoichiometric thiol-acrylate Michael addition reaction (stage 1). At a later point in time, the excess acrylate functional groups are homopolymerized via a photoinitiated free radical polymerization to form a second stage polymer network (stage 2). By varying the monomers within the system as well as the stoichiometery of the thiol to acrylate functional groups, we demonstrate the ability of the two-stage polymer network forming systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations. Using urethane di- and hexa-acrylates within the formulations led to two-stage reactive polymeric systems with stage 1 Tgs that ranged from −12 to 30 °C. The systems were then photocured, upon which the Tg of the systems increases by up to 90 °C while also achieving a nearly 20 fold modulus increase. PMID:22798700

  9. Van der Waals Interactions in Density Functional Theory: Intermolecular Complexes

    NASA Astrophysics Data System (ADS)

    Kannemann, Felix; Becke, Axel

    2010-03-01

    Conventional density functional theory (GGA and hybrid functionals) fails to account for dispersion interactions and is therefore not applicable to systems where van der Waals interactions play a dominant role, such as intermolecular complexes and biomolecules. The exchange-hole dipole moment (XDM) dispersion model of Becke and Johnson [A. D. Becke and E. R. Johnson, J. Chem. Phys. 127, 154108 (2007)] corrects for this deficiency. We have previously shown that the XDM dispersion model can be combined with standard GGA functionals (PW86 for exchange and PBE for correlation) to give accurate binding energy curves for rare-gas diatomics [F. O. Kannemann and A. D. Becke, J. Chem. Theory Comput. 5, 719 (2009)]. Here we present further tests of the GGA-XDM method using benchmark sets including hydrogen bonding, electrostatic, dispersion and stacking interactions, and systems ranging from rare-gas diatomics to biomolecular complexes.

  10. Orthogonal canonical forms for second-order systems

    NASA Technical Reports Server (NTRS)

    Williams, Trevor; Laub, Alan J.

    1992-01-01

    It is shown that a linear second-order system with arbitrary damping cannot be reduced to Hessenberg-triangular form by means of orthogonal transformations. However, it is also shown that such an orthogonal reduction is always possible for the modal damping commonly assumed for models of flexible structures. It is shown that modally damped models can be orthogonally reduced to a new triangular second-order Schur form.

  11. Spray forming system for producing molds, dies and related tooling

    DOEpatents

    McHugh, Kevin M.

    2000-01-01

    A system for the spray forming manufacturing of near-net-shape molds, dies and related toolings, wherein liquid material such as molten metal, metallic alloys, or polymers are atomized into fine droplets by a high temperature, high velocity gas and deposited onto a pattern. Quenching of the atomized droplets provides a heat sink, thereby allowing undercooled and partially solidified droplets to be formed in-flight. Composites can be formed by combining the atomized droplets with solid particles such as powders, whiskers or fibers.

  12. Frontier orbital symmetry control of intermolecular electron transfer. Final report, September 15, 1988--December 31, 1994

    SciTech Connect

    Stevens, B.

    1997-07-01

    This report discusses the following topics: the recovery of intermolecular transfer parameters from fluorescence quenching in liquids; photoinduced intramolecular electron transfer in flexible donor/space/acceptor systems containing an extended unsaturated spacer; electron transfer sensitized reaction; the recovery of solute and fractal dimensions from electron transfer quenching data; and frontier orbital symmetry control of back electron transfer.

  13. Intermolecular vibrations and fast relaxations in supercooled ionic liquids

    NASA Astrophysics Data System (ADS)

    Ribeiro, Mauro C. C.

    2011-06-01

    Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < ω < 100 cm-1) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (˜19 Å) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids.

  14. Advanced manufacturing by spray forming: Aluminum strip and microelectromechanical systems

    SciTech Connect

    McHugh, K.M.

    1994-12-31

    Spray forming is an advanced materials processing technology that converts a bulk liquid metal to a near-net-shape solid by depositing atomized droplets onto a suitably shaped substrate. By combining rapid solidification processing with product shape control, spray forming can reduce manufacturing costs while improving product quality. INEL is developing a unique spray-forming method based on de Laval (converging/diverging) nozzle designs to produce near-net-shape solids and coatings of metals, polymers, and composite materials. Properties of the spray-formed material are tailored by controlling the characteristics of the spray plume and substrate. Two examples are described: high-volume production of aluminum alloy strip, and the replication of micron-scale features in micropatterned polymers during the production of microelectromechanical systems.

  15. Glassy behavior of two-dimensional stripe-forming systems

    NASA Astrophysics Data System (ADS)

    Ribeiro Teixeira, Ana C.; Stariolo, Daniel A.; Barci, Daniel G.

    2013-06-01

    We study two-dimensional frustrated but nondisordered systems applying a replica approach to a stripe-forming model with competing interactions. The phenomenology of the model is representative of several well-known systems, like high-Tc superconductors and ultrathin ferromagnetic films, which have been the subject of intense research. We establish the existence of a glass transition to a nonergodic regime accompanied by an exponential number of long-lived metastable states, responsible for slow dynamics and nonequilibrium effects.

  16. Influence of intermolecular interactions on solid state luminescence of imidazopyridines: theoretical interpretations using FMO-TDDFT and ONIOM approaches.

    PubMed

    Shigemitsu, Yasuhiro; Mutai, Toshiki; Houjou, Hirohiko; Araki, Koji

    2014-07-28

    6-Cyano-2-(2'-hydroxyphenyl)imidazo[1,2-a]-pyridine (6CN-HPIP) shows polymorph-dependent luminescence with the three different crystal forms exhibiting the packing-controlled tuning of bright colors, orange, yellow, and red. The distinctive emission in aggregated states was treated with finite cluster models and analyzed by means of quantum chemistry calculations. The influence of structural displacements and intermolecular interactions in the crystalline state on solid state luminescence was examined in detail using the Fragment Molecular Orbital (FMO) scheme, suitable for studies of aggregated molecular systems. The FMO pair interaction analysis of the S1-S0 emission maxima indicated that the intermolecular side-to-side interactions cause hypsochromic shifts; facial interactions induce bathochromic shifts; and crystal packing effects in total induce hypsochromic shifts. The FMO predictions of the emission maxima offered qualitatively satisfactory agreements with the experiments. However, the small cluster models including up to 17 molecules did not reach quantitative convergence, i.e., the emission colour order among them was not well reproduced. PMID:24598819

  17. Resolving Intra- and Inter-Molecular Structure with Non-Contact Atomic Force Microscopy

    PubMed Central

    Jarvis, Samuel Paul

    2015-01-01

    A major challenge in molecular investigations at surfaces has been to image individual molecules, and the assemblies they form, with single-bond resolution. Scanning probe microscopy, with its exceptionally high resolution, is ideally suited to this goal. With the introduction of methods exploiting molecularly-terminated tips, where the apex of the probe is, for example, terminated with a single CO, Xe or H2 molecule, scanning probe methods can now achieve higher resolution than ever before. In this review, some of the landmark results related to attaining intramolecular resolution with non-contact atomic force microscopy (NC-AFM) are summarised before focussing on recent reports probing molecular assemblies where apparent intermolecular features have been observed. Several groups have now highlighted the critical role that flexure in the tip-sample junction plays in producing the exceptionally sharp images of both intra- and apparent inter-molecular structure. In the latter case, the features have been identified as imaging artefacts, rather than real intermolecular bonds. This review discusses the potential for NC-AFM to provide exceptional resolution of supramolecular assemblies stabilised via a variety of intermolecular forces and highlights the potential challenges and pitfalls involved in interpreting bonding interactions. PMID:26307976

  18. Resolving Intra- and Inter-Molecular Structure with Non-Contact Atomic Force Microscopy.

    PubMed

    Jarvis, Samuel Paul

    2015-01-01

    A major challenge in molecular investigations at surfaces has been to image individual molecules, and the assemblies they form, with single-bond resolution. Scanning probe microscopy, with its exceptionally high resolution, is ideally suited to this goal. With the introduction of methods exploiting molecularly-terminated tips, where the apex of the probe is, for example, terminated with a single CO, Xe or H2 molecule, scanning probe methods can now achieve higher resolution than ever before. In this review, some of the landmark results related to attaining intramolecular resolution with non-contact atomic force microscopy (NC-AFM) are summarised before focussing on recent reports probing molecular assemblies where apparent intermolecular features have been observed. Several groups have now highlighted the critical role that flexure in the tip-sample junction plays in producing the exceptionally sharp images of both intra- and apparent inter-molecular structure. In the latter case, the features have been identified as imaging artefacts, rather than real intermolecular bonds. This review discusses the potential for NC-AFM to provide exceptional resolution of supramolecular assemblies stabilised via a variety of intermolecular forces and highlights the potential challenges and pitfalls involved in interpreting bonding interactions. PMID:26307976

  19. X-ray Intermolecular Structure Factor (XISF): separation of intra- and intermolecular interactions from total X-ray scattering data

    SciTech Connect

    Mou, Q.; Benmore, C. J.; Yarger, J. L.

    2015-06-01

    XISF is a MATLAB program developed to separate intermolecular structure factors from total X-ray scattering structure factors for molecular liquids and amorphous solids. The program is built on a trust-region-reflective optimization routine with the r.m.s. deviations of atoms physically constrained. XISF has been optimized for performance and can separate intermolecular structure factors of complex molecules.

  20. Are polymers standard glass-forming systems? The role of intramolecular barriers on the glass-transition phenomena of glass-forming polymers

    NASA Astrophysics Data System (ADS)

    Colmenero, J.

    2015-03-01

    Traditionally, polymer melts have been considered archetypal glass-formers. This has been mainly due to the fact that these systems can easily be obtained as glasses by cooling from the melt, even at low cooling rates. However, the macromolecules, i.e. the structural units of polymer systems in general, are rather different from the standard molecules. They are long objects (‘chains’) made by repetition of a given chemical motif (monomer) and have intra-macromolecular barriers that limit their flexibility. The influence of these properties on, for instance, the glass-transition temperature of polymers, is a topic that has been widely studied by the polymer community almost from the early times of polymer science. However, in the framework of the glass-community, the relevant influence of intra-macromolecular barriers and chain connectivity on glass-transition phenomena of polymers has started to be recognized only recently. The aim of this review is to give an overview and to critically revise the results reported on this topic over the last years. From these results, it seems to be evident that there are two different mechanisms involved in the dynamic arrest in glass-forming polymers: (i) the intermolecular packing effects, which dominate the dynamic arrest of low molecular weight glass-forming systems; and (ii) the effect of intra-macromolecular barriers combined with chain connectivity. It has also been shown that the mode coupling theory (MCT) is a suitable theoretical framework to discuss these questions. The values found for polymers for the central MCT parameter—the so-called λ-exponent—are of the order of 0.9, clearly higher than the standard values (λ ≈ 0.7) found in systems where the dynamic arrest is mainly driven by packing effects (‘standard’ glass-formers). Within the MCT, this is a signature of the presence of two competing mechanisms of dynamic arrest, as it has been observed in short-ranged attractive colloids or two component

  1. Are polymers standard glass-forming systems? The role of intramolecular barriers on the glass-transition phenomena of glass-forming polymers.

    PubMed

    Colmenero, J

    2015-03-18

    Traditionally, polymer melts have been considered archetypal glass-formers. This has been mainly due to the fact that these systems can easily be obtained as glasses by cooling from the melt, even at low cooling rates. However, the macromolecules, i.e. the structural units of polymer systems in general, are rather different from the standard molecules. They are long objects ('chains') made by repetition of a given chemical motif (monomer) and have intra-macromolecular barriers that limit their flexibility. The influence of these properties on, for instance, the glass-transition temperature of polymers, is a topic that has been widely studied by the polymer community almost from the early times of polymer science. However, in the framework of the glass-community, the relevant influence of intra-macromolecular barriers and chain connectivity on glass-transition phenomena of polymers has started to be recognized only recently. The aim of this review is to give an overview and to critically revise the results reported on this topic over the last years. From these results, it seems to be evident that there are two different mechanisms involved in the dynamic arrest in glass-forming polymers: (i) the intermolecular packing effects, which dominate the dynamic arrest of low molecular weight glass-forming systems; and (ii) the effect of intra-macromolecular barriers combined with chain connectivity. It has also been shown that the mode coupling theory (MCT) is a suitable theoretical framework to discuss these questions. The values found for polymers for the central MCT parameter--the so-called λ-exponent--are of the order of 0.9, clearly higher than the standard values (λ ≈ 0.7) found in systems where the dynamic arrest is mainly driven by packing effects ('standard' glass-formers). Within the MCT, this is a signature of the presence of two competing mechanisms of dynamic arrest, as it has been observed in short-ranged attractive colloids or two component mixtures with

  2. Intermolecular interactions of reduced nicotinamide adenine dinucleotide (NADH) in solution

    NASA Astrophysics Data System (ADS)

    Jasensky, Joshua; Junaid Farooqi, M.; Urayama, Paul

    2008-10-01

    Nicotinamide adenine dinucleotide (NAD^+/NADH) is a coenzyme involved in cellular respiration as an electron transporter. In aqueous solution, the molecule exhibits a folding transition characterized by the stacking of its aromatic moieties. A transition to an unfolded conformation is possible using chemical denaturants like methanol. Because the reduced NADH form is fluorescent, the folding transition can be monitored using fluorescence spectroscopy, e.g., via a blue-shift in the UV-excited emission peak upon methanol unfolding. Here we present evidence of interactions between NADH molecules in solution. We measure the excited-state emission from NADH at various concentrations (1-100 μM in MOPS buffer, pH 7.5; 337-nm wavelength excitation). Unlike for the folded form, the emission peak wavelength of the unfolded form is concentration dependent, exhibiting a red-shift with higher NADH concentration, suggesting the presence of intermolecular interactions. An understanding of NADH spectra in solution would assist in interpreting intercellular NADH measurements used for the in vivo monitoring cellular energy metabolism.

  3. Intermolecular Sulfur···Oxygen Interactions: Theoretical and Statistical Investigations.

    PubMed

    Zhang, Xuejin; Gong, Zhen; Li, Jian; Lu, Tao

    2015-10-26

    Intermolecular S···O interactions are very common and are important in biological systems, but until recently, the presence of these contacts in protein-ligand systems largely depended on serendipitous discovery instead of rational design. Here we provide insight into the phenomenon of intermolecular S···O contacts by focusing on three sulfur-containing aromatic rings. Quantum mechanics is employed to characterize the strength and directionality of the S···O interactions and to determine their energy dependence on their geometric parameters. Protein Data Bank mining is performed to systematically determine the occurrence and geometry of intermolecular S···O interactions, and several representative examples are discussed. Three typical cases are investigated using a combined quantum mechanics/molecular mechanics approach to demonstrate the potential of these interactions in improving binding affinities and physiochemical properties. Overall, our work elucidates the structures and energy features of intermolecular S···O interactions and addresses their use in molecular design. PMID:26393532

  4. Contrasting intermolecular and intramolecular exciplex formation of a 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad.

    PubMed

    Imoto, Mitsutaka; Ikeda, Hiroshi; Fujii, Takayuki; Taniguchi, Hisaji; Tamaki, Akihiro; Takeda, Motonori; Mizuno, Kazuhiko

    2010-05-01

    An intramolecular exciplex is formed upon excitation of the cyclohexane solution of the 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad, but little if any intramolecular CT complex exists in the ground state of this substance in solution. In contrast, in the crystalline state, the dyad forms an intermolecular mixed-stack CT complex in the ground state and an intermolecular exciplex when it is photoexcited. PMID:20353197

  5. Distinguishability and chiral stability in solution: Effects of decoherence and intermolecular interactions

    SciTech Connect

    Han, Heekyung; Wardlaw, David M.; Frolov, Alexei M.

    2014-05-28

    We examine the effect of decoherence and intermolecular interactions (chiral discrimination energies) on the chiral stability and the distinguishability of initially pure versus mixed states in an open chiral system. Under a two-level approximation for a system, intermolecular interactions are introduced by a mean-field theory, and interaction between a system and an environment is modeled by a continuous measurement of a population difference between the two chiral states. The resultant equations are explored for various parameters, with emphasis on the combined effects of the initial condition of the system, the chiral discrimination energies, and the decoherence in determining: the distinguishability as measured by a population difference between the initially pure and mixed states, and the decoherence process; the chiral stability as measured by the purity decay; and the stationary state of the system at times long relative to the time scales of the system dynamics and of the environmental effects.

  6. Strong orbital interaction in a weak CH-π hydrogen bonding system.

    PubMed

    Li, Jianfu; Zhang, Rui-Qin

    2016-01-01

    For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms "bonding" and "antibonding" orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-π hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least -1.51 kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex. PMID:26927609

  7. Propagation studies of metastable intermolecular composites (MIC).

    SciTech Connect

    Son, S. F.; Busse, J. R.; Asay, B. W.; Peterson, P. D.; Mang, J. T.; Bockmon, B.; Pantoya, M.

    2002-01-01

    Thermite materials are attractive energetic materials because the reactions are highly exothermic, have high energy densities, and high temperatures of combustion. However, the application of thermite materials has been limited because of the relative slow release of energy compared to other energetic materials. Engineered nano-scale composite energetic materials, such as Al/MoO{sub 3}, show promise for additional energetic material applications because they can react very rapidly. The composite material studied in this work consists of tailored, ultra-fine grain (30-200 nm diameter) aluminum particles that dramatically increase energy release rates of these thermite materials. These reactant clusters of fuel and oxidizer particles are in nearly atomic scale proximity to each other but are constrained from reaction until triggered. Despite the growing importance of nano-scale energetic materials, even the most basic combustion characteristics of these materials have not been thoroughly studied. This paper reports initial studies of the ignition and combustion of metastable intermolecular composites (MIC) materials. The goals were lo obtain an improved understanding of flame propagation mechanisms and combustion behaviors associated with nano-structured energetic materials. Information on issues such as reaction rate and behavior as a function of composition (mixture ratio), initial static charge, and particle size are essential and will allow scientists to design applications incorporating the benefits of these compounds. The materials have been characterized, specifically focusing on particle size, shape, distribution and morphology.

  8. [Form of the psyche. Psychoanalysis and recent systems theory].

    PubMed

    Simon, F B

    1994-01-01

    Modern systems theory is not concerned with objects but with the form of processes and structures. It is thus equipped to provide a unified theoretical framework for those varieties of phenomena that psychoanalysis has to deal with. The author discusses recent systems theory models and demonstrates the critique of epistemology that they by their nature imply. These models proceed from the process of observation and show that in the interaction between observers--say, analyst and analysand--observing each other observe, observation may either change or stabilise what is being observed. This is not without consequence for the way psychoanalysis envisions its own identity. Psychoanalysis can no longer naively apply "knowledge" in the traditional sense but must always be aware of the self-reflective nature of that knowledge. Its "application" is thus invariably a form of social intervention. PMID:8127976

  9. Minimum-variance fixed-form compensation of linear systems

    NASA Technical Reports Server (NTRS)

    Johnson, T. L.

    1979-01-01

    The problem of determining the linear time-invariant compensator of a specified dimension which minimizes the asymptotic expected value of a quadratic form in the state variables of a linear stochastic system of arbitrary order, is considered. It is shown that under appropriate assumptions, the solution of this problem can be interpreted as a minimum-order observer-based or dual observer-based compensator for an optimally aggregated model of the plant.

  10. Intermolecular interactions in rifabutin-2-hydroxypropyl-β-cyclodextrin-water solutions, according to solubility data

    NASA Astrophysics Data System (ADS)

    Anshakova, A. V.; Vinogradov, E. V.; Sedush, N. G.; Kurtikyan, T. S.; Zhokhov, S. S.; Polshakov, V. I.; Ermolenko, Yu. V.; Konyukhov, V. Yu.; Maksimenko, O. O.; Gelperin, S. E.

    2016-05-01

    The formulations of rifabutin (RB) and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD), obtained using different preparation techniques, are studied by means of differential scanning calorimetry and molecular spectroscopy (FTIR, NMR, Raman scattering, and photon correlation light scattering). It is established that molecules of RB do not form inclusion complexes with the molecules of HP-β-CD, and an increase in the solubility of RB determined earlier is caused by the formation of weak intermolecular associates.

  11. Transformations of PTCDA structures on rutile TiO2 induced by thermal annealing and intermolecular forces.

    PubMed

    Godlewski, Szymon; Prauzner-Bechcicki, Jakub S; Glatzel, Thilo; Meyer, Ernst; Szymoński, Marek

    2015-01-01

    Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed. PMID:26199854

  12. Transformations of PTCDA structures on rutile TiO2 induced by thermal annealing and intermolecular forces

    PubMed Central

    Godlewski, Szymon; Glatzel, Thilo; Meyer, Ernst; Szymoński, Marek

    2015-01-01

    Summary Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed. PMID:26199854

  13. Control and monitoring method and system for electromagnetic forming process

    DOEpatents

    Kunerth, Dennis C.; Lassahn, Gordon D.

    1990-01-01

    A process, system, and improvement for a process for electromagnetic forming of a workpiece in which characteristics of the workpiece such as its geometry, electrical conductivity, quality, and magnetic permeability can be determined by monitoring the current and voltage in the workcoil. In an electromagnet forming process in which a power supply provides current to a workcoil and the electromagnetic field produced by the workcoil acts to form the workpiece, the dynamic interaction of the electromagnetic fields produced by the workcoil with the geometry, electrical conductivity, and magnetic permeability of the workpiece, provides information pertinent to the physical condition of the workpiece that is available for determination of quality and process control. This information can be obtained by deriving in real time the first several time derivatives of the current and voltage in the workcoil. In addition, the process can be extended by injecting test signals into the workcoil during the electromagnetic forming and monitoring the response to the test signals in the workcoil.

  14. Dimorphic intra- and intermolecular aryl motifs in symmetrical hexafaceted molecules (ArnX)3Y-Z-Y(XArn)3.

    PubMed

    Scudder, Marcia; Dance, Ian

    2002-12-01

    A variety of crystals containing molecules formulated generally as (ArnX)3Y-Z-Y(XArn)3 with exact or pseudo S6 symmetry have been analysed for the presence of intra- and intermolecular multiple aryl embraces composed of offset-face-to-face (OFF) and edge-to-face (EF) local motifs. Ar is phenyl or substituted phenyl; n = 1, 2 or 3; the linkage Z is linear diatomic, linear monatomic, absent (Y-Y bond), or void (Y atoms unconnected). Representative molecular systems analysed are (PhCH2)3Si-O-Si(CH2Ph)3, (PhCH2)3Sn-Sn(CH2Ph)3, (4-Me-C6H4CH2)3Ge-O-Ge(CH2C6H4-4-Me)3, [(PhS)3Fe-O-Fe(SPh)3]-, [(PhCH2)3P-Cu-P(CH2Ph)3]+ and [(Ph3P)3Ag-CN-Ag(PPh3)3]+. One characteristic intramolecular motif is a sixfold phenyl embrace (6PE) in which aryl groups fold back to the central domain of the molecule forming a rhombohedral box maintained by (EF)6. When the aryl groups are in exo positions there is an (EF)3 motif, like a tractor wheel, at each end of the molecule: [(Ph2N)3Ti-O-Ti(NPh2)3] possesses both intramolecular motifs as (EF)3-(EF)6-(EF)3. The molecules in this set are hexafaceted, and the crystal packing is generally based on intermolecular EF or OFF motifs with these faces, either from the central (EF)6 set or the end (EF)3-(EF)3 sets. Three types of subtle crystal packing isomerism occur: 1) the faces of the rhombohedral boxlike molecules slide over each other with variation of the intermolecular motifs, forming dimorphic crystals in space groups R3 or P1; 2) the faces of the tractor wheels (EF)3 slide over each other or 3) very similar molecules crystallise with the rhombohedral box or tractor wheel structures. In general the molecules considered are shape auspicious rather than shape awkward; solvent is included in a small proportion of the crystals and the crystal packing in these compounds is evidently efficient. Some principles for elaboration of these systems and the design of molecular crystal lattices are considered. PMID:12561318

  15. The origins of the directionality of noncovalent intermolecular interactions.

    PubMed

    Wang, Changwei; Guan, Liangyu; Danovich, David; Shaik, Sason; Mo, Yirong

    2016-01-01

    The recent σ-hole concept emphasizes the contribution of electrostatic attraction to noncovalent bonds, and implies that the electrostatic force has an angular dependency. Here a set of clusters, which includes hydrogen bonding, halogen bonding, chalcogen bonding, and pnicogen bonding systems, is investigated to probe the magnitude of covalency and its contribution to the directionality in noncovalent bonding. The study is based on the block-localized wavefunction (BLW) method that decomposes the binding energy into the steric and the charge transfer (CT) (hyperconjugation) contributions. One unique feature of the BLW method is its capability to derive optimal geometries with only steric effect taken into account, while excluding the CT interaction. The results reveal that the overall steric energy exhibits angular dependency notably in halogen bonding, chalcogen bonding, and pnicogen bonding systems. Turning on the CT interactions further shortens the intermolecular distances. This bond shortening enhances the Pauli repulsion, which in turn offsets the electrostatic attraction, such that in the final sum, the contribution of the steric effect to bonding is diminished, leaving the CT to dominate the binding energy. In several other systems particularly hydrogen bonding systems, the steric effect nevertheless still plays the major role whereas the CT interaction is minor. However, in all cases, the CT exhibits strong directionality, suggesting that the linearity or near linearity of noncovalent bonds is largely governed by the charge-transfer interaction whose magnitude determines the covalency in noncovalent bonds. PMID:26010349

  16. Portable Electron-Beam Free-Form Fabrication System

    NASA Technical Reports Server (NTRS)

    Watson, J. Kevin; Petersen, Daniel D.; Taminger, Karen M.; Hafley, Robert A.

    2005-01-01

    A portable electron-beam free-form fabrication (EB F3) system, now undergoing development, is intended to afford a capability for manufacturing metal parts in nearly net sizes and shapes. Although the development effort is oriented toward the eventual use of systems like this one to supply spare metal parts aboard spacecraft in flight, the basic system design could also be adapted to terrestrial applications in which there are requirements to supply spare parts on demand at locations remote from warehouses and conventional manufacturing facilities. Prior systems that have been considered for satisfying the same requirements (including prior free-form fabrication systems) are not easily portable because of their bulk and massive size. The mechanical properties of the components that such systems produce are often inferior to the mechanical properties of the corresponding original, conventionally fabricated components. In addition, the prior systems are not efficient in the utilization of energy and of feedstock. In contrast, the present developmental system is designed to be sufficiently compact and lightweight to be easily portable, to utilize both energy and material more efficiently, and to produce components that have mechanical properties approximating those of the corresponding original components. The developmental EB F3 system will include a vacuum chamber and associated vacuum pumps, an electron-beam gun and an associated power supply, a multiaxis positioning subsystem, a precise wire feeder, and an instrumentation system for monitoring and control. The electron-beam gun, positioning subsystem, and wire feeder will be located inside the vacuum chamber (see figure). The electron beam gun and the wire feeder will be mounted in fixed positions inside the domed upper portion of the vacuum chamber. The positioning subsystem and ports for the vacuum pumps will be located on a base that could be dropped down to provide full access to the interior of the chamber

  17. Interatomic (Intermolecular) Decay Processes in Clusters: Current Status and Outlook

    SciTech Connect

    Averbukh, V.; Cederbaum, L. S.

    2007-11-29

    Since their theoretical prediction a decade ago, interatomic (intermolecular) Coulombic decay (ICD) and related processes have been in the focus of intensive theoretical and experimental research. The spectacular progress in this direction has been stimulated both by the fundamental importance of the new electronic decay phenomena and by the exciting possibility of their practical application, for example in spectroscopy. We review the current status of the research of interatomic (intermolecular) decay phenomena in clusters and discuss some perspectives of this new field.

  18. Evolutionary meandering of intermolecular interactions along the drift barrier.

    PubMed

    Lynch, Michael; Hagner, Kyle

    2015-01-01

    Many cellular functions depend on highly specific intermolecular interactions, for example transcription factors and their DNA binding sites, microRNAs and their RNA binding sites, the interfaces between heterodimeric protein molecules, the stems in RNA molecules, and kinases and their response regulators in signal-transduction systems. Despite the need for complementarity between interacting partners, such pairwise systems seem to be capable of high levels of evolutionary divergence, even when subject to strong selection. Such behavior is a consequence of the diminishing advantages of increasing binding affinity between partners, the multiplicity of evolutionary pathways between selectively equivalent alternatives, and the stochastic nature of evolutionary processes. Because mutation pressure toward reduced affinity conflicts with selective pressure for greater interaction, situations can arise in which the expected distribution of the degree of matching between interacting partners is bimodal, even in the face of constant selection. Although biomolecules with larger numbers of interacting partners are subject to increased levels of evolutionary conservation, their more numerous partners need not converge on a single sequence motif or be increasingly constrained in more complex systems. These results suggest that most phylogenetic differences in the sequences of binding interfaces are not the result of adaptive fine tuning but a simple consequence of random genetic drift. PMID:25535374

  19. Evolutionary meandering of intermolecular interactions along the drift barrier

    PubMed Central

    Lynch, Michael; Hagner, Kyle

    2015-01-01

    Many cellular functions depend on highly specific intermolecular interactions, for example transcription factors and their DNA binding sites, microRNAs and their RNA binding sites, the interfaces between heterodimeric protein molecules, the stems in RNA molecules, and kinases and their response regulators in signal-transduction systems. Despite the need for complementarity between interacting partners, such pairwise systems seem to be capable of high levels of evolutionary divergence, even when subject to strong selection. Such behavior is a consequence of the diminishing advantages of increasing binding affinity between partners, the multiplicity of evolutionary pathways between selectively equivalent alternatives, and the stochastic nature of evolutionary processes. Because mutation pressure toward reduced affinity conflicts with selective pressure for greater interaction, situations can arise in which the expected distribution of the degree of matching between interacting partners is bimodal, even in the face of constant selection. Although biomolecules with larger numbers of interacting partners are subject to increased levels of evolutionary conservation, their more numerous partners need not converge on a single sequence motif or be increasingly constrained in more complex systems. These results suggest that most phylogenetic differences in the sequences of binding interfaces are not the result of adaptive fine tuning but a simple consequence of random genetic drift. PMID:25535374

  20. Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-05-01

    Benzene carboxylic acids and benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by 1H, 13C and 15N NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations.

  1. Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

    NASA Astrophysics Data System (ADS)

    Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

    2011-03-01

    The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

  2. Comparison of interionic/intermolecular vibrational dynamics between ionic liquids and concentrated electrolyte solutions.

    PubMed

    Fujisawa, Tomotsumi; Nishikawa, Keiko; Shirota, Hideaki

    2009-12-28

    In this study, we have compared the interionic/intermolecular vibrational dynamics of ionic liquids (ILs) and concentrated electrolyte solutions measured by femtosecond optically heterodyne-detected Raman-induced Kerr effect spectroscopy. A typical anion in ILs, bis(trifluoromethanesulfonyl)amide ([NTf(2)](-)), has been chosen as the anion for the sample ILs and concentrated electrolyte solutions. ILs used in this study are 1-butyl-3-methylimidazolium, 1-butylpyridinium, N-butyl-N,N,N-triethylammonium, and 1-butyl-1-methylpyrrolidinium with [NTf(2)](-). Li[NTf(2)] solutions (approximately 3.3 M) of water, methanol, propylene carbonate, and poly(ethylene glycol) have been selected as control samples. Kerr transients of the ILs and electrolyte solutions show intra- and interionic/intermolecular vibrational dynamics followed by slow picosecond overdamped relaxation. Fourier transform Kerr spectra have shown a difference in the relative intensities of intraionic vibrational bands of [NTf(2)](-) (280-350 cm(-1)) between the ILs and electrolyte solutions. The origin of the difference is attributed to the change in the conformational equilibrium between cisoid and transoid forms of [NTf(2)](-), which is caused by a favorable stabilization of dipolar cisoid form due to Li(+) and dipolar solvent molecules in the electrolyte solutions. Low-frequency Kerr spectra (0-200 cm(-1)) exhibit unique features with the variation of cation and solvent species. The aromatic ILs have a prominent high-frequency librational motion at about 100 cm(-1) in contrast to the case for the nonaromatic ones. The common structure of the spectra observed at about 20 cm(-1) likely comes from an interionic motion of [NTf(2)](-). The nonaromatic ILs allow a fair comparison with the electrolyte solutions of propylene carbonate and poly(ethylene glycol) because of the structural similarities. The comparison based on the first moment of the interionic/intermolecular vibrational spectrum suggests the

  3. Comparison of interionic/intermolecular vibrational dynamics between ionic liquids and concentrated electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Fujisawa, Tomotsumi; Nishikawa, Keiko; Shirota, Hideaki

    2009-12-01

    In this study, we have compared the interionic/intermolecular vibrational dynamics of ionic liquids (ILs) and concentrated electrolyte solutions measured by femtosecond optically heterodyne-detected Raman-induced Kerr effect spectroscopy. A typical anion in ILs, bis(trifluoromethanesulfonyl)amide ([NTf2]-), has been chosen as the anion for the sample ILs and concentrated electrolyte solutions. ILs used in this study are 1-butyl-3-methylimidazolium, 1-butylpyridinium, N-butyl-N,N,N-triethylammonium, and 1-butyl-1-methylpyrrolidinium with [NTf2]-. Li[NTf2] solutions (˜3.3M) of water, methanol, propylene carbonate, and poly(ethylene glycol) have been selected as control samples. Kerr transients of the ILs and electrolyte solutions show intra- and interionic/intermolecular vibrational dynamics followed by slow picosecond overdamped relaxation. Fourier transform Kerr spectra have shown a difference in the relative intensities of intraionic vibrational bands of [NTf2]- (280-350 cm-1) between the ILs and electrolyte solutions. The origin of the difference is attributed to the change in the conformational equilibrium between cisoid and transoid forms of [NTf2]-, which is caused by a favorable stabilization of dipolar cisoid form due to Li+ and dipolar solvent molecules in the electrolyte solutions. Low-frequency Kerr spectra (0-200 cm-1) exhibit unique features with the variation of cation and solvent species. The aromatic ILs have a prominent high-frequency librational motion at about 100 cm-1 in contrast to the case for the nonaromatic ones. The common structure of the spectra observed at about 20 cm-1 likely comes from an interionic motion of [NTf2]-. The nonaromatic ILs allow a fair comparison with the electrolyte solutions of propylene carbonate and poly(ethylene glycol) because of the structural similarities. The comparison based on the first moment of the interionic/intermolecular vibrational spectrum suggests the stronger interionic/intermolecular interaction in

  4. Simulation of Absorption Systems in Flexible and Modular Form

    Energy Science and Technology Software Center (ESTSC)

    1994-09-23

    The computer code has been developed for simulation of absorption systems at steady-state in a flexible and modular form, making it possible to investigate various cycle configurations with different working fluids. The code is based on unit subroutines containing the governing equations for the system''s components. When all the equations have been established, a mathematical solver routine is employed to solve them simultaneously. Property subroutines contained in a separate data base serve to provide thermodynamicmore » properties of the working fluids. The code is user-oriented and requires a relatively simple input containing the given operating conditions and the working fluid at each state point. the user conveys to the computer an image of the cycle by specifying the different components and their interconnections. Based on this information, the program calculates the temperature, flowrate, concentration, pressure and vapor fraction at each state point in the system and the heat duty at each unit, from which the coefficient of performance may be determined. A graphical user-interface is provided to facilitate interactive input and study of the output.« less

  5. Evidence for a strong intermolecular bond in the phenolṡN2 cation

    NASA Astrophysics Data System (ADS)

    Haines, S. R.; Geppert, W. D.; Chapman, D. M.; Watkins, M. J.; Dessent, C. E. H.; Cockett, M. C. R.; Müller-Dethlefs, K.

    1998-12-01

    The phenolṡN2 complex cation has been studied with a combination of two-color resonant zero kinetic energy (ZEKE) and mass analyzed threshold ionization (MATI) spectroscopies to probe the interaction of a polar cation with a quadrupolar solvent molecule. Extended vibrational progressions are observed in three modes which are assigned as the in-plane bend (35 cm-1), the stretch (117 cm-1), and in-plane wag (130 cm-1) intermolecular vibrations, and are consistent with a structure where the N2 forms a directional bond to the phenol OH group in the plane of the aromatic ring. Ab initio calculations at the UMP2/6-31G*, UHF/cc-pVDZ, and UMP2/cc-pVDZ levels of theory support this assignment. The spectra also provide a value for the adiabatic ionization energy (67 423 cm-1±4.5 cm-1) and an estimate of the dissociation energy of the cluster (1650±20 cm-1) which illustrate that the quadrupolar nitrogen molecule binds considerably more strongly to the phenol cation than a rare gas atom. These results constitute the first report of an aromaticṡN2 complex where the interaction can be described in terms of weak hydrogen bonding, rather than in terms of a van der Waals bond to the π-system of the benzene ring.

  6. Interpreting the widespread nonlinear force spectra of intermolecular bonds

    PubMed Central

    Friddle, Raymond W.; Noy, Aleksandr; De Yoreo, James J.

    2012-01-01

    Single molecule force spectroscopy probes the strength, lifetime, and energetic details of intermolecular interactions in a simple experiment. A growing number of these studies have reported distinctly nonlinear trends in rupture force with loading rate that are typically explained in conventional models by invoking complex escape pathways. Recent analyses suggested that these trends should be expected even for simple barriers based on the basic assumptions of bond rupture dynamics and thus may represent the norm rather than the exception. Here we explore how these nonlinear trends reflect the two fundamental regimes of bond rupture: (i) a near-equilibrium regime, produced either by bond reforming in the case of a single bond or by asynchronized rupture of multiple individual bonds, and (ii) a kinetic regime produced by fast, non-equilibrium bond rupture. We analyze both single- and multi-bonded cases, describe the full evolution of the system as it transitions between near- and far-from-equilibrium loading regimes, and show that both interpretations produce essentially identical force spectra. Data from 10 different molecular systems show that this model provides a comprehensive description of force spectra for a diverse suite of bonds over experimentally relevant loading rates, removes the inconsistencies of previous interpretations of transition state distances, and gives ready access to both kinetic and thermodynamic information about the interaction. These results imply that single-molecule binding free energies for a vast number of bonds have already been measured. PMID:22869712

  7. Detection of the water reservoir in a forming planetary system.

    PubMed

    Hogerheijde, Michiel R; Bergin, Edwin A; Brinch, Christian; Cleeves, L Ilsedore; Fogel, Jeffrey K J; Blake, Geoffrey A; Dominik, Carsten; Lis, Dariusz C; Melnick, Gary; Neufeld, David; Panić, Olja; Pearson, John C; Kristensen, Lars; Yildiz, Umut A; van Dishoeck, Ewine F

    2011-10-21

    Icy bodies may have delivered the oceans to the early Earth, yet little is known about water in the ice-dominated regions of extrasolar planet-forming disks. The Heterodyne Instrument for the Far-Infrared on board the Herschel Space Observatory has detected emission lines from both spin isomers of cold water vapor from the disk around the young star TW Hydrae. This water vapor likely originates from ice-coated solids near the disk surface, hinting at a water ice reservoir equivalent to several thousand Earth oceans in mass. The water's ortho-to-para ratio falls well below that of solar system comets, suggesting that comets contain heterogeneous ice mixtures collected across the entire solar nebula during the early stages of planetary birth. PMID:22021851

  8. The speakers' bureau system: a form of peer selling.

    PubMed

    Reid, Lynette; Herder, Matthew

    2013-01-01

    In the speakers' bureau system, physicians are recruited and trained by pharmaceutical, biotechnology, and medical device companies to deliver information about products to other physicians, in exchange for a fee. Using publicly available disclosures, we assessed the thesis that speakers' bureau involvement is not a feature of academic medicine in Canada, by estimating the prevalence of participation in speakers' bureaus among Canadian faculty in one medical specialty, cardiology. We analyzed the relevant features of an actual contract made public by the physician addressee and applied the Canadian Medical Association (CMA) guidelines on physician-industry relations to participation in a speakers' bureau. We argue that speakers' bureau participation constitutes a form of peer selling that should be understood to contravene the prohibition on product endorsement in the CMA Code of Ethics. Academic medical institutions, in conjunction with regulatory colleges, should continue and strengthen their policies to address participation in speakers' bureaus. PMID:24348883

  9. System and method for accumulative double sided incremental forming

    DOEpatents

    Cao, Jian; Malhotra, Rajiv

    2015-10-27

    A forming system includes first and second tools, moving assemblies, and a control unit. The moving assemblies move the first tool and the second tool relative to the sheet. The control unit is configured to control movement of the first tool and the second tool by the one or more moving assemblies by moving at least one of the first tool or the second tool in a first deformation direction to deform the sheet, then moving the first and second tools laterally relative to the sheet to a subsequent location while engaging the sheet, then moving at least one of the first tool or the second tool in the first deformation direction or an opposite second deformation direction to deform the sheet, and then continue moving the first and second tools to deform the sheet in order to create a three-dimensional component from the sheet.

  10. The speakers’ bureau system: a form of peer selling

    PubMed Central

    Reid, Lynette; Herder, Matthew

    2013-01-01

    Abstract In the speakers’ bureau system, physicians are recruited and trained by pharmaceutical, biotechnology, and medical device companies to deliver information about products to other physicians, in exchange for a fee. Using publicly available disclosures, we assessed the thesis that speakers’ bureau involvement is not a feature of academic medicine in Canada, by estimating the prevalence of participation in speakers’ bureaus among Canadian faculty in one medical specialty, cardiology. We analyzed the relevant features of an actual contract made public by the physician addressee and applied the Canadian Medical Association (CMA) guidelines on physician–industry relations to participation in a speakers’ bureau. We argue that speakers’ bureau participation constitutes a form of peer selling that should be understood to contravene the prohibition on product endorsement in the CMA Code of Ethics. Academic medical institutions, in conjunction with regulatory colleges, should continue and strengthen their policies to address participation in speakers’ bureaus. PMID:24348883

  11. An old disk still capable of forming a planetary system.

    PubMed

    Bergin, Edwin A; Cleeves, L Ilsedore; Gorti, Uma; Zhang, Ke; Blake, Geoffrey A; Green, Joel D; Andrews, Sean M; Evans, Neal J; Henning, Thomas; Oberg, Karin; Pontoppidan, Klaus; Qi, Chunhua; Salyk, Colette; van Dishoeck, Ewine F

    2013-01-31

    From the masses of the planets orbiting the Sun, and the abundance of elements relative to hydrogen, it is estimated that when the Solar System formed, the circumstellar disk must have had a minimum mass of around 0.01 solar masses within about 100 astronomical units of the star. (One astronomical unit is the Earth-Sun distance.) The main constituent of the disk, gaseous molecular hydrogen, does not efficiently emit radiation from the disk mass reservoir, and so the most common measure of the disk mass is dust thermal emission and lines of gaseous carbon monoxide. Carbon monoxide emission generally indicates properties of the disk surface, and the conversion from dust emission to gas mass requires knowledge of the grain properties and the gas-to-dust mass ratio, which probably differ from their interstellar values. As a result, mass estimates vary by orders of magnitude, as exemplified by the relatively old (3-10 million years) star TW Hydrae, for which the range is 0.0005-0.06 solar masses. Here we report the detection of the fundamental rotational transition of hydrogen deuteride from the direction of TW Hydrae. Hydrogen deuteride is a good tracer of disk gas because it follows the distribution of molecular hydrogen and its emission is sensitive to the total mass. The detection of hydrogen deuteride, combined with existing observations and detailed models, implies a disk mass of more than 0.05 solar masses, which is enough to form a planetary system like our own. PMID:23364742

  12. Intermolecular Interactions and Cooperative Effects from Electronic Structure Calculations: An Effective Means for Developing Interaction Potentials for Condensed Phase Simulations

    SciTech Connect

    Xantheas, Sotiris S.

    2004-05-01

    The modeling of the macroscopic properties of homogeneous and inhomogeneous systems via atomistic simulations such as molecular dynamics (MD) or Monte Carlo (MC) techniques is based on the accurate description of the relevant solvent-solute and solvent-solvent intermolecular interactions. The total energy (U) of an n-body molecular system can be formally written as [1,2,3

  13. Combined Electrostatics and Hydrogen Bonding Determine PIP2 Intermolecular Interactions

    PubMed Central

    Levental, Ilya; Cebers, Andrejs; Janmey, Paul A.

    2010-01-01

    Membrane lipids are active contributors to cell function as key mediators in signaling pathways of inflammation, apoptosis, migration, and proliferation. Recent work on multimolecular lipid structures suggests a critical role for lipid organization in regulating the function of both lipids and proteins. Of particular interest in this context are the polyphosphoinositides (PPI’s), specifically phosphatidylinositol (4,5) bisphosphate (PIP2). The cellular functions of PIP2 are numerous but the factors controlling targeting of PIP2 to specific proteins and organization of PIP2 in the inner leaflet of the plasma membrane remain poorly understood. To analyze the organization of PIP2 in a simplified planar system, we used Langmuir monolayers to study the effects of subphase conditions on monolayers of purified naturally derived PIP2 and other anionic or zwitterionic phospholipids. We report a significant molecular area expanding effect of subphase monovalent salts on PIP2 at biologically relevant surface densities. This effect is shown to be specific to PIP2 and independent of subphase pH. Chaotropic agents (e.g. salts, trehalose, urea, temperature) that disrupt water structure and the ability of water to mediate intermolecular hydrogen bonding also specifically expanded PIP2 monolayers. These results suggest a combination of water-mediated hydrogen bonding and headgroup charge in determining the organization of PIP2, and may provide an explanation for the unique functionality of PIP2 compared to other anionic phospholipids. PMID:18572937

  14. Determination of stepsize parameters for intermolecular vibrational energy transfer

    SciTech Connect

    Tardy, D.C.

    1992-03-01

    Intermolecular energy transfer of highly excited polyatomic molecules plays an important role in many complex chemical systems: combustion, high temperature and atmospheric chemistry. By monitoring the relaxation of internal energy we have observed trends in the collisional efficiency ({beta}) for energy transfer as a function of the substrate's excitation energy and the complexities of substrate and deactivator. For a given substrate {beta} increases as the deactivator's mass increase to {approximately}30 amu and then exhibits a nearly constant value; this is due to a mass mismatch between the atoms of the colliders. In a homologous series of substrate molecules (C{sub 3}{minus}C{sub 8}) {beta} decreases as the number of atoms in the substrate increases; replacing F with H increases {beta}. All substrates, except for CF{sub 2}Cl{sub 2} and CF{sub 2}HCl below 10,000 cm{sup {minus}1}, exhibited that {beta} is independent of energy, i.e. <{Delta}E>{sub all} is linear with energy. The results are interpreted with a simple model which considers that {beta} is a function of the ocillators energy and its vibrational frequency. Limitations of current approximations used in high temperature unimolecular reactions were evaluated and better approximations were developed. The importance of energy transfer in product yields was observed for the photoactivation of perfluorocyclopropene and the photoproduction of difluoroethyne. 3 refs., 18 figs., 4 tabs.

  15. Intermolecular structure determination of amyloid fibrils with magic-angle spinning and dynamic nuclear polarization NMR

    PubMed Central

    Bayro, Marvin J.; Debelouchina, Galia T.; Eddy, Matthew T.; Birkett, Neil R.; MacPhee, Catherine E.; Rosay, Melanie; Maas, Werner E.; Dobson, Christopher M.

    2011-01-01

    We describe magic-angle spinning NMR experiments designed to elucidate the interstrand architecture of amyloid fibrils. Three methods are introduced for this purpose, two being based on the analysis of long-range 13C-13C correlation spectra and a third based on the identification of intermolecular interactions in 13C-15N spectra. We show, in studies of fibrils formed by the 86-residue SH3 domain of PI3 kinase (PI3-SH3), that efficient 13C-13C correlation spectra display a resonance degeneracy that establishes a parallel, in-register alignment of the proteins in the amyloid fibrils. In addition, this degeneracy can be circumvented to yield direct intermolecular constraints. The 13C-13C experiments are corroborated by 15N-13C correlation spectrum obtained from a mixed [15N,12C]/[14N,13C] sample which directly quantifies interstrand distances. Furthermore, when the spectra are recorded with signal enhancement provided by dynamic nuclear polarization (DNP) at 100 K, we demonstrate a dramatic increase (from 23 to 52) in the number of intermolecular 15N-13C constraints present in the spectra. The increase in the information content is due to the enhanced signal intensities and to the fact that dynamic processes, leading to spectral intensity losses, are quenched at low temperatures. Thus, acquisition of low temperature spectra addresses a problem that is frequently encountered in MAS spectra of proteins. In total the experiments provide 111 intermolecular 13C-13C and 15N-13C constraints that establish that the PI3-SH3 protein strands are aligned in a parallel, in-register arrangement within the amyloid fibril. PMID:21774549

  16. Raft forming system-an upcoming approach of gastroretentive drug delivery system.

    PubMed

    Prajapati, Vipul D; Jani, Girish K; Khutliwala, Tohra A; Zala, Bhumi S

    2013-06-10

    In recent era various technologies have been made in research and development of controlled release oral drug delivery system to overcome various physiological difficulties such as variation in gastric retention and emptying time. To overcome this drawback and to maximize the oral absorption of various drugs, novel drug delivery systems have been developed. Gastroretentive drug delivery system is facing many challenges which can be overcome by upcoming newly emerging approach i.e. raft forming system. The purpose of writing this review is to focus on recent development of stomach specific floating drug delivery system to circumvent the difficulties associated with formulation design. Various gastroretentive approaches that have been developed till now are also discussed. The present study provides valuable information & highlights advances in this raft forming system. This review attempts to discuss various factors like physiological factors, physicochemical factors and formulation factors to be considered in the development of the raft forming system. Different types of smart polymers used for their formulation have also been summarized. The review focuses on the mechanism, formulation and development of the raft forming system. This review also summarizes the studies to evaluate the performance and application of these systems. The study finally highlights advantages, disadvantages, and marketed preparation of the raft forming system. PMID:23500062

  17. Fast dynamics in glass forming systems: Vibrations vs relaxation

    SciTech Connect

    Sokolov, A.P.

    1997-12-31

    Two contributions specific for the spectra of the fast dynamics in glass forming systems, a broad quasielastic scattering and the boson peak, are analyzed. It is shown that the vibrational contribution (the boson peak) decreases strongly in fragile systems. Some speculations about dependence of the degree of fragility (a la Angell) on peculiarity of the spectrum of fast dynamics are presented. The existence of some intrinsic relation between the broad quasielastic contribution and the boson peak is demonstrated from analysis of the recent neutron and Raman scattering data. It is shown that this relation can be explained in framework of the model of damped oscillator. The model ascribes the quasielastic contribution to the scattering of light or neutrons on the vibrations around the boson peak, which are damped by some relaxation channel and have a quasielastic part in their response function. It is demonstrated that the model can explain many peculiar properties of the fast dynamics in the Raman, neutron and far-infrared absorption spectra.

  18. New compact forms of the trigonometric Ruijsenaars-Schneider system

    NASA Astrophysics Data System (ADS)

    Fehér, L.; Kluck, T. J.

    2014-05-01

    The reduction of the quasi-Hamiltonian double of SU(n) that has been shown to underlie Ruijsenaars' compactified trigonometric n-body system is studied in its natural generality. The constraints contain a parameter y, restricted in previous works to 0forms of two qualitatively different types depending on the value of y. The type (i) cases are similar to the standard case in that the reduced phase space comes equipped with globally smooth action and position variables, and turns out to be symplectomorphic to CP as a Hamiltonian toric manifold. In the type (ii) cases both the position variables and the action variables develop singularities on a nowhere dense subset. A full classification is derived for the parameter y according to the type (i) versus type (ii) dichotomy. The simplest new type (i) systems, for which π/n

  19. Tip relaxation in atomic force microscopy imaging simulations to resolve intermolecular bonds

    NASA Astrophysics Data System (ADS)

    Lee, Alex; Sakai, Yuki; Chelikowsky, Jim

    Experimental noncontact atomic force microscopy (AFM) studies have reported distinct lines in regions with no electron density for a variety of systems. The appearance of these lines is unexpected because Pauli repulsion is thought to be the dominant factor in the AFM imaging mechanism. These lines have been proposed to represent intermolecular bonding. Recent theoretical studies have shown that accounting for tip probe relaxation can sharpen images and highlight features that make simulations more comparable to experiment. We will apply a similar tip relaxation scheme to our computational method-which uses an ab initio real-space pseudopotential formalism with frozen density embedding theory added-to the study of dibenzo[a,h]thianthrene and an 8-hydroxyquinoline dimer to develop our interpretation of imaged intermolecular bonds. Work is supported by the DOE under DOE/DE-FG02-06ER46286 and by the Welch Foundation under Grant F-1837. Computational resources were provided by NERSC and XSEDE.

  20. Study of intermolecular interactions in binary mixtures of ethanol in methanol

    NASA Astrophysics Data System (ADS)

    Maharolkar, Aruna P.; Khirade, P. W.; Murugkar, A. G.

    2016-05-01

    Present paper deals with study of physicochemical properties like viscosity, density and refractive index for the binary mixtures of ethanol and methanol over the entire concentration range were measured at 298.15 K. The experimental data further used to determine the excess properties viz. excess molar volume, excess viscosity, excess molar refraction. The values of excess properties further fitted with Redlich-Kister (R-K Fit) equation to calculate the binary coefficients and standard deviation. The resulting excess parameters are used to indicate the presence of intermolecular interactions and strength of intermolecular interactions between the molecules in the binary mixtures. Excess parameters indicate structure making factor in the mixture predominates in the system.

  1. Intermolecular artifacts in probe microscope images of C60 assemblies

    NASA Astrophysics Data System (ADS)

    Jarvis, Samuel Paul; Rashid, Mohammad Abdur; Sweetman, Adam; Leaf, Jeremy; Taylor, Simon; Moriarty, Philip; Dunn, Janette

    2015-12-01

    Claims that dynamic force microscopy has the capability to resolve intermolecular bonds in real space continue to be vigorously debated. To date, studies have been restricted to planar molecular assemblies with small separations between neighboring molecules. Here we report the observation of intermolecular artifacts over much larger distances in 2D assemblies of C60 molecules, with compelling evidence that in our case the tip apex is terminated by a C60 molecule (rather than the CO termination typically exploited in ultrahigh resolution force microscopy). The complete absence of directional interactions such as hydrogen or halogen bonding, the nonplanar structure of C60, and the fullerene termination of the tip apex in our case highlight that intermolecular artifacts are ubiquitous in dynamic force microscopy.

  2. Qualitative change of character of dispersive interaction with intermolecular distance.

    PubMed

    Haslmayr, Johannes; Renger, Thomas

    2013-07-28

    The dispersive interaction between molecules results from Coulomb-correlated fluctuations of electrons and for large intermolecular distances it can be related to the molecular polarizabilities as in London's theory (F. London, Trans. Faraday Soc. 33, 8-26 (1937)). Here, we investigate the interaction between molecules with anisotropic polarizabilities at arbitrary distances using symmetry adapted perturbation theory, which allows us to analyze the different parts of the intermolecular potential separately. Whereas at large distances, in accordance with London's theory, there is no way to describe the dispersive interaction by a sum over pairwise isotropic atom-centered energy terms, at short distances such a description becomes possible. This surprising result has consequences for the development of molecular mechanics force fields, supports the dispersion energy terms applied in dispersion corrected density functional theory, and indicates that there is a qualitative change in electron correlation with distance. Apparently, at short distances intermolecular electron correlation is less influenced by intramolecular electron delocalization. PMID:23901956

  3. Visualizing coherent intermolecular dipole-dipole coupling in real space.

    PubMed

    Zhang, Yang; Luo, Yang; Zhang, Yao; Yu, Yun-Jie; Kuang, Yan-Min; Zhang, Li; Meng, Qiu-Shi; Luo, Yi; Yang, Jin-Long; Dong, Zhen-Chao; Hou, J G

    2016-03-31

    Many important energy-transfer and optical processes, in both biological and artificial systems, depend crucially on excitonic coupling that spans several chromophores. Such coupling can in principle be described in a straightforward manner by considering the coherent intermolecular dipole-dipole interactions involved. However, in practice, it is challenging to directly observe in real space the coherent dipole coupling and the related exciton delocalizations, owing to the diffraction limit in conventional optics. Here we demonstrate that the highly localized excitations that are produced by electrons tunnelling from the tip of a scanning tunnelling microscope, in conjunction with imaging of the resultant luminescence, can be used to map the spatial distribution of the excitonic coupling in well-defined arrangements of a few zinc-phthalocyanine molecules. The luminescence patterns obtained for excitons in a dimer, which are recorded for different energy states and found to resemble σ and π molecular orbitals, reveal the local optical response of the system and the dependence of the local optical response on the relative orientation and phase of the transition dipoles of the individual molecules in the dimer. We generate an in-line arrangement up to four zinc-phthalocyanine molecules, with a larger total transition dipole, and show that this results in enhanced 'single-molecule' superradiance from the oligomer upon site-selective excitation. These findings demonstrate that our experimental approach provides detailed spatial information about coherent dipole-dipole coupling in molecular systems, which should enable a greater understanding and rational engineering of light-harvesting structures and quantum light sources. PMID:27029277

  4. Visualizing coherent intermolecular dipole–dipole coupling in real space

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Luo, Yang; Zhang, Yao; Yu, Yun-Jie; Kuang, Yan-Min; Zhang, Li; Meng, Qiu-Shi; Luo, Yi; Yang, Jin-Long; Dong, Zhen-Chao; Hou, J. G.

    2016-03-01

    Many important energy-transfer and optical processes, in both biological and artificial systems, depend crucially on excitonic coupling that spans several chromophores. Such coupling can in principle be described in a straightforward manner by considering the coherent intermolecular dipole–dipole interactions involved. However, in practice, it is challenging to directly observe in real space the coherent dipole coupling and the related exciton delocalizations, owing to the diffraction limit in conventional optics. Here we demonstrate that the highly localized excitations that are produced by electrons tunnelling from the tip of a scanning tunnelling microscope, in conjunction with imaging of the resultant luminescence, can be used to map the spatial distribution of the excitonic coupling in well-defined arrangements of a few zinc-phthalocyanine molecules. The luminescence patterns obtained for excitons in a dimer, which are recorded for different energy states and found to resemble σ and π molecular orbitals, reveal the local optical response of the system and the dependence of the local optical response on the relative orientation and phase of the transition dipoles of the individual molecules in the dimer. We generate an in-line arrangement up to four zinc-phthalocyanine molecules, with a larger total transition dipole, and show that this results in enhanced ‘single-molecule’ superradiance from the oligomer upon site-selective excitation. These findings demonstrate that our experimental approach provides detailed spatial information about coherent dipole–dipole coupling in molecular systems, which should enable a greater understanding and rational engineering of light-harvesting structures and quantum light sources.

  5. Effect of the electronic structure of quinoline and its derivatives on the capacity for intermolecular interactions

    SciTech Connect

    Privalova, N.Yu.; Sokolova, I.V.

    1985-05-01

    Calculations of the ground and excited states of quinoline and its 20H-, 70H-, 7NH2-, 7N(CH3)2-, and 7N(C2H5)2- substituted derivatives were undertaken by the INDO method, and the effect of intramolecular proton transfer (IPT) on their electronic structure was studied. The proton-accepting capacity of the compounds for intermolecular interactions was estimated by the molecular electrostatic potential method. It was shown that the proton-accepting capacity with respect to intermolecular interactions increases during the tautomeric transformation of the enolic form of 2-OH-quinoline to its keto form. The change in the basicity of the two forms of the molecules is affected by the orbital nature, and the multiplicity of the state is also important for the keto form. Substitution by electron-donating groups leads to increase in the proton-accepting capacity of both forms of the compounds in the S0, S/sub */, and T/sub */ states.

  6. Intermolecular Vibrational Modes Speed Up Singlet Fission in Perylenediimide Crystals.

    PubMed

    Renaud, Nicolas; Grozema, Ferdinand C

    2015-02-01

    We report numerical simulations based on a non-Markovian density matrix propagation scheme of singlet fission (SF) in molecular crystals. Ab initio electronic structure calculations were used to parametrize the exciton and phonon Hamiltonian as well as the interactions between the exciton and the intramolecular and intermolecular vibrational modes. We demonstrate that the interactions of the exciton with intermolecular vibrational modes are highly sensitive to the stacking geometry of the crystal and can, in certain cases, significantly accelerate SF. This result may help in understanding the fast SF experimentally observed in a broad range of molecular crystals and offers a new direction for the engineering of efficient SF sensitizers. PMID:26261948

  7. Competing resonances in spatially forced pattern-forming systems.

    PubMed

    Mau, Yair; Haim, Lev; Hagberg, Aric; Meron, Ehud

    2013-09-01

    Spatial periodic forcing can entrain a pattern-forming system in the same way as temporal periodic forcing can entrain an oscillator. The forcing can lock the pattern's wave number to a fraction of the forcing wave number within tonguelike domains in the forcing parameter plane, it can increase the pattern's amplitude, and it can also create patterns below their onset. We derive these results using a multiple-scale analysis of a spatially forced Swift-Hohenberg equation in one spatial dimension. In two spatial dimensions the one-dimensional forcing can induce a symmetry-breaking instability that leads to two-dimensional (2D) patterns, rectangular or oblique. These patterns resonate with the forcing by locking their wave-vector component in the forcing direction to half the forcing wave number. The range of this type of 2:1 resonance overlaps with the 1:1 resonance tongue of stripe patterns. Using a multiple-scale analysis in the overlap region we show that the 2D patterns can destabilize the 1:1 resonant stripes even at exact resonance. This result sheds new light on the use of spatial periodic forcing for controlling patterns. PMID:24125335

  8. Simulating two-dimensional infrared-Raman and Raman spectroscopies for intermolecular and intramolecular modes of liquid water.

    PubMed

    Ito, Hironobu; Tanimura, Yoshitaka

    2016-02-21

    Full classical molecular dynamics (MD) simulations of two-dimensional (2D) infrared-Raman and 2D Raman spectroscopies of liquid water were carried out to elucidate a mode-mode coupling mechanism using a polarizable water model for intermolecular and intramolecular vibrational spectroscopy (POLI2VS). This model is capable of describing both infrared and Raman spectra. Second-order response functions, which consist of one molecular polarizability and two molecular dipole moments for 2D IR-Raman and three molecular polarizabilities for 2D Raman spectroscopies, were calculated using an equilibrium-non-equilibrium hybrid MD approach. The obtained signals were analyzed using a multi-mode Brownian oscillator (BO) model with nonlinear system-bath interactions representing the intramolecular OH stretching, intramolecular HOH bending, hydrogen bonded (HB)-intermolecular librational motion and HB-intermolecular vibrational (translational) motion of liquid water. This model was applied through use of hierarchal Fokker-Planck equations. The qualitative features of the peak profiles in the 2D spectra obtained from the MD simulations are accurately reproduced with the BO model. This indicates that this model captures the essential features of the intermolecular and intramolecular motion. We elucidate the mechanisms governing the 2D signal profiles involving anharmonic mode-mode coupling, the nonlinearities of the polarizability and dipole moment, and the vibrational dephasing processes of liquid water even in the case that the 2D spectral peaks obtained from the MD simulation overlap or are unclear. The mode coupling peaks caused by electrical anharmonic coupling (EAHC) and mechanical anharmonic coupling (MAHC) are observed in all of the 2D spectra. We find that the strength of the MAHC between the OH-stretching and HB-intermolecular vibrational modes is comparable to that between the OH-stretching and HOH bending modes. Moreover, we find that this OH-stretching and HB-intermolecular

  9. Mikrokristallbildung und intermolekulare Triplett-Triplett-Energieiibertragung in festen transparenten Glasern bei 77 K. Das System N-Methylcarbazol/Naphthalin / Microcrystal Formation and Intermolecular Triplet-Triplet Energy Transfer in Rigid Transparent Glasses at 77 K. The System N-Methyl-earbazole / Naphthalene

    NASA Astrophysics Data System (ADS)

    Zander, M.

    1984-05-01

    The efficient intermolecular triplet-triplet energy transfer between N-methylcarbazole (donor) and naphthalene (acceptor) observed at 10-2 ᴍ concentration of donor and acceptor in a rigid transparent methylcyclohexane/n-pentane glass at 77 K is shown to occur in microcrystals of the donor containing small amounts of the acceptor

  10. Theory of specific heat in glass-forming systems.

    PubMed

    Hentschel, H G E; Ilyin, Valery; Procaccia, Itamar; Schupper, Nurith

    2008-12-01

    Experimental measurements of the specific heat in glass-forming systems are obtained from the linear response to either slow cooling (or heating) or to oscillatory perturbations with a given frequency about a constant temperature. The latter method gives rise to a complex specific heat with the constraint that the zero frequency limit of the real part should be identified with thermodynamic measurements. Such measurements reveal anomalies in the temperature dependence of the specific heat, including the so called "specific heat peak" in the vicinity of the glass transition. The aim of this paper is to provide theoretical explanations of these anomalies in general and a quantitative theory in the case of a simple model of glass formation. We first present interesting simulation results for the specific heat in a classical model of a binary mixture glass former. We show that in addition to the formerly observed specific heat peak there is a second peak at lower temperatures which was not observable in earlier simulations. Second, we present a general relation between the specific heat, a caloric quantity, and the bulk modulus of the material, a mechanical quantity, and thus offer a smooth connection between the liquid and amorphous solid states. The central result of this paper is a connection between the micromelting of clusters in the system and the appearance of specific heat peaks; we explain the appearance of two peaks by the micromelting of two types of clusters. We relate the two peaks to changes in the bulk and shear moduli. We propose that the phenomenon of glass formation is accompanied by a fast change in the bulk and the shear moduli, but these fast changes occur in different ranges of the temperature. Last, we demonstrate how to construct a theory of the frequency dependent complex specific heat, expected from heterogeneous clustering in the liquid state of glass formers. A specific example is provided in the context of our model for the dynamics of

  11. Intermolecular potentials from shock structure experiments. [for monatomic gases

    NASA Technical Reports Server (NTRS)

    Sturtevant, B.; Steinhilper, E. A.

    1974-01-01

    Ground-state intermolecular interaction potentials determined from shock structure experiments with four monatomic gases are reported. These potentials are assessed for self-consistency, using the law of corresponding states, and their suitability for engineering applications in rarefied gas dynamics is discussed.

  12. Learning about Intermolecular Interactions from the Cambridge Structural Database

    ERIC Educational Resources Information Center

    Battle, Gary M.; Allen, Frank H.

    2012-01-01

    A clear understanding and appreciation of noncovalent interactions, especially hydrogen bonding, are vitally important to students of chemistry and the life sciences, including biochemistry, molecular biology, pharmacology, and medicine. The opportunities afforded by the IsoStar knowledge base of intermolecular interactions to enhance the…

  13. Direct observation of intermolecular interactions mediated by hydrogen bonding

    NASA Astrophysics Data System (ADS)

    De Marco, Luigi; Thämer, Martin; Reppert, Mike; Tokmakoff, Andrei

    2014-07-01

    Although intermolecular interactions are ubiquitous in physicochemical phenomena, their dynamics have proven difficult to observe directly, and most experiments rely on indirect measurements. Using broadband two-dimensional infrared spectroscopy (2DIR), we have measured the influence of hydrogen bonding on the intermolecular vibrational coupling between dimerized N-methylacetamide molecules. In addition to strong intramolecular coupling between N-H and C=O oscillators, cross-peaks in the broadband 2DIR spectrum appearing upon dimerization reveal strong intermolecular coupling that changes the character of the vibrations. In addition, dimerization changes the effects of intramolecular coupling, resulting in Fermi resonances between high and low-frequency modes. These results illustrate how hydrogen bonding influences the interplay of inter- and intramolecular vibrations, giving rise to correlated nuclear motions and significant changes in the vibrational structure of the amide group. These observations have direct impact on modeling and interpreting the IR spectra of proteins. In addition, they illustrate a general approach to direct molecular characterization of intermolecular interactions.

  14. Direct observation of intermolecular interactions mediated by hydrogen bonding

    SciTech Connect

    De Marco, Luigi; Reppert, Mike; Thämer, Martin; Tokmakoff, Andrei

    2014-07-21

    Although intermolecular interactions are ubiquitous in physicochemical phenomena, their dynamics have proven difficult to observe directly, and most experiments rely on indirect measurements. Using broadband two-dimensional infrared spectroscopy (2DIR), we have measured the influence of hydrogen bonding on the intermolecular vibrational coupling between dimerized N-methylacetamide molecules. In addition to strong intramolecular coupling between N–H and C=O oscillators, cross-peaks in the broadband 2DIR spectrum appearing upon dimerization reveal strong intermolecular coupling that changes the character of the vibrations. In addition, dimerization changes the effects of intramolecular coupling, resulting in Fermi resonances between high and low-frequency modes. These results illustrate how hydrogen bonding influences the interplay of inter- and intramolecular vibrations, giving rise to correlated nuclear motions and significant changes in the vibrational structure of the amide group. These observations have direct impact on modeling and interpreting the IR spectra of proteins. In addition, they illustrate a general approach to direct molecular characterization of intermolecular interactions.

  15. Copper-catalyzed intermolecular asymmetric propargylic dearomatization of indoles.

    PubMed

    Shao, Wen; Li, He; Liu, Chuan; Liu, Chen-Jiang; You, Shu-Li

    2015-06-22

    The first copper-catalyzed intermolecular dearomatization of indoles by an asymmetric propargylic substitution reaction was developed. This method provides a highly efficient synthesis of versatile furoindoline and pyrroloindoline derivatives containing a quaternary carbon stereogenic center and a terminal alkyne moiety with up to 86 % yield and 98 % ee. PMID:25968474

  16. Student Understanding of Intermolecular Forces: A Multimodal Study

    ERIC Educational Resources Information Center

    Cooper, Melanie M.; Williams, Leah C.; Underwood, Sonia M.

    2015-01-01

    The ability to use representations of molecular structure to predict the macroscopic properties of a substance is central to the development of a robust understanding of chemistry. Intermolecular forces (IMFs) play an important role in this process because they provide a mechanism for how and why molecules interact. In this study, we investigate…

  17. Hydrogen-hydrogen intermolecular structure of polyethylene in the melt

    NASA Astrophysics Data System (ADS)

    Londono, J. D.; Annis, B. K.; Habenschuss, A.; Smith, G. D.; Borodin, O.; Tso, C.; Hsieh, E. T.; Soper, A. K.

    1999-05-01

    Three polyethylene samples, which differed in their degree of deuteration, were studied in neutron diffraction isotopic substitution (NDIS) experiments at 428 K. These results were complemented at small wavevectors by small angle neutron measurements. The intermolecular hydrogen-hydrogen (HH) structure function, hHH(Q), was obtained without recourse to intramolecular structure models, as demonstrated in a prior report. The PE experimental results are compared to computer simulation results for the alkanes C100 at 509 K and C44 at 350, 400, and 450 K. The small temperature dependence of the HH intermolecular radial distribution functions, gHH(r) for C44 indicates that the differences observed between the PE, C100, and C44 (450 K) results are, for the most part, not due to just temperature differences. It is shown that the string model, an analytic result from an integral equation theory of polymers (PRISM), can account approximately for the overall shape of the gHH(r) functions, and that this overall shape is dependent on the radius of gyration of the molecule. Further analysis shows that there are two other contributions to gHH(r), both of which are independent of chain length to first order. The first is due to chain-chain packing, and the second is due to local HH intermolecular correlations. These results are significant because they demonstrate that hHH(Q) is a useful function for studying intermolecular polymer structure, which has been shown to underpin phase behavior in polyolefin blends.

  18. Intermolecular energy-band dispersion in PTCDA multilayers

    NASA Astrophysics Data System (ADS)

    Yamane, Hiroyuki; Kera, Satoshi; Okudaira, Koji K.; Yoshimura, Daisuke; Seki, Kazuhiko; Ueno, Nobuo

    2003-07-01

    The electronic structure of a well-oriented perylene-3,4,9,10-tetracarboxylic acid-dianhydride multilayer prepared on MoS2 single crystal surface were studied by angle-resolved ultraviolet photoemission spectroscopy using synchrotron radiation. From the photon energy dependence of normal emission spectra, we observed an intermolecular energy-band dispersion of about 0.2 eV for the highest occupied molecular orbital (HOMO) band of single π character. The observed energy-band dispersion showed a cosine curve, which originates from the intermolecular π-π interaction. Analyses using the tight-binding model gave that the transfer integral of about 0.05 eV for the π-π interaction, the effective mass of HOMO hole m*h=5.28m0, and the hole mobility μh>3.8 cm2/V s. This is the first observation of the intermolecular energy-band dispersion of a conventional single-component organic semiconductor only with the weak intermolecular van der Waals interaction.

  19. Interatomic and intermolecular Coulombic decay: the coming of age story

    NASA Astrophysics Data System (ADS)

    Jahnke, T.

    2015-04-01

    In pioneering work by Cederbaum et al an excitation mechanism was proposed that occurs only in loosely bound matter (Cederbaum et al 1997 Phys. Rev. Lett. 79 4778): it turned out, that (in particular) in cases where a local Auger decay is energetically forbidden, an excited atom or molecule is able to decay in a scheme which was termed ‘interatomic Coulombic decay’ (or ‘intermolecular Coulombic decay’) (ICD). As ICD occurs, the excitation energy is released by transferring it to an atomic or molecular neighbor of the initially excited particle. As a consequence the neighboring atom or molecule is ionized as it receives the energy. A few years later the existence of ICD was confirmed experimentally (Marburger et al 2003 Phys. Rev. Lett. 90 203401; Jahnke et al 2004 Phys. Rev. Lett. 93 163401; Öhrwall et al 2004 Phys. Rev. Lett. 93 173401) by different techniques. Since this time it has been found that ICD is not (as initially suspected) an exotic feature of van der Waals or hydrogen bonded systems, but that ICD is a very general and common feature occurring after a manifold of excitation schemes and in numerous weakly bound systems, as revealed by more than 200 publications. It was even demonstrated, that ICD can become more efficient than a local Auger decay in some system. This review will concentrate on recent experimental investigations on ICD. It will briefly introduce the phenomenon and give a short summary of the ‘early years’ of ICD (a detailed view on this episode of investigations can be found in the review article by U Hergenhahn with the same title (Hergenhahn 2011 J. Electron Spectrosc. Relat. Phenom. 184 78)). More recent articles will be presented that investigate the relevance of ICD in biological systems and possible radiation damage of such systems due to ICD. The occurrence of ICD and ICD-like processes after different excitation schemes and in different systems is covered in the middle section: in that context the helium dimer (He2

  20. Weak Intermolecular Hydrogen Bonds with Fluorine: Detection and Implications for Enzymatic/Chemical Reactions, Chemical Properties, and Ligand/Protein Fluorine NMR Screening.

    PubMed

    Dalvit, Claudio; Vulpetti, Anna

    2016-05-23

    It is known that strong hydrogen-bonding interactions play an important role in many chemical and biological systems. However, weak or very weak hydrogen bonds, which are often difficult to detect and characterize, may also be relevant in many recognition and reaction processes. Fluorine serving as a hydrogen-bond acceptor has been the subject of many controversial discussions and there are different opinions about it. It now appears that there is compelling experimental evidence for the involvement of fluorine in weak intramolecular or intermolecular hydrogen bonds. Using established NMR methods, we have previously characterized and measured the strengths of intermolecular hydrogen-bond complexes involving the fluorine moieties CH2 F, CHF2 , and CF3 , and have compared them with the well-known hydrogen-bond complex formed between acetophenone and the strong hydrogen-bond donor p-fluorophenol. We now report evidence for the formation of hydrogen bonds involving fluorine with significantly weaker donors, namely 5-fluoroindole and water. A simple NMR method is proposed for the simultaneous measurement of the strengths of hydrogen bonds between an acceptor and a donor or water. Important implications of these results for enzymatic/chemical reactions involving fluorine, for chemical and physical properties, and for ligand/protein (19) F NMR screening are analyzed through experiments and theoretical simulations. PMID:27112430

  1. Intermolecular interaction and the extended wormlike chain conformation of chitin in NaOH/urea aqueous solution.

    PubMed

    Fang, Yan; Duan, Bo; Lu, Ang; Liu, Maili; Liu, Huili; Xu, Xiaojuan; Zhang, Lina

    2015-04-13

    The intra- and intermolecular interactions of chitin in NaOH/urea aqueous system were studied by a combination of NMR measurements (including (13)C NMR, (23)Na NMR, and (15)N NMR) and differential scanning calorimetry. The results revealed that the NaOH and chitin formed a hydrogen-bonded complex that was surrounded by the urea hydrates to form a sheath-like structure, leading to the good dissolution. The optimal concentration range, in which chitin was molecularly dispersed in NaOH/urea aqueous, was found to investigate the chain conformation in the dilute solution with a combination of static and dynamic light scattering. The weight-average molecular weight (Mw), radii of gyration (⟨Rg⟩z), and hydrodynamic radii (⟨Rh⟩z) values of chitin were determined, and the structure-sensitive parameter (ρ) and persistent length (Lp) were calculated to be >2.0 and ∼30 nm, respectively, suggesting an extended wormlike chain conformation. The visualized images from TEM, cryo-TEM, and AFM indicated that, chitin nanofibers were fabricated from the parallel aggregation of chitin chains in NaOH/urea system. This work would provide a theoretical guidance for constructing novel chitin-based nanomaterials via "bottom-up" method at the molecular level. PMID:25712045

  2. Using electronic polarization from the internal continuum (EPIC) for intermolecular interactions.

    PubMed

    Truchon, Jean-François; Nicholl's, Anthony; Grant, J Andrew; Iftimie, Radu I; Roux, Benoît; Bayly, Christopher I

    2010-03-01

    Recently, the vacuum-phase molecular polarizability tensor of various molecules has been accurately modeled (Truchon et al., J Chem Theory Comput 2008, 4, 1480) with an intramolecular continuum dielectric model. This preliminary study showed that electronic polarization can be accurately modeled when combined with appropriate dielectric constants and atomic radii. In this article, using the parameters developed to reproduce ab initio quantum mechanical (QM) molecular polarizability tensors, we extend the application of the "electronic polarization from internal continuu" (EPIC) approach to intermolecular interactions. We first derive a dielectric-adapted least-square-fit procedure similar to RESP, called DRESP, to generate atomic partial charges based on a fit to a QM abinitio electrostatic potential (ESP). We also outline a procedure to adapt any existing charge model to EPIC. The ability of this to reproduce local polarization, as opposed to uniform polarization, is also examined leading to an induced ESP relative root mean square deviation of 1%, relative to ab initio, when averaged over 37 molecules including aromatics and alkanes. The advantage of using a continuum model as opposed to an atom-centered polarizable potential is illustrated with a symmetrically perturbed atom and benzene. We apply EPIC to a cation-pi binding system formed by an atomic cation and benzene and show that the EPIC approach can accurately account for the induction energy. Finally, this article shows that the ab initio electrostatic component in the difficult case of the H-bonded 4-pyridone dimer, a highly polar and polarized interaction, is well reproduced without adjusting the vacuum-phase parameters. PMID:19598266

  3. Spectroscopic proof for intermolecular or intramolecular hydrogen bonds in ketoenol tautomers of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

    NASA Astrophysics Data System (ADS)

    Ueda, Toyotoshi; Akama, Yoshifumi

    1994-06-01

    The broad infrared bands of the polymorphic crystals of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) were assigned unequivocally by examining the IR spectra of solutions and Raman spectra. The strong band at 2550 cm -1 of a colourless crystal was attributed to an intermolecular hydrogen bond NH…OC of the NH keto form, and the strong band at 3100 cm -1 of a yellow crystal, to an intermolecular hydrogen bond OH…OC of the O(1)H enol forms.

  4. Intermolecular vs molecule–substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001)

    PubMed Central

    Roos, Michael; Uhl, Benedikt; Künzel, Daniela; Hoster, Harry E; Groß, Axel

    2011-01-01

    Summary The competition between intermolecular interactions and long-range lateral variations in the substrate–adsorbate interaction was studied by scanning tunnelling microscopy (STM) and force field based calculations, by comparing the phase formation of (sub-) monolayers of the organic molecules (i) 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl)pyridin-2-yl)pyrimidine (3,3'-BTP) and (ii) 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA) on graphene/Ru(0001). For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results. PMID:22003444

  5. Intermolecular vs molecule-substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001).

    PubMed

    Roos, Michael; Uhl, Benedikt; Künzel, Daniela; Hoster, Harry E; Groß, Axel; Behm, R Jürgen

    2011-01-01

    The competition between intermolecular interactions and long-range lateral variations in the substrate-adsorbate interaction was studied by scanning tunnelling microscopy (STM) and force field based calculations, by comparing the phase formation of (sub-) monolayers of the organic molecules (i) 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl)pyridin-2-yl)pyrimidine (3,3'-BTP) and (ii) 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA) on graphene/Ru(0001). For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results. PMID:22003444

  6. Conformational diversity in prion protein variants influences intermolecular [beta]-sheet formation

    SciTech Connect

    Lee, Seungjoo; Antony, Lizamma; Hartmann, Rune; Knaus, Karen J.; Surewicz, Krystyna; Surewicz, Witold K.; Yee, Vivien C.

    2010-04-19

    A conformational transition of normal cellular prion protein (PrP{sup C}) to its pathogenic form (PrP{sup Sc}) is believed to be a central event in the transmission of the devastating neurological diseases known as spongiform encephalopathies. The common methionine/valine polymorphism at residue 129 in the PrP influences disease susceptibility and phenotype. We report here seven crystal structures of human PrP variants: three of wild-type (WT) PrP containing V129, and four of the familial variants D178N and F198S, containing either M129 or V129. Comparison of these structures with each other and with previously published WT PrP structures containing M129 revealed that only WT PrPs were found to crystallize as domain-swapped dimers or closed monomers; the four mutant PrPs crystallized as non-swapped dimers. Three of the four mutant PrPs aligned to form intermolecular {beta}-sheets. Several regions of structural variability were identified, and analysis of their conformations provides an explanation for the structural features, which can influence the formation and conformation of intermolecular {beta}-sheets involving the M/V129 polymorphic residue.

  7. Validation of intermolecular transfer integral and bandwidth calculations for organic molecular materials.

    PubMed

    Huang, Jingsong; Kertesz, Miklos

    2005-06-15

    We present an interpretation of the intermolecular transfer integral that is independent from the origin of the energy scale allowing convergence studies of this important parameter of organic molecular materials. We present extensive numerical studies by using an ethylene pi dimer to investigate the dependence of transfer integrals on the level of theory and intermolecular packing. Transfer integrals obtained from semiempirical calculations differ substantially from one another and from ab initio results. The ab initio results are consistent across all the levels used including Hartree-Fock, outer valence Green's function, and various forms of density functional theory (DFT). Validation of transfer integrals and bandwidths is performed by comparing the calculated values with the experimental values of tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ), bis[1,2,5]thiadiazolo-p-quinobis(1,3-dithiole), (BTQBT) K-TCNQ, and hexagonal graphite. DFT in one of its presently popular forms, such as Perdew-Wang functionals (PW91), in combination with sufficient basis sets provides reliable transfer integrals, and therefore can serve as a basis for energy band calculations for soft organic materials with van der Waals gaps. PMID:16008473

  8. The Nature of Intermolecular Interactions Between Aromatic Amino Acid Residues

    SciTech Connect

    Gervasio, Francesco; Chelli, Riccardo; Procacci, Piero; Schettino, Vincenzo

    2002-05-01

    The nature of intermolecular interactions between aromatic amino acid residues has been investigated by a combination of molecular dynamics and ab initio methods. The potential energy surface of various interacting pairs, including tryptophan, phenilalanine, and tyrosine, was scanned for determining all the relevant local minima by a combined molecular dynamics and conjugate gradient methodology with the AMBER force field. For each of these minima, single-point correlated ab initio calculations of the binding energy were performed. The agreement between empirical force field and ab initio binding energies of the minimum energy structures is excellent. Aromatic-aromatic interactions can be rationalized on the basis of electrostatic and van der Waals interactions, whereas charge transfer or polarization phenomena are small for all intermolecular complexes and, particularly, for stacked structures.

  9. Thermal history of caldera-forming magmatic systems

    NASA Astrophysics Data System (ADS)

    Bradshaw, R. W.; Kent, A. J.; Cooper, K. M.; Huber, C.

    2015-12-01

    Large, caldera-forming silicic eruptions require the assembly and storage of a large volume of magma, and are though to result from either (1) rare high magma flux events needed to maintain melt-rich (eruptible) magma for extended timescales, or (2) magma accumulation at lower magma fluxes, storage for extended timescales as low temperature crystal mushes and rapid rejuvenation prior to eruption. The thermal history of these magmas prior to eruption thus provides an important clue into the processes that lead to eruption, but has been difficult to quantify. However in-situ measurement of Sr and other trace elements in plagioclase, coupled with diffusion models, can be used to constrain the time magmas spend at different temperatures. Progressive differentiation of plagioclase from a silicic magma produces plagioclase with lower Sr at low An—producing a positive correlation between Sr and An, which is the opposite of what is predicted by equilibrium partitioning. Forward modeling of the temperature-dependent diffusion of Sr from this initial disequilibrium condition toward equilibrium concentrations, based on partitioning relationships of An and Sr, gives an estimate of the time individual crystals spend at specific temperatures. Preliminary high spatial resolution LA-ICP-MS analysis of Sr in plagioclase from five caldera-forming eruptions show overall positive correlations of Sr and An, suggesting that little diffusive re-equilibration has occurred. Thus, over the lifetime that these magmas reside in the upper crust (>10 k.y.) they likely spend less than a few thousand years at temperatures above 750 °C (the approximate temperature of rheological lockup). These results suggest that the magmas that feed many large caldera-forming eruptions are kept in cold storage for long timescales, and that rapid rejuvenation of mush occurs without extended thermal conditioning prior to eruption.

  10. Planetary science: How the Solar System didn't form

    NASA Astrophysics Data System (ADS)

    Tsiganis, Kleomenis

    2015-12-01

    Standard planet-formation models have been unable to reconstruct the distributions of the Solar System's small, rocky planets and asteroids in the same simulation. A new analysis suggests that it cannot be done.

  11. Geometric method for forming periodic orbits in the Lorenz system

    NASA Astrophysics Data System (ADS)

    Nicholson, S. B.; Kim, Eun-jin

    2016-04-01

    Many systems in nature are out of equilibrium and irreversible. The non-detailed balance observable representation (NOR) provides a useful methodology for understanding the evolution of such non-equilibrium complex systems, by mapping out the correlation between two states to a metric space where a small distance represents a strong correlation [1]. In this paper, we present the first application of the NOR to a continuous system and demonstrate its utility in controlling chaos. Specifically, we consider the evolution of a continuous system governed by the Lorenz equation and calculate the NOR by following a sufficient number of trajectories. We then show how to control chaos by converting chaotic orbits to periodic orbits by utilizing the NOR. We further discuss the implications of our method for potential applications given the key advantage that this method makes no assumptions of the underlying equations of motion and is thus extremely general.

  12. Using corresponding state theory to obtain intermolecular potentials to calculate pure liquid shock Hugoniots

    SciTech Connect

    Hobbs, M.L.

    1997-12-01

    Determination of product species, equations-of-state (EOS) and thermochemical properties of high explosives and pyrotechnics remains a major unsolved problem. Although, empirical EOS models may be calibrated to replicate detonation conditions within experimental variability (5--10%), different states, e.g. expansion, may produce significant discrepancy with data if the basic form of the EOS model is incorrect. A more physically realistic EOS model based on intermolecular potentials, such as the Jacobs Cowperthwaite Zwisler (JCZ3) EOS, is needed to predict detonation states as well as expanded states. Predictive capability for any EOS requires a large species data base composed of a wide variety of elements. Unfortunately, only 20 species have known JCZ3 molecular force constants. Of these 20 species, only 10 have been adequately compared to experimental data such as molecular scattering or shock Hugoniot data. Since data in the strongly repulsive region of the molecular potential is limited, alternative methods must be found to deduce force constants for a larger number of species. The objective of the present study is to determine JCZ3 product species force constants by using a corresponding states theory. Intermolecular potential parameters were obtained for a variety of gas species using a simple corresponding states technique with critical volume and critical temperature. A more complex, four parameter corresponding state method with shape and polarity corrections was also used to obtain intermolecular potential parameters. Both corresponding state methods were used to predict shock Hugoniot data obtained from pure liquids. The simple corresponding state method is shown to give adequate agreement with shock Hugoniot data.

  13. Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

    SciTech Connect

    González, M.; Lemus-Santana, A.A.; Rodríguez-Hernández, J.; Aguirre-Velez, C.I.; Knobel, M.; Reguera, E.

    2013-08-15

    This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN){sub 4}] layers to form a solid of formula unit T(ImD){sub 2}[Ni(CN){sub 4}]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN){sub 4}] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. These intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives.

  14. Isotopic enrichment of forming planetary systems from supernova pollution

    NASA Astrophysics Data System (ADS)

    Lichtenberg, Tim; Parker, Richard J.; Meyer, Michael R.

    2016-08-01

    Heating by short-lived radioisotopes (SLRs) such as 26Al and 60Fe fundamentally shaped the thermal history and interior structure of Solar System planetesimals during the early stages of planetary formation. The subsequent thermo-mechanical evolution, such as internal differentiation or rapid volatile degassing, yields important implications for the final structure, composition and evolution of terrestrial planets. SLR-driven heating in the Solar System is sensitive to the absolute abundance and homogeneity of SLRs within the protoplanetary disk present during the condensation of the first solids. In order to explain the diverse compositions found for extrasolar planets, it is important to understand the distribution of SLRs in active planet formation regions (star clusters) during their first few Myr of evolution. By constraining the range of possible effects, we show how the imprint of SLRs can be extrapolated to exoplanetary systems and derive statistical predictions for the distribution of 26Al and 60Fe based on N-body simulations of typical to large clusters (103-104 stars) with a range of initial conditions. We quantify the pollution of protoplanetary disks by supernova ejecta and show that the likelihood of enrichment levels similar to or higher than the Solar System can vary considerably, depending on the cluster morphology. Furthermore, many enriched systems show an excess in radiogenic heating compared to Solar System levels, which implies that the formation and evolution of planetesimals could vary significantly depending on the birth environment of their host stars.

  15. Energetics of Intermolecular Hydrogen Bonds in a Hydrophobic Protein Cavity

    NASA Astrophysics Data System (ADS)

    Liu, Lan; Baergen, Alyson; Michelsen, Klaus; Kitova, Elena N.; Schnier, Paul D.; Klassen, John S.

    2014-05-01

    This work explores the energetics of intermolecular H-bonds inside a hydrophobic protein cavity. Kinetic measurements were performed on the gaseous deprotonated ions (at the -7 charge state) of complexes of bovine β-lactoglobulin (Lg) and three monohydroxylated analogs of palmitic acid (PA): 3-hydroxypalmitic acid (3-OHPA), 7-hydroxypalmitic acid (7-OHPA), and 16-hydroxypalmitic acid (16-OHPA). From the increase in the activation energy for the dissociation of the (Lg + X-OHPA)7- ions, compared with that of the (Lg + PA)7- ion, it is concluded that the -OH groups of the X-OHPA ligands participate in strong (5 - 11 kcal mol-1) intermolecular H-bonds in the hydrophobic cavity of Lg. The results of molecular dynamics (MD) simulations suggest that the -OH groups of 3-OHPA and 16-OHPA act as H-bond donors and interact with backbone carbonyl oxygens, whereas the -OH group of 7-OHPA acts as both H-bond donor and acceptor with nearby side chains. The capacity for intermolecular H-bonds within the Lg cavity, as suggested by the gas-phase measurements, does not necessarily lead to enhanced binding in aqueous solution. The association constant (Ka) measured for 7-OHPA [(2.3 ± 0.2) × 105 M-1] is similar to the value for the PA [(3.8 ± 0.1) × 105 M-1]; Ka for 3-OHPA [(1.1 ± 0.3) × 106 M-1] is approximately three-times larger, whereas Ka for 16-OHPA [(2.3 ± 0.2) × 104 M-1] is an order of magnitude smaller. Taken together, the results of this study suggest that the energetic penalty to desolvating the ligand -OH groups, which is necessary for complex formation, is similar in magnitude to the energetic contribution of the intermolecular H-bonds.

  16. Studies of interdiffusion, chemical bonding, and intermolecular interactions in fiber-matrix adhesion

    SciTech Connect

    Chou, Chiate.

    1990-01-01

    A study of the key factors involved in adhesion was conducted to determine a quantitative relation between the underlying physicochemical mechanisms of adhesion and the adhesive performance at the fiber-matrix interface. Aramid fiber was modified by attaching pendent chains to its surface to change the nature of its interaction with matrix materials. The relative importance of the three fundamental factors of adhesion (interdiffusion, intermolecular interactions, and chemical bonding) was studied by evaluating the fiber-matrix adhesive performance of these modified fiber-matrix systems.

  17. Intermolecular forces in phase-change heat transfer: 1998 Kern award review

    SciTech Connect

    Wayner, P.C. Jr.

    1999-10-01

    The variation of long-range intermolecular forces near interfaces profoundly affects the performance of change-of-phase heat exchangers. Starting with the fundamental electromagnetic force between molecules (dielectric properties), the effects of shape (Kelvin effect), temperature (Clapeyron effect) and concentration on the heat-transfer characteristics of thin films and larger systems are reviewed and connected. A judicious selection of literature gives a consistent set of models of particular use in heat transfer. Examples of experimental verification of these interfacial models in this rapidly developing field are also presented.

  18. Intermolecular interactions of thrombospondins drive their accumulation in extracellular matrix

    PubMed Central

    Kim, Dae Joong; Christofidou, Elena D.; Keene, Douglas R.; Hassan Milde, Marwah; Adams, Josephine C.

    2015-01-01

    Thrombospondins participate in many aspects of tissue organization in adult tissue homeostasis, and their dysregulation contributes to pathological processes such as fibrosis and tumor progression. The incorporation of thrombospondins into extracellular matrix (ECM) as discrete puncta has been documented in various tissue and cell biological contexts, yet the underlying mechanisms remain poorly understood. We find that collagen fibrils are disorganized in multiple tissues of Thbs1−/− mice. In investigating how thrombospondins become retained within ECM and thereby affect ECM organization, we find that accumulation of thrombospondin-1 or thrombospondin-5 puncta within cell-derived ECM is controlled by a novel, conserved, surface-exposed site on the thrombospondin L-type lectin domain. This site acts to recruit thrombospondin molecules into ECM by intermolecular interactions in trans. This mechanism is fibronectin independent, can take place extracellularly, and is demonstrated to be direct in vitro. The trans intermolecular interactions can also be heterotypic—for example, between thrombospondin-1 and thrombospondin-5. These data identify a novel concept of concentration-dependent, intermolecular “matrix trapping” as a conserved mechanism that controls the accumulation and thereby the functionality of thrombospondins in ECM. PMID:25995382

  19. Towards a Functionally-Formed Air Traffic System-of-Systems

    NASA Technical Reports Server (NTRS)

    Conway, Sheila R.; Consiglio, Maria C.

    2005-01-01

    Incremental improvements to the national aviation infrastructure have not resulted in sufficient increases in capacity and flexibility to meet emerging demand. Unfortunately, revolutionary changes capable of substantial and rapid increases in capacity have proven elusive. Moreover, significant changes have been difficult to implement, and the operational consequences of such change, difficult to predict due to the system s complexity. Some research suggests redistributing air traffic control functions through the system, but this work has largely been dismissed out of hand, accused of being impractical. However, the case for functionally-based reorganization of form can be made from a theoretical, systems perspective. This paper investigates Air Traffic Management functions and their intrinsic biases towards centralized/distributed operations, grounded in systems engineering and information technology theories. Application of these concepts to a small airport operations design is discussed. From this groundwork, a robust, scalable system transformation plan may be made in light of uncertain demand.

  20. System and method of forming nanostructured ferritic alloy

    DOEpatents

    Dial, Laura Cerully; DiDomizio, Richard; Alinger, Matthew Joseph; Huang, Shenyan

    2016-07-26

    A system for mechanical milling and a method of mechanical milling are disclosed. The system includes a container, a feedstock, and milling media. The container encloses a processing volume. The feedstock and the milling media are disposed in the processing volume of the container. The feedstock includes metal or alloy powder and a ceramic compound. The feedstock is mechanically milled in the processing volume using metallic milling media that includes a surface portion that has a carbon content less than about 0.4 weight percent.

  1. Methods of forming thermal management systems and thermal management methods

    DOEpatents

    Gering, Kevin L.; Haefner, Daryl R.

    2012-06-05

    A thermal management system for a vehicle includes a heat exchanger having a thermal energy storage material provided therein, a first coolant loop thermally coupled to an electrochemical storage device located within the first coolant loop and to the heat exchanger, and a second coolant loop thermally coupled to the heat exchanger. The first and second coolant loops are configured to carry distinct thermal energy transfer media. The thermal management system also includes an interface configured to facilitate transfer of heat generated by an internal combustion engine to the heat exchanger via the second coolant loop in order to selectively deliver the heat to the electrochemical storage device. Thermal management methods are also provided.

  2. Lake phosphorus loading form septic systems by seasonally perched groundwater

    USGS Publications Warehouse

    Gilliom, R.J.; Patmont, C.R.

    1983-01-01

    The movement of effluent phosphorus (P) from old septic systems by seasonally perched groundwater was investigated. A previous study indicated a correlation between P loadings and the presence of old homes. Water samples were taken from shallow wells installed 10 to 50 m downgradient from seven septic systems 20 to 40 years old. The equivalent volumetric fraction of each sample consisting of undiluted effluent was estimated from chloride concentration. A Monte Carlo analysis was used to account for the various sources of uncertainty. Movement of diluted septic effluent to the lake was common, but transport of more than 1% of effluent P through the soil was probable for only 4 of 26 samples. The greatest apparent P movement was associated with persistently saturated conditions.

  3. Local normal forms of smooth weakly hyperbolic integrable systems

    NASA Astrophysics Data System (ADS)

    Jiang, Kai

    2016-01-01

    In the smooth ( C∞) category, a completely integrable system near a nondegenerate singularity is geometrically linearizable if the action generated by the vector fields is weakly hyperbolic. This proves partially a conjecture of Nguyen Tien Zung [11]. The main tool used in the proof is a theorem of Marc Chaperon [3] and the slight hypothesis of weak hyperbolicity is generic when all the eigenvalues of the differentials of the vector fields at the non-degenerate singularity are real.

  4. Rodlike localized structure in isotropic pattern-forming systems

    NASA Astrophysics Data System (ADS)

    Bordeu, Ignacio; Clerc, Marcel G.

    2015-10-01

    Stationary two-dimensional localized structures have been observed in a wide variety of dissipative systems. The existence, stability properties, dynamical evolution, and bifurcation diagram of an azimuthal symmetry breaking, rodlike localized structure in the isotropic prototype model of pattern formation, the Swift-Hohenberg model, is studied. These rodlike structures persist under the presence of nongradient perturbations. Interaction properties of the rodlike structures are studied. This allows us to envisage the possibility of different crystal-like configurations.

  5. Configurational entropy of glass-forming systems from graph isomorphism

    NASA Astrophysics Data System (ADS)

    Zhou, Yuxing; Milner, Scott

    The configurational entropy plays a central role in the thermodynamic scenarios of glass transition, such as Adam-Gibbs theory and random first-order transition theory. By definition, the configurational entropy Sc is the difference between the entropy of liquid and the vibrational entropy with structural rearrangement restricted, both of which can be obtained by means of thermodynamic integration. On the other hand, Sc is essentially a measure of the number of basins in the energy landscape, and therefore it can also be estimated by explicitly enumerating inherent structures. To this end, we first coarse-grain the vibrational motions by mapping configurations to Voronoi diagrams and then categorize them using canonical labelling. The Voronoi graph entropy is calculated as SG /kB = - ∑pi log (pi) , where pi is the probability of finding distinct graph i. We find for an n-particle subsystem of glass-forming hard-disk/sphere fluids, SG (n) scales linearly with n, and Sc can be estimated from the slope.

  6. Molecular cooperativity in the dynamics of glass-forming systems

    NASA Astrophysics Data System (ADS)

    Hong, Liang; Gujrati, Purushottam; Novikov, Vladimier; Sokolov, Alexei

    2010-03-01

    The mechanism behind the sharp slowing down of the main structural relaxation in a glass-forming liquid upon approaching the glass transition remains a great puzzle. Most of the theories relate this mechanism to the cooperativity in molecular motion. On the other hand, the collective vibration in the pico-second time region, the so-called boson peak, is also described as a cooperative process. In our recent work (L. Hong, et al., J. Chem. Phys., in print), we demonstrated that the collective vibrations and the main structural relaxation involve a similar length scale of cooperative molecular motions. More importantly, we found that the cooperativity length scale in different materials directly correlates to only one part of the mechanism of slowing down the structural relaxation, i.e., the dependence of the structural relaxation on volume. In this presentation, we will further demonstrate that this correlation holds true not only for different chemical species, but also for the same chemical specie with different molecular weight or under pressure. The results are compared to predictions of theoretical models.

  7. Spatial rogue waves in a photorefractive pattern-forming system.

    PubMed

    Marsal, N; Caullet, V; Wolfersberger, D; Sciamanna, M

    2014-06-15

    We have experimentally analyzed pattern formation in an optical system composed of a bulk photorefractive crystal subjected to a single optical feedback. In a highly nonlinear regime far above the modulational instability threshold, we are reporting on turbulent spatiotemporal dynamics that leads to rare, intense localized optical peaks. We have proven that the statistics and features of those peaks correspond to the signatures of two-dimensional spatial rogue events. These optical rogue waves occur erratically in space and time and live typically the same amount of time as the response time of the photorefractive material. PMID:24978569

  8. Invariants reveal multiple forms of robustness in bifunctional enzyme systems.

    PubMed

    Dexter, Joseph P; Dasgupta, Tathagata; Gunawardena, Jeremy

    2015-08-01

    Experimental and theoretical studies have suggested that bifunctional enzymes catalyzing opposing modification and demodification reactions can confer steady-state concentration robustness to their substrates. However, the types of robustness and the biochemical basis for them have remained elusive. Here we report a systematic study of the most general biochemical reaction network for a bifunctional enzyme acting on a substrate with one modification site, along with eleven sub-networks with more specialized biochemical assumptions. We exploit ideas from computational algebraic geometry, introduced in previous work, to find a polynomial expression (an invariant) between the steady state concentrations of the modified and unmodified substrate for each network. We use these invariants to identify five classes of robust behavior: robust upper bounds on concentration, robust two-sided bounds on concentration ratio, hybrid robustness, absolute concentration robustness (ACR), and robust concentration ratio. This analysis demonstrates that robustness can take a variety of forms and that the type of robustness is sensitive to many biochemical details, with small changes in biochemistry leading to very different steady-state behaviors. In particular, we find that the widely-studied ACR requires highly specialized assumptions in addition to bifunctionality. An unexpected result is that the robust bounds derived from invariants are strictly tighter than those derived by ad hoc manipulation of the underlying differential equations, confirming the value of invariants as a tool to gain insight into biochemical reaction networks. Furthermore, invariants yield multiple experimentally testable predictions and illuminate new strategies for inferring enzymatic mechanisms from steady-state measurements. PMID:26021467

  9. Cyclopropenium Cations Break the Rules of Attraction to Form Closely Bound Dimers.

    PubMed

    Wallace, Andrew J; Jayasinghe, Chaminda D; Polson, Matthew I J; Curnow, Owen J; Crittenden, Deborah L

    2015-12-16

    The crystal structures of tris(ethylmethylamino)-cyclopropenium chloride and tris(diethylamino)-cyclopropenium iodide reveal the presence of closely bound dicationic dimers formed from two closed-shell monomer units. The distances between the C3 centroids of the staggered monomers are at the short end of those normally found in π-stacked neutral arenes, let alone charged aromatic rings. Computational analysis reveals that short-range interactions are dominated by strong dispersion forces, enabling metastable dicationic dimers to form without covalent intermolecular bonding. Surrounding counterions then provide a background source of charge balance, imparting strong thermodynamic stability to the system. Additionally, these counterions form a weak but attractive electrostatic bridge between the monomer units, contributing to the surprisingly short observed intermolecular C3-C3 centroid distance. PMID:26584632

  10. The effect of intermolecular hydrogen bonding on the planarity of amides.

    PubMed

    Platts, James A; Maarof, Hasmerya; Harris, Kenneth D M; Lim, Gin Keat; Willock, David J

    2012-09-14

    Ab initio and density functional theory (DFT) calculations on some model systems are presented to assess the extent to which intermolecular hydrogen bonding can affect the planarity of amide groups. Formamide and urea are examined as archetypes of planar and non-planar amides, respectively. DFT optimisations suggest that appropriately disposed hydrogen-bond donor or acceptor molecules can induce non-planarity in formamide, with OCNH dihedral angles deviating by up to ca. 20° from planarity. Ab initio energy calculations demonstrate that the energy required to deform an amide molecule from the preferred geometry of the isolated molecule is more than compensated by the stabilisation due to hydrogen bonding. Similarly, the NH(2) group in urea can be made effectively planar by the presence of appropriately positioned hydrogen-bond acceptors, whereas hydrogen-bond donors increase the non-planarity of the NH(2) group. Small clusters (a dimer, two trimers and a pentamer) extracted from the crystal structure of urea indicate that the crystal field acts to force planarity of the urea molecule; however, the interaction with nearest neighbours alone is insufficient to induce the molecule to become completely planar, and longer-range effects are required. Finally, the potential for intermolecular hydrogen bonding to induce non-planarity in a model of a peptide is explored. Inter alia, the insights obtained in the present work on the extent to which the geometry of amide groups may be deformed under the influence of intermolecular hydrogen bonding provide structural guidelines that can assist the interpretation of the geometries of such groups in structure determination from powder X-ray diffraction data. PMID:22847473

  11. Effect of intermolecular hydrogen bonding, vibrational analysis and molecular structure of 4-chlorobenzothioamide

    NASA Astrophysics Data System (ADS)

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2013-09-01

    In the present work, the experimental and theoretical vibrational spectra of 4-chlorobenzothioamide were investigated. The FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of 4-chlorobenzothioamide in the solid phase were recorded. The geometric parameters (bond lengths and bond angles), vibrational frequencies, Infrared and Raman intensities of the title molecule in the ground state were calculated using ab initio Hartree-Fock and density functional theory (B3LYP) methods with the 6-311++G(d,p) basis set for the first time. The optimized geometric parameters and the theoretical vibrational frequencies were found to be in good agreement with the corresponding experimental data and with the results found in the literature. The vibrational frequencies were assigned based on the potential energy distribution using the VEDA 4 program. The dimeric form of 4-chlorobenzothioamide was also simulated to evaluate the effect of intermolecular hydrogen bonding on the vibrational frequencies. It was observed that the Nsbnd H stretching modes shifted to lower frequencies, while the in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular Nsbnd H⋯S hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

  12. Effect of intermolecular hydrogen bonding, vibrational analysis and molecular structure of a biomolecule: 5-Hydroxymethyluracil

    NASA Astrophysics Data System (ADS)

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2014-06-01

    In the present work, the experimental and theoretical vibrational spectra of 5-hydroxymethyluracil were investigated. The FT-IR (4000-400 cm-1) spectrum of the molecule in the solid phase was recorded. The geometric parameters (bond lengths and bond angles), vibrational frequencies, Infrared intensities of the title molecule in the ground state were calculated using density functional B3LYP and M06-2X methods with the 6-311++G(d,p) basis set for the first time. The optimized geometric parameters and theoretical vibrational frequencies were found to be in good agreement with the corresponding experimental data, and with the results found in the literature. The vibrational frequencies were assigned based on the potential energy distribution using the VEDA 4 program. The dimeric form of 5-hydroxymethyluracil molecule was also simulated to evaluate the effect of intermolecular hydrogen bonding on its vibrational frequencies. It was observed that the Nsbnd H stretching modes shifted to lower frequencies, while its in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular Nsbnd H⋯O hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

  13. Intermolecular stabilization of 3,3'-diamino-4,4'-azoxyfurazan (DAAF) compressed to 20 GPa.

    PubMed

    Chellappa, Raja S; Dattelbaum, Dana M; Coe, Joshua D; Velisavljevic, Nenad; Stevens, Lewis L; Liu, Zhenxian

    2014-08-01

    The room temperature stability of 3,3'-diamino-4,4'-azoxyfurazan (DAAF) has been investigated using synchrotron far-infrared, mid-infrared, Raman spectroscopy, and synchrotron X-ray diffraction (XRD) up to 20 GPa. The as-loaded DAAF samples exhibited subtle pressure-induced ordering phenomena (associated with positional disorder of the azoxy "O" atom) resulting in doubling of the a-axis, to form a superlattice similar to the low-temperature polymorph. Neither high pressure synchrotron XRD, nor high pressure infrared or Raman spectroscopies indicated the presence of structural phase transitions up to 20 GPa. Compression was accommodated in the unit cell by a reduction of the c-axis between the planar DAAF layers, distortion of the β-angle of the monoclinic lattice, and an increase in intermolecular hydrogen bonding. Changes in the ring and -NH2 deformation modes and increased intermolecular hydrogen bonding interactions with compression suggest molecular reorganizations and electronic transitions at ∼ 5 GPa and ∼ 10 GPa that are accompanied by a shifting of the absorption band edge into the visible. A fourth-order Birch-Murnaghan fit to the room temperature isotherm afforded an estimate of the zero-pressure isothermal bulk modulus, K0 = 12.4 ± 0.6 GPa and its pressure derivative K0' = 7.7 ± 0.3. PMID:25011055

  14. Optimization of intermolecular potential parameters for the CO2/H2O mixture.

    PubMed

    Orozco, Gustavo A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2014-10-01

    Monte Carlo simulations in the Gibbs ensemble were used to obtain optimized intermolecular potential parameters to describe the phase behavior of the mixture CO2/H2O, over a range of temperatures and pressures relevant for carbon capture and sequestration processes. Commonly used fixed-point-charge force fields that include Lennard-Jones 12-6 (LJ) or exponential-6 (Exp-6) terms were used to describe CO2 and H2O intermolecular interactions. For force fields based on the LJ functional form, changes of the unlike interactions produced higher variations in the H2O-rich phase than in the CO2-rich phase. A major finding of the present study is that for these potentials, no combination of unlike interaction parameters is able to adequately represent properties of both phases. Changes to the partial charges of H2O were found to produce significant variations in both phases and are able to fit experimental data in both phases, at the cost of inaccuracies for the pure H2O properties. By contrast, for the Exp-6 case, optimization of a single parameter, the oxygen-oxygen unlike-pair interaction, was found sufficient to give accurate predictions of the solubilities in both phases while preserving accuracy in the pure component properties. These models are thus recommended for future molecular simulation studies of CO2/H2O mixtures. PMID:25198539

  15. Forming Stereogenic Centers in Acyclic Systems from Alkynes.

    PubMed

    Vabre, Roxane; Island, Biana; Diehl, Claudia J; Schreiner, Peter R; Marek, Ilan

    2015-08-17

    The combined carbometalation/zinc homologation followed by reactions with α-heterosubstituted aldehydes and imines proceed through a chair-like transition structure with the substituent of the incoming aldehyde residue preferentially occupying a pseudo-axial position to avoid the two gauche interactions. The heteroatom in the axial position produces a chelated intermediate (and not a Cornforth-Evans transition structure for α-chloro aldehydes and imines) leading to a face differentiation in the allylation reaction. This method provides access to functionalized products in which three new carbon-carbon bonds and two to three stereogenic centers, including a quaternary one, were created in acyclic systems in a single-pot operation from simple alkynes. PMID:26130570

  16. Are there environmental forms of systemic autoimmune diseases?

    PubMed Central

    Hess, E V

    1999-01-01

    A large number of drugs and an increasing number of environmental agents reportedly result in the appearance of a number of autoantibodies and in many instances in the appearance of a range of autoimmune clinical syndromes. The major disorders so recognized have marked resemblances to the autoimmune disease systemic lupus erythematosus. The commonly used term is drug-induced lupus; a better term is drug-related lupus. There is considerable interest at the present time in an increasing number of environmental agents. There have been two epidemics in recent years--one in Spain to a contaminant of rapeseed oil and one in the United States to a contaminant of l-tryptophan that caused an eosinophilic myositis. It is important for physicians and others involved in health care to recognize the potential associations of these diseases of unknown cause or causes. PMID:10502535

  17. A structural study of the intermolecular interactions of tyramine in the solid state and in solution

    NASA Astrophysics Data System (ADS)

    Quevedo, Rodolfo; Nuñez-Dallos, Nelson; Wurst, Klaus; Duarte-Ruiz, Álvaro

    2012-12-01

    The nature of the interactions between tyramine units was investigated in the solid state and in solution. Crystals of tyramine in its free base form were analyzed by Fourier transform infrared (FT-IR) spectroscopy and single-crystal X-ray diffraction (XRD). The crystal structure shows a linear molecular organization held together by "head-to-tail" intermolecular hydrogen bonds between the amino groups and the phenolic hydroxyl groups. These chains are arranged in double layers that can geometrically favor the formation of templates in solution, which may facilitate macrocyclization reactions to form azacyclophane-type compounds. Computational calculations using the PM6-DH+ method and electrospray ionization mass spectrometry (ESI-HRMS) reveal that the formation of a hydrogen-bonded tyramine dimer is favored in solution.

  18. Subunit–subunit interactions are critical for proton sensitivity of ROMK: Evidence in support of an intermolecular gating mechanism

    PubMed Central

    Leng, Qiang; MacGregor, Gordon G.; Dong, Ke; Giebisch, Gerhard; Hebert, Steven C.

    2006-01-01

    The tetrameric K channel ROMK provides an important pathway for K secretion by the mammalian kidney, and the gating of this channel is highly sensitive to changes in cytosolic pH. Although charge–charge interactions have been implicated in pH sensing by this K channel tetramer, the molecular mechanism linking pH sensing and the gating of ion channels is poorly understood. The x-ray crystal structure KirBac1.1, a prokaryotic ortholog of ROMK, has suggested that channel gating involves intermolecular interactions of the N- and C-terminal domains of adjacent subunits. Here we studied channel gating behavior to changes in pH using giant patch clamping of Xenopus laevis oocytes expressing WT or mutant ROMK, and we present evidence that no single charged residue provides the pH sensor. Instead, we show that N–C- and C–C-terminal subunit–subunit interactions form salt bridges, which function to stabilize ROMK in the open state and which are modified by protons. We identify a highly conserved C–C-terminal arginine–glutamate (R-E) ion pair that forms an intermolecular salt bridge and responds to changes in proton concentration. Our results support the intermolecular model for pH gating of inward rectifier K channels. PMID:16446432

  19. The forms of knowledge mobilized in some machine vision systems.

    PubMed Central

    Brady, M

    1997-01-01

    This paper describes a number of computer vision systems that we have constructed, and which are firmly based on knowledge of diverse sorts. However, that knowledge is often represented in a way that is only accessible to a limited set of processes, that make limited use of it, and though the knowledge is amenable to change, in practice it can only be changed in rather simple ways. The rest of the paper addresses the questions: (i) what knowledge is mobilized in the furtherance of a perceptual task?; (ii) how is that knowledge represented?; and (iii) how is that knowledge mobilized? First we review some cases of early visual processing where the mobilization of knowledge seems to be a key contributor to success yet where the knowledge is deliberately represented in a quite inflexible way. After considering the knowledge that is involved in overcoming the projective nature of images, we move the discussion to the knowledge that was required in programs to match, register, and recognize shapes in a range of applications. Finally, we discuss the current state of process architectures for knowledge mobilization. PMID:9304690

  20. Transition Metal Free Intermolecular Direct Oxidative C-N Bond Formation to Polysubstituted Pyrimidines Using Molecular Oxygen as the Sole Oxidant.

    PubMed

    Guo, Wei; Li, Chunsheng; Liao, Jianhua; Ji, Fanghua; Liu, Dongqing; Wu, Wanqing; Jiang, Huanfeng

    2016-07-01

    Various polysubstituted pyrimidines are smoothly formed via a base-promoted intermolecular oxidation C-N bond formation of allylic C(sp(3))-H and vinylic C(sp(2))-H of allyllic compounds with amidines using O2 as the sole oxidant. This protocol features protecting group free nitrogen sources, good functional group tolerance, high atom economy, and environmental advantages. PMID:27275869

  1. Combination Bands of the Nonpolar OCS Dimer Involving Intermolecular Modes

    NASA Astrophysics Data System (ADS)

    Rezaei, M.; Oliaee, J. Norooz; Moazzen-Ahmadi, N.; McKellar, A. R. W.

    2012-06-01

    Spectra of the nonpolar carbonyl sulfide in the region of the OCS ν_1 fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a tunable diode laser employed in a rapid-scan signal averaging mode. Three bands centered at 2085.906, 2103.504, and 2114.979 cm-1 were observed and anlysed. The rotational assignment and fitting of the bands were made by fixing the lower state parameters to those for the ground state of nonpolar (OCS)_2, thus confirming that they were indeed combination bands of the of the most stable isomer of OCS dimer. The band centered at 2085.906 cm-1 is a combination of the forbidden A_g intramolecular mode plus the geared bend intermolecular mode and that centered at 2114.979 cm-1 is a combination of the allowed B_u intramolecular mode plus the intermolecular van der Waals stretch. The combination at 2103.504 cm-1 can be assigned as a band whose upper state involves four quanta of the intramolecular bend or the B_u intramolecular mode plus two quanta of the intermolecular torsional mode. Isotopic work is needed to conclusively identify the vibrational assignment of this band. Our experimental frequencies for the geared bend and van der Waals modes are in good agreement with a recent high level ab initio calculation by Brown et al. J. Brown, Xiao-Gang Wang, T. Carrington Jr. and Richard Dawes, Journal of Chemical Physics, submitted.

  2. Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions

    PubMed Central

    Haubenreisser, Stefan; Wöste, Thorsten H.; Martínez, Claudio; Ishihara, Kazuaki

    2015-01-01

    Abstract Molecular structures of the most prominent chiral non‐racemic hypervalent iodine(III) reagents to date have been elucidated for the first time. The formation of a chirally induced supramolecular scaffold based on a selective hydrogen‐bonding arrangement provides an explanation for the consistently high asymmetric induction with these reagents. As an exploratory example, their scope as chiral catalysts was extended to the enantioselective dioxygenation of alkenes. A series of terminal styrenes are converted into the corresponding vicinal diacetoxylation products under mild conditions and provide the proof of principle for a truly intermolecular asymmetric alkene oxidation under iodine(I/III) catalysis. PMID:26596513

  3. Photon Antibunching in Complex Intermolecular Fluorescence Quenching Kinetics.

    PubMed

    Sharma, Arjun; Enderlein, Jörg; Kumbhakar, Manoj

    2016-08-18

    We present a novel fluorescence spectroscopic method, which combines fluorescence antibunching, time-correlated single-photon counting (TCSPC), and steady-state emission spectroscopy, to study chemical reactions at the single molecule level. We exemplify our method on investigating intermolecular fluorescence quenching of Rhodamine110 by aniline. We demonstrate that the combination of measurements of fluorescence antibunching, fluorescence lifetime, and fluorescence steady state intensity, captures the full picture of the complex quenching kinetics, which involves static and dynamics quenching, and which cannot be seen by steady-state or lifetime measurements alone. PMID:27468007

  4. Intermolecular interactions in the bilirubin-cholate-silica system

    NASA Astrophysics Data System (ADS)

    Vlasova, N. N.; Golovkova, L. P.; Severinovskaya, O. V.

    2007-06-01

    Bilirubin-cholate interactions in aqueous solutions were studied. The constants of binding of bilirubin with taurocholate dimers and taurodeoxycholate trimers were calculated. The adsorption of bilirubin and cholates on the surface of highly dispersed silica was studied. It was shown that taurine-conjugated cholates are poorly adsorbed from micellar solutions on the silica surface, the specific amount of bilirubin adsorbed decreases with increasing concentration of cholates in the solution, the affinity of free bilirubin for the silica surface is independent of the nature of the cholic acid, and that the affinity of cholate-bilirubin complexes for the silica surface is lower than the affinity of free bilirubin.

  5. Systems and methods for forming defects on graphitic materials and curing radiation-damaged graphitic materials

    DOEpatents

    Ryu, Sunmin; Brus, Louis E.; Steigerwald, Michael L.; Liu, Haitao

    2012-09-25

    Systems and methods are disclosed herein for forming defects on graphitic materials. The methods for forming defects include applying a radiation reactive material on a graphitic material, irradiating the applied radiation reactive material to produce a reactive species, and permitting the reactive species to react with the graphitic material to form defects. Additionally, disclosed are methods for removing defects on graphitic materials.

  6. Systemic study on fluorescent switching systems composed of naphthopyran and benzimidazole in solution and film forms

    NASA Astrophysics Data System (ADS)

    He, Yi; Wang, Guang; Wang, Mingxin

    2016-07-01

    The fluorescent photo-switching systems were prepared based on fluorescent benzimidazole and photochromic naphthopyran. Naphthopyran in this systems displayed excellent photochromic performance in tetrahydrofuran solutions and in PMMA films. The fluorescent emission of benzimidazole was modulated between "on" and "off" via the photoisomerization of naphthopyran in high-contrast due to the photoinduced energy transfer from benzimidazole to the open-form naphthopyran. Both the fluorescent photoswitching and the photochromism of benzimidazole-naphthopyran dyads in solutions and films displayed excellent fatigue resistance. The spaces between benzimidazole and naphthopyran affect the absorbance and fluorescence spectra of benzimidazole-naphthopyran dyads. The non-destructive readout ability of synthesized dyads in doped PMMA film was achieved.

  7. Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions

    PubMed Central

    Archambault, Fabien; Soteras, Ignacio; Luque, F. Javier; Schulten, Klaus

    2010-01-01

    A complete derivation of polarizable intermolecular potentials based on high-level, gas-phase quantum-mechanical calculations is proposed. The importance of appreciable accuracy together with inherent simplicity represents a significant endeavor when enhancement of existing force fields for biological systems is sought. Toward this end, symmetry-adapted perturbation theory (SAPT) can provide an expansion of the total interaction energy into physically meaningful e.g. electrostatic, induction and van der Waals terms. Each contribution can be readily compared with its counterpart in classical force fields. Since the complexity of the different intermolecular terms cannot be fully embraced using a minimalist description, it is necessary to resort to polyvalent expressions capable of encapsulating overlooked contributions from the quantum-mechanical expansion. This choice results in consistent force field components that reflect the underlying physical principles of the phenomena. This simplified potential energy function is detailed and definitive guidelines are drawn. As a proof of concept, the methodology is illustrated through a series of test cases that include the interaction of water and benzene with halide and metal ions. In each case considered, the total energy is reproduced accurately over a range of biologically relevant distances. PMID:21113276

  8. Probing Intermolecular Interactions in Polycyclic Aromatic Hydrocarbons with 2D IR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Krummel, Amber

    2014-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment and impact geochemical processes that are critical to sustainable energy resources. For example, asphaltenes exist naturally in geologic formations and their aggregates heavily impact the petroleum economy. Unfortunately, the chemical dynamics that drive asphaltene nanoaggregation processes are still poorly understood. Solvent dynamics and intermolecular interactions such as π-stacking interactions play integral roles in asphaltene nanoaggregation. Linear and nonlinear vibrational spectroscopy including two-dimensional infrared spectroscopy (2DIR), are well suited to explore these fundamental interactions. Teasing apart the vibrational characteristics in PAHs that model asphaltenic compounds represents an important step towards utilizing 2D IR spectroscopy to understand the intermolecular interactions that are prevalent in asphaltene nanoaggregation. A solar dye, N,N'-Dioctyl-3,4,9,10-perylenedicarboximide, is used in this work to model aphaltenes. Carbonyl and ring vibrations are used to probe the nanoaggregates of the model compounds. However, the characteristics of these normal modes change as a function of the size of the conjugated ring system. Thus, in order to fully understand the nature of these normal modes, we include a systematic study of a series of quinones. Our investigation employs a combination of 2DIR spectroscopy and electronic structure calculations to explore vibrational coupling in quinones and PAHs. We compare the calculated vibrational characteristics to those extracted from 2DIR spectra. ATK acknowledges the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  9. A new hydrate form of diflunisal precipitated from a microemulsion system.

    PubMed

    Sung, Hsuan-Lei; Fan, Yueh-Lin; Yeh, Kimberly; Chen, Yen-Fu; Chen, Li-Jen

    2013-09-01

    Three microemulsion systems were applied as solvents for polymorph screening of seven active pharmaceutical ingredients (APIs): carbamazepine, piroxicam, sulfaguanidine, nitrofurantoin, theophylline, quercetin, and diflunisal. All the recrystallized compounds were examined by using powder X-ray diffractometry, differential scanning calorimetry, elemental analysis, Karl Fischer titration and dissolution rate. A new crystal form of diflunisal hydrate was discovered by the cooling method of recrystallization in a water-in-oil microemulsion system, composed of water, alkane and dioctyl sodium sulfosuccinate. The new hydrate form of diflunisal was characterized and confirmed to be a stoichiometry of diflunisal:water of 1:1. The other two microemulsion systems were able to convert the anhydrous diflunisal Form I to Form III. The dissolution rate of diflunisal hydrate is unexpectedly much higher than that of anhydrous ones (Forms I and III). All the other six APIs (carbamazepine, piroxicam, sulfaguanidine, nitrofurantoin, theophylline and quercetin) recrystallized from the microemulsion systems were all converted into hydrate form. PMID:23624616

  10. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    SciTech Connect

    Hathwar, Venkatesha R.; Sist, Mattia; Jørgensen, Mads R. V.; Mamakhel, Aref H.; Wang, Xiaoping; Hoffmann, Christina M.; Sugimoto, Kunihisa; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2015-08-14

    Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically, the presence of Cπ...Cπinteractions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI) analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H—H interactions. The electron density features of H—H bonding, and the interaction energy of molecular dimers connected by H—H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. Finally, the quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations.

  11. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    DOE PAGESBeta

    Hathwar, Venkatesha R.; Sist, Mattia; Jørgensen, Mads R. V.; Mamakhel, Aref H.; Wang, Xiaoping; Hoffmann, Christina M.; Sugimoto, Kunihisa; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2015-08-14

    Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically,more » the presence of Cπ...Cπinteractions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI) analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H—H interactions. The electron density features of H—H bonding, and the interaction energy of molecular dimers connected by H—H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. Finally, the quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations.« less

  12. Intermolecular Hybridization Creating Nanopore Orbital in a Supramolecular Hydrocarbon Sheet.

    PubMed

    Zhang, Yi-Qi; Björk, Jonas; Barth, Johannes V; Klappenberger, Florian

    2016-07-13

    Molecular orbital engineering is a key ingredient for the design of organic devices. Intermolecular hybridization promises efficient charge carrier transport but usually requires dense packing for significant wave function overlap. Here we use scanning tunneling spectroscopy to spatially resolve the electronic structure of a surface-confined nanoporous supramolecular sheet of a prototypical hydrocarbon compound featuring terminal alkyne (-CCH) groups. Surprisingly, localized nanopore orbitals are observed, with their electron density centered in the cavities surrounded by the functional moieties. Density functional theory calculations reveal that these new electronic states originate from the intermolecular hybridization of six in-plane π-orbitals of the carbon-carbon triple bonds, exhibiting significant electronic splitting and an energy downshift of approximately 1 eV. Importantly, these nanopore states are distinct from previously reported interfacial states. We unravel the underlying connection between the formation of nanopore orbital and geometric arrangements of functional groups, thus demonstrating the generality of applying related orbital engineering concepts in various types of porous organic structures. PMID:27253516

  13. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    PubMed Central

    Hathwar, Venkatesha R.; Sist, Mattia; Jørgensen, Mads R. V.; Mamakhel, Aref H.; Wang, Xiaoping; Hoffmann, Christina M.; Sugimoto, Kunihisa; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2015-01-01

    Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically, the presence of Cπ⋯Cπ interactions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI) analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H—H interactions. The electron density features of H—H bonding, and the interaction energy of molecular dimers connected by H—H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. The quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations. PMID:26306198

  14. Factor Structure of the BASC-2 Behavioral and Emotional Screening System Student Form

    ERIC Educational Resources Information Center

    Dowdy, Erin; Twyford, Jennifer M.; Chin, Jenna K.; DiStefano, Christine A.; Kamphaus, Randy W.; Mays, Kristen L.

    2011-01-01

    The BASC-2 Behavioral and Emotional Screening System (BESS) Student Form (Kamphaus & Reynolds, 2007) is a recently developed youth self-report rating scale designed to identify students at risk for behavioral and emotional problems. The BESS Student Form was derived from the Behavior Assessment System for Children-Second Edition Self-Report of…

  15. Intermolecular symmetry-adapted perturbation theory study of large organic complexes

    SciTech Connect

    Heßelmann, Andreas; Korona, Tatiana

    2014-09-07

    Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atom-atom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies.

  16. Dynamics of intermolecular interactions in CCl4via the isotope effect by femtosecond time-resolved spectroscopy.

    PubMed

    Konarska, Jadwiga; Gadomski, Wojciech; Ratajska-Gadomska, Bożena; Polok, Kamil; Pudłowski, Grzegorz; Kardaś, Tomasz M

    2016-06-21

    We report our study on the ultrafast dynamics of intermolecular interactions in liquid CCl4. A transient transmission time domain signal, obtained in the 40 ps delay range, exhibits beating at the difference frequency of the totally symmetric stretching vibrations of the tetrachloride isotopologues. We show that the spectra obtained as the windowed Fourier transform of different parts of the time domain signal in the range of this totally symmetric vibration, split due to the isotope effect, carry the information about the dynamics of the coherently excited, coupled molecules. We use a simple theoretical model in order to prove that the intermolecular interaction influences the relative amplitudes of the isotopologue peaks in the spectrum. Moreover, we demonstrate that the pump induced coherence in the system leads to additional strengthening of the interaction, which can be observed in the spectra obtained from the experimental time domain signal. PMID:27244535

  17. Gibb's energy and intermolecular free length of 'Borassus Flabellifier' (BF) and Adansonia digitata (AnD) aqueous binary mixture

    NASA Astrophysics Data System (ADS)

    Phadke, Sushil; Darshan Shrivastava, Bhakt; Ujle, S. K.; Mishra, Ashutosh; Dagaonkar, N.

    2014-09-01

    One of the potential driving forces behind a chemical reaction is favourable a new quantity known as the Gibbs free energy (G) of the system, which reflects the balance between these forces. Ultrasonic velocity and absorption measurements in liquids and liquid mixtures find extensive application to study the nature of intermolecular forces. Ultrasonic velocity measurements have been successfully employed to detect weak and strong molecular interactions present in binary and ternary liquid mixtures. After measuring the density and ultrasonic velocity of aqueous solution of 'Borassus Flabellifier' BF and Adansonia digitata And, we calculated Gibb's energy and intermolecular free length. The velocity of ultrasonic waves was measured, using a multi-frequency ultrasonic interferometer with a high degree of accuracy operating Model M-84 by M/s Mittal Enterprises, New Delhi, at a fixed frequency of 2MHz. Natural sample 'Borassus Flabellifier' BF fruit pulp and Adansonia digitata AnD powder was collected from Dhar, District of MP, India for this study.

  18. Intermolecular interactions during complex coacervation of pea protein isolate and gum arabic.

    PubMed

    Liu, Shuanghui; Cao, Yuan-Long; Ghosh, Supratim; Rousseau, Dérick; Low, Nicholas H; Nickerson, Michael T

    2010-01-13

    The nature of intermolecular interactions during complexation between pea protein isolate (PPI) and gum arabic (GA) was investigated as a function of pH (4.30-2.40) by turbidimetric analysis and confocal scanning microscopy in the presence of destabilizing agents (100 mM NaCl or 100 mM urea) and at different temperatures (6-60 degrees C). Complex formation followed two pH-dependent structure-forming events associated with the formation of soluble and insoluble complexes and involved interactions between GA and PPI aggregates. Complex formation was driven by electrostatic attractive forces between complementary charged biopolymers, with secondary stabilization by hydrogen bonding. Hydrophobic interactions were found to enhance complex stability at lower pH (pH 3.10), but not with its formation. PMID:19938857

  19. Intermolecular control of thermoswitching and photoswitching phenomena in two spin-crossover polymorphs

    NASA Astrophysics Data System (ADS)

    Buron-Le Cointe, M.; Hébert, J.; Baldé, C.; Moisan, N.; Toupet, L.; Guionneau, P.; Létard, J. F.; Freysz, E.; Cailleau, H.; Collet, E.

    2012-02-01

    We discuss here the important role of intermolecular coupling for the thermal- and light-induced molecular state switching in the solid state. Investigations were performed on the two crystalline polymorphs of the spin-crossover [Fe-(PM-BIA)2(NCS)2] material. In addition to structural studies at thermal equilibrium, light-induced phenomena were investigated through photocrystallography, photomagnetic, and dynamical optical measurements. Strong similarities between the thermal-equilibrium and the out-of-equilibrium light-induced transformations are observed in each polymorph: strong cooperative phenomena in one polymorph versus weak cooperative ones in the second polymorph. These different responses of the two crystalline forms of the compound to external perturbations are discussed at the microscopic level in terms of Ising-like model and two-mode description of on-site molecular potentials.

  20. Substituent-induced intermolecular interaction in organic crystals revealed by precise band-dispersion measurements.

    PubMed

    Yamane, Hiroyuki; Kosugi, Nobuhiro

    2013-08-23

    We reveal quite small but different intermolecular valence band dispersions of sub-100-meV scale in crystalline films of Zn and Mn phthalocyanine (ZnPc and MnPc) and fluorinated ZnPc (F16ZnPc). The intermolecular transfer integrals are found to be reasonably dependent on the intermolecular distance with the 75±5 meV/Å relation. Furthermore, the angle-resolved photoemission spectra show anomalous dispersive behaviors such as phase flips and local-dimerization-derived periodicities, which originate from the site-specific intermolecular interaction induced by substituents. PMID:24010459

  1. Substituent-Induced Intermolecular Interaction in Organic Crystals Revealed by Precise Band-Dispersion Measurements

    NASA Astrophysics Data System (ADS)

    Yamane, Hiroyuki; Kosugi, Nobuhiro

    2013-08-01

    We reveal quite small but different intermolecular valence band dispersions of sub-100-meV scale in crystalline films of Zn and Mn phthalocyanine (ZnPc and MnPc) and fluorinated ZnPc (F16ZnPc). The intermolecular transfer integrals are found to be reasonably dependent on the intermolecular distance with the 75±5meV/Å relation. Furthermore, the angle-resolved photoemission spectra show anomalous dispersive behaviors such as phase flips and local-dimerization-derived periodicities, which originate from the site-specific intermolecular interaction induced by substituents.

  2. Stability of linear systems in second-order form based on structure preserving similarity transformations

    SciTech Connect

    Stoustrup, Jakob; Pommer, Christian; Kliem, Wolfhard

    2015-10-31

    This paper deals with two stability aspects of linear systems of the form I ¨ x +B˙ x +Cx = 0 given by the triple (I;B;C). A general transformation scheme is given for a structure and Jordan form preserving transformation of the triple. We investigate how a system can be transformed by suitable choices of the transformation parameters into a new system (I;B1;C1) with a symmetrizable matrix C1. This procedure facilitates stability investigations. We also consider systems with a Hamiltonian spectrum which discloses marginal stability after a Jordan form preserving transformation.

  3. Intermolecular Association Provides Specific Optical and NMR Signatures for Serotonin at Intravesicular Concentrations

    PubMed Central

    Nag, Suman; Balaji, J.; Madhu, P. K.; Maiti, S.

    2008-01-01

    Neurotransmitter vesicles contain biomolecules at extraordinarily high concentrations (hundreds of millimoles/liter). Such concentrations can drive intermolecular associations, which may affect vesicular osmolarity and neuronal signaling. Here we investigate whether aqueous serotonin (a monoamine neurotransmitter) forms oligomers at intravesicular concentrations and whether these oligomers have specific spectroscopic signatures that can potentially be used for monitoring neuronal storage and release. We report that, as serotonin concentration is increased from 60 μM to 600 mM, the normalized fluorescence spectrum of serotonin displays a growing long-wavelength tail, with an isoemissive point at 376 nm. The fluorescence decay is monoexponential with a lifetime of 4 ns at low concentrations but is multiexponential with an average lifetime of 0.41 ns at 600 mM. A 600 mM serotonin solution has 30% less osmolarity than expected for monomeric serotonin, indicating oligomer formation. The proton NMR chemical shifts move upfield by as much as 0.3 ppm at 600 mM compared to those at 10 mM, indicating a stacking of the serotonin indole moieties. However, no intermolecular crosspeak is evident in the two-dimensional NMR rotating frame Overhauser effect spectroscopy spectrum even at 600 mM, suggesting that oligomeric structures are possibly weakly coupled. The appearance of a single peak for each proton suggests that the rate of interconversion between the monomeric and the oligomeric structures is faster than 240 Hz. A stopped-flow kinetic experiment also confirms that the rate of dissociation is faster than 100 ms. We conclude that serotonin forms oligomers at intravesicular concentrations but becomes monomeric quickly on dilution. NMR signatures of the oligomers provide potential contrast agents for monitoring the activity of serotonergic neurons in vivo. PMID:18234835

  4. Interfacial and intermolecular interactions determining the rotational orientation of C60 adsorbed on Au(111)

    NASA Astrophysics Data System (ADS)

    Paßens, Michael; Karthäuser, Silvia

    2015-12-01

    Close-packed monolayers of fullerenes on metallic substrates are very rich systems with respect to their rotational degrees of freedom and possible interactions with different adsorption sites or next neighbours. In this connection, we report in detail on the (2√3 × 2√3)R30°-superstructure of C60 with respect to the Au(111)-surface. We use molecular orbital imaging in systematic UHV-STM studies to reveal the delicate balance of interfacial and intermolecular interactions in this system. Thus, bright C60-molecules in 5:6-top and 6:6-top geometries are observed depending on the respective next neighbours. Moreover, tiny changes in the appearance of the unoccupied molecular orbitals of dim C60-molecules in hex-vac positions are identified which are caused by the respective interaction with the facets surrounding the Au-vacancy.

  5. On the symmetric form of systems of conservation laws with entropy

    NASA Technical Reports Server (NTRS)

    Harten, A.

    1983-01-01

    The present investigation has the objective to review the general structure of system of conservation laws with entropy, giving particular attention to a presentation of symmetric formulations of the equations of gas dynamics. Systems of hyperbolic conservation laws are considered, taking into account the case in which a system of equations is symmetric hyperbolic, questions of symmetrization, and entropy functions. The Euler equations for a polytropic gas in conservation form are considered. The symmetric form retains the conservation properties of the equations. Weak solutions remain, therefore, unchanged. Of particular computational interest is the possibility of using the symmetric form.

  6. Visualizing the orientational dependence of an intermolecular potential

    PubMed Central

    Sweetman, Adam; Rashid, Mohammad A.; Jarvis, Samuel P.; Dunn, Janette L.; Rahe, Philipp; Moriarty, Philip

    2016-01-01

    Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard–Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation. PMID:26879386

  7. Intermolecular forces and energies between ligands and receptors.

    PubMed

    Moy, V T; Florin, E L; Gaub, H E

    1994-10-14

    The recognition mechanisms and dissociation pathways of the avidin-biotin complex and of actin monomers in actin filaments were investigated. The unbinding forces of discrete complexes of avidin or streptavidin with biotin analogs are proportional to the enthalpy change of the complex formation but independent of changes in the free energy. This result indicates that the unbinding process is adiabatic and that entropic changes occur after unbinding. On the basis of the measured forces and binding energies, an effective rupture length of 9.5 +/- 1 angstroms was calculated for all biotin-avidin pairs and approximately 1 to 3 angstroms for the actin monomer-monomer interaction. A model for the correlation among binding forces, intermolecular potential, and molecular function is proposed. PMID:7939660

  8. Visualizing the orientational dependence of an intermolecular potential

    NASA Astrophysics Data System (ADS)

    Sweetman, Adam; Rashid, Mohammad A.; Jarvis, Samuel P.; Dunn, Janette L.; Rahe, Philipp; Moriarty, Philip

    2016-02-01

    Scanning probe microscopy can now be used to map the properties of single molecules with intramolecular precision by functionalization of the apex of the scanning probe tip with a single atom or molecule. Here we report on the mapping of the three-dimensional potential between fullerene (C60) molecules in different relative orientations, with sub-Angstrom resolution, using dynamic force microscopy (DFM). We introduce a visualization method which is capable of directly imaging the variation in equilibrium binding energy of different molecular orientations. We model the interaction using both a simple approach based around analytical Lennard-Jones potentials, and with dispersion-force-corrected density functional theory (DFT), and show that the positional variation in the binding energy between the molecules is dominated by the onset of repulsive interactions. Our modelling suggests that variations in the dispersion interaction are masked by repulsive interactions even at displacements significantly larger than the equilibrium intermolecular separation.

  9. Transetherification on Polyols by Intra- and Intermolecular Nucleophilic Substitutions

    PubMed Central

    Muraoka, Takahiro; Adachi, Kota; Chowdhury, Rainy; Kinbara, Kazushi

    2014-01-01

    Transetherification on polyols involving intra- and intermolecular nucleophilic substitutions is reported. Di- or trialkoxide formation of propane-1,3-diol or 2-(hydroxymethyl)propane-1,3-diol derivatives by NaH triggers the reaction via oxetanes formation, where the order to add NaH and a polyol significantly influences the yields of products. It was demonstrated that the protective group on the pentaerythritol skeleton is apparently transferred to the hydrophilic and hydrophobic chain molecules bearing a leaving group in one-step, and a protective group conversion from tosyl to benzyl was successful using a benzyl-appending triol to afford a desired product in 67% yield. PMID:24663293

  10. Intermolecular interactions in the crystalline state of some organotellurium antioxidants

    NASA Astrophysics Data System (ADS)

    Engman, L.; Kania, I.; Oleksyn, B. J.; Śliwiński, J.; Wojtoń, A.

    2002-05-01

    The X-ray crystal structure analysis was performed for single crystals of bis (4-aminophenyl) telluride ( 1), bis [4-( N, N-dimethylamino)phenyl] telluride ( 2) and bis (4-hydroxyphenyl) telluride hemihydrate ( 3). The molecules of the diaryl tellurides 1- 3 display two types of non-planar conformations: 'butterfly' and 'T-shaped'. They differ in the torsion angles around Te-C bonds. Intermolecular hydrogen bonds occur between water molecules and hydroxyl groups in compound 3 and also between phenyl rings and proton donors in compounds 2 and 3 with -H⋯π distances 2.56(8)-2.95(6) Å. Also, in compounds 1 and 2 short -H⋯π contacts (3.02(4)-3.29(5) Å) were observed.

  11. An assay for intermolecular exchange of alpha crystallin

    NASA Technical Reports Server (NTRS)

    Gopalakrishnan, S.; Takemoto, L.; Spooner, B. S. (Principal Investigator)

    1992-01-01

    An affinity column of alpha crystallin linked to cyanogen bromide-activated Sepharose was developed to study the exchange of alpha subunits. Alpha crystallin bound to the Sepharose-alpha complex was dissociated with 8 mol/l urea, followed by quantitation using high-performance reverse-phase liquid chromatography. The time course of binding at 37 degrees C showed a hyperbolic binding pattern reaching equilibrium between 6-18 hr. Under these conditions, binding of beta and gamma crystallins to the same matrix was less than 10% of the alpha values, as was binding of alpha to glycine-coupled Sepharose. This assay was used to demonstrate changes in the subunit exchange of alpha crystallins present in high molecular weight versus lower molecular weight aggregates of the human lens. These results show that this binding procedure was a specific reproducible assay that might be used to study intermolecular interactions of the alpha crystallins.

  12. MOLECULAR PACKING AND NPT-MOLECULAR DYNAMICS INVESTIGATION OF THE TRANSFERABILITY OF THE RDX INTERMOLECULAR POTENTIAL TO 2,4,6,8,1O,12- HEXANITROHEXAAZAISOWURTZITANE (HNIW)

    EPA Science Inventory

    We have explored the degree to which an intermolecular potential for the explosive hexahydro-1,3,5-trinitro-1,3,5-s-triazine (RDX) is transferable for predictions of crystal structures (within the approximation of rigid molecules) of a similar chemical system,in this case, polymo...

  13. Exploring How Technology Mediates the Types of Relationships Formed in Sociotechnical Systems

    ERIC Educational Resources Information Center

    Chu, Kar-Hai

    2012-01-01

    This work presents an exploratory study of how technology mediates the different types of relationships that are formed in sociotechnical systems. More people each day are connecting with each other through social networks, online communities, and other forms of virtual environments. Whether for education, information seeking, friendship,…

  14. Work Organisation, Forms of Employee Learning and National Systems of Education and Training

    ERIC Educational Resources Information Center

    Lorenz, Edward; Lundvall, Bengt-Åke; Kraemer-Mbula, Erika; Rasmussen, Palle

    2016-01-01

    This article uses a multi-level framework to investigate for 17 European nations the links between forms of work organisation and style of employee learning at the workplace on the one hand, and the characteristics of national educational and training systems on the other. The analysis shows that forms of work organisation characterised by…

  15. Arginine-phosphate salt bridges between histones and DNA: Intermolecular actuators that control nucleosome architecture

    NASA Astrophysics Data System (ADS)

    Yusufaly, Tahir I.; Li, Yun; Singh, Gautam; Olson, Wilma K.

    2014-10-01

    Structural bioinformatics and van der Waals density functional theory are combined to investigate the mechanochemical impact of a major class of histone-DNA interactions, namely, the formation of salt bridges between arginine residues in histones and phosphate groups on the DNA backbone. Principal component analysis reveals that the configurational fluctuations of the sugar-phosphate backbone display sequence-specific directionality and variability, and clustering of nucleosome crystal structures identifies two major salt-bridge configurations: a monodentate form in which the arginine end-group guanidinium only forms one hydrogen bond with the phosphate, and a bidentate form in which it forms two. Density functional theory calculations highlight that the combination of sequence, denticity, and salt-bridge positioning enables the histones to apply a tunable mechanochemical stress to the DNA via precise and specific activation of backbone deformations. The results suggest that selection for specific placements of van der Waals contacts, with high-precision control of the spatial distribution of intermolecular forces, may serve as an underlying evolutionary design principle for the structure and function of nucleosomes, a conjecture that is corroborated by previous experimental studies.

  16. 75 FR 4101 - Enterprise Income Verification (EIV) System User Access Authorization Form and Rules of Behavior...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-01-26

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF HOUSING AND URBAN DEVELOPMENT Enterprise Income Verification (EIV) System User Access Authorization Form and Rules.... This notice also lists the following information: Title of Proposal: Enterprise Income...

  17. The use of intermolecular potential functions in fitting pressure induced spectra

    NASA Technical Reports Server (NTRS)

    Goorvitch, D.; Silvaggio, P. M.; Boese, R. W.

    1981-01-01

    An example is presented which demonstrates the importance of using physically realistic derivatives of the intermolecular potential when fitting pressure-induced spectra. The use of nonrealistic derivatives may mask second-order temperature effects in the theory. As the temperature decreases, the intermolecular potential may have an important angular dependence.

  18. Problem-Based Learning in 9th Grade Chemistry Class: "Intermolecular Forces"

    ERIC Educational Resources Information Center

    Tarhan, Leman; Ayar-Kayali, Hulya; Urek, Raziye Ozturk; Acar, Burcin

    2008-01-01

    This research study aims to examine the effectiveness of a problem-based learning (PBL) on 9th grade students' understanding of intermolecular forces (dipole-dipole forces, London dispersion forces and hydrogen bonding). The student's alternate conceptions about intermolecular bonding and their beliefs about PBL were also measured. Seventy-eight…

  19. Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines

    SciTech Connect

    Dou, Wei-Dong; Huang, Shu-Ping; Lee, Chun-Sing

    2015-10-07

    Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π–π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc and CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface.

  20. Metal-Free Intermolecular Azide-Alkyne Cycloaddition Promoted by Glycerol.

    PubMed

    Rodríguez-Rodríguez, Marta; Gras, Emmanuel; Pericàs, Miquel A; Gómez, Montserrat

    2015-12-14

    Metal-free intermolecular Huisgen cycloadditions using nonactivated internal alkynes have been successfully performed in neat glycerol, both under thermal and microwave dielectric heating. In sharp contrast, no reaction occurs in other protic solvents, such as water, ethanol, or diols. DFT calculations have shown that the BnN3/glycerol adduct promotes a more important stabilization of the corresponding LUMO than that produced in the analogous BnN3/alcohol adducts, favoring the reactivity with the alkyne in the first case. The presence of copper salts in the medium did not change the reaction pathway (Cu(I) acts as spectator), except for disubstituted silylalkynes, for which desilylation takes place in contrast to the metal-free system. PMID:26541267

  1. Density Analysis of Intra- and Intermolecular Vibronic Couplings toward Bath Engineering for Singlet Fission.

    PubMed

    Ito, Soichi; Nagami, Takanori; Nakano, Masayoshi

    2015-12-17

    Vibronic coupling plays a crucial role in singlet fission whereby a singlet exciton splits into two triplet excitons. In order to reveal the physicochemical origin of the vibronic coupling associated with singlet fission as well as to clarify its relationship with chemical structure, we evaluate relevant vibronic couplings from the viewpoint of their spatial contributions described by vibronic coupling density. From the analysis using a model tetracene dimer, a typical singlet fission system, the frequency dependence of vibronic couplings in each electronic state is found to be significantly different from that of another depending on the nature of the electronic structure (intra/intermolecular excitation) and the related vibrational motion. These findings contribute not only to the fundamental understanding of the singlet fission mechanism from the viewpoint of vibronic couplings but also to opening a new path to designing highly efficient singlet fission materials through phonon-bath engineering. PMID:26673196

  2. Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines

    NASA Astrophysics Data System (ADS)

    Dou, Wei-Dong; Huang, Shu-Ping; Lee, Chun-Sing

    2015-10-01

    Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π-π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc and CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface.

  3. Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines.

    PubMed

    Dou, Wei-Dong; Huang, Shu-Ping; Lee, Chun-Sing

    2015-10-01

    Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π-π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc and CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface. PMID:26450327

  4. Crystal structures and intermolecular interactions of two novel antioxidant triazolyl-benzimidazole compounds

    SciTech Connect

    Karayel, A. E-mail: yccaoh@hotmail.com; Özbey, S.; Ayhan-Kılcıgil, G.; Kuş, C.

    2015-12-15

    The crystal structures of 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(3-fluorophenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G6C) and 5-(2-(p-chlorophenylbenzimidazol-1-yl-methyl)-4-(2-methylphenyl)-2, 4-dihydro-[1,2,4]-triazole-3-thione (G4C) have been determined by single-crystal X-ray diffraction. Benzimidazole ring systems in both molecules are planar. The triazole part is almost perpendicular to the phenyl and the benzimidazole parts of the molecules in order to avoid steric interactions between the rings. The crystal structures are stabilized by intermolecular hydrogen bonds between the amino group of the triazole and the nitrogen atom of benzimidazole of a neighboring molecule.

  5. Genetic analysis of response regulator activation in bacterial chemotaxis suggests an intermolecular mechanism

    PubMed Central

    Re, Sandra Da; Tolstykh, Tatiana; Wolanin, Peter M.; Stock, Jeffry B.

    2002-01-01

    Response regulator proteins of two-component systems are usually activated by phosphorylation. The phosphorylated response regulator protein CheY∼P mediates the chemotaxis response in Escherichia coli. We performed random mutagenesis and selected CheY mutants that are constitutively active in the absence of phosphorylation. Although a single amino acid substitution can lead to constitutive activation, no single DNA base change can effect such a transition. Numerous different sets of mutations that activate in synergy were selected in several different combinations. These mutations were all located on the side of CheY defined by α4, β5, α5, and α1. Our findings argue against the two-state hypothesis for response regulator activation. We propose an alternative intermolecular mechanism that involves a dynamic interplay between response regulators and their effector targets. PMID:12381847

  6. Crystal structures and intermolecular interactions of two novel antioxidant triazolyl-benzimidazole compounds

    NASA Astrophysics Data System (ADS)

    Karayel, A.; Özbey, S.; Ayhan-Kılcıgil, G.; Kuş, C.

    2015-12-01

    The crystal structures of 5-(2-( p-chlorophenylbenzimidazol-1-yl-methyl)-4-(3-fluorophenyl)-2,4-dihydro-[1,2,4]-triazole-3-thione (G6C) and 5-(2-( p-chlorophenylbenzimidazol-1-yl-methyl)-4-(2-methylphenyl)-2,4-dihydro-[1,2,4]-triazole-3-thione (G4C) have been determined by single-crystal X-ray diffraction. Benzimidazole ring systems in both molecules are planar. The triazole part is almost perpendicular to the phenyl and the benzimidazole parts of the molecules in order to avoid steric interactions between the rings. The crystal structures are stabilized by intermolecular hydrogen bonds between the amino group of the triazole and the nitrogen atom of benzimidazole of a neighboring molecule.

  7. Carleman linearization and normal forms for differential systems with quasi-periodic coefficients.

    PubMed

    Chermnykh, Sergey V

    2016-01-01

    We study the matrix representation of Poincaré normalization using the Carleman linearization technique for non-autonomous differential systems with quasi-periodic coefficients. We provide a rigorous proof of the validity of the matrix representation of the normalization and obtain a recursive algorithm for computing the normalizing transformation and the normal form of the differential systems. The algorithm provides explicit formulas for the coefficients of the normal form and the corresponding transformation. PMID:27588240

  8. Intermolecular Tl···H-C anagostic interactions in luminescent pyridyl functionalized thallium(I) dithiocarbamates.

    PubMed

    Kumar, Vinod; Singh, Vikram; Gupta, Ajit N; Drew, Michael G B; Singh, Nanhai

    2015-01-28

    Crystal structures of novel pyridyl functionalised [Tl(L)]∞ (L = (N-benzyl-N-methylpyridyl) dithiocarbamate(L1) 1, bis(N-methylpyridyl) dithiocarbamate(L2) 2, (N-methyl(1,4-benzodioxane-6-yl)-N-methylpyridyl)dithiocarbamate(L3) 3, (N-ferrocenyl-N-methylpyridyl) dithiocarbamate(L4) 4) complexes revealed rare intermolecular C-H···Tl anagostic and C-S···Tl interactions forming a six-membered chelate ring about the metal center, which have been assessed by DFT calculations. The strong thallophilic bonding is responsible for the strong luminescent characteristics of the complexes in the solid phase. PMID:25461980

  9. The Divergent Synthesis of Nitrogen Heterocycles by Rhodium(I)-Catalyzed Intermolecular Cycloadditions of Vinyl Aziridines and Alkynes.

    PubMed

    Feng, Jian-Jun; Lin, Tao-Yan; Zhu, Chao-Ze; Wang, Huamin; Wu, Hai-Hong; Zhang, Junliang

    2016-02-24

    Catalyst-controlled divergent intermolecular cycloadditions of vinylaziridines with alkynes have been developed. By using [Rh(NBD)2]BF4 as the catalyst, a [3 + 2] cycloaddition reaction was achieved with broad substrate scope and high stereoselectivity under mild reaction conditions. Moreover, the chirality of vinylaziridines can be completely transferred to the [3 + 2] cycloadducts. When the catalyst was changed to [Rh(η(6)-C10H8) (COD)]SbF6, the alternative [5 + 2] cycloadducts were selectively formed under otherwise identical conditions. PMID:26859710

  10. Noncovalent intermolecular interactions between dehydroepiandrosterone and the active site of human dehydroepiandrosterone sulphotransferase: A density functional theory based treatment

    NASA Astrophysics Data System (ADS)

    Astani, Elahe; Heshmati, Emran; Chen, Chun-Jung; Hadipour, Nasser L.; Shekarsaraei, Setareh

    2016-04-01

    A theoretical study was performed to characterize noncovalent intermolecular interactions, especially hydrogen bond (HB), in the active site of enzyme human dehydroepiandrosterone sulphotransferase (SULT2A1/DHEA) using the local (M06-L) and hybrid (M06, M06-2X) meta-GGA functionals of density functional theory (DFT). Results revealed that DHEA is able to form HBs with residues His99, Tyr231, Met137 and Met16 in the active site of the SULT2A1/DHEA. It was found that DHEA interacts with the other residues through electrostatic and Van der Waals interactions.

  11. Squeezing water clusters between graphene sheets: energetics, structure, and intermolecular interactions.

    PubMed

    McKenzie, S; Kang, H C

    2014-12-21

    The behavior of water confined at the nanoscale between graphene sheets has attracted much theoretical and experimental attention recently. However, the interactions, structure, and energy of water at the molecular scale underpinning the behavior of confined water have not been characterized by first-principles calculations. In this work we consider small water clusters up to the hexamer adsorbed between graphene sheets using density functional theory calculations with van der Waals corrections. We investigate the effects on structure, energy, and intermolecular interactions due to confinement between graphene sheets. For interlayer distances of about one nanometer or more, the cluster adsorption energy increases approximately linearly with the cluster size by 0.1 eV per molecule in the cluster. As the interlayer distance decreases, the cluster adsorption energy reaches a maximum at 6 to 7 Å with approximately 0.16 eV stabilization energy relative to large interlayer distances. This suggests the possibility of controlling the amount of adsorption in graphene nanomaterials by varying the interlayer distance. We also quantify the intermolecular hydrogen bonding in the clusters by calculating the dissociation energy required to remove one molecule from each cluster. For each cluster size, this is constant for interlayer distances larger than approximately 6 to 8 Å. For smaller distances the intermolecular interaction decreases rapidly thus leading to weaker cohesion between molecules in a squeezed cluster. We expect a mechanism of concerted motion for hydrogen-bonded water molecules confined between graphene sheets, as has been observed for water confined within the carbon nanotubes. Thus, the decrease in the dissociation energy we observed here is consistent with experimental results for water transport through graphene and related membranes that are of interest in nanofiltration. We also calculate the corrugation in the interaction potential between graphene

  12. Molecular simulation of fluids with non-identical intermolecular potentials: Thermodynamic properties of 10-5 + 12-6 Mie potential binary mixtures

    NASA Astrophysics Data System (ADS)

    Stiegler, Thomas; Sadus, Richard J.

    2015-02-01

    General methods for combining interactions between particles characterised by non-identical intermolecular potentials are investigated. The combination methods are tested by performing molecular dynamics simulations to determine the pressure, energy, isochoric and isobaric heat capacities, thermal expansion coefficient, isothermal compressibility, Joule-Thomson coefficient, and speed of sound of 10-5 + 12-6 Mie potential binary mixtures. In addition to the two non-identical Mie potentials, mixtures are also studied with non-identical intermolecular parameters. The combination methods are compared with results obtained by simply averaging the Mie exponents. When either the energy or size parameters are non-identical, very significant differences emerge in the thermodynamic properties predicted by the alternative combination methods. The isobaric heat capacity is the thermodynamic property that is most affected by the relative magnitude of the intermolecular potential parameters and the method for combining non-identical potentials. Either the arithmetic or geometric combination of potentials provides a simple and effective way of performing simulations involving mixtures of components characterised by non-identical intermolecular potentials, which is independent of their functional form.

  13. Molecular simulation of fluids with non-identical intermolecular potentials: Thermodynamic properties of 10-5 + 12-6 Mie potential binary mixtures

    SciTech Connect

    Stiegler, Thomas; Sadus, Richard J.

    2015-02-28

    General methods for combining interactions between particles characterised by non-identical intermolecular potentials are investigated. The combination methods are tested by performing molecular dynamics simulations to determine the pressure, energy, isochoric and isobaric heat capacities, thermal expansion coefficient, isothermal compressibility, Joule-Thomson coefficient, and speed of sound of 10-5 + 12-6 Mie potential binary mixtures. In addition to the two non-identical Mie potentials, mixtures are also studied with non-identical intermolecular parameters. The combination methods are compared with results obtained by simply averaging the Mie exponents. When either the energy or size parameters are non-identical, very significant differences emerge in the thermodynamic properties predicted by the alternative combination methods. The isobaric heat capacity is the thermodynamic property that is most affected by the relative magnitude of the intermolecular potential parameters and the method for combining non-identical potentials. Either the arithmetic or geometric combination of potentials provides a simple and effective way of performing simulations involving mixtures of components characterised by non-identical intermolecular potentials, which is independent of their functional form.

  14. Corrigendum: New Form of Kane's Equations of Motion for Constrained Systems

    NASA Technical Reports Server (NTRS)

    Roithmayr, Carlos M.; Bajodah, Abdulrahman H.; Hodges, Dewey H.; Chen, Ye-Hwa

    2007-01-01

    A correction to the previously published article "New Form of Kane's Equations of Motion for Constrained Systems" is presented. Misuse of the transformation matrix between time rates of change of the generalized coordinates and generalized speeds (sometimes called motion variables) resulted in a false conclusion concerning the symmetry of the generalized inertia matrix. The generalized inertia matrix (sometimes referred to as the mass matrix) is in fact symmetric and usually positive definite when one forms nonminimal Kane's equations for holonomic or simple nonholonomic systems, systems subject to nonlinear nonholonomic constraints, and holonomic or simple nonholonomic systems subject to impulsive constraints according to Refs. 1, 2, and 3, respectively. The mass matrix is of course symmetric when one forms minimal equations for holonomic or simple nonholonomic systems using Kane s method as set forth in Ref. 4.

  15. In situ gel-forming system: an attractive alternative for nasal drug delivery.

    PubMed

    Wang, Xiaoqing; Liu, Guiyang; Ma, Jianli; Guo, Shaolai; Gao, Lei; Jia, Yanhua; Li, Xiang; Zhang, Qingzhe

    2013-01-01

    Intranasal delivery is one of the most interesting and challenging endeavors facing pharmaceutical scientists. The conventional nasal drug delivery systems including solutions, suspensions, and ointments show drawbacks such as short residence in the nasal cavity, highly variable efficiency, low permeability, and inconvenient administration. In situ gel-forming systems are an interesting polymeric system that exists as flowing aqueous solution before administration and undergoes phase transition to form a viscoelastic gel in a physiologic environment. Benefiting from the merits of both a solution and a gel, an impressive number of in situ gel-forming systems induced by temperature, pH, and ions have been prepared for use in nasal drug delivery in the past few years. In situ gel-forming systems increase the retention of drugs in the nasal cavity, and some of them also show permeation-enhancing capabilities. This article reviews the in situ gel-forming systems used for nasal drug delivery and introduces their gelling mechanisms and other favorable features for intranasal delivery. It also describes the release patterns and drug stability of in situ gels as well as their in vivo performances and local safety following nasal administration. PMID:24099327

  16. A Colloidal Description of Intermolecular Interactions Driving Fibril-Fibril Aggregation of a Model Amphiphilic Peptide.

    PubMed

    Owczarz, Marta; Motta, Anna C; Morbidelli, Massimo; Arosio, Paolo

    2015-07-14

    We apply a kinetic analysis platform to study the intermolecular interactions underlying the colloidal stability of dispersions of charged amyloid fibrils consisting of a model amphiphilic peptide (RADA 16-I). In contrast to the aggregation mechanisms observed in the large majority of proteins and peptides, where several elementary reactions involving both monomers and fibrils are present simultaneously, the system selected in this work allows the specific investigation of the fibril-fibril aggregation process. We examine the intermolecular interactions driving the aggregation reaction at pH 2.0 by changing the buffer composition in terms of salt concentration, type of ion as well as type and concentration of organic solvent. The aggregation kinetics are followed by dynamic light scattering, and the experimental data are simulated by Smoluchowski population balance equations, which allow to estimate the energy barrier between two colliding fibrils in terms of the Fuchs stability ratio (W). When normalized on a dimensionless time weighted on the Fuchs stability ratio, the aggregation profiles under a broad range of conditions collapse on a single master curve, indicating that the buffer composition modifies the aggregation kinetics without affecting the aggregation mechanism. Our results show that the aggregation process does not occur under diffusion-limited conditions. Rather, the reaction rate is limited by the presence of an activation energy barrier that is largely dominated by electrostatic repulsive interactions. Such interactions could be reduced by increasing the concentration of salt, which induces charge screening, or the concentration of organic solvent, which affects the dielectric constant. It is remarkable that the dependence of the activation energy on the ionic strength can be described quantitatively in terms of charge screening effects in the frame of the DLVO theory, although specific anion and cation effects are also observed. While anion

  17. Intermolecular Interactions of Cardiac Transcription Factors NKX2.5 and TBX5.

    PubMed

    Pradhan, Lagnajeet; Gopal, Sunil; Li, Shichang; Ashur, Shayan; Suryanarayanan, Saai; Kasahara, Hideko; Nam, Hyun-Joo

    2016-03-29

    Heart development in mammalian systems is controlled by combinatorial interactions of master cardiac transcription factors such as TBX5 and NKX2.5. They bind to promoters/enhancers of downstream targets as homo- or heteromultimeric complexes. They physically interact and synergistically regulate their target genes. To elucidate the molecular basis of the intermolecular interactions, a heterodimer and a homodimer of NKX2.5 and TBX5 were studied using X-ray crystallography. Here we report a crystal structure of human NKX2.5 and TBX5 DNA binding domains in a complex with a 19 bp target DNA and a crystal structure of TBX5 homodimer. The ternary complex structure of NKX2.5 and TBX5 with the target DNA shows physical interactions between the two proteins through Lys158 (NKX2.5), Asp140 (TBX5), and Pro142 (TBX5), residues that are highly conserved in TBX and NKX families across species. Extensive homodimeric interactions were observed between the TBX5 proteins in both crystal structures. In particular, in the crystal structure of TBX5 protein that includes the N-terminal and DNA binding domains, intermolecular interactions were mediated by the N-terminal domain of the protein. The N-terminal domain of TBX5 was predicted to be "intrinsically unstructured", and in one of the two molecules in an asymmetric unit, the N-terminal domain assumes a β-strand conformation bridging two β-sheets from the two molecules. The structures reported here may represent general mechanisms for combinatorial interactions among transcription factors regulating developmental processes. PMID:26926761

  18. Development of an automated form generating system for menu item data.

    PubMed

    Anderson, A L; Moore, A N; Hoover, L W

    1977-08-01

    At the University of Missouri-Columbia, an Automated Form Generating System consisting of six computer programs was developed to generate the master menu, production forecast and usage forms, production worksheet, food order report, and selective menus for patients. In the initial testing of the programs, this computer-assisted system showed a 30 per cent reduction in time requirred by dietitians and clerks when compared with the manual system. Some expected benefits include ease in making menu changes, substantial reduction in errors, automatic updating of documents, and reduction in storage space for forms because documents will be generated just prior to a production week. The system will be implemented at a later date. PMID:881530

  19. Pick and Pack: a just-in-time forms order and delivery system.

    PubMed

    Stewart, M

    1993-01-01

    Since the University of Alabama Hospital at Birmingham (UAB) had an in-plant print shop, the idea of purchasing forms from an outside supplier on a JIT order and delivery system didn't occur to them. But after establishing a successful medical/surgical JIT system at University of Alabama Hospital at Birmingham (UAB), the Director of Support Services and the Director of Purchasing looked at and developed a program to have a JIT forms inventory system by using their own print shop in conjunction with an outside supplier. The system, called Pick and Pack, basically works like this: An outside supplier buys flat-bed forms printed by the UAB Print Shop for resale back to UAB, and also produces their own custom, continuous forms to sell to UAB. The supplier warehouses, then picks and packs per individual UAB patient care unit order and delivers the forms to the UAB Material Management loading dock. Requisitioning is on-line for each patient care unit, Materiel Management and the supplier. Success was achieved in a step-by-step manner, reducing a time-consuming, labor-intensive receiving process to a one-person process. Inventory of forms is estimated to have been reduced by $90,000 and approximately 2,160 cubic feet of space freed for other uses. PMID:10123864

  20. Effects of quenched disorder on critical transitions in pattern-forming systems

    NASA Astrophysics Data System (ADS)

    Yizhaq, Hezi; Bel, Golan

    2016-02-01

    Critical transitions are of great interest to scientists in many fields. Most knowledge about these transitions comes from systems exhibiting the multistability of spatially uniform states. In spatially extended and, particularly, in pattern-forming systems, there are many possible scenarios for transitions between alternative states. Quenched disorder may affect the dynamics, bifurcation diagrams and critical transitions in nonlinear systems. However, only a few studies have explored the effects of quenched disorder on pattern-forming systems, either experimentally or by using theoretical models. Here, we use a fundamental model describing pattern formation, the Swift-Hohenberg model and a well-explored mathematical model describing the dynamics of vegetation in drylands to study the effects of quenched disorder on critical transitions in pattern-forming systems. We find that the disorder affects the patterns formed by introducing an interplay between the imposed pattern and the self-organized one. We show that, in both systems considered here, the disorder significantly increases the durability of the patterned state and makes the transition between the patterned state and the uniform state more gradual. In addition, the disorder induces hysteresis in the response of the system to changes in the bifurcation parameter well before the critical transition occurs. We also show that the cross-correlation between the disordered parameter and the dynamical variable can serve as an early indicator for an imminent critical transition.

  1. A Godunov scheme for solving hyperbolic systems in a nonconservative form

    NASA Astrophysics Data System (ADS)

    Zalzali, I.; Abbas, H.

    2005-05-01

    In this paper, we developed a Godunov scheme for solving nonconservative systems. The main idea of this method is a new type of projection which illustrated the essential role of the numerical viscosity to determine the solution with shocks for system in a nonconservative form. We apply our study to a system modeling elasticity and we observe a complete agreement between the theory and the numerical results.

  2. Normal form solutions of dynamical systems in the basin of attraction of their fixed points

    NASA Astrophysics Data System (ADS)

    Bountis, Tassos; Tsarouhas, George; Herman, Russell

    1998-10-01

    The normal form theory of Poincaré, Siegel and Arnol'd is applied to an analytically solvable Lotka-Volterra system in the plane, and a periodically forced, dissipative Duffing's equation with chaotic orbits in its 3-dimensional phase space. For the planar model, we determine exactly how the convergence region of normal forms about a nodal fixed point is limited by the presence of singularities of the solutions in the complex t-plane. Despite such limitations, however, we show, in the case of a periodically driven system, that normal forms can be used to obtain useful estimates of the basin of attraction of a stable fixed point of the Poincaré map, whose ``boundary'' is formed by the intersecting invariant manifolds of a second hyperbolic fixed point nearby.

  3. Predicting Behavior Assessment System for Children-Second Edition Self-Report of Personality Child Form Results Using the Behavioral and Emotional Screening System Student Form: A Replication Study with an Urban, Predominantly Latino/a Sample

    ERIC Educational Resources Information Center

    Kiperman, Sarah; Black, Mary S.; McGill, Tia M.; Harrell-Williams, Leigh M.; Kamphaus, Randy W.

    2014-01-01

    This study assesses the ability of a brief screening form, the Behavioral and Emotional Screening System-Student Form (BESS-SF), to predict scores on the much longer form from which it was derived: the Behavior Assessment System for Children-Second Edition Self-Report of Personality-Child Form (BASC-2-SRP-C). The present study replicates a former…

  4. Alternatives for high-level waste forms, containers, and container processing systems

    SciTech Connect

    Crawford, T.W.

    1995-09-22

    This study evaluates alternatives for high-level waste forms, containers, container processing systems, and onsite interim storage. Glass waste forms considered are cullet, marbles, gems, and monolithic glass. Small and large containers configured with several combinations of overpack confinement and shield casks are evaluated for these waste forms. Onsite interim storage concepts including canister storage building, bore holes, and storage pad were configured with various glass forms and canister alternatives. All favorable options include the monolithic glass production process as the waste form. Of the favorable options the unshielded 4- and 7-canister overpack options have the greatest technical assurance associated with their design concepts due to their process packaging and storage methods. These canisters are 0.68 m and 0.54 m in diameter respectively and 4.57 m tall. Life-cycle costs are not a discriminating factor in most cases, varying typically less than 15 percent.

  5. Communication: Spectroscopic observation of the O-bonded T-shaped isomer of the CO-CO2 dimer and two of its intermolecular frequencies.

    PubMed

    Sheybani-Deloui, S; Barclay, A J; Michaelian, K H; McKellar, A R W; Moazzen-Ahmadi, N

    2015-09-28

    Infrared spectra in the carbon monoxide CO stretch region (≈2150 cm(-1)) are assigned to the previously unobserved O-bonded form of the CO2-CO dimer ("isomer 2"), which has a planar T-shaped structure like that of the previously observed C-bonded form ("isomer 1"), but with the CO rotated by 180°. The effective center of mass intermolecular distances are 3.58 Å for isomer 2 as compared to 3.91 Å for isomer 1. In addition to the fundamental band, two combination bands are observed for isomer 2, yielding values for two intermolecular vibrational modes: 14.19 cm(-1) for the in-plane CO bend and 22.68 cm(-1) for the out-of-plane bend. PMID:26428988

  6. Communication: Spectroscopic observation of the O-bonded T-shaped isomer of the CO-CO2 dimer and two of its intermolecular frequencies

    NASA Astrophysics Data System (ADS)

    Sheybani-Deloui, S.; Barclay, A. J.; Michaelian, K. H.; McKellar, A. R. W.; Moazzen-Ahmadi, N.

    2015-09-01

    Infrared spectra in the carbon monoxide CO stretch region (≈2150 cm-1) are assigned to the previously unobserved O-bonded form of the CO2-CO dimer ("isomer 2"), which has a planar T-shaped structure like that of the previously observed C-bonded form ("isomer 1"), but with the CO rotated by 180°. The effective center of mass intermolecular distances are 3.58 Å for isomer 2 as compared to 3.91 Å for isomer 1. In addition to the fundamental band, two combination bands are observed for isomer 2, yielding values for two intermolecular vibrational modes: 14.19 cm-1 for the in-plane CO bend and 22.68 cm-1 for the out-of-plane bend.

  7. Thermal selectivity of intermolecular versus intramolecular reactions on surfaces

    NASA Astrophysics Data System (ADS)

    Cirera, Borja; Giménez-Agulló, Nelson; Björk, Jonas; Martínez-Peña, Francisco; Martin-Jimenez, Alberto; Rodriguez-Fernandez, Jonathan; Pizarro, Ana M.; Otero, Roberto; Gallego, José M.; Ballester, Pablo; Galan-Mascaros, José R.; Ecija, David

    2016-03-01

    On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure.

  8. Development of an optimized intermolecular potential for sulfur dioxide.

    PubMed

    Ketko, MaryBeth H; Kamath, Ganesh; Potoff, Jeffrey J

    2011-05-01

    A new force field for sulfur dioxide, capable of predicting accurately the vapor-liquid equilibria, critical properties, vapor pressure, and heats of vaporization is presented. The new force field reproduces the saturated liquid densities, vapor pressures and heats of vaporization to within 0.5, 2, and 2% of experiment, respectively. The predicted critical properties and the normal boiling point are in excellent agreement with experimental results. Pair distribution functions are calculated for the S-S, S-O, and O-O interactions are in close agreement with neutron and X-ray scattering experiments. In addition to the new force field, similar calculations are performed for four SO(2) intermolecular potentials proposed by Sokolic et al. (Sokolic, F.; Guissani, Y. and Guillot, B. J. Phys. Chem. 1985, 89, 3023], which show that these models work reasonably well near the state point where they were originally parametrized, but large errors in the predicted coexistence properties are displayed at higher and lower temperatures. Comparison of the radial distribution functions show the local structure is only weakly affected by the different force field parameters. PMID:21476503

  9. Thermal selectivity of intermolecular versus intramolecular reactions on surfaces

    PubMed Central

    Cirera, Borja; Giménez-Agulló, Nelson; Björk, Jonas; Martínez-Peña, Francisco; Martin-Jimenez, Alberto; Rodriguez-Fernandez, Jonathan; Pizarro, Ana M.; Otero, Roberto; Gallego, José M.; Ballester, Pablo; Galan-Mascaros, José R.; Ecija, David

    2016-01-01

    On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure. PMID:26964764

  10. When do we need attractive-repulsive intermolecular potentials?

    SciTech Connect

    Venkattraman, Ayyaswamy

    2014-12-09

    The role of attractive-repulsive interactions in direct simulation Monte Carlo (DSMC) simulations is studied by comparing with traditional purely repulsive interactions. The larger collision cross section of the long-range LJ potential is shown to result in a higher collision frequency and hence a lower mean free path, by at least a factor of two, for given conditions. This results in a faster relaxation to equilibrium as is shown by comparing the fourth and sixth moments of the molecular velocity distribution obtained using 0-D DSMC simulations. A 1-D Fourier-Couette flow with a large temperature and velocity difference between the walls is used to show that matching transport properties will result in identical solutions using both LJPA and VSS models in the near-continuum regime. However, flows in the transitional regime with Knudsen number, Kn ∼ 0.5 show a dependence on the intermolecular potential in spite of matching the viscosity coefficient due to differences in the collision frequency. Attractive-repulsive potentials should be used when both transport coefficients and collision frequencies should be matched.

  11. Thermal selectivity of intermolecular versus intramolecular reactions on surfaces.

    PubMed

    Cirera, Borja; Giménez-Agulló, Nelson; Björk, Jonas; Martínez-Peña, Francisco; Martin-Jimenez, Alberto; Rodriguez-Fernandez, Jonathan; Pizarro, Ana M; Otero, Roberto; Gallego, José M; Ballester, Pablo; Galan-Mascaros, José R; Ecija, David

    2016-01-01

    On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure. PMID:26964764

  12. On the use and computation of the Jordan canonical form in system theory

    NASA Technical Reports Server (NTRS)

    Sridhar, B.; Jordan, D.

    1974-01-01

    This paper investigates various aspects of the application of the Jordan canonical form of a matrix in system theory and develops a computational approach to determining the Jordan form for a given matrix. Applications include pole placement, controllability and observability studies, serving as an intermediate step in yielding other canonical forms, and theorem proving. The computational method developed in this paper is both simple and efficient. The method is based on the definition of a generalized eigenvector and a natural extension of Gauss elimination techniques. Examples are included for demonstration purposes.

  13. Research: Care Delivery Development and validation of the Diabetes Medication System Rating Questionnaire-Short Form

    PubMed Central

    Peyrot, M; Xu, Y; Rubin, R R

    2014-01-01

    Aims To develop and validate a short form of the 54-item Diabetes Medication System Rating Questionnaire that maintains the domains and performance characteristics of the long-form questionnaire. Methods Data from the Diabetes Medication System Rating Questionnaire validation study were analysed to select items representing the nine scales (convenience, negative events, interference, self-monitoring of blood glucose burden, efficacy, social burden, psychological well-being, treatment satisfaction and treatment preference). The resulting 20-item Diabetes Medication System Rating Questionnaire Short-Form was administered online, with validated criterion measures of treatment satisfaction and medication adherence, with a retest within 2 weeks. Participants were US adults (N = 413) with Type 2 diabetes using oral agents alone; insulin by syringe and/or pen with or without oral agents; or glucagon-like peptide-1 agents. Most participants (82%) completed the retest. Results The median inter-item agreement of scales was 0.76 and the total composite (mean of all items except treatment preference) was 0.88. The median test-retest reliability of scales was 0.86, and of the total composite was 0.95. All statistically significant correlations between Diabetes Medication System Rating Questionnaire Short-Form scales and criterion measures of treatment satisfaction and adherence were in the expected direction. The median correlation of the Diabetes Medication System Rating Questionnaire Short-Form with corresponding criterion measures of treatment satisfaction was 0.59; the mean correlation of the same Diabetes Medication System Rating Questionnaire Short-Form measures with adherence was 0.42. The Diabetes Medication System Rating Questionnaire Short-Form scales were more powerful predictors of adherence than were the criterion measures of treatment satisfaction. The Diabetes Medication System Rating Questionnaire Short-Form scales differentiated between those taking different

  14. Correlations of Life Form, Pollination Mode and Sexual System in Aquatic Angiosperms

    PubMed Central

    Du, Zhi-Yuan; Wang, Qing-Feng

    2014-01-01

    Aquatic plants are phylogenetically well dispersed across the angiosperms. Reproductive and other life-history traits of aquatic angiosperms are closely associated with specific growth forms. Hydrophilous pollination exhibits notable examples of convergent evolution in angiosperm reproductive structures, and hydrophiles exhibit great diversity in sexual system. In this study, we reconstructed ancestral characters of aquatic lineages based on the phylogeny of aquatic angiosperms. Our aim is to find the correlations of life form, pollination mode and sexual system in aquatic angiosperms. Hydrophily is the adaptive evolution of completely submersed angiosperms to aquatic habitats. Hydroautogamy and maleflower-ephydrophily are the transitional stages from anemophily and entomophily to hydrophily. True hydrophily occurs in 18 submersed angiosperm genera, which is associated with an unusually high incidence of unisexual flowers. All marine angiosperms are submersed, hydrophilous species. This study would help us understand the evolution of hydrophilous pollination and its correlations with life form and sexual system. PMID:25525810

  15. Process of forming compounds using reverse micelle or reverse microemulsion systems

    DOEpatents

    Linehan, John C.; Fulton, John L.; Bean, Roger M.

    1998-01-01

    The present invention is directed to a process for producing a nanometer-sized metal compound. The process comprises forming a reverse micelle or reverse microemulsion system comprising a polar fluid in a non-polar or low-polarity fluid. A first reactant comprising a multi-component, water-soluble metal compound is introduced into the polar fluid in a non-polar or low-polarity fluid. This first reactant can be introduced into the reverse micelle or reverse microemulsion system during formation thereof or subsequent to the formation of the reverse micelle or microemulsion system. The water-soluble metal compound is then reacted in the reverse micelle or reverse microemulsion system to form the nanometer-sized metal compound. The nanometer-sized metal compound is then precipitated from the reverse micelle or reverse microemulsion system.

  16. Properties of multilayer optical systems formed by layers with small absorption in inclined falling of radiation

    NASA Astrophysics Data System (ADS)

    Karyaev, Konstantin V.; Zhoga, Eugene V.; Putilin, Eduard S.

    2000-10-01

    Multilayer dielectric systems find wide employment in different fields of science and engineering. Dielectric systems, formed by layers with small absorption, attract particular interest. Value of absorption, as a rule, depends on structure of the system (order and optical thickness of layers), angle of incidence and wavelength of radiation. Experiment shows that there are peaks of absorption on certain angles of incidence and wavelength, but behavior of absorption wasn't studied well. Model of a system, formed by isotropic layers settled on semiinfinite substate proved to be a good approximation for many of real optical systems. We studied pecularities in spectral dependencies of reflection, transmission and absorption coefficients in dependance on the angle of incidence and wavelength of falling radiation with flat wave front. Problem was solved on the basis of Maxwell equations and corresponding boundary conditions.

  17. Theoretical study on the effect of solvent and intermolecular fluctuations in proton transfer reactions: General theory

    SciTech Connect

    Kato, Nobuhiko; Ida, Tomonori; Endo, Kazunaka

    2004-04-30

    We present a theory of proton transfer reactions which incorporate the modulation of the proton's potential surface by intermolecular vibrations and the effect of coupling to solvent degree of freedom. The proton tunnels between states corresponding to it being localized in the wells of a double minimum potential. The resulting tunnel splitting depends on the intermolecular separation. The solvent response to the proton's charge is modeled as that of a continuous distribution of harmonic oscillators and the intermolecular stretching mode is also damped because of the interaction with solvent degree of freedom. The transition rate is given by the Fermi Gorlden Rule expression.

  18. Technology maturation project on optimization of sheet metal forming of aluminum for use in transportation systems

    NASA Astrophysics Data System (ADS)

    Johnson, Ken I.; Smith, Mark T.; Lavender, Curt A.; Khalell, Mohammad A.

    1994-10-01

    Using aluminum instead of steel in transportation systems could dramatically reduce the weight of vehicles, an effective way of decreasing energy consumption and emissions. The current cost of sheet metal formed (SMF) aluminum alloys (about $4 per pound) and the relatively long forming times of current materials are serious drawbacks to the widespread use of SMF in industry. The interdependence of materials testing and model development is critical to optimizing SMF since the current process is conducted in a heated, pressurized die where direct measurement of critical SMF parameters is extremely difficult. Numerical models provide a means of tracking the forming process, allowing the applied gas pressure to be adjusted to maintain the optimum SMF behavior throughout the forming process. Thus, models can help produce the optimum SMF component in the least amount of time. The Pacific Northwest Laboratory is integrating SMF model development with research in improved aluminum alloys for SMF. The objectives of this research are: develop and characterize competitively priced aluminum alloys for SMF applications in industry; improve numerical models to accurately predict the optimum forming cycle for reduced forming time and improved quality; and verify alloy performance and model accuracy with forming tests conducted in PNL's Superplastic Forming User Facility. The activities performed in this technology maturation project represent a critical first step in achieving these objectives through cooperative research among industry, PNL, and universities.

  19. Inter-molecular β-sheet structure facilitates lung-targeting siRNA delivery

    PubMed Central

    Zhou, Jihan; Li, Dong; Wen, Hao; Zheng, Shuquan; Su, Cuicui; Yi, Fan; Wang, Jue; Liang, Zicai; Tang, Tao; Zhou, Demin; Zhang, Li-He; Liang, Dehai; Du, Quan

    2016-01-01

    Size-dependent passive targeting based on the characteristics of tissues is a basic mechanism of drug delivery. While the nanometer-sized particles are efficiently captured by the liver and spleen, the micron-sized particles are most likely entrapped within the lung owing to its unique capillary structure and physiological features. To exploit this property in lung-targeting siRNA delivery, we designed and studied a multi-domain peptide named K-β, which was able to form inter-molecular β-sheet structures. Results showed that K-β peptides and siRNAs formed stable complex particles of 60 nm when mixed together. A critical property of such particles was that, after being intravenously injected into mice, they further associated into loose and micron-sized aggregates, and thus effectively entrapped within the capillaries of the lung, leading to a passive accumulation and gene-silencing. The large size aggregates can dissociate or break down by the shear stress generated by blood flow, alleviating the pulmonary embolism. Besides the lung, siRNA enrichment and targeted gene silencing were also observed in the liver. This drug delivery strategy, together with the low toxicity, biodegradability, and programmability of peptide carriers, show great potentials in vivo applications. PMID:26955887

  20. New insights into the dual fluorescence of methyl salicylate: effects of intermolecular hydrogen bonding and solvation.

    PubMed

    Zhou, Panwang; Hoffmann, Mark R; Han, Keli; He, Guozhong

    2015-02-12

    In this paper, we propose a new and complete mechanism for dual fluorescence of methyl salicylate (MS) under different conditions using a combined experimental (i.e., steady-state absorption and emission spectra and time-resolved fluorescence spectra) and theoretical (i.e., time-dependent density function theory) study. First, our theoretical study indicates that the barrier height for excited state intramolecular proton transfer (ESIPT) reaction of ketoB depends on the solvent polarity. In nonpolar solvents, the ESIPT reaction of ketoB is barrierless; the barrier height will increase with increasing solvent polarity. Second, we found that, in alcoholic solvents, intermolecular hydrogen bonding plays a more important role. The ketoB form of MS can form two hydrogen bonds with alcoholic solvents; one will facilitate ESIPT and produce the emission band in the blue region; the other one precludes ESIPT and produces the emission band in the near-UV region. Our proposed new mechanism can well explain previous results as well as our new experimental results. PMID:24678946

  1. Inter-molecular β-sheet structure facilitates lung-targeting siRNA delivery

    NASA Astrophysics Data System (ADS)

    Zhou, Jihan; Li, Dong; Wen, Hao; Zheng, Shuquan; Su, Cuicui; Yi, Fan; Wang, Jue; Liang, Zicai; Tang, Tao; Zhou, Demin; Zhang, Li-He; Liang, Dehai; Du, Quan

    2016-03-01

    Size-dependent passive targeting based on the characteristics of tissues is a basic mechanism of drug delivery. While the nanometer-sized particles are efficiently captured by the liver and spleen, the micron-sized particles are most likely entrapped within the lung owing to its unique capillary structure and physiological features. To exploit this property in lung-targeting siRNA delivery, we designed and studied a multi-domain peptide named K-β, which was able to form inter-molecular β-sheet structures. Results showed that K-β peptides and siRNAs formed stable complex particles of 60 nm when mixed together. A critical property of such particles was that, after being intravenously injected into mice, they further associated into loose and micron-sized aggregates, and thus effectively entrapped within the capillaries of the lung, leading to a passive accumulation and gene-silencing. The large size aggregates can dissociate or break down by the shear stress generated by blood flow, alleviating the pulmonary embolism. Besides the lung, siRNA enrichment and targeted gene silencing were also observed in the liver. This drug delivery strategy, together with the low toxicity, biodegradability, and programmability of peptide carriers, show great potentials in vivo applications.

  2. Inter-molecular β-sheet structure facilitates lung-targeting siRNA delivery.

    PubMed

    Zhou, Jihan; Li, Dong; Wen, Hao; Zheng, Shuquan; Su, Cuicui; Yi, Fan; Wang, Jue; Liang, Zicai; Tang, Tao; Zhou, Demin; Zhang, Li-He; Liang, Dehai; Du, Quan

    2016-01-01

    Size-dependent passive targeting based on the characteristics of tissues is a basic mechanism of drug delivery. While the nanometer-sized particles are efficiently captured by the liver and spleen, the micron-sized particles are most likely entrapped within the lung owing to its unique capillary structure and physiological features. To exploit this property in lung-targeting siRNA delivery, we designed and studied a multi-domain peptide named K-β, which was able to form inter-molecular β-sheet structures. Results showed that K-β peptides and siRNAs formed stable complex particles of 60 nm when mixed together. A critical property of such particles was that, after being intravenously injected into mice, they further associated into loose and micron-sized aggregates, and thus effectively entrapped within the capillaries of the lung, leading to a passive accumulation and gene-silencing. The large size aggregates can dissociate or break down by the shear stress generated by blood flow, alleviating the pulmonary embolism. Besides the lung, siRNA enrichment and targeted gene silencing were also observed in the liver. This drug delivery strategy, together with the low toxicity, biodegradability, and programmability of peptide carriers, show great potentials in vivo applications. PMID:26955887

  3. A quantum chemical insight to intermolecular hydrogen bonding interaction between cytosine and nitrosamine: Structural and energetic investigations

    NASA Astrophysics Data System (ADS)

    Khalili, Behzad

    2016-03-01

    Hydrogen bond interactions which are formed during complex formation between cytosine and nitrosamine have been fully investigated using B3LYP, B3PW91 and MP2 methods in conjunction with various basis sets including 6-311++G (d,p), 6-311++G (2d,2p), 6-311++G (df,pd) and AUG-cc-pVDZ. Three regions around the most stable conformer of cytosine in the gas phase with six possible double H-bonded interactions were considered. Two intermolecular hydrogen bonds of type NC-N-HNA and O-H(N-H)C-ONA were found on the potential energy surface in a cyclic system with 8-member in CN1, CN3, CN5 and 7-member in CN2, CN4, CN6 systems. Results of binding energy calculation at all applied methods reveal that the CN1 structure is the most stable one which is formed by interaction of nitrosamine with cytosine in S1 region. The BSSE-corrected binding energy for six complex system is ranging from -23.8 to -43.6 kJ/mol at MP2/6-311++G (df,pd) level and the stability order is as CN1 > CN2 > CN3 > CN4 > CN5 > CN6 in all studied levels of theories. The NBO results reveal that the charge transfer occurred from cytosine to nitrosamine in CN1, CN3, CN5 and CN6 whereas this matter in the case of CN2 and CN4 was reversed. The relationship between BEs with red shift of H-bond involved bonds vibrational frequencies, charge transfer energies during complex formation and electron densities at H-bond BCPs were discussed. In addition activation energetic properties related to the proton transfer process between cytosine and nitrosamine have been calculated at MP2/6-311++G (df,pd) level. AIM results imply that H-bond interactions are electrostatic with partially covalent characteristic in nature.

  4. On the global structure of normal forms for slow-fast Hamiltonian systems

    NASA Astrophysics Data System (ADS)

    Avendaño Camacho, M.; Vorobiev, Yu.

    2013-04-01

    In the framework of Lie transforms and the global method of averaging, the normal forms of a multidimensional slow-fast Hamiltonian system are studied in the case when the flow of the unperturbed (fast) system is periodic and the induced {S}^1 1-action is not necessarily free and trivial. An intrinsic splitting of the second term in a {S}^1 1-invariant normal form of first order is derived in terms of the Hannay-Berry connection assigned to the periodic flow.

  5. 49 CFR Appendix H to Part 40 - DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Information System (MIS) Data Collection Form H Appendix H to Part 40 Transportation Office of the Secretary..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form The following form is the MIS Data Collection form required for use beginning in 2011...

  6. Coordination compounds of tetravalent silicon, germanium and tin: the structure, chemical bonding and intermolecular interactions in them

    NASA Astrophysics Data System (ADS)

    Korlyukov, A. A.

    2015-04-01

    The review is devoted to analysis and generalization of the results of (i) quantum chemical studies on the structure, chemical bonding and intermolecular interactions in coordination compounds of tetravalent silicon, germanium and tin in crystals, in solutions and in the gas phase and (ii) experimental investigations of the electron density distribution in these systems. The bibliography includes 147 references. In memoriam of Corresponding Member of the Russian Academy of Sciences M Yu Antipin (1951 - 2013), Academician of the Russian Academy of Sciences M G Voronkov (1921 - 2014) and Dr. S P Knyazev, Lomonosov Moscow University of Fine Chemical Technology (1949 - 2012).

  7. Ground test bed design for self-forming network in disaggregated satellites system

    NASA Astrophysics Data System (ADS)

    Liu, Pengfei; Yang, Lei; Chen, Xiaoqian

    2016-02-01

    Disaggregated spacecraft architecture arouses an increasing attention in the realm of distributed space systems in recent years. One of the main technical challenges for disaggregated spacecraft system is self-forming network, in which new satellite nodes are allowed to join in a 'plug-and-play' fashion. To facilitate the protocol design for self-forming network, high-fidelity simulation tools are required. To that end, with the aid of OPNET Modeler's co-simulation mechanism provided by the external system (Esys) module, a ground test bed solution for self-forming network in disaggregated satellites system is presented, and then tested in a self-forming network scenario during the ingress process of a new-added satellite module. Simulation results show that this test bed can support for the evaluation of network performance, as well as mobility modeling which enables reflecting both the effects of orbital dynamic behaviors and in-orbit maneuver or control efforts. Though this test bed is mainly developed for the purpose of further study in disaggregated satellites system, its architecture can also be extended to other satellite network applications.

  8. Ethylene-forming Systems in Etiolated Pea Seedling and Apple Tissue

    PubMed Central

    Lieberman, Morris; Kunishi, Alice T.

    1975-01-01

    Auxin-induced ethylene formation in etiolated pea (Pisum sativum L. var. Alaska) stem segments was inhibited by inhibitors of RNA and protein synthesis. Kinetics of the inhibitions is described for actinomycin D, cordycepin, α-amanitin, and cycloheximide. α-Amanitin was the most potent and fast-acting inhibitor, when added before induction or 6 hours after induction of the ethylene-forming system. The ethylene-forming system of postclimacteric apple (Malus sylvestris L.) tissue, which is already massively induced, was not further stimulated by auxin. Ethylene production in apples was inhibited least by α-amanitin and most by actinomycin D. The relative responses of the ethylene system in apples to RNA inhibitors were different from the ethylene system of pea stems. However, the protein synthesis inhibitor, cycloheximide, appeared to act equally in both tissue systems. The effect of cycloheximide on ethylene production in postclimacteric apple tissue, already producing large quantities of ethylene, suggests a dynamic regulating system for the synthesis and degradation of the ethylene-forming system. PMID:16659213

  9. Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory

    NASA Astrophysics Data System (ADS)

    Witte, Jonathon; Neaton, Jeffrey B.; Head-Gordon, Martin

    2016-05-01

    With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions—noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms—with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen's pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.

  10. [Familial forms of central nervous system cavernomas: from recognition to gene therapy].

    PubMed

    Labauge, P

    2007-06-01

    Ten percent of all cavernomas are familial forms. 300 independent families have been identified in France since 1995. Clinical manifestations are more frequent in familial (50%) than in sporadic forms (5%). The symptoms are the same in both forms: epilepsy, hemorrhages, neurological focal deficits and headache, but hemorrhages are more frequent and the age of revelation is younger, before 30 years. It is also frequent to observe extraneural location, cutaneous and retinal. On MRI, four types of lesional aspects were described and lesions are multiple in all cases with numerous "de novo" cavernomas. The prognostic does not depend on the number of lesions, but on their topography, especially in the brain stem. Familial forms may be considered not only as a neurological but as a systemic disease for which global management with a genetic counseling should be considered. Gene therapy is not today available, but perhaps in the future. PMID:17498752

  11. The chemokine system in diverse forms of macrophage activation and polarization.

    PubMed

    Mantovani, Alberto; Sica, Antonio; Sozzani, Silvano; Allavena, Paola; Vecchi, Annunciata; Locati, Massimo

    2004-12-01

    Plasticity and functional polarization are hallmarks of the mononuclear phagocyte system. Here we review emerging key properties of different forms of macrophage activation and polarization (M1, M2a, M2b, M2c), which represent extremes of a continuum. In particular, recent evidence suggests that differential modulation of the chemokine system integrates polarized macrophages in pathways of resistance to, or promotion of, microbial pathogens and tumors, or immunoregulation, tissue repair and remodeling. PMID:15530839

  12. Normal and quasinormal forms for systems of difference and differential-difference equations

    NASA Astrophysics Data System (ADS)

    Kashchenko, Ilya; Kaschenko, Sergey

    2016-09-01

    The local dynamics of systems of difference and singularly perturbed differential-difference equations is studied in the neighborhood of a zero equilibrium state. Critical cases in the problem of stability of its state of equilibrium have infinite dimension. Special nonlinear evolution equations, which act as normal forms, are set up. It is shown that their dynamics defines the behavior of solutions to the initial system.

  13. Non-covalent intermolecular carbon-carbon interactions in polyynes.

    PubMed

    Remya, Karunakaran; Suresh, Cherumuttathu H

    2015-10-28

    Polyynes, the smaller analogues of one dimensional infinite chain carbon allotrope carbyne, have been studied for the type and strength of the intermolecular interactions in their dimer and tetramer complexes using density functional theory. The nature of end group functionalities and the chain length of the polyynes are varied to assess their role in modulating the non-covalent interaction energy. As seen in molecular electrostatic potential analysis, all the polyyne complexes showed a multitude of non-covalent CC interactions, resulting from complementary electrostatic interactions between relatively electron rich formal triple bond region of one monomer and the electron deficient formal single bond region of the other monomer. This type of paired (C[triple bond, length as m-dash]C)(C-C) bonding interaction, also characterized using quantum theory of atoms-in-molecules, increases with increase in the monomer chain length leading to substantial increase in interaction energy (Eint); -1.07 kcal mol(-1) for the acetylene dimer to -45.83 kcal mol(-1) for the 50yne dimer. The magnitude of Eint increases with substitutions at end positions of the polyyne and this effect persists even up to 50 triple bonds, the largest chain length analyzed in this paper. The role of CC interactions in stabilizing the polyyne dimers is also shown by sliding one monomer in a dimer over the other, which resulted in multiple minima with a reduced number of CC interactions and lower values of Eint. Furthermore, strong cooperativity in the CC bond strength in tetramers is observed as the interaction energy per monomer (Em) of the polyyne is 2.5-2.8 times higher compared to that of the dimer in a test set of four tetramers. The huge gain in energy observed in large polyyene dimers and tetramers predicts the formation of polyyne bundles which may find use in the design of new functional molecular materials. PMID:26412713

  14. Correlation techniques to determine model form in robust nonlinear system realization/identification

    NASA Technical Reports Server (NTRS)

    Stry, Greselda I.; Mook, D. Joseph

    1991-01-01

    The fundamental challenge in identification of nonlinear dynamic systems is determining the appropriate form of the model. A robust technique is presented which essentially eliminates this problem for many applications. The technique is based on the Minimum Model Error (MME) optimal estimation approach. A detailed literature review is included in which fundamental differences between the current approach and previous work is described. The most significant feature is the ability to identify nonlinear dynamic systems without prior assumption regarding the form of the nonlinearities, in contrast to existing nonlinear identification approaches which usually require detailed assumptions of the nonlinearities. Model form is determined via statistical correlation of the MME optimal state estimates with the MME optimal model error estimates. The example illustrations indicate that the method is robust with respect to prior ignorance of the model, and with respect to measurement noise, measurement frequency, and measurement record length.

  15. The intermolecular vibrational dynamics of substituted benzene and cyclohexane liquids, studied by femtosecond OHD-RIKES

    SciTech Connect

    Castner, E.W. Jr.; Chang, Yong Joon

    1995-06-01

    By using the femtosecond optical-heterodyne detected, Raman-induced Kerr effect spectroscopy (OHD-RIKES), we have studied the intermolecular dynamics of toluene, benzyl alcohol, benzonitrile, cyclohexane, and methylcyclohexane in both the time and frequency domains.

  16. Determining the Intermolecular Potential Energy in a Gas: A Physical Chemistry Experiment

    ERIC Educational Resources Information Center

    Olbregts, J.; Walgraeve, J. P.

    1976-01-01

    Describes an experiment in which gas viscosity coefficients over a large temperature range are used to determine the parameters of the intermolecular potential energy and other properties such as virial coefficients. (MLH)

  17. The origins of intra- and inter-molecular vibrational couplings: A case study of H2O-Ar on full and reduced-dimensional potential energy surface

    NASA Astrophysics Data System (ADS)

    Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long; Li, Hui

    2016-01-01

    The origin and strength of intra- and inter-molecular vibrational coupling is difficult to probe by direct experimental observations. However, explicitly including or not including some specific intramolecular vibrational modes to study intermolecular interaction provides a precise theoretical way to examine the effects of anharmonic coupling between modes. In this work, a full-dimension intra- and inter-molecular ab initio potential energy surface (PES) for H2O-Ar, which explicitly incorporates interdependence on the intramolecular (Q1, Q2, Q3) normal-mode coordinates of the H2O monomer, has been calculated. In addition, four analytic vibrational-quantum-state-specific PESs are obtained by least-squares fitting vibrationally averaged interaction energies for the (v1, v2, v3) = (0, 0, 0), (0, 0, 1), (1, 0, 0), (0, 1, 0) states of H2O to the three-dimensional Morse/long-range potential function. Each vibrationally averaged PES fitted to 442 points has root-mean-square (rms) deviation smaller than 0.15 cm-1, and required only 58 parameters. With the 3D PESs of H2O-Ar dimer system, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels. This showed that the resulting vibrationally averaged PESs provide good representations of the experimental infrared data, with rms discrepancies smaller than 0.02 cm-1 for all three rotational branches of the asymmetric stretch fundamental transitions. The infrared band origin shifts associated with three fundamental bands of H2O in H2O-Ar complex are predicted for the first time and are found to be in good agreement with the (extrapolated) experimental values. Upon introduction of additional intramolecular degrees of freedom into the intermolecular potential energy surface, there is clear spectroscopic evidence of intra- and intermolecular vibrational couplings.

  18. Waste vitrification: prediction of acceptable compositions in a lime-soda-silica glass-forming system

    SciTech Connect

    Gilliam, T.M.; Jantzen, C.M.

    1996-10-01

    A model is presented based upon calculated bridging oxygens which allows the prediction of the region of acceptable glass compositions for a lime-soda-silica glass-forming system containing mixed waste. The model can be used to guide glass formulation studies (e.g., treatability studies) or assess the applicability of vitrification to candidate waste streams.

  19. Asymmetric crystallization during cooling and heating in model glass-forming systems.

    PubMed

    Wang, Minglei; Zhang, Kai; Li, Zhusong; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D; O'Hern, Corey S

    2015-03-01

    We perform molecular dynamics (MD) simulations of the crystallization process in binary Lennard-Jones systems during heating and cooling to investigate atomic-scale crystallization kinetics in glass-forming materials. For the cooling protocol, we prepared equilibrated liquids above the liquidus temperature Tl and cooled each sample to zero temperature at rate Rc. For the heating protocol, we first cooled equilibrated liquids to zero temperature at rate Rp and then heated the samples to temperature T>Tl at rate Rh. We measured the critical heating and cooling rates Rh* and Rc*, below which the systems begin to form a substantial fraction of crystalline clusters during the heating and cooling protocols. We show that Rh*>Rc* and that the asymmetry ratio Rh*/Rc* includes an intrinsic contribution that increases with the glass-forming ability (GFA) of the system and a preparation-rate dependent contribution that increases strongly as Rp→Rc* from above. We also show that the predictions from classical nucleation theory (CNT) can qualitatively describe the dependence of the asymmetry ratio on the GFA and preparation rate Rp from the MD simulations and results for the asymmetry ratio measured in Zr- and Au-based bulk metallic glasses (BMG). This work emphasizes the need for and benefits of an improved understanding of crystallization processes in BMGs and other glass-forming systems. PMID:25871112

  20. Modeling Multiple Human-Automation Distributed Systems using Network-form Games

    NASA Technical Reports Server (NTRS)

    Brat, Guillaume

    2012-01-01

    The paper describes at a high-level the network-form game framework (based on Bayes net and game theory), which can be used to model and analyze safety issues in large, distributed, mixed human-automation systems such as NextGen.

  1. Forms of Mediation: The Case of Interpreter-Mediated Interactions in Medical Systems

    ERIC Educational Resources Information Center

    Baraldi, Claudio

    2009-01-01

    This paper analyses the forms of mediation in interlinguistic interactions performed in Italian healthcare services and in contexts of migration. The literature encourages dialogic transformative mediation, empowering participants' voices and changing cultural presuppositions in social systems. It may be doubtful, however, whether mediation can…

  2. Asymmetric crystallization during cooling and heating in model glass-forming systems

    NASA Astrophysics Data System (ADS)

    Wang, Minglei; Zhang, Kai; Li, Zhusong; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O'Hern, Corey S.

    2015-03-01

    We perform molecular dynamics (MD) simulations of the crystallization process in binary Lennard-Jones systems during heating and cooling to investigate atomic-scale crystallization kinetics in glass-forming materials. For the cooling protocol, we prepared equilibrated liquids above the liquidus temperature Tl and cooled each sample to zero temperature at rate Rc. For the heating protocol, we first cooled equilibrated liquids to zero temperature at rate Rp and then heated the samples to temperature T >Tl at rate Rh. We measured the critical heating and cooling rates Rh* and Rc*, below which the systems begin to form a substantial fraction of crystalline clusters during the heating and cooling protocols. We show that Rh*>Rc* and that the asymmetry ratio Rh*/Rc* includes an intrinsic contribution that increases with the glass-forming ability (GFA) of the system and a preparation-rate dependent contribution that increases strongly as Rp→Rc* from above. We also show that the predictions from classical nucleation theory (CNT) can qualitatively describe the dependence of the asymmetry ratio on the GFA and preparation rate Rp from the MD simulations and results for the asymmetry ratio measured in Zr- and Au-based bulk metallic glasses (BMG). This work emphasizes the need for and benefits of an improved understanding of crystallization processes in BMGs and other glass-forming systems.

  3. Normal form and Nekhoroshev stability for nearly integrable hamiltonian systems with unconditionally slow aperiodic time dependence

    NASA Astrophysics Data System (ADS)

    Fortunati, Alessandro; Wiggins, Stephen

    2014-05-01

    The aim of this paper is to extend the result of Giorgilli and Zehnder for aperiodic time dependent systems to a case of nearly integrable convex analytic Hamiltonians. The existence of a normal form and then a stability result are shown in the case of a slow aperiodic time dependence that, under some smallness conditions, is independent of the size of the perturbation.

  4. O-ring tube fittings form leakproof seal in hydraulic systems

    NASA Technical Reports Server (NTRS)

    1966-01-01

    Leakproof fittings for hydraulic systems are designed to be welded to the ends of the tubing to be joined and mated to form a seal with one o-ring at the joint. Since the fittings are coupled at only one joint, they tend to be more reliable than standard fittings coupled at two joints.

  5. A program to form a multidisciplinary data base and analysis for dynamic systems

    NASA Technical Reports Server (NTRS)

    Taylor, L. W.; Suit, W. T.; Mayo, M. H.

    1984-01-01

    Diverse sets of experimental data and analysis programs have been assembled for the purpose of facilitating research in systems identification, parameter estimation and state estimation techniques. The data base analysis programs are organized to make it easy to compare alternative approaches. Additional data and alternative forms of analysis will be included as they become available.

  6. Using Form and Function Analogy Object Boxes to Teach Human Body Systems

    ERIC Educational Resources Information Center

    Rule, Audrey C.; Furletti, Charles

    2004-01-01

    This study compares the use of form and function analogy object boxes to more traditional lecture and worksheet instruction during a 10th-grade unit on human body systems. The study was conducted with two classes (N = 32) of mixed ability students at a high-needs rural high school in central New York State. The study used a pretest/posttest…

  7. The Raman and vibronic activity of intermolecular vibrations in aromatic-containing complexes and clusters

    SciTech Connect

    Maxton, P.M.; Schaeffer, M.W.; Ohline, S.M.; Kim, W.; Venturo, V.A.; Felker, P.M. )

    1994-11-15

    Theoretical and experimental results pertaining to the excitation of intermolecular vibrations in the Raman and vibronic spectra of aromatic-containing, weakly bound complexes and clusters are reported. The theoretical analysis of intermolecular Raman activity is based on the assumption that the polarizability tensor of a weakly bound species is given by the sum of the polarizability tensors of its constituent monomers. The analysis shows that the van der Waals bending fundamentals in aromatic--rare gas complexes may be expected to be strongly Raman active. More generally, it predicts strong Raman activity for intermolecular vibrations that involve the libration or internal rotation of monomer moieties having appreciable permanent polarizability anisotropies. The vibronic activity of intermolecular vibrations in aromatic-rare gas complexes is analyzed under the assumption that every vibronic band gains its strength from an aromatic-localized transition. It is found that intermolecular vibrational excitations can accompany aromatic-localized vibronic excitations by the usual Franck--Condon mechanism or by a mechanism dependent on the librational amplitude of the aromatic moiety during the course of the pertinent intermolecular vibration. The latter mechanism can impart appreciable intensity to bands that are forbidden by rigid-molecule symmetry selection rules. The applicability of such rules is therefore called into question. Finally, experimental spectra of intermolecular transitions, obtained by mass-selective, ionization-detected stimulated Raman spectroscopies, are reported for benzene--X (X=Ar, --Ar[sub 2], N[sub 2], HCl, CO[sub 2], and --fluorene), fluorobenzene--Ar and --Kr, aniline--Ar, and fluorene--Ar and --Ar[sub 2]. The results support the conclusions of the theoretical analyses and provide further evidence for the value of Raman methods in characterizing intermolecular vibrational level structures.

  8. A supramolecular photoswitch constructed by intermolecular hydrogen bond between BTEPy and TTF COOH

    NASA Astrophysics Data System (ADS)

    Feng, Yanli; Zhang, Qiong; Tan, Wenjuan; Zhang, Deqing; Tu, Yaoquan; Ågren, Hans; Tian, He

    2008-04-01

    A novel supramolecular photoswitch containing bisthienylethene-pyridine (BTEPy) and carboxyl attached tetrathiafluvalene (TTF-COOH) was constructed via intermolecular hydrogen bond. FT-IR spectra, XPS characterizations, 1H NMR and theoretical calculation were carried out to verify the formation of the intermolecular hydrogen bond. The supramolecular self-assemblies BTEPy · 2TTF show good photochromic properties. A molecular switch with UV/vis light as inputs and electrochemical signals as outputs was obtained.

  9. Embryonic Origins of a Motor System:Motor Dendrites Form a Myotopic Mapin Drosophila

    PubMed Central

    2003-01-01

    The organisational principles of locomotor networks are less well understood than those of many sensory systems, where in-growing axon terminals form a central map of peripheral characteristics. Using the neuromuscular system of the Drosophila embryo as a model and retrograde tracing and genetic methods, we have uncovered principles underlying the organisation of the motor system. We find that dendritic arbors of motor neurons, rather than their cell bodies, are partitioned into domains to form a myotopic map, which represents centrally the distribution of body wall muscles peripherally. While muscles are segmental, the myotopic map is parasegmental in organisation. It forms by an active process of dendritic growth independent of the presence of target muscles, proper differentiation of glial cells, or (in its initial partitioning) competitive interactions between adjacent dendritic domains. The arrangement of motor neuron dendrites into a myotopic map represents a first layer of organisation in the motor system. This is likely to be mirrored, at least in part, by endings of higher-order neurons from central pattern-generating circuits, which converge onto the motor neuron dendrites. These findings will greatly simplify the task of understanding how a locomotor system is assembled. Our results suggest that the cues that organise the myotopic map may be laid down early in development as the embryo subdivides into parasegmental units. PMID:14624243

  10. Closed-Form Equation of Data Dependent Jitter in First Order Low Pass System

    PubMed Central

    2014-01-01

    This paper presents a closed-form equation of data dependent jitter (DDJ) in first order low pass systems. The DDJ relates to the system bandwidth, the bit rate, the input rise/fall time, and the number of maximum consecutive identical bits of the data pattern. To confirm the derived equation, simulations have been done with a first order RC low pass circuit for various system bandwidths, bit rates, input rise/fall times, and data patterns. The simulation results agree well with the calculated DDJ values by the derived equation. PMID:25386614

  11. Interactions between motion and form processing in the human visual system

    PubMed Central

    Mather, George; Pavan, Andrea; Bellacosa Marotti, Rosilari; Campana, Gianluca; Casco, Clara

    2013-01-01

    The predominant view of motion and form processing in the human visual system assumes that these two attributes are handled by separate and independent modules. Motion processing involves filtering by direction-selective sensors, followed by integration to solve the aperture problem. Form processing involves filtering by orientation-selective and size-selective receptive fields, followed by integration to encode object shape. It has long been known that motion signals can influence form processing in the well-known Gestalt principle of common fate; texture elements which share a common motion property are grouped into a single contour or texture region. However, recent research in psychophysics and neuroscience indicates that the influence of form signals on motion processing is more extensive than previously thought. First, the salience and apparent direction of moving lines depends on how the local orientation and direction of motion combine to match the receptive field properties of motion-selective neurons. Second, orientation signals generated by “motion-streaks” influence motion processing; motion sensitivity, apparent direction and adaptation are affected by simultaneously present orientation signals. Third, form signals generated by human body shape influence biological motion processing, as revealed by studies using point-light motion stimuli. Thus, form-motion integration seems to occur at several different levels of cortical processing, from V1 to STS. PMID:23730286

  12. GT1_vgeers_1: Tracing Remnant Gas in Planet Forming Debris Disk Systems

    NASA Astrophysics Data System (ADS)

    Geers, V.

    2010-03-01

    Recent studies of gas emission lines with Spitzer and sub-millimeter telescopes have shown that 10-100 Myr old stars with debris disks have too little gas left to form Jupiter like gas giant planets. Whether enough gas remains in these systems to form ice giant planets is still unanswered. The [OI] emission line at 63 micron is one of the most sensitive tracers of gas mass in the ice-giant region of 10-50 AU in disks, and Herschel PACS is therefore uniquely suited to trace the remnant gas in planet-forming disks. We propose to obtain PACS line spectroscopy of [OI] (63 micron) for two nearby young stars, HR 8799 and HD 15115, which are two systems with detected giant planets or signs of planet formation, while still harbouring prominent debris disks that could be in the process of forming ice giants such as Neptune and Uranus. The proposed observations will probe down to gas masses of 0.01 Earth masses, and allow us to constrain prospects for ice giant formation, measure gas-to-dust ratios in evolved disks to compare with planet formation / disk evolution models, and put constraints on whether the dust dynamics in these systems is driven by the remnant gas or by the radiation. Note: this proposal is submitted under the Swiss part of the HIFI Guaranteed Time program; HIFI PI: Frank Helmich, HIFI Swiss Lead CoI: Arnold Benz.

  13. Influence of intermolecular amide hydrogen bonding on the geometry, atomic charges, and spectral modes of acetanilide: An ab initio study

    NASA Astrophysics Data System (ADS)

    Binoy, J.; Prathima, N. B.; Murali Krishna, C.; Santhosh, C.; Hubert Joe, I.; Jayakumar, V. S.

    2006-08-01

    Acetanilide, a compound of pharmaceutical importance possessing pain-relieving properties due to its blocking the pulse dissipating along the nerve fiber, is subjected to vibrational spectral investigation using NIR FT Raman, FT-IR, and SERS. The geometry, Mulliken charges, and vibrational spectrum of acetanilide have been computed using the Hartree-Fock theory and density functional theory employing the 6-31G (d) basis set. To investigate the influence of intermolecular amide hydrogen bonding, the geometry, charge distribution, and vibrational spectrum of the acetanilide dimer have been computed at the HF/6-31G (d) level. The computed geometries reveal that the acetanilide molecule is planar, while twisting of the secondary amide group with respect to the phenyl ring is found upon hydrogen bonding. The trans isomerism and “amido” form of the secondary amide, hyperconjugation of the C=O group with the adjacent C-C bond, and donor-acceptor interaction have been investigated using computed geometry. The carbonyl stretching band position is found to be influenced by the tendency of the phenyl ring to withdraw nitrogen lone pair, intermolecular hydrogen bonding, conjugation, and hyperconjugation. A decrease in the NH and C=O bond orders and increase in the C-N bond orders due to donor-acceptor interaction can be observed in the vibrational spectra. The SERS spectral analysis reveals that the flat orientation of the molecule on the adsorption plane is preferred.

  14. Investigation on Intermolecular Interaction in Supersaturation State of Cadmium Sulphate Mixed Zinc tris-THIOUREA Sulphate Solutions

    NASA Astrophysics Data System (ADS)

    Muley, G. G.; Naik, A. B.; Gambhire, A. B.

    2014-06-01

    Zinc tris-thiourea sulphate (ZTS) is a well known nonlinear optical (NLO) crystal widely used for various NLO applications. The NLO, physical and chemical properties can be modified by adding impurities and/or modifying crystal growth conditions. The impurities present in the growth solution and growth conditions can affect the crystal growth parameters at great extent. Thus, the study on the nature of intermolecular interaction with the dopant in the solution during crystal growth process becomes important. In the present investigation, the ultrasonic velocity was measured in the aqueous solutions of pure and cadmium sulphate mixed ZTS in the supersaturation state at 313.15 K. The thermodynamic parameters such as adiabatic compressibility, inter molecular free length, acoustic impedance and relative associations have been calculated from the ultrasonic data and densities of water and solutions at 313.15 K, and the nature of intermolecular interaction has been discussed. FT-IR spectra of all mixtures in the solid form at room temperature were recorded and the shifts in the absorption peaks corresponding to the functional groups of ZTS have been reported.

  15. Spectral Moments of Collision-Induced Absorption of CO2 Pairs: The Role of the Intermolecular Potential

    NASA Technical Reports Server (NTRS)

    Gruszka, Marcin; Borysow, Aleksandra

    1994-01-01

    In this paper we examine the role of the anisotropy of the intermolecular potential in the rototranslational collision-induced absorption of the CO2 pairs. Using newly developed formulas that include the effects of anisotropy of the potential to all orders, we calculate the two lowest spectral moments gamma(prime), and alpha(prime), for four different classes of C02 pair potentials and compare the results with the experimental values. We assumed only multipolar induction in the process of forming the induced dipole, with the second-order contributions included. Using a site-site LJ and a site-site semi-ab initio intermolecular potentials we were able to reproduce the experimental values of gamma(prime), and alpha(prime) moments over entire temperature range from 230 to 330 K. Also, the role of an electrostatic interaction between two C02 molecules and its impact on the spectral moments is thoroughly investigated. An isotropic core with a point quadrupole centered at each molecule is shown to be an inadequate representation of the C02-CO2 potential. Additionally, we show the results obtained with the first- and second-order perturbation theory to be more than twice too small.

  16. Faint Lyα Emitters, Star-forming Galaxies, and Damped Lyα Systems

    NASA Astrophysics Data System (ADS)

    Rauch, M.; Haehnelt, M.; Bunker, A.; Becker, G.; Marleau, F.; Graham, J.; Cristiani, S.; Jarvis, M.; Lacey, C.; Morris, S.; Peroux, C.; Roettgering, H.; Theuns, T.

    2008-10-01

    We have discovered a population of faint single line emitters, likely to be identified with faint z˜ 3 Lyα emitters and with the host galaxies of damped Lyman alpha systems. The objects appear to constitute the bulk of the star-forming galaxies detected so far from the ground, and are likely to provide the gaseous reservoir from which present-day Milky way type galaxies have formed. Unlike color-selected (yman break galaxies, these objects appear to have low star-formation rates, relatively strong Lyalpha emission, and low masses, metallicities, and dust content (s.a. arXiv:0711.1354).

  17. Chemistry as mathematical system - Involutory forms of molecules and their genetic codes

    NASA Astrophysics Data System (ADS)

    Schulz, Lech P.

    2012-12-01

    Molecules are considered herein as mathematical forms expressed by groups grounded by certain involutory functions characterized axiomatically. For the first time, the basic involutory properties have been determined in the way covering both non-coordination and coordination chemical compounds approached from one view point. Thence, a general notion of a molecule has been derived equivalently to another system of axioms determining molecular forms of chemistry as the result of saturation-unsaturation phenomena. Groups generated by underlying chemical involutions turn out to be different from point or crystallographic ones explored in chemistry. Genetic codes (Dyck's presentations) of molecular involutory groups have been elicited for a few compounds.

  18. Predicted occupancies in gas hydrates on Titan and Mars: sensitivity on treatment of intermolecular interactions.

    NASA Astrophysics Data System (ADS)

    Thomas, Caroline; Picaud, Sylvain; Ballenegger, Vincent; Mousis, Olivier

    2010-05-01

    We investigate here the sensitivity of gas hydrate occupancies predicted on the basis of van der Waals-Platteeuw theory, as a function of the treatment of the intermolecular guest-water interaction potential. First, we determine the minimum number of water molecules that have to be taken into account in the calculations of this interaction potential. We show that analytical correction terms that account for the interactions with the water molecules beyond the cutoff distance (typically chosen to take into account at least 4 water layers around the guest molecule) must be introduced to improve significantly the convergence rate, and hence the efficiency of the computation of the Langmuir constants. Then we use different recent guest-water interaction potential models to calculate the cage occupancies in pure methane or carbon dioxide clathrates. We show that the corresponding predicted cage occupancies can vary significantly depending on the model, although all the results are within the uncertainties of the available experimental data. That sensitivity becomes especially strong in the case of multiple guest clathrates, and, for instance, the results obtained for guest clathrate hydrates potentially formed on the surface of Mars can vary by more than two orders of magnitude depending on the model. These results underline the strong need for experimental data on pure and multiple guest clathrate hydrates, in particular in the temperature and pressure range that are relevant in extreme environment conditions, to discriminate among the theoretical models.

  19. Sensitivity of predicted gas hydrate occupancies on treatment of intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Thomas, Caroline; Picaud, Sylvain; Ballenegger, Vincent; Mousis, Olivier

    2010-03-01

    The sensitivity of gas hydrate occupancies predicted on the basis of van der Waals-Platteeuw theory is investigated, as a function of the intermolecular guest-water interaction potential model, and of the number of water molecules taken into account. Simple analytical correction terms that account for the interactions with the water molecules beyond the cutoff distance are introduced, and shown to improve significantly the convergence rate, and hence the efficiency of the computation of the Langmuir constants. The predicted cage occupancies in pure methane and pure carbon dioxide clathrates, calculated using different recent guest-water pair potentials models derived from ab initio calculations, can vary significantly depending on the model. That sensitivity becomes especially strong in the case of multiple guest clathrates. It is shown that the abundances of coenclathrated molecules in multiple guest clathrate hydrates potentially formed on the surface of Mars can vary by more than two orders of magnitude depending on the model. These results underline the strong need for experimental data on pure and multiple guest clathrate hydrates, in particular in the temperature and pressure range that are relevant in extreme environment conditions, to discriminate among the theoretical models.

  20. Intermolecular interactions and conformation of antibody dimers present in IgG1 biopharmaceuticals.

    PubMed

    Iwura, Takafumi; Fukuda, Jun; Yamazaki, Katsuyoshi; Kanamaru, Shuji; Arisaka, Fumio

    2014-01-01

    Intermolecular interactions and conformation in dimer species of Palivizumab, a monoclonal antibody (IgG1), were investigated to elucidate the physical and chemical properties of the dimerized antibody. Palivizumab solution contains ∼1% dimer and 99% monomer. The dimer species was isolated by size-exclusion chromatography and analysed by a number of methods including analytical ultracentrifugation-sedimantetion velocity (AUC-SV). AUC-SV in the presence of sodium dodecyl sulphate indicated that approximately half of the dimer fraction was non-covalently associated, whereas the other half was dimerized by covalent bond. Disulphide bond and dityrosine formation were likely to be involved in the covalent dimerization. Limited proteolysis of the isolated dimer by Lys-C and mass spectrometry for the resultant products indicated that the dimer species were formed by Fab-Fc or Fab-Fab interactions, whereas Fc-Fc interactions were not found. It is thus likely that the dimerization occurs mainly via the Fab region. With regard to the conformation of the dimer species, the secondary and tertiary structures were shown to be almost identical to those of the monomer. Furthermore, the thermal stability turned out also to be very similar between the dimer and monomer. PMID:24155259

  1. Architecture based on the integration of intermolecular G-quadruplex structure with sticky-end pairing and colorimetric detection of DNA hybridization

    NASA Astrophysics Data System (ADS)

    Li, Hongbo; Wu, Zai-Sheng; Shen, Zhifa; Shen, Guoli; Yu, Ruqin

    2014-01-01

    An interesting discovery is reported in that G-rich hairpin-based recognition probes can self-assemble into a nano-architecture based on the integration of an intermolecular G-quadruplex structure with the sticky-end pairing effect in the presence of target DNAs. Moreover, GNPs modified with partly complementary DNAs can intensively aggregate by hybridization-based intercalation between intermolecular G-quadruplexes, indicating an inspiring assembly mechanism and a powerful colorimetric DNA detection. The proposed intermolecular G-quadruplex-integrated sticky-end pairing assembly (called GISA)-based colorimetric system allows a specific and quantitative assay of p53 DNA with a linear range of more than two orders of magnitude and a detection limit of 0.2 nM, suggesting a considerably improved analytical performance. And more to the point, the discrimination of single-base mismatched target DNAs can be easily conducted via visual observation. The successful development of the present colorimetric system, especially the GISA-based aggregation mechanism of GNPs is different from traditional approaches, and offers a critical insight into the dependence of the GNP aggregation on the structural properties of oligonucleotides, opening a good way to design colorimetric sensing probes and DNA nanostructure. An interesting discovery is reported in that G-rich hairpin-based recognition probes can self-assemble into a nano-architecture based on the integration of an intermolecular G-quadruplex structure with the sticky-end pairing effect in the presence of target DNAs. Moreover, GNPs modified with partly complementary DNAs can intensively aggregate by hybridization-based intercalation between intermolecular G-quadruplexes, indicating an inspiring assembly mechanism and a powerful colorimetric DNA detection. The proposed intermolecular G-quadruplex-integrated sticky-end pairing assembly (called GISA)-based colorimetric system allows a specific and quantitative assay of p53 DNA

  2. Finite-time stabilization of uncertain nonholonomic systems in feedforward-like form by output feedback.

    PubMed

    Gao, Fangzheng; Wu, Yuqiang; Zhang, Zhongcai

    2015-11-01

    This paper investigates the problem of finite-time stabilization by output feedback for a class of nonholonomic systems in chained form with uncertainties. Comparing with the existing relevant literature, a distinguishing feature of the systems under investigation is that the x-subsystem is a feedforward-like rather than feedback-like system. This renders the existing control methods inapplicable to the control problems of the systems. A constructive design procedure for output feedback control is given. The designed controller renders that the states of closed-loop system are regulated to zero in a finite time. Two simulation examples are provided to illustrate the effectiveness of the proposed approach. PMID:26434417

  3. Building complexity in O2-binding copper complexes. Site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand.

    PubMed

    Serrano-Plana, Joan; Costas, Miquel; Company, Anna

    2014-12-15

    A novel unsymmetric dinucleating ligand (L(N3N4)) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. L(N3N4) is able to discriminate between Cu(I) and a complementary metal (M' = Cu(I), Zn(II), Fe(II), Cu(II), or Ga(III)) so that pure heterodimetallic complexes with a general formula [Cu(I)M'(L(N3N4))](n+) are synthesized. Reaction of the dicopper(I) complex [Cu(I)2(L(N3N4))](2+) with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and (T)P) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM'(L(N3N4))](n+) with O2 at low temperature is used as a tool to determine the final position of the Cu(I) center in the system because only one of the two Cu2O2 species is formed. PMID:25424176

  4. Control of the intermolecular coupling of dibromotetracene on Cu(110) by the sequential activation of C-Br and C-H bonds.

    PubMed

    Ferrighi, Lara; Píš, Igor; Nguyen, Thanh Hai; Cattelan, Mattia; Nappini, Silvia; Basagni, Andrea; Parravicini, Matteo; Papagni, Antonio; Sedona, Francesco; Magnano, Elena; Bondino, Federica; Di Valentin, Cristiana; Agnoli, Stefano

    2015-04-01

    Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions. PMID:25711882

  5. Fast acquisition of high-resolution NMR spectra in inhomogeneous fields via intermolecular double-quantum coherences

    PubMed Central

    Chen, Zhong; Cai, Shuhui; Chen, Zhiwei; Zhong, Jianhui

    2009-01-01

    A pulse sequence, IDEAL-II, is proposed based on the concept of intermolecular dipolar-interaction enhanced all lines [Z. Chen et al., J. Am. Chem. Soc. 126, 446 (2004)] for obtaining one-dimensional (1D) high-resolution liquid NMR spectra in inhomogeneous fields via two-dimensional acquisitions. With the new acquisition scheme, the range of magnetic field inhomogeneity rather than chemical shift is sampled in the indirect dimension. This enables a great reduction in acquisition time and amount of data, much improved over the original IDEAL implementation. It is applicable to both isolated and J-coupled spin systems in liquid. For the latter, apparent J coupling constants are magnified threefold in spectra obtained with this sequence. This allows a more accurate measurement of J coupling constants in the cases of small J coupling constants or large inhomogeneous fields. Analytical expression was derived based on intermolecular multiple-quantum coherence treatments. Solution samples that were purposely deshimmed and biological samples with intrinsic field inhomogeneities were tested. Experimental results demonstrate that this sequence retains useful structural information including chemical shifts, relative peak areas, and multiplet patterns of J coupling even when the field inhomogeneity is severe enough to almost erase all spectroscopic information with conventional 1D single-quantum coherence techniques. This sequence is more applicable to weakly coupled and uncoupled spin systems, potentially useful for studying metabolites in in vivo NMR spectroscopy and for characterizing technologically important new materials in combinatorial chemistry. PMID:19256612

  6. Control of nonlinear systems represented in quasilinear form. Ph.D. Thesis, 1994 Final Report

    NASA Technical Reports Server (NTRS)

    Coetsee, Josef A.

    1993-01-01

    Methods to synthesize controllers for nonlinear systems are developed by exploiting the fact that under mild differentiability conditions, systems of the form: x-dot = f(x) + G(x)u can be represented in quasilinear form, viz: x-dot = A(x)x + B(x)u. Two classes of control methods are investigated. The first is zero-look-ahead control, where the control input depends only on the current values of A(x) and B(x). For this case the control input is computed by continuously solving a matrix Riccati equation as the system progresses along a trajectory. The second is controllers with look-ahead, where the control input depends on the future behavior of A(x) and B(x). These controllers use the similarity between quasilinear systems and linear time varying systems to find approximate solutions to optimal control type problems. The methods that are developed are not guaranteed to be globally stable. However in simulation studies they were found to be useful alternatives for synthesizing control laws for a general class of nonlinear systems.

  7. Epicutaneous breast forms. A new system promises to improve body image after mastectomy.

    PubMed

    Münstedt, K; Schüttler, B; Milch, W; Sachsse, S; Zygmunt, M; Kullmer, U; Vahrson, H

    1998-05-01

    Mastectomies will remain a treatment alternative for breast cancer in spite of efforts to perform more breast-conserving treatment. Restoration of body symmetry may then be an important issue, which can be achieved by surgical breast reconstruction or with an epicutaneous breast prosthesis. A new improved system has recently been developed, which is self-adhesive to the thorax wall. In this study we investigated the advantages and disadvantages of the new system. The body image of 55 patients after unilateral mastectomy was assessed before they entered the study and after approximately 6 months of experience with the system. The "Frankfurter Körperkonzeptskalen" plus additional questions concerning problems after mastectomy and the handling of the new breast form were used for the assessment. About 50% of the patients had problems with the adhesiveness of the breast form, which remains a problem to be solved. Patients who suffered badly from mastectomy, have a smooth and plane mastectomy scar, and who were not suffering from hot flushes, which can impair the adhesiveness of the prosthesis, were more likely to profit from the new self-supporting breast forms. Significant differences were observed in the scales "self-acceptance of the body", acceptance of the body by others" for the subsets of patients mentioned above. The differences were less pronounced in patients who were already familiar with another type of epicutaneous breast form, which is attached to an adhesive plate on the thorax wall by nylon touch and close fasteners. Most (90.7%) of the patients would recommend this new type of breast prosthesis for other patients with mastectomy. The concept of self-supporting breast forms is an improvement with respect to social and psychological rehabilitation. According to the manufacturer, the problem with adhesion has meanwhile been solved. PMID:9629886

  8. Modeling intermolecular interactions of physisorbed organic molecules using pair potential calculations

    SciTech Connect

    Kroeger, Ingo; Stadtmueller, Benjamin; Wagner, Christian; Weiss, Christian; Temirov, Ruslan; Tautz, F. Stefan; Kumpf, Christian

    2011-12-21

    The understanding and control of epitaxial growth of organic thin films is of crucial importance in order to optimize the performance of future electronic devices. In particular, the start of the submonolayer growth plays an important role since it often determines the structure of the first layer and subsequently of the entire molecular film. We have investigated the structure formation of 3,4,9,10-perylene-tetracarboxylic dianhydride and copper-phthalocyanine molecules on Au(111) using pair-potential calculations based on van der Waals and electrostatic intermolecular interactions. The results are compared with the fundamental lateral structures known from experiment and an excellent agreement was found for these weakly interacting systems. Furthermore, the calculations are even suitable for chemisorptive adsorption as demonstrated for copper-phthalocyanine/Cu(111), if the influence of charge transfer between substrate and molecules is known and the corresponding charge redistribution in the molecules can be estimated. The calculations are of general applicability for molecular adsorbate systems which are dominated by electrostatic and van der Waals interaction.

  9. Biaxial Dielectrophoresis Force Spectroscopy: A Stoichiometric Approach for Examining Intermolecular Weak Binding Interactions.

    PubMed

    Park, In Soo; Kwak, Tae Joon; Lee, Gyudo; Son, Myeonggu; Choi, Jeong Woo; Choi, Seungyeop; Nam, Kihwan; Lee, Sei-Young; Chang, Woo-Jin; Eom, Kilho; Yoon, Dae Sung; Lee, Sangyoup; Bashir, Rashid; Lee, Sang Woo

    2016-04-26

    The direct quantification of weak intermolecular binding interactions is very important for many applications in biology and medicine. Techniques that can be used to investigate such interactions under a controlled environment, while varying different parameters such as loading rate, pulling direction, rupture event measurements, and the use of different functionalized probes, are still lacking. Herein, we demonstrate a biaxial dielectrophoresis force spectroscopy (BDFS) method that can be used to investigate weak unbinding events in a high-throughput manner under controlled environments and by varying the pulling direction (i.e., transverse and/or vertical axes) as well as the loading rate. With the BDFS system, we can quantitatively analyze binding interactions related to hydrogen bonding or ionic attractions between functionalized microbeads and a surface within a microfluidic device. Our BDFS system allowed for the characterization of the number of bonds involved in an interaction, bond affinity, kinetic rates, and energy barrier heights and widths from different regimes of the energy landscape. PMID:27007455

  10. Precursors of dangerous substances formed in the loss of control of chemical systems.

    PubMed

    Cozzani, V; Zanelli, S

    1999-03-01

    Article 2 of Directive 96/82/EC on the control of major accident hazards caused by dangerous substances requires to consider also the hazards due to the dangerous substances "which it is believed may be generated during loss of control of an industrial chemical process", although no generally accepted guidelines are available for the identification of these substances. In the present study, the accidents involving the unwanted formation of dangerous substances as a consequence of the loss of control of chemical systems were investigated. A specifically developed database was used, containing data on more than 400 of these accidents and on the substances involved. The hazardous substances formed in the accidents and the precursors of these substances were identified. The influence of accident characteristics on the substances formed was investigated. In the context of the application of Directive 96/82/EC, an accident severity index and a hazard rating of the precursors of dangerous substances formed in the accidents were proposed. A lumping approach was used in order to develop schemes for the preliminary identification of substances that may be formed in the loss of control of chemical system. The results of accident analysis were used to test the schemes developed. PMID:10337407

  11. Strong orbital interaction in a weak CH-π hydrogen bonding system

    NASA Astrophysics Data System (ADS)

    Li, Jianfu; Zhang, Rui-Qin

    2016-03-01

    For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms “bonding” and “antibonding” orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-π hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least -1.51 kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex.

  12. Strong orbital interaction in a weak CH-π hydrogen bonding system

    PubMed Central

    Li, Jianfu; Zhang, Rui-Qin

    2016-01-01

    For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms “bonding” and “antibonding” orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-π hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least −1.51 kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex. PMID:26927609

  13. Closed-form solutions of performability. [modeling of a degradable buffer/multiprocessor system

    NASA Technical Reports Server (NTRS)

    Meyer, J. F.

    1981-01-01

    Methods which yield closed form performability solutions for continuous valued variables are developed. The models are similar to those employed in performance modeling (i.e., Markovian queueing models) but are extended so as to account for variations in structure due to faults. In particular, the modeling of a degradable buffer/multiprocessor system is considered whose performance Y is the (normalized) average throughput rate realized during a bounded interval of time. To avoid known difficulties associated with exact transient solutions, an approximate decomposition of the model is employed permitting certain submodels to be solved in equilibrium. These solutions are then incorporated in a model with fewer transient states and by solving the latter, a closed form solution of the system's performability is obtained. In conclusion, some applications of this solution are discussed and illustrated, including an example of design optimization.

  14. An expert system for ensuring the reliability of the technological process of cold sheet metal forming

    NASA Astrophysics Data System (ADS)

    Kashapova, L. R.; Pankratov, D. L.; Utyaganov, P. P.

    2016-06-01

    In order to exclude periodic defects in the parts manufacturing obtained by cold sheet metal forming a method of automated estimation of technological process reliability was developed. The technique is based on the analysis of reliability factors: detail construction, material, mechanical and physical requirements; hardware settings, tool characteristics, etc. In the work the expert system is presented based on a statistical accumulation of the knowledge of the operator (technologist) and decisions of control algorithms.

  15. Shuttle-like supramolecular nanostructures formed by self-assembly of a porphyrin via an oil/water system

    PubMed Central

    2011-01-01

    In this paper, in terms of the concentration of an aqueous solution of a surfactant, we investigate the self-assembly behavior of a porphyrin, 5, 10, 15, 20-tetra(4-pyridyl)-21H, 23H-porphine [H2TPyP], by using an oil/water system as the medium. We find that when a chloroform solution of H2TPyP is dropwise added into an aqueous solution of cetyltrimethylammonium bromide [CTAB] with a lower concentration, a large amount of irregular nanoarchitectures, together with a small amount of well-defined shuttle-like nanostructures, hollow nanospheres, and nanotubes, could be produced. While a moderate amount of shuttle-like nanostructures accompanied by a few irregular nanoarchitectures, solid nanospheres, and nanorods are produced when a CTAB aqueous solution in moderate concentration is employed, in contrast, a great quantity of shuttle-like nanostructures together with a negligible amount of solid nanospheres, nanofibers, and irregular nanostructures are manufactured when a high-concentration CTAB aqueous solution is involved. An explanation on the basis of the molecular geometry of H2TPyP and in terms of the intermolecular π-π interactions between H2TPyP units, and hydrophobic interactions between CTAB and H2TPyP has been proposed. The investigation gives deep insights into the self-assembly behavior of porphyrins in an oil/water system and provides important clues concerning the design of appropriate porphyrins when related subjects are addressed. Our investigation suggests that an oil/aqueous system might be an efficient medium for producing unique organic-based nanostructures. PMID:21943330

  16. 15N Fractionation in Star-Forming Regions and Solar System Objects

    NASA Technical Reports Server (NTRS)

    Wirstrom, Eva; Milam, Stefanie; Adande, GIlles; Charnley, Steven; Cordiner, Martin

    2015-01-01

    A central issue for understanding the formation and evolution of matter in the early Solar System is the relationship between the chemical composition of star-forming interstellar clouds and that of primitive Solar System materials. The pristinemolecular content of comets, interplanetary dust particles and carbonaceous chondrites show significant bulk nitrogen isotopic fractionation relative to the solar value, 14N15N 440. In addition, high spatial resolution measurements in primitive materials locally show even more extreme enhancements of 14N15N 100.

  17. Practical output tracking of switched nonlinear systems in p-normal form with unstable subsystems

    NASA Astrophysics Data System (ADS)

    Long, Lijun; Zhao, Jun

    2016-08-01

    This paper studies practical output tracking of switched nonlinear systems in p-normal form. No solvability of the practical output tracking problem for subsystems is required. A constructive scheme to solve the problem for a switched nonlinear system is set up by exploiting the single Lyapunov function method and the tool of adding a power integrator. Also, we design a proper switching law and construct state-feedback controllers of subsystems. A two inverted pendulums as a practical example, which cannot be handled by the existing approaches, illustrates our theoretical result.

  18. Differentiating lexical form, meaning, and structure in the neural language system.

    PubMed

    Tyler, L K; Marslen-Wilson, W D; Stamatakis, E A

    2005-06-01

    A technique for studying the relationship between brain and language, which involves correlating scores on two continuous variables, signal intensity across the entire brains of brain-damaged patients and behavioral priming scores, was used to investigate a central issue in cognitive neuroscience: Are the components of the neural language system organized as a single undifferentiated process, or do they respond differentially to different types of linguistic structure? Differences in lexical structure, in the form of the regular and irregular past tense, have proven to be critical in this debate by contrasting a highly predictable rule-like process (e.g., jump-jumped) with an unpredictable idiosyncratic process typified by the irregulars (e.g., think-thought). The key issue raised by these contrasts is whether processing regular and irregular past tense forms differentially engages different aspects of the neural language system or whether they are processed within a single system that distinguishes between them purely on the basis of phonological and semantic differences. The correlational analyses provide clear evidence for a functional differentiation between different brain regions associated with the processing of lexical form, meaning, and morphological structure. PMID:15923263

  19. Optimal control of nonlinear continuous-time systems in strict-feedback form.

    PubMed

    Zargarzadeh, Hassan; Dierks, Travis; Jagannathan, Sarangapani

    2015-10-01

    This paper proposes a novel optimal tracking control scheme for nonlinear continuous-time systems in strict-feedback form with uncertain dynamics. The optimal tracking problem is transformed into an equivalent optimal regulation problem through a feedforward adaptive control input that is generated by modifying the standard backstepping technique. Subsequently, a neural network-based optimal control scheme is introduced to estimate the cost, or value function, over an infinite horizon for the resulting nonlinear continuous-time systems in affine form when the internal dynamics are unknown. The estimated cost function is then used to obtain the optimal feedback control input; therefore, the overall optimal control input for the nonlinear continuous-time system in strict-feedback form includes the feedforward plus the optimal feedback terms. It is shown that the estimated cost function minimizes the Hamilton-Jacobi-Bellman estimation error in a forward-in-time manner without using any value or policy iterations. Finally, optimal output feedback control is introduced through the design of a suitable observer. Lyapunov theory is utilized to show the overall stability of the proposed schemes without requiring an initial admissible controller. Simulation examples are provided to validate the theoretical results. PMID:26111400

  20. Facile Incorporation of Pd(PPh3)2Hal Substituents into Polymethines, Merocyanines, and Perylene Diimides as a Means of Suppressing Intermolecular Interactions.

    PubMed

    Davydenko, Iryna; Barlow, Stephen; Sharma, Rajesh; Benis, Sepehr; Simon, Janos; Allen, Taylor G; Cooper, Matthew W; Khrustalev, Victor; Jucov, Evgheni V; Castañeda, Raúl; Ordonez, Carlos; Li, Zhong'an; Chi, San-Hui; Jang, Sei-Hum; Parker, Timothy C; Timofeeva, Tatiana V; Perry, Joseph W; Jen, Alex K-Y; Hagan, David J; Van Stryland, Eric W; Marder, Seth R

    2016-08-17

    Compounds with polarizable π systems that are susceptible to attack with nucleophiles at C-Hal (Hal = Cl, Br) bonds react with Pd(PPh3)4 to yield net oxidative addition. X-ray structures show that the resulting Pd(PPh3)2Hal groups greatly reduce intermolecular π-π interactions. The Pd-functionalized dyes generally exhibit solution-like absorption spectra in films, whereas their Hal analogues exhibit features attributable to aggregation. PMID:27494823

  1. Metallicity gradients and newly created star-forming systems in interacting galaxies

    NASA Astrophysics Data System (ADS)

    Mendes de Oliveira, Claudia L.

    2015-08-01

    Interactions play an extremely important role in the evolution of galaxies, changing their morphologies and kinematics. Galaxy collisions may result in the formation of intergalactic star-forming objects, such as HII regions, young clusters and/or tidal dwarf galaxies. Several studies have found a wealth of newly created objects in interacting systems. We will exemplify the problems and challenges in this field and will describe observations of the interacting group NGC 6845, which contains four bright galaxies, two of which have extended tidal tails. We obtained Gemini/GMOS spectra for 28 of the regions located in the galaxies and in the tails. All regions in the latter are star-forming objects according to their line ratios, with ages younger than 10 Myr. A super luminous star forming complex is found in the brightest member of the group, NGC 6845A. Its luminosity reveals a star formation density of 0.19 solar masses, per year, per kpc^2, suggesting that this object is a localized starburst. We derived the gas-phase metallicity gradients across NGC 6845A and its two tails and we find that these are shallower than those for isolated galaxies. We speculate that the observed metallicity gradient may be related to one or more of the following mechanisms: (1) interaction induced inflow of fresh gas to the galaxy center, as seen in simulations, which is expected to dilute the metallicity of the central burst, (2) the formation of young metal-rich star forming regions in the tidal tails, which were born out of enriched gas expelled from the central regions of the system during the interaction and (3) the incremental growth of metals accumulated over time, due to the successful generations of star forming regions along the tails. Finally we will describe our plans to do a search for such objects on Halpha images that will soon be available for 17.5k degrees of the sky, with the A-PLUS survey.

  2. Characterization of a new anhydrous form of Rotundine and its monohydrate

    NASA Astrophysics Data System (ADS)

    Yang, Shiying; Du, Guanhua; Lu, Yang

    2015-09-01

    Rotundine is a chemical drug developed from Chinese traditional medicines that exhibits pseudopolymorphism. The anhydrous form and monohydrate are isolated and prepared via systemic crystallization screening, and the anhydrous form is reported for the first time. In this article single crystal X-ray diffractometry, powder X-ray diffractometry and FT-IR spectroscopy are used to characterize the Rotundine modifications. The analysis results show that the factors of crystal symmetry, intermolecular arrangements, conformational flexibility, hydrogen bonding interactions, and the incorporation of water finally lead to produce the polymorphic phenomenon. Via the in-vivo bioavailability of two forms, it is found that the new anhydrous form presents absorbable superiority relative to monohydrate, specifically Cmax and AUC of anhydrous form were approximately 1.5 times those of monohydrate. Study on the transformation of two forms show that they can convert to each other in certain conditions at solid state.

  3. Benchmark Calculations of Three-Body Intermolecular Interactions and the Performance of Low-Cost Electronic Structure Methods.

    PubMed

    Řezáč, Jan; Huang, Yuanhang; Hobza, Pavel; Beran, Gregory J O

    2015-07-14

    Many-body noncovalent interactions are increasingly important in large and/or condensed-phase systems, but the current understanding of how well various models predict these interactions is limited. Here, benchmark complete-basis set coupled cluster singles, doubles, and perturbative triples (CCSD(T)) calculations have been performed to generate a new test set for three-body intermolecular interactions. This "3B-69" benchmark set includes three-body interaction energies for 69 total trimer structures, consisting of three structures from each of 23 different molecular crystals. By including structures that exhibit a variety of intermolecular interactions and packing arrangements, this set provides a stringent test for the ability of electronic structure methods to describe the correct physics involved in the interactions. Both MP2.5 (the average of second- and third-order Møller-Plesset perturbation theory) and spin-component-scaled CCSD for noncovalent interactions (SCS-MI-CCSD) perform well. MP2 handles the polarization aspects reasonably well, but it omits three-body dispersion. In contrast, many widely used density functionals corrected with three-body D3 dispersion correction perform comparatively poorly. The primary difficulty stems from the treatment of exchange and polarization in the functionals rather than from the dispersion correction, though the three-body dispersion may also be moderately underestimated by the D3 correction. PMID:26575743

  4. Method for Slater-Type Density Fitting for Intermolecular Electrostatic Interactions with Charge Overlap. I. The Model.

    PubMed

    Öhrn, Anders; Hermida-Ramon, Jose M; Karlström, Gunnar

    2016-05-10

    The effects of charge overlap, or charge penetration, are neglected in most force fields and interaction terms in QM/MM methods. The effects are however significant at intermolecular distances near the van der Waals minimum. In the present study, we propose a method to evaluate the intermolecular Coloumb interaction using Slater-type functions, thus explicitly modeling the charge overlap. The computational cost of the method is low, which allows it to be used in large systems with most force fields as well as in QM/MM schemes. The charge distribution is modeled as a distributed multipole expansion up to quadrupole and Slater-type functions of angular momentum up to L = 1. The exponents of the Slater-type functions are obtained using a divide-and-conquer method to avoid the curse of dimensionality that otherwise is present for large nonlinear optimizations. A Levenberg-Marquardt algorithm is applied in the fitting process. A set of parameters is obtained for each molecule, and the process is fully automated. Calculations have been performed in the carbon monoxide and the water dimers to illustrate the model. Results show a very good accuracy of the model with relative errors in the electrostatic potential lower than 3% over all reasonable separations. At very short distances where the charge overlaps is the most significant, errors are lower than 8% and lower than 3.5% at distances near the van der Waals minimum. PMID:27015000

  5. Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

    SciTech Connect

    Shcherbina, M. A. Bakirov, A. V.; Yakunin, A. N.; Percec, V.; Beginn, U.; Moeller, M.; Chvalun, S. N.

    2012-03-15

    The main stages of the self-assembling of supramolecular ensembles have been revealed by studying different functional wedged macromolecules: polymethacrylates with tapered side chains based on gallic acid, their macromonomers, and salts of 2,3,4- and 3,4,5-tris(dodecyloxy)benzenesulphonic acid. The first stage is the formation of individual supramolecular aggregates (long cylinders or spherical micelles) due to the weak noncovalent interactions of mesogenic groups and the subsequent ordering in these aggregates, which is accompanied by a decrease in the free energy of the system. Supramolecular aggregates, in turn, form 2D or 3D lattices. The shape of supramolecular aggregates and its change with temperature are delicate functions of the mesogen chemical structure; this circumstance makes it possible to rationally design complex self-assembling systems with the ability to respond smartly to external stimuli. X-ray diffraction analysis allows one to study the structure of supramolecular systems with different degrees of order, determine the type of mesophases formed by these systems, and reveal the phase behavior of the material. Particular attention has been paid to the method for reconstruction of electron density distribution from the relative reflection intensity. The application of a suite of experimental methods, including wide- and small-angle X-ray diffraction, molecular modeling, differential scanning calorimetry, and polarization optical microscopy, allows one to establish the relationship between the shape of the structural unit (molecule or molecular aggregate), the nature of the interaction, and the phase behavior of the material.

  6. Closed-form solutions for linear regulator design of mechanical systems including optimal weighting matrix selection

    NASA Technical Reports Server (NTRS)

    Hanks, Brantley R.; Skelton, Robert E.

    1991-01-01

    Vibration in modern structural and mechanical systems can be reduced in amplitude by increasing stiffness, redistributing stiffness and mass, and/or adding damping if design techniques are available to do so. Linear Quadratic Regulator (LQR) theory in modern multivariable control design, attacks the general dissipative elastic system design problem in a global formulation. The optimal design, however, allows electronic connections and phase relations which are not physically practical or possible in passive structural-mechanical devices. The restriction of LQR solutions (to the Algebraic Riccati Equation) to design spaces which can be implemented as passive structural members and/or dampers is addressed. A general closed-form solution to the optimal free-decay control problem is presented which is tailored for structural-mechanical system. The solution includes, as subsets, special cases such as the Rayleigh Dissipation Function and total energy. Weighting matrix selection is a constrained choice among several parameters to obtain desired physical relationships. The closed-form solution is also applicable to active control design for systems where perfect, collocated actuator-sensor pairs exist.

  7. A computer model for simulation of absorption systems in flexible and modular form

    SciTech Connect

    Grossman, G; Gommed, K; Gadoth, D

    1991-08-01

    A computer code in a flexible and modular form developed for simulation of absorption systems makes it possible to investigate various cycle configurations with different working fluids. The code is based on unit subroutines containing the governing equations for the system's components. The equations are linked by a main program according to the user's specifications to form the complete system. The equations are solved simultaneously, and fluid properties are taken from a property data base. The code is user oriented and requires a relatively simple input containing the given operating conditions and the working fluid at each state point. The user conveys to the computer an image of his or her cycle by specifying the different subunits and their interconnection. Based on this information, the program calculates (1) the temperature, flow rate, concentration, pressure, and vapor fraction at each state point in the system and (2) the heat duty at each unit, from which the coefficient of performance may be determined. The program has been used successfully to simulate a variety of single-stage, double-stage, and dual-loop heat pumps and heat transformers, with the working fluids LiBr-H{sup 2}O,H{sub 2}O-NH{sub 3}, LiBr/H{sub 2}O-NH{sub 3}, LiBr/ZnBr{sub 2}-CH{sub 3}OH, and more. 23 refs., 10 figs., 13 tabs.

  8. Kinetics of color development of melanoidins formed from fructose/amino acid model systems.

    PubMed

    Echavarría, A P; Pagán, J; Ibarz, A

    2014-03-01

    The formation of soluble melanoidins from a single combination of sugar (fructose) and amino acid model systems were evaluated kinetically. The selected amino acids, commonly found in apple juice and highly reactive in the Maillard reaction, were asparagine, aspartic acid, and glutamic acid. The effect of these reagents and the treatment at different temperatures (50 , 85 , and 100 ) during 96 h on the color intensity of the melanoidin formed was measured by absorbance at different wavelengths (280, 325, 405, and 420 nm). The absorbance of the melanoidin formed from all model systems was located on the wavelength of 405 nm, that is, the area of the visible spectrum close to the UV region. The color of the melanoidins was directly measured using the CIELAB color space system. A first-order kinetic model was applied to the evolution of the ΔE * (color difference) and L * (lightness) of the color. The fructose/aspartic acid model system values of a * (redness) and b * (yellowness) were found in the brown-red zone. Therefore, the color development of the melanoidins was influenced by the type of amino acid and temperature. Especially, it is thought that the a * and b * values can be used to explain the differences among the amino acids in the color development of melanoidins. PMID:23744115

  9. Resolution enhancement in MR spectroscopy of red bone marrow fat via intermolecular double-quantum coherences

    NASA Astrophysics Data System (ADS)

    Bao, Jianfeng; Cui, Xiaohong; Huang, Yuqing; Zhong, Jianhui; Chen, Zhong

    2015-08-01

    High-resolution 1H magnetic resonance spectroscopy (MRS) is generally inaccessible in red bone marrow (RBM) tissues using conventional MRS techniques. This is because signal from these tissues suffers from severe inhomogeneity in the main static B0 field originated from the intrinsic honeycomb structures in trabecular bone. One way to reduce effects of B0 field inhomogeneity is by using the intermolecular double quantum coherence (iDQC) technique, which has been shown in other systems to obtain signals insensitive to B0 field inhomogeneity. In the present study, we employed an iDQC approach to enhance the spectral resolution of RBM. The feasibility and performance of this method for achieving high resolution MRS was verified by experiments on phantoms and pig vertebral bone samples. Unsaturated fatty acid peaks which overlap in the conventional MRS were well resolved and identified in the iDQC spectrum. Quantitative comparison of fractions of three types of fatty acids was performed between iDQC spectra on the in situ RMB and conventional MRS on the extracted fat from the same RBM. Observations of unsaturated fatty acids with iDQC MRS may provide valuable information and may hold potential in diagnosis of diseases such as obesity, diabetes, and leukemia.

  10. Rates of intra- and intermolecular electron transfers in hydrogenase deduced from steady-state activity measurements.

    PubMed

    Dementin, Sébastien; Burlat, Bénédicte; Fourmond, Vincent; Leroux, Fanny; Liebgott, Pierre-Pol; Abou Hamdan, Abbas; Léger, Christophe; Rousset, Marc; Guigliarelli, Bruno; Bertrand, Patrick

    2011-07-01

    Electrons are transferred over long distances along chains of FeS clusters in hydrogenases, mitochondrial complexes, and many other respiratory enzymes. It is usually presumed that electron transfer is fast in these systems, despite the fact that there has been no direct measurement of rates of FeS-to-FeS electron transfer in any respiratory enzyme. In this context, we propose and apply to NiFe hydrogenase an original strategy that consists of quantitatively interpreting the variations of steady-state activity that result from changing the nature of the FeS clusters which connect the active site to the redox partner, and/or the nature of the redox partner. Rates of intra- and intermolecular electron transfer are deduced from such large data sets. The mutation-induced variations of electron transfer rates cannot be explained by changes in intercenter distances and reduction potentials. This establishes that FeS-to-FeS rate constants are extremely sensitive to the nature and coordination of the centers. PMID:21615141

  11. Density-based Energy Decomposition Analysis for Intermolecular Interactions with Variationally Determined Intermediate State Energies

    SciTech Connect

    Wu, Q.; Ayers, P.W.; Zhang, Y.

    2009-10-28

    The first purely density-based energy decomposition analysis (EDA) for intermolecular binding is developed within the density functional theory. The most important feature of this scheme is to variationally determine the frozen density energy, based on a constrained search formalism and implemented with the Wu-Yang algorithm [Q. Wu and W. Yang, J. Chem. Phys. 118, 2498 (2003) ]. This variational process dispenses with the Heitler-London antisymmetrization of wave functions used in most previous methods and calculates the electrostatic and Pauli repulsion energies together without any distortion of the frozen density, an important fact that enables a clean separation of these two terms from the relaxation (i.e., polarization and charge transfer) terms. The new EDA also employs the constrained density functional theory approach [Q. Wu and T. Van Voorhis, Phys. Rev. A 72, 24502 (2005)] to separate out charge transfer effects. Because the charge transfer energy is based on the density flow in real space, it has a small basis set dependence. Applications of this decomposition to hydrogen bonding in the water dimer and the formamide dimer show that the frozen density energy dominates the binding in these systems, consistent with the noncovalent nature of the interactions. A more detailed examination reveals how the interplay of electrostatics and the Pauli repulsion determines the distance and angular dependence of these hydrogen bonds.

  12. Spatiotemporal patterns enhanced by intra- and inter-molecular fluctuations in arrays of allosterically regulated enzymes

    NASA Astrophysics Data System (ADS)

    Togashi, Yuichi; Casagrande, Vanessa

    2015-03-01

    Enzymatic reactions often involve slow conformational changes, with reaction cycles that sometimes require milliseconds or seconds to complete. The dynamics are strongly affected by fluctuations at the nanoscale. However, such enzymes often occur in small numbers in a cell; hence, the fluctuations caused by finite numbers of molecules should also be substantial. Because of these factors, the behavior of the system is likely to deviate from that of classical reaction-diffusion equations, in which immediate reaction events are assumed to occur without memory and between a huge number of molecules. In this work, we model each enzyme as a unit represented by a phase variable to investigate the effects of fluctuations in arrays of enzymes. Using an analysis based on partial differential equations and stochastic simulations, we show that fluctuations arising from internal states of enzymes (intramolecular fluctuations) and those arising from the stochastic nature of interactions between molecules (intermolecular fluctuations) have distinctive effects on spatiotemporal patterns; the former generally disturb synchronization at high frequencies, whereas the latter can enhance synchronization. The balance of the two types of fluctuations may determine the spatiotemporal behavior of biochemical processes.

  13. A minichaperone-based fusion system for producing insoluble proteins in soluble stable forms.

    PubMed

    Sharapova, Olga A; Yurkova, Maria S; Fedorov, Alexey N

    2016-02-01

    We have developed a fusion system for reliable production of insoluble hydrophobic proteins in soluble stable forms. A carrier is thermophilic minichaperone, GroEL apical domain (GrAD), a 15 kDa monomer able to bind diverse protein substrates. The Met-less variant of GrAD has been made for further convenient use of Met-specific CNBr chemical cleavage, if desired. The Met-less GrAD retained stability and solubility of the original protein. Target polypeptides can be fused to either C-terminus or N-terminus of GrAD. The system has been tested with two unrelated insoluble proteins fused to the C-terminus of GrAD. One of the proteins was also fused to GrAD N-terminus. The fusions formed inclusion bodies at 25°C and above and were partly soluble only at lower expression temperatures. Most importantly, however, after denaturation in urea, all fusions without exception were completely renatured in soluble stable forms that safely survived freezing-thawing as well as lyophilization. All fusions for both tested target proteins retained solubility at high concentrations for days. Functional analysis revealed that a target protein may retain functionality in the fusion. Convenience features include potential thermostability of GrAD fusions, capacity for chemical and enzymatic cleavage of a target and His6 tag for purification. PMID:26612097

  14. A paper form processing system with an error correcting function for reading handwritten Kanji strings

    SciTech Connect

    Katsumi Marukawa; Kazuki Nakashima; Masashi Koga; Yoshihiro Shima; Hiromichi Fujisawa

    1994-12-31

    This paper presents a paper form processing system with an error correcting function for reading handwritten kanji strings. In the paper form processing system, names and addresses are important key data, and especially this paper takes up an error correcting method for name and address recognition. The method automatically corrects errors of the kanji OCR (Optical Character Reader) with the help of word dictionaries and other knowledge. Moreover, it allows names and addresses to be written in any style. The method consists of word matching {open_quotes}furigana{close_quotes} verification for name strings, and address approval for address strings. For word matching, kanji name candidates are extracted by automaton-type word matching. In {open_quotes}furigana{close_quotes} verification, kana candidate characters recognized by the kana OCR are compared with kana`s searched from the name dictionary based on kanji name candidates, given by the word matching. The correct name is selected from the results of word matching and furigana verification. Also, the address approval efficiently searches for the right address based on a bottom-up procedure which follows hierarchical relations from a lower placename to a upper one by using the positional condition among the placenames. We ascertained that the error correcting method substantially improves the recognition rate and processing speed in experiments on 5,032 forms.

  15. Aqueous polymer two-phase systems formed by new thermoseparating polymers.

    PubMed

    Persson, J; Johansson, H O; Galaev, I; Mattiasson, B; Tjerneld, F

    2000-01-01

    A set of new polymers that can be used as phase forming components in aqueous two-phase systems is presented. All polymers studied have thermoseparating properties i.e. form one separate polymer enriched phase and one aqueous solution when heated above the critical temperature. This property makes the polymers attractive alternatives to the polymers used in traditional aqueous two-phase systems such as poly(ethylene glycol) (PEG) and dextran. The thermal phase separation simplifies recycling of the polymers, thus making the aqueous two-phase systems more cost efficient and suitable for use in large scale. Thermoseparating polymers studied have been copolymers of ethylene oxide and propylene oxide (EO-PO), poly (N-isopropylacrylamide) (poly-NIPAM), poly vinyl caprolactam (poly-VCL) and copolymers of N-isopropylacrylamide and vinyl caprolactam with vinyl imidazole (poly(NIPAM-VI) and poly(VCL-VI), respectively). In addition, the copolymer poly(NIPAM-VI) has the property to be uncharged at pH above 7.0 and positively charged at lower pH. This allows the partitioning of protein to be directed by changing the pH in the system instead of the traditional addition of salt to direct the partitioning. Hydrophobically modified EO-PO copolymer (HM-(EO-PO)) with alkyl groups (C14) at both ends forms two-phase system with for example poly(NIPAM-VI). The phase diagram for poly(NIPAM-VI)/HM-(EO-PO) was determined and the model proteins lysozyme and BSA were partitioned in this system. For BSA in poly(NIPAM-VI)/HM-(EO-PO) system a change in pH from 8.0 to 5.4 results in a change of partition coefficient from K = 0.8 to K = 5.1, i.e. BSA could be transferred from the HM-(EO-PO) phase to the poly(NIPAM-VI) phase. BSA partitioning in poly(NIPAM-VI)/HM-(EO-PO) system allows quantitative BSA recovery, and recoveries of poly(NIPAM-VI) and HM-(EO-PO) were 53% and 92%, respectively, after the thermoseparation step. PMID:10892544

  16. Alternative analytical forms to model diatomic systems based on the deformed exponential function.

    PubMed

    da Fonsêca, José Erinaldo; de Oliveira, Heibbe Cristhian B; da Cunha, Wiliam Ferreira; Gargano, Ricardo

    2014-07-01

    Using a deformed exponential function and the molecular-orbital theory for the simplest molecular ion, two new analytical functions are proposed to represent the potential energy of ground-state diatomic systems. The quality of these new forms was tested by fitting the ab initio electronic energies of the system LiH, LiNa, NaH, RbH, KH, H2, Li2, K2, H 2 (+) , BeH(+) and Li 2 (+) . From these fits, it was verified that these new proposals are able to adequately describe homonuclear, heteronuclear and cationic diatomic systems with good accuracy. Vibrational spectroscopic constant results obtained from these two proposals are in good agreement with experimental data. PMID:24939465

  17. An effective desiccant system to regulate the humidity inside the chambers of the solid dosage forms.

    PubMed

    Lehto, Vesa-Pekka; Erling, Ida

    2007-11-01

    The most common way to protect moisture-sensitive pharmaceutical powders is to utilize protective packaging. However, the most convenient package materials are all permeable to water molecules to some extent and limited protection is normally achieved with this arrangement even though desiccants are employed. In the present study we introduce a novel system that can regulate the internal humidity of the containers used with solid dosage forms for a desired time at a requested level. Instead of the widely used solid adsorbents the system utilizes saturated salt solutions loaded in desiccant bags made of various polymer materials with appropriate permeation properties. By utilizing salt solutions the size of the desiccant bag can be further reduced. A wide variety of commonly used powder chambers and desiccant bags are tested, proving the effectiveness of the introduced system. PMID:18058320

  18. Periodic orbits analysis of the form factor: from ballistic to diffusive systems

    NASA Astrophysics Data System (ADS)

    Agam, Oded; Fishman, Shmuel

    1996-05-01

    The energy level correlator K(s) and the form factor 0305-4470/29/9/016/img1 are calculated for a hypercubic billiard with small hyperspheres placed at random in its interior. Various regimes, characterized by the elastic mean free path l, resulting from the scattering on impurities, are identified. The analysis extends from the ballistic regime, where l is much larger than the size of the system, via intermediate regimes, to the diffusive regime, where l is much smaller than its size. Semiclassical expressions for the density of states of chaotic and integrable systems in terms of classical periodic orbits are used. The diagonal approximation for 0305-4470/29/9/016/img1 is made for short times, while non-perturbative methods are used for long times. The analysis makes use of analytic properties of classical dynamical zeta function associated with the Perron - Frobenius operator. The general features are relevant for mesoscopic systems.

  19. Hopf normal form with SN symmetry and reduction to systems of nonlinearly coupled phase oscillators

    NASA Astrophysics Data System (ADS)

    Ashwin, Peter; Rodrigues, Ana

    2016-06-01

    Coupled oscillator models where N oscillators are identical and symmetrically coupled to all others with full permutation symmetry SN are found in a variety of applications. Much, but not all, work on phase descriptions of such systems consider the special case of pairwise coupling between oscillators. In this paper, we show this is restrictive-and we characterize generic multi-way interactions between oscillators that are typically present, except at the very lowest order near a Hopf bifurcation where the oscillations emerge. We examine a network of identical weakly coupled dynamical systems that are close to a supercritical Hopf bifurcation by considering two parameters, ɛ (the strength of coupling) and λ (an unfolding parameter for the Hopf bifurcation). For small enough λ > 0 there is an attractor that is the product of N stable limit cycles; this persists as a normally hyperbolic invariant torus for sufficiently small ɛ > 0. Using equivariant normal form theory, we derive a generic normal form for a system of coupled phase oscillators with SN symmetry. For fixed N and taking the limit 0 < ɛ ≪ λ ≪ 1, we show that the attracting dynamics of the system on the torus can be well approximated by a coupled phase oscillator system that, to lowest order, is the well-known Kuramoto-Sakaguchi system of coupled oscillators. The next order of approximation generically includes terms with up to four interacting phases, regardless of N. Using a normalization that maintains nontrivial interactions in the limit N → ∞, we show that the additional terms can lead to new phenomena in terms of coexistence of two-cluster states with the same phase difference but different cluster size.

  20. Disks, Young Stars, and Radio Waves: The Quest for Forming Planetary Systems

    NASA Astrophysics Data System (ADS)

    Chandler, C. J.; Shepherd, D. S.

    2008-08-01

    Kant and Laplace suggested the Solar System formed from a rotating gaseous disk in the 18th century, but convincing evidence that young stars are indeed surrounded by such disks was not presented for another 200 years. As we move into the 21st century the emphasis is now on disk formation, the role of disks in star formation, and on how planets form in those disks. Radio wavelengths play a key role in these studies, currently providing some of the highest-spatial-resolution images of disks, along with evidence of the growth of dust grains into planetesimals. The future capabilities of EVLA and ALMA provide extremely exciting prospects for resolving disk structure and kinematics, studying disk chemistry, directly detecting protoplanets, and imaging disks in formation.

  1. [Forming a community at risk for circulatory system diseases among workers engaged into underground mining].

    PubMed

    Shliapnikov, D M; Shur, P Z; Kostarev, V G; Alexeyev, V B; Vlasova, E M; Uhabov, V M

    2015-01-01

    Forming a community at risk for circulatory system diseases will increase efficiency of medical and prophylactic measures on managing risk of arterial hypertension. Epidemiologic analysis helped to reveal reliable connection between arterial hypertension predictors and work conditions of mining machine operators and supported actualization of high occupational risk suggested in a priori evaluation. Mathematic modelling helped to forecast increase in the disease probability: with noise level of 94 dB after 10 years of work, 17.9% of workers are expected to have arterial hypertension preventing from further occupational activity. Forecasting results of arterial hypertension probability help to form risk groups for medical and preventive technologies managing occupational risk, and predictors enable to specify necessity of individual medical preventive measures. PMID:27024920

  2. Devices, systems, and methods for harvesting energy and methods for forming such devices

    DOEpatents

    Kotter, Dale K.; Novack, Steven D.

    2012-12-25

    Energy harvesting devices include a substrate coupled with a photovoltaic material and a plurality of resonance elements associated with the substrate. The resonance elements are configured to collect energy in at least visible and infrared light spectra. Each resonance element is capacitively coupled with the photovoltaic material, and may be configured to resonate at a bandgap energy of the photovoltaic material. Systems include a photovoltaic material coupled with a feedpoint of a resonance element. Methods for harvesting energy include exposing a resonance element having a resonant electromagnetic radiation having a frequency between approximately 20 THz and approximately 1,000 THz, absorbing at least a portion of the electromagnetic radiation with the resonance element, and resonating the resonance element at a bandgap energy of an underlying photovoltaic material. Methods for forming an energy harvesting device include forming resonance elements on a substrate and capacitively coupling the resonance elements with a photovoltaic material.

  3. Copper-Catalyzed Cascade Reaction via Intramolecular Hydroamination Cyclization of Homopropargylic Amines and Intermolecular Povarov Reaction with Imines.

    PubMed

    Wang, Hongkai; Wang, Chan; Huang, Kaimeng; Liu, Lingyan; Chang, Weixing; Li, Jing

    2016-05-20

    A new one-pot cascade reaction of homopropargylic amines with simple imines is developed in the presence of Cu(OTf)2 and affords a series of hexahydro-1H-pyrrolo[3,2-c]quinoline derivatives in good to high yields. This reaction proceeds through an intramolecular hydroamination cyclization of homopropargylic amine to generate a highly reactive dihydropyrrole intermediate in situ. It subsequently reacts with imine via an intermolecular inverse-electron-demand aza-Diels-Alder reaction and a 1,3-H shift to give the fused pyrroloquinoline structures, forming two new C-C bonds and one C-N bond and one N-H bond. PMID:27128977

  4. Physical nature of intermolecular interactions inside Sir2 homolog active site: molecular dynamics and ab initio study.

    PubMed

    Czeleń, Przemysław; Czyżnikowska, Żaneta

    2016-06-01

    In the present study, we analyze the interactions of NAD+-dependent deacetylase (Sir2 homolog yeast Hst2) with carba-nicotinamide-adenine-dinucleotide (ADP-HPD). For the Sir2 homolog, a yeast Hst2 docking procedure was applied. The structure of the protein-ADP-HPD complex obtained during the docking procedure was used as a starting point for molecular dynamics simulation. The intermolecular interaction energy partitioning was performed for protein-ADP-HPD complex resulting from molecular dynamics simulation. The analysis was performed for ADP-HPD and 15 amino acids forming a deacetylase binding pocket. Although the results indicate that the first-order electrostatic interaction energy is substantial, the presence of multiple hydrogen bonds in investigated complexes can lead to significant value of induction component. PMID:27154340

  5. Helical folding of conjugated oligo(phenyleneethynylene): chain-length dependence, solvent effects, and intermolecular assembly.

    PubMed

    Zhu, Ningbo; Yan, Qifan; Luo, Zhouyang; Zhai, You; Zhao, Dahui

    2012-10-01

    As a representative folding system that features a conjugated backbone, a series of monodispersed (o-phenyleneethynylene)-alt-(p-phenyleneethynylene) (PE) oligomers of varied chain length and different side chains were studied. Molecules with the same backbone but different side-chain structures were shown to exhibit similar helical conformations in respectively suitable solvents. Specifically, oligomers with dodecyloxy side chains folded into the helical structure in apolar aliphatic solvents, whereas an analogous oligomer with tri(ethylene glycol) (Tg) side chains adopted the same conformation in polar solvents. The fact that the oligomers with the same backbone manifested a similar folded conformation independent of side chains and the nature of the solvent confirmed the concept that the driving force for folding was the intramolecular aromatic stacking and solvophobic interactions. Although all were capable of inducing folding, different solvents were shown to bestow slightly varied folding stability. The chain-length dependence study revealed a nonlinear correlation between the folding stability with backbone chain length. A critical size of approximately 10 PE units was identified for the system, beyond which folding occurred. This observation corroborated the helical nature of the folded structure. Remarkably, based on the absorption and emission spectra, the effective conjugation length of the system extended more effectively under the folded state than under random conformations. Moreover, as evidenced by the optical spectra and dynamic light-scattering studies, intermolecular association took place among the helical oligomers with Tg side chains in aqueous solution. The demonstrated ability of such a conjugated foldamer in self-assembling into hierarchical supramolecular structures promises application potential for the system. PMID:22829335

  6. Nutraceutical delivery systems: resveratrol encapsulation in grape seed oil nanoemulsions formed by spontaneous emulsification.

    PubMed

    Davidov-Pardo, Gabriel; McClements, David Julian

    2015-01-15

    The aim of this work was to fabricate nanoemulsions-based delivery systems to encapsulate resveratrol. Nanoemulsions were formed using spontaneous emulsification method: 10% oil phase (grape seed oil plus orange oil) and 10% surfactant (Tween 80) were titrated into 80% aqueous phase. An optimum orange oil-to-grape seed oil ratio of 1:1(w/w) formed small droplets (d ≈ 100 nm) with good stability to droplet growth. The maximum amount of resveratrol that could be dissolved in the oil phase was 120 ± 10 μg/ml. The effect of droplet size on the chemical stability of encapsulated resveratrol was examined by preparing systems with different mean droplet diameters of 220 ± 2; 99 ± 3; and 45 ± 0.4 nm. Encapsulation of resveratrol improved its chemical stability after exposure to UV-light: 88% retention in nanoemulsions compared to 50% in dimethylsulphoxide (DMSO). This study showed that resveratrol could be encapsulated within low-energy nanoemulsion-based delivery systems and protected against degradation. PMID:25148980

  7. Aqueous-Based Latex Systems for Producing Durable Waste Forms-Initial Characterization

    SciTech Connect

    Terry, Troy N.; Russell, Renee L. ); Smith, Harry D. ); Liang, Liang ); Smith, Gary L. )

    2000-11-01

    The overall objective of this project is to identify and successfully demonstrate a water-based polyceram system suitable for producing an environmentally stable waste form highly loaded with salt wastes. The backbone for this idea is the development of aqueous based sol-gel technology. Most interest in sol-gel synthesis of ceramics in recent years has concentrated on the hydrolysis of metal alkoxides in organic media, but the alternative sol-gel process in aqueous media may offer acceptable results without the need for hazardous precursors or waste products. To accomplish this, water micelle (like an emulsion) systems will be substituted for the organic based systems already identified. Preliminary tests show that emulsions such as Styrene/Butadiene and Acrylic latex are good candidates for the aqueous media. Both of these materials when mixed with a percentage of natural latex have been shown to effectively immobilize salt wastes with loadings over 10 wt%. The low cost, availability, and ease of preparation (low temperature of cure) of these products makes them strong contenders as a waste form. Techniques for improving both chemical and physical properties, such as adding cross-linking agents and fine-tuning the curing process, are currently in development at Pacific Northwest National Laboratories along with collaboration with staff from the University of Arizona.

  8. How Do Multiple-Star Systems Form? VLA Study Reveals "Smoking Gun"

    NASA Astrophysics Data System (ADS)

    2006-12-01

    Astronomers have used the National Science Foundation's Very Large Array (VLA) radio telescope to image a young, multiple-star system with unprecedented detail, yielding important clues about how such systems are formed. Most Sun-sized or larger stars in the Universe are not single, like our Sun, but are members of multiple-star systems. Astronomers have been divided on how such systems can form, producing competing theoretical models for this process. Multiple Star Formation Graphic Proposed Formation Process for L1551 IRS5 CREDIT: Bill Saxton, NRAO/AUI/NSF Click on image for page of graphics and full information The new VLA study produced a "smoking gun" supporting one of the competing models, said Jeremy Lim, of the Institute of Astronomy & Astrophysics, Academia Sinica, in Taipei, Taiwan, whose study, done with Shigehisa Takakuwa of the National Astronomical Observatory of Japan, is published in the December 10 issue of the Astrophysical Journal. Ironically, their discovery of a third, previously-unknown, young star in the system may support a second theoretical model. "There may be more than one way to make a multiple-star system," Lim explained. The astronomers observed an object called L1551 IRS5, young, still-forming protostars enshrouded in a cloud of gas and dust, some 450 light-years from Earth in the direction of the constellation Taurus. Invisible to optical telescopes because of the gas and dust, this object was discovered in 1976 by astronomers using infrared telescopes. A VLA study in 1998 showed two young stars orbiting each other, each surrounded by a disk of dust that may, in time, congeal into a system of planets. Lim and Takakuwa re-examined the system, using improved technical capabilities that greatly boosted the quality of their images. "In the earlier VLA study, only half of the VLA's 27 antennas had receivers that could collect the radio waves, at a frequency of 43 GigaHertz (GHz), coming from the dusty disks. When we re-observed this

  9. Nonlinear control design for stressed power systems using normal forms of vector fields

    NASA Astrophysics Data System (ADS)

    Jang, Gilsoo

    Large stressed interconnected power systems exhibit complicated dynamic behavior when subjected to disturbances. This nonlinear complex behavior is not well analyzed with present tools, and a complete theoretical analysis of this is not feasible in large systems. In stressed power systems, due to the presence of increased nonlinearity and the existence of nonlinear modal interactions, there exist some limitation to the use of conventional linear control design techniques. Therefore there is a need to understand the nature of nonlinear modal interactions and their influences on control performance for optimal controller setting. This work deals with control design in power systems using the method of normal forms. The objective of this work is to understand the effect of the nonlinear modal interaction on control performance and to develop a procedure to design controls incorporating the nonlinear information. For power systems equipped with fast exciters, the exciter gains have crucial influence on the system dynamic behavior. In order to be able to tune the exciter gains for optimal system performance, one has to understand, how the system response changes with different gain settings. In linear analysis, this consists of determining the eigenvalues for various gains, and computing the sensitivity of the eigenvalues under gain variations. If one takes into account the influence of the second order normal forms on the system response, then the corresponding interaction coefficients and their sensitivity with respect to gain variations has to be studied as well. This is the topic of the study presented here. The concept of nonlinear participation factors, and sensitivity of the normal forms coefficient, together with linear participation factors and eigenvalue sensitivity are used to vary control settings. The control settings are varied to obtain improved stability and to reduce the nonlinearity in the system. The proposed procedure was applied to the 50-generator

  10. Development of a Leave-in-Place Slab Edge Insulating Form System

    SciTech Connect

    Marc Hoeschele; Eric Lee

    2009-08-31

    Concrete slabs represent the primary foundation type in residential buildings in the fast-growing markets throughout the southern and southwestern United States. Nearly 75% of the 2005 U.S. population growth occurred in these southern tier states. Virtually all of these homes have uninsulated slab perimeters that transfer a small, but steady, flow of heat from conditioned space to outdoors during the heating season. It is estimated that new home foundations constructed each year add 0.016 quads annually to U.S. national energy consumption; we project that roughly one quarter of this amount can be attributed to heat loss through the slab edge and the remaining three quarters to deep ground transfers, depending upon climate. With rising concern over national energy use and the impact of greenhouse gas emissions, it is becoming increasingly imperative that all cost-effective efforts to improve building energy efficiency be implemented. Unlike other building envelope components that have experienced efficiency improvements over the years, slab edge heat loss has largely been overlooked. From our vantage point, a marketable slab edge insulation system would offer significant benefits to homeowners, builders, and the society as a whole. Conventional slab forming involves the process of digging foundation trenches and setting forms prior to the concrete pour. Conventional wood form boards (usually 2 x 10's) are supported by vertical stakes on the outer form board surface, and by supporting 'kickers' driven diagonally from the top of the form board into soil outside the trench. Typically, 2 x 10's can be used only twice before they become waste material, contributing to an additional 400 pounds of construction waste per house. Removal of the form boards and stakes also requires a follow-up trip to the jobsite by the concrete subcontractor and handling (storage/disposal) of the used boards. In the rare cases where the slab is insulated (typically custom homes with radiant

  11. Challenges in forming the solar system's giant planet cores via pebble accretion

    SciTech Connect

    Kretke, K. A.; Levison, H. F.

    2014-12-01

    Though ∼10 M {sub ⊕} mass rocky/icy cores are commonly held as a prerequisite for the formation of gas giants, theoretical models still struggle to explain how these embryos can form within the lifetimes of gaseous circumstellar disks. In recent years, aerodynamic-aided accretion of 'pebbles', objects ranging from centimeters to meters in size, has been suggested as a potential solution to this long-standing problem. While pebble accretion has been demonstrated to be extremely effective in local simulations that look at the detailed behavior of these pebbles in the vicinity of a single planetary embryo, to date there have been no global simulations demonstrating the effectiveness of pebble accretion in a more complicated, multi-planet environment. Therefore, we have incorporated the aerodynamic-aided accretion physics into LIPAD, a Lagrangian code that can follow the collisional/accretional/dynamical evolution of a protoplanetary system, to investigate how pebble accretion manifests itself in the larger planet formation picture. We find that under generic circumstances, pebble accretion naturally leads to an 'oligarchic' type of growth in which a large number of planetesimals grow to similar-sized planets. In particular, our simulations tend to form hundreds of Mars- and Earth-mass objects between 4 and 10 AU. While merging of some oligarchs may grow massive enough to form giant planet cores, leftover oligarchs lead to planetary systems that cannot be consistent with our own solar system. We investigate various ideas presented in the literature (including evaporation fronts and planet traps) and find that none easily overcome this tendency toward oligarchic growth.

  12. Probing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy

    NASA Astrophysics Data System (ADS)

    Paarmann, A.; Hayashi, T.; Mukamel, S.; Miller, R. J. D.

    2008-05-01

    Two-dimensional infrared photon echo and pump probe studies of the OH stretch vibration provide a sensitive probe of the correlations and couplings in the hydrogen bond network of liquid water. The nonlinear response is simulated using numerical integration of the Schrödinger equation with a Hamiltonian constructed to explicitly treat intermolecular coupling and nonadiabatic effects in the highly disordered singly and doubly excited vibrational exciton manifolds. The simulated two-dimensional spectra are in close agreement with our recent experimental results. The high sensitivity of the OH stretch vibration to the bath dynamics is found to arise from intramolecular mixing between states in the two-dimensional anharmonic OH stretch potential. Surprisingly small intermolecular couplings reproduce the experimentally observed intermolecular energy transfer times.

  13. Comment on 'Intermolecular interaction potentials of the methane dimer from the local density approximation'

    SciTech Connect

    Li, Arvin H.-T.; Chao, S.D.

    2006-01-15

    To verify the recently calculated intermolecular interaction potentials of the methane dimer within the density functional theory using the (Perdew) local density approximation (LDA) [Chen et al., Phys. Rev. A 69, 034701 (2004)], we have performed a parallel series of calculations using the LDA/6-311++G (3df, 3pd) level of theory with selected exchange functionals (B, G96, MPW, O, PBE, PW91, S, and XA). None of the above calculated intermolecular interaction potentials from the local density approximation reproduce the results reported in the commented paper. In addition, we point out the inappropriateness of using the Lennard-Jones function to model the long-range parts of the calculated intermolecular interaction potentials, as suggested positively by Chen et al.

  14. Compound Natural Gas Hydrate: A Natural System for Separation of Hydrate-Forming Gases

    NASA Astrophysics Data System (ADS)

    Max, M. D.; Osegovic, J. P.

    2007-12-01

    Natural processes that separate materials from a mixture may exert a major influence on the development of the atmospheres and surfaces of planets, moons, and other planetary bodies. Natural distillation and gravity separation, amongst others, are well known means of differentiating materials through liquid-gas partitioning. One of the least known attributes of clathrate (gas) hydrates is their potential effect on the evolution of planetary system oceans and atmospheres. Gas hydrates separate gases from mixtures of gases by concentrating preferred hydrate-forming materials (HFM) guests within the water-molecule cage structure of crystalline hydrate. Different HFMs have very different fields of stability. When multiple hydrate formers are present, a preference series based on their selective uptake exists. Compound hydrate, which is formed from two or more species of HFM, extract preferred HFM from a mixture in very different proportions to their relative percentages of the original mixture. These compound hydrates can have different formation and dissociation conditions depending on the evolution of the environment. That is, the phase boundary of the compound hydrate that is required for dissociation lies along a lower pressure - higher temperature course. Compound hydrates respond to variations in temperature, pressure, and HFM composition. On Earth, the primary naturally occurring hydrate of interest to global climate modeling is methane hydrate. Oceanic hydrate on Earth is the largest store of carbon in the biosphere that is immediately reactive to environmental change, and is capable of releasing large amounts of methane into the atmosphere over a short geological time span. Hydrate formation is essentially metastable and is very sensitive to environmental change and to gas flux. Where natural variations in temperature and pressure varies so that hydrate will form and dissociate in some cyclical manner, such as in oceans where sea level is capable of rising and

  15. Aqueous Two-Phase Systems formed by Biocompatible and Biodegradable Polysaccharides and Acetonitrile

    PubMed Central

    de Brito Cardoso, Gustavo; Souza, Isabela Nascimento; Pereira, Matheus M.; Freire, Mara G.; Soares, Cleide Mara Faria; Lima, Álvaro Silva

    2015-01-01

    In this work, it is shown that novel aqueous two-phase systems can be formed by the combination of acetonitrile and polysaccharides, namely dextran. Several ternary phase diagrams were determined at 25 °C for the systems composed of water + acetonitrile + dextran. The effect of the dextran molecular weight (6,000, 40,000 and 100,000 g.mol−1) was ascertained toward their ability to undergo liquid-liquid demixing. An increase in the dextran molecular weight favors the phase separation. Furthermore, the effect of temperature (25, 35 and 45 °C) was evaluated for the system constituted by the dextran of higher molecular weight. Lower temperatures are favorable for phase separation since lower amounts of dextran and acetonitrile are required for the creation of aqueous two-phase systems. In general, acetonitrile is enriched in the top phase while dextran is majorly concentrated in the bottom phase. The applicability of this new type of two-phase systems as liquid-liquid extraction approaches was also evaluated by the study of the partition behavior of a well-known antioxidant – vanillin - and used here as a model biomolecule. The optimized conditions led to an extraction efficiency of vanillin of 95% at the acetonitrile-rich phase. PMID:25729320

  16. Systemic effects of urban form on air pollution and environmental quality

    SciTech Connect

    Okamoto, P.C.

    1997-12-31

    The form and design of cities and towns have a direct impact on the quality of the natural environment, particularly air and water quality. This paper illustrates some of the dynamic relationships between the form of urban environments and air and water pollution. Recent research suggests how urban form affects environmental quality in at least three ways: (a) how suburban development and its dependency on the private motor vehicle increases air pollution, (b) how exterior building materials help to generate urban heat islands and ozone precursors, and (c) how conventional stormwater drainage systems transport polluted urban runoff into waterways. Today`s aging urban infrastructure provides an important and timely opportunity to re-examine the design of cities and towns with a goal of enhancing overall environmental quality. Many miles of roads, freeways, bridges, and stormwater culverts and pipes are in poor condition and need to be repaired or replaced, while many cities are now failing to meet air and water quality standards designed to protect human and environmental health. This paper also explores seven urban planning and design concepts that could reduce the magnitude of air and water pollution in urban environments and help to improve the health of both cities and their residents.

  17. Statistical description of glass-forming alloys with chemical interaction: Application to Al-R systems

    NASA Astrophysics Data System (ADS)

    Ryltsev, R. E.; Son, L. D.

    2011-10-01

    The statistical model for describing network-forming systems, developed in our previous works, is applied to study of metallic alloys with chemical bonding. The model is based on the representation of the sum of statistical weights over all possible configurations for a thermoreversible network in the form of a functional integral over a scalar field. The mean-field solution of the model is derived, and for particular case of a binary alloy having single element of chemical short-range order A 2B-type, thermodynamic and structural properties have been analyzed. This analysis allows to plot the temperature-concentration phase diagram of the model representing two immiscibility gap meeting in the distectic point. It is shown that at some temperatures and concentrations, geometry percolation of the network of chemical bonds and thus a sol-gel transition may take place. The critical percolation line was plotted in common with phase diagram. Then, the structural transitions, glass-forming ability and magnetic properties of Al-R alloys are discussed in the frames of this conception. It is proposed that the range of easy glass formation is confined on the left by the minimal concentration for the sol-gel transition and on the right by the concentration corresponding to the fractal-to-Euclidian crossover in the structure of percolation cluster. Finally, the abnormal growth of Al-REM magnetic susceptibility occurring above melting point of Al 2R compound is also explained.

  18. Fabrication and electrical characterization of graphene formed chemically on nickel nano electro mechanical system (NEMS) switch.

    PubMed

    Choe, Byeong-In; Lee, Jung-Kyu; Lee, Bora; Kim, Kwanyong; Choi, Woo Young; Hong, Byung Hee; Lee, Jong-Ho

    2014-12-01

    In this work, we successfully fabricated a reliable nano-electro-mechanical system (NEMS) switch with graphene formed chemically on pre-patterned nickel (Ni) film movable beam. Its electrical characteristics were investigated in terms of current-voltage (I-V) and repetitive switching (on/off) properties. The graphene in the movable beam was selectively formed chemically only on the patterned Ni film. Graphene material may help overcome the stiction and reliability problems in nano-electro-mechanical devices. A study on graphene cantilever already has been reported by using only single or multi-layer of transferred graphene. However, the graphene selectively grown on Ni film has not been reported for NEMS switch. The graphene grown on Ni film by chemical vapor deposition method (CVD) were characterized by Raman spectroscopy. The fabricated lateral NEMS switch has w/l/t = 500 nm/20 μm/150 nm as a Ni dimension and an air-gap of -300 nm in lateral direction. The fabricated graphene movable beam formed chemically on Ni film shows reduced pull-in voltage and improved endurance (extended repetitive switching operations). PMID:25971076

  19. A General Closed-Form Solution for the Lunar Reconnaissance Orbiter (LRO) Antenna Pointing System

    NASA Technical Reports Server (NTRS)

    Shah, Neerav; Chen, J. Roger; Hashmall, Joseph A.

    2010-01-01

    The National Aeronautics and Space Administration s (NASA) Lunar Reconnaissance Orbiter (LRO) launched on June 18, 2009 from the Cape Canaveral Air Force Station aboard an Atlas V launch vehicle into a direct insertion trajectory to the Moon LRO, designed, built, and operated by the NASA Goddard Space Flight Center in Greenbelt, MD, is gathering crucial data on the lunar environment that will help astronauts prepare for long-duration lunar expeditions. During the mission s nominal life of one year its six instruments and one technology demonstrator will find safe landing site, locate potential resources, characterize the radiation environment and test new technology. To date, LRO has been operating well within the bounds of its requirements and has been collecting excellent science data images taken from the LRO Camera Narrow Angle Camera (LROC NAC) of the Apollo landing sites have appeared on cable news networks. A significant amount of information on LRO s science instruments is provided at the LRO mission webpage. LRO s Attitude Control System (ACS), in addition to controlling the orientation of the spacecraft is also responsible for pointing the High Gain Antenna (HGA). A dual-axis (or double-gimbaled) antenna, deployed on a meter-long boom, is required to point at a selected Earth ground station. Due to signal loss over the distance from the Moon to Earth, pointing precision for the antenna system is very tight. Since the HGA has to be deployed in spaceflight, its exact geometry relative to the spacecraft body is uncertain. In addition, thermal distortions and mechanical errors/tolerances must be characterized and removed to realize the greatest gain from the antenna system. These reasons necessitate the need for an in-flight calibration. Once in orbit around the moon, a series of attitude maneuvers was conducted to provide data needed to determine optimal parameters to load onboard, which would account for the environmental and mechanical errors at any

  20. Intermolecular potential functions and high resolution molecular spectroscopy of weakly bound complexes. Final progress report

    SciTech Connect

    Muenter, J.S.

    1997-04-01

    This report describes accomplishments over the past year in research supported by this grant. Two papers published in this period are briefly discussed. The general goal of the work is to consolidate the understanding of experimental results through a theoretical model of intermolecular potential energy surfaces. Progress in the experimental and theoretical phases of the program are presented and immediate goals outlined. The ability to construct analytic intermolecular potential functions that accurately predict the energy of interaction between small molecules will have great impact in many areas of chemistry, biochemistry, and biology.

  1. Analysis of hypersonic nozzles including vibrational nonequilibrium and intermolecular force effects

    NASA Technical Reports Server (NTRS)

    Canupp, Patrick W.; Candler, Graham V.; Perkins, John N.; Erickson, Wayne D.

    1992-01-01

    A computational fluid dynamics algorithm is developed for the study of high-pressure axisymmetric hypersonic nozzle flows. The effects of intermolecular forces and vibrational nonequilibrium are included in the analysis. The numerical simulation of gases with an arbitrary equation of state is discussed. Simulations for a high pressure nozzle (p(0) = 138 MPa) demonstrate that both intermolecular forces and vibrational nonequilibrium have a significant affect on the flow. These nonideal effects tend to increase the Mach number at the nozzle exit plane. Thus, they must be included in the design and analysis of high pressure hypersonic nozzles.

  2. Enantioselective intermolecular cross Rauhut-Currier reactions of activated alkenes with acrolein.

    PubMed

    Zhou, Wei; Chen, Peng; Tao, Mengna; Su, Xiao; Zhao, Qingjie; Zhang, Junliang

    2016-06-18

    The enantioselective intermolecular cross Rauhut-Currier reaction of acrolein with active olefins has been a long-standing challenge because of the competitive MBH reaction and polymerization. Herein a highly enantioselective intermolecular cross Rauhut-Currier reaction of acrolein with 3-acyl acrylates and 2-ene-1,4-diones, which is enabled by newly designed Peng-Phos catalysts. This method is scalable and highly enantioselective (up to 96% ee). Several transformations of the R-C products are carried out to showcase the synthetic utility. PMID:27225510

  3. Computational Analysis of Intermolecular Coulombic Decay Effects in DNA nucleotide Photoionization

    NASA Astrophysics Data System (ADS)

    Vargas, E. L.; Robertson, J.; Andrianarijaona, V. M.

    2016-03-01

    Intermolecular Coulombic Decay (ICD) is the process of how electrons return to their original state after excitation and how this affects their immediate environment. In a previous research presentationwe had considered the hypothetical applications of Intermolecular Coulombic Decay on the adhesiveness of coding proteins within DNA molecules. This presentation is a continuation of the previous in that the results of our DFT-based computational calculations of the ionization potentials of nucleotides and their excitation energies will be presented, as well as how they influence their surroundings. Author would like to acknowledge the PUC Student Senate for financial assistance.

  4. Modulation of the intermolecular interaction of myoglobin by removal of the heme

    PubMed Central

    Imamura, Hiroshi; Morita, Takeshi; Sumi, Tomonari; Isogai, Yasuhiro; Kato, Minoru; Nishikawa, Keiko

    2013-01-01

    Toward understanding intermolecular interactions governing self-association of proteins, the present study investigated a model protein, myoglobin, using a small-angle X-ray scattering technique. It has been known that removal of the heme makes myoglobin aggregation-prone. The interparticle interferences of the holomyoglobin and the apomyoglobin were compared in terms of the structure factor. Analysis of the structure factor using a model potential of Derjaguin–Laudau–Verwey–Overbeek (DLVO) suggests that the intermolecular interaction potential of apomyoglobin is more attractive than that of holomyoglobin at short range from the protein molecule. PMID:24121340

  5. The role of entropy and polarity in intermolecular contacts in protein crystals

    SciTech Connect

    Cieślik, Marcin; Derewenda, Zygmunt S.

    2009-05-01

    Logistic regression was used to study the amino-acid composition and structure of crystal contacts in monomeric proteins. Crystal contacts are generally depleted of large flexible amino acids and enriched in small and hydrophobic residues such as Gly and Leu; additionally, larger contacts have cores depleted of polar residues. The integrity and X-ray diffraction quality of protein crystals depend on the three-dimensional order of relatively weak but reproducible intermolecular contacts. Despite their importance, relatively little attention has been paid to the chemical and physical nature of these contacts, which are often regarded as stochastic and thus not different from randomly selected protein surface patches. Here, logistic regression was used to analyze crystal contacts in a database of 821 unambiguously monomeric proteins with structures determined to 2.5 Å resolution or better. It is shown that the propensity of a surface residue for incorporation into a crystal contact is not a linear function of its solvent-accessible surface area and that amino acids with low exposed surfaces, which are typically small and hydrophobic, have been underestimated with respect to their contact-forming potential by earlier area-based calculations. For any given solvent-exposed surface, small and hydrophobic residues are more likely to be involved in crystal contacts than large and charged amino acids. Side-chain entropy is the single physicochemical property that is most negatively correlated with the involvement of amino acids in crystal contacts. It is also shown that crystal contacts with larger buried surfaces containing eight or more amino acids have cores that are depleted of polar amino acids.

  6. Form of an evolutionary tradeoff affects eco-evolutionary dynamics in a predator–prey system

    PubMed Central

    Kasada, Minoru; Yamamichi, Masato; Yoshida, Takehito

    2014-01-01

    Evolution on a time scale similar to ecological dynamics has been increasingly recognized for the last three decades. Selection mediated by ecological interactions can change heritable phenotypic variation (i.e., evolution), and evolution of traits, in turn, can affect ecological interactions. Hence, ecological and evolutionary dynamics can be tightly linked and important to predict future dynamics, but our understanding of eco-evolutionary dynamics is still in its infancy and there is a significant gap between theoretical predictions and empirical tests. Empirical studies have demonstrated that the presence of genetic variation can dramatically change ecological dynamics, whereas theoretical studies predict that eco-evolutionary dynamics depend on the details of the genetic variation, such as the form of a tradeoff among genotypes, which can be more important than the presence or absence of the genetic variation. Using a predator–prey (rotifer–algal) experimental system in laboratory microcosms, we studied how different forms of a tradeoff between prey defense and growth affect eco-evolutionary dynamics. Our experimental results show for the first time to our knowledge that different forms of the tradeoff produce remarkably divergent eco-evolutionary dynamics, including near fixation, near extinction, and coexistence of algal genotypes, with quantitatively different population dynamics. A mathematical model, parameterized from completely independent experiments, explains the observed dynamics. The results suggest that knowing the details of heritable trait variation and covariation within a population is essential for understanding how evolution and ecology will interact and what form of eco-evolutionary dynamics will result. PMID:25336757

  7. Form of an evolutionary tradeoff affects eco-evolutionary dynamics in a predator-prey system.

    PubMed

    Kasada, Minoru; Yamamichi, Masato; Yoshida, Takehito

    2014-11-11

    Evolution on a time scale similar to ecological dynamics has been increasingly recognized for the last three decades. Selection mediated by ecological interactions can change heritable phenotypic variation (i.e., evolution), and evolution of traits, in turn, can affect ecological interactions. Hence, ecological and evolutionary dynamics can be tightly linked and important to predict future dynamics, but our understanding of eco-evolutionary dynamics is still in its infancy and there is a significant gap between theoretical predictions and empirical tests. Empirical studies have demonstrated that the presence of genetic variation can dramatically change ecological dynamics, whereas theoretical studies predict that eco-evolutionary dynamics depend on the details of the genetic variation, such as the form of a tradeoff among genotypes, which can be more important than the presence or absence of the genetic variation. Using a predator-prey (rotifer-algal) experimental system in laboratory microcosms, we studied how different forms of a tradeoff between prey defense and growth affect eco-evolutionary dynamics. Our experimental results show for the first time to our knowledge that different forms of the tradeoff produce remarkably divergent eco-evolutionary dynamics, including near fixation, near extinction, and coexistence of algal genotypes, with quantitatively different population dynamics. A mathematical model, parameterized from completely independent experiments, explains the observed dynamics. The results suggest that knowing the details of heritable trait variation and covariation within a population is essential for understanding how evolution and ecology will interact and what form of eco-evolutionary dynamics will result. PMID:25336757

  8. Extracellular matrix-associated proteins form an integral and dynamic system during Pseudomonas aeruginosa biofilm development

    PubMed Central

    Zhang, Weipeng; Sun, Jin; Ding, Wei; Lin, Jinshui; Tian, Renmao; Lu, Liang; Liu, Xiaofen; Shen, Xihui; Qian, Pei-Yuan

    2015-01-01

    Though the essential role of extracellular matrix in biofilm development has been extensively documented, the function of matrix-associated proteins is elusive. Determining the dynamics of matrix-associated proteins would be a useful way to reveal their functions in biofilm development. Therefore, we applied iTRAQ-based quantitative proteomics to evaluate matrix-associated proteins isolated from different phases of Pseudomonas aeruginosa ATCC27853 biofilms. Among the identified 389 proteins, 54 changed their abundance significantly. The increased abundance of stress resistance and nutrient metabolism-related proteins over the period of biofilm development was consistent with the hypothesis that biofilm matrix forms micro-environments in which cells are optimally organized to resist stress and use available nutrients. Secreted proteins, including novel putative effectors of the type III secretion system were identified, suggesting that the dynamics of pathogenesis-related proteins in the matrix are associated with biofilm development. Interestingly, there was a good correlation between the abundance changes of matrix-associated proteins and their expression. Further analysis revealed complex interactions among these modulated proteins, and the mutation of selected proteins attenuated biofilm development. Collectively, this work presents the first dynamic picture of matrix-associated proteins during biofilm development, and provides evidences that the matrix-associated proteins may form an integral and well regulated system that contributes to stress resistance, nutrient acquisition, pathogenesis and the stability of the biofilm. PMID:26029669

  9. Improving R-value in brick systems using various pore-forming agents

    NASA Astrophysics Data System (ADS)

    Shepherd, Graham Miller

    Energy efficiency and energy savings are two topics that have continued to gain momentum over the last decade. This topic is extremely important when it comes to the construction of buildings and homes. Efforts have been ongoing to increase the insulation value of brick systems to hinder the conductive heat transfer through the material. The use of pore-forming agents (PFA's have been studied to increase the porosity within a ceramic system, through sacrificial burnout or place-holder method, which leave a residual, defined pore size distribution. This increase in porosity leads to better insulating capabilities and inherently lower conductivity values. In this study, varying types and sizes of pore-forming agents were investigated, such as organic fuels/wastes such as peanut hulls, commercially produced ceramic hollow spheres, and aluminum hydroxide. After extrusion and firing, the physical properties (bulk density, cold water absorption, flexural strength, pore size distribution) were investigated to relate to the effect on the thermal conductivity. Both size fractions of peanut hulls (-24/+50 M & -50/+100 M) suggested the lowest recorded thermal conductivity fired to 1100°C at 15% weight addition level at 0.399+/-;0.010 and 0.422+/-0.011 W/m K, respectively.

  10. A method for the quantification of model form error associated with physical systems.

    SciTech Connect

    Wallen, Samuel P.; Brake, Matthew Robert

    2014-03-01

    In the process of model validation, models are often declared valid when the differences between model predictions and experimental data sets are satisfactorily small. However, little consideration is given to the effectiveness of a model using parameters that deviate slightly from those that were fitted to data, such as a higher load level. Furthermore, few means exist to compare and choose between two or more models that reproduce data equally well. These issues can be addressed by analyzing model form error, which is the error associated with the differences between the physical phenomena captured by models and that of the real system. This report presents a new quantitative method for model form error analysis and applies it to data taken from experiments on tape joint bending vibrations. Two models for the tape joint system are compared, and suggestions for future improvements to the method are given. As the available data set is too small to draw any statistical conclusions, the focus of this paper is the development of a methodology that can be applied to general problems.

  11. Effect of retinal ischemia on the non-image forming visual system.

    PubMed

    González Fleitas, María Florencia; Bordone, Melina; Rosenstein, Ruth E; Dorfman, Damián

    2015-03-01

    Retinal ischemic injury is an important cause of visual impairment. The loss of retinal ganglion cells (RGCs) is a key sign of retinal ischemic damage. A subset of RGCs expressing the photopigment melanopsin (mRGCs) regulates non-image-forming visual functions such as the pupillary light reflex (PLR), and circadian rhythms. We studied the effect of retinal ischemia on mRGCs and the non-image-forming visual system function. For this purpose, transient ischemia was induced by raising intraocular pressure to 120 mm Hg for 40 min followed by retinal reperfusion by restoring normal pressure. At 4 weeks post-treatment, animals were subjected to electroretinography and histological analysis. Ischemia induced a significant retinal dysfunction and histological alterations. At this time point, a significant decrease in the number of Brn3a(+) RGCs and in the anterograde transport from the retina to the superior colliculus and lateral geniculate nucleus was observed, whereas no differences in the number of mRGCs, melanopsin levels, and retinal projections to the suprachiasmatic nuclei and the olivary pretectal nucleus were detected. At low light intensity, a decrease in pupil constriction was observed in intact eyes contralateral to ischemic eyes, whereas at high light intensity, retinal ischemia did not affect the consensual PLR. Animals with ischemia in both eyes showed a conserved locomotor activity rhythm and a photoentrainment rate which did not differ from control animals. These results suggest that the non-image forming visual system was protected against retinal ischemic damage. PMID:25238585

  12. 17 CFR 249.821 - Form PILOT, information required of self-regulatory organizations operating pilot trading systems...

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Note: For Federal Register citations affecting Form PILOT, see the List of CFR Sections Affected, which... required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... trading systems pursuant to § 240.19b-5 of this chapter. This form shall be used by all...

  13. 17 CFR 249.821 - Form PILOT, information required of self-regulatory organizations operating pilot trading systems...

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Note: For Federal Register citations affecting Form PILOT, see the List of CFR Sections Affected, which... required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... trading systems pursuant to § 240.19b-5 of this chapter. This form shall be used by all...

  14. 17 CFR 249.821 - Form PILOT, information required of self-regulatory organizations operating pilot trading systems...

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Note: For Federal Register citations affecting Form PILOT, see the List of CFR Sections Affected, which... required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... trading systems pursuant to § 240.19b-5 of this chapter. This form shall be used by all...

  15. 17 CFR 249.821 - Form PILOT, information required of self-regulatory organizations operating pilot trading systems...

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Note: For Federal Register citations affecting Form PILOT, see the List of CFR Sections Affected, which... required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... trading systems pursuant to § 240.19b-5 of this chapter. This form shall be used by all...

  16. 17 CFR 249.821 - Form PILOT, information required of self-regulatory organizations operating pilot trading systems...

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Note: For Federal Register citations affecting Form PILOT, see the List of CFR Sections Affected, which... required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... trading systems pursuant to § 240.19b-5 of this chapter. This form shall be used by all...

  17. Length scales in glass-forming liquids and related systems: a review

    NASA Astrophysics Data System (ADS)

    Karmakar, Smarajit; Dasgupta, Chandan; Sastry, Srikanth

    2016-01-01

    The central problem in the study of glass-forming liquids and other glassy systems is the understanding of the complex structural relaxation and rapid growth of relaxation times seen on approaching the glass transition. A central conceptual question is whether one can identify one or more growing length scale(s) associated with this behavior. Given the diversity of molecular glass-formers and a vast body of experimental, computational and theoretical work addressing glassy behavior, a number of ideas and observations pertaining to growing length scales have been presented over the past few decades, but there is as yet no consensus view on this question. In this review, we will summarize the salient results and the state of our understanding of length scales associated with dynamical slow down. After a review of slow dynamics and the glass transition, pertinent theories of the glass transition will be summarized and a survey of ideas relating to length scales in glassy systems will be presented. A number of studies have focused on the emergence of preferred packing arrangements and discussed their role in glassy dynamics. More recently, a central object of attention has been the study of spatially correlated, heterogeneous dynamics and the associated length scale, studied in computer simulations and theoretical analysis such as inhomogeneous mode coupling theory. A number of static length scales have been proposed and studied recently, such as the mosaic length scale discussed in the random first-order transition theory and the related point-to-set correlation length. We will discuss these, elaborating on key results, along with a critical appraisal of the state of the art. Finally we will discuss length scales in driven soft matter, granular fluids and amorphous solids, and give a brief description of length scales in aging systems. Possible relations of these length scales with those in glass-forming liquids will be discussed.

  18. Length scales in glass-forming liquids and related systems: a review.

    PubMed

    Karmakar, Smarajit; Dasgupta, Chandan; Sastry, Srikanth

    2016-01-01

    The central problem in the study of glass-forming liquids and other glassy systems is the understanding of the complex structural relaxation and rapid growth of relaxation times seen on approaching the glass transition. A central conceptual question is whether one can identify one or more growing length scale(s) associated with this behavior. Given the diversity of molecular glass-formers and a vast body of experimental, computational and theoretical work addressing glassy behavior, a number of ideas and observations pertaining to growing length scales have been presented over the past few decades, but there is as yet no consensus view on this question. In this review, we will summarize the salient results and the state of our understanding of length scales associated with dynamical slow down. After a review of slow dynamics and the glass transition, pertinent theories of the glass transition will be summarized and a survey of ideas relating to length scales in glassy systems will be presented. A number of studies have focused on the emergence of preferred packing arrangements and discussed their role in glassy dynamics. More recently, a central object of attention has been the study of spatially correlated, heterogeneous dynamics and the associated length scale, studied in computer simulations and theoretical analysis such as inhomogeneous mode coupling theory. A number of static length scales have been proposed and studied recently, such as the mosaic length scale discussed in the random first-order transition theory and the related point-to-set correlation length. We will discuss these, elaborating on key results, along with a critical appraisal of the state of the art. Finally we will discuss length scales in driven soft matter, granular fluids and amorphous solids, and give a brief description of length scales in aging systems. Possible relations of these length scales with those in glass-forming liquids will be discussed. PMID:26684508

  19. Evidence for a noncovalent intermolecular interaction of opiates with thiamine.

    PubMed

    Misra, A L; Vadlamani, N L; Pontani, R B

    1977-11-01

    Opiate agonists and antagonists formed reversible molecular complexes with thiamine. The absorption maxima of these complexes were at wavelengths longer than those of the individual components and their intensities depended on the concentration and nature of the opiate component. The possible implications of such an interaction are discussed. PMID:928957

  20. BeSocratic: An Intelligent Tutoring System for the Recognition, Evaluation, and Analysis of Free-Form Student Input

    ERIC Educational Resources Information Center

    Bryfczynski, Samuel Paul

    2012-01-01

    This dissertation describes a novel intelligent tutoring system, BeSocratic, which aims to help fill the gap between simple multiple-choice systems and free-response systems. BeSocratic focuses on targeting questions that are free-form in nature yet defined to the point which allows for automatic evaluation and analysis. The system includes a set…

  1. Multi-input control-affine systems static feedback equivalent to a triangular form and their flatness

    NASA Astrophysics Data System (ADS)

    Li, Shunjie; Nicolau, Florentina; Respondek, Witold

    2016-01-01

    In this paper, we give a complete geometric characterisation of systems locally static feedback equivalent to a triangular form compatible with the chained form, for m = 1, respectively with the m-chained form, for m ≥ 2, where the number of controls is m + 1. They are x-flat systems. We provide a system of first-order PDE's to be solved in order to find all x-flat outputs, for m = 1, respectively all minimal x-flat outputs, for m ≥ 2. We illustrate our results by examples, in particular, by an application to a mechanical system: the coin rolling without slipping on a moving table.

  2. Structural characterization of an intermolecular RNA-RNA interaction involved in the transcription regulation element of a bipartite plant virus.

    PubMed

    Guenther, Richard H; Sit, Tim L; Gracz, Hanna S; Dolan, Michael A; Townsend, Hannah L; Liu, Guihua; Newman, Winnell H; Agris, Paul F; Lommel, Steven A

    2004-01-01

    The 34-nucleotide trans-activator (TA) located within the RNA-2 of Red clover necrotic mosaic virus folds into a simple hairpin. The eight-nucleotide TA loop base pairs with eight complementary nucleotides in the TA binding sequence (TABS) of the capsid protein subgenomic promoter on RNA-1 and trans-activates subgenomic RNA synthesis. Short synthetic oligoribonucleotide mimics of the RNA-1 TABS and the RNA-2 TA form a weak 1:1 bimolecular complex in vitro with a K(a) of 5.3 x 10(4) M(-1). K(a) determination for a series of RNA-1 and RNA-2 mimic variants indicated optimum stability is obtained with seven-base complementarity. Thermal denaturation and NMR show that the RNA-1 TABS 8mers are weakly ordered in solution while RNA-2 TA oligomers form the predicted hairpin. NMR diffusion studies confirmed RNA-1 and RNA-2 oligomer complex formation in vitro. MC-Sym generated structural models suggest that the bimolecular complex is composed of two stacked helices, one being the stem of the RNA-2 TA hairpin and the other formed by the intermolecular base pairing between RNA-1 and RNA-2. The RCNMV TA structural model is similar to those for the Simian retrovirus frameshifting element and the Human immunodeficiency virus-1 dimerization kissing hairpins, suggesting a conservation of form and function. PMID:15155850

  3. The Two Visual Systems Hypothesis: New Challenges and Insights from Visual form Agnosic Patient DF.

    PubMed

    Whitwell, Robert L; Milner, A David; Goodale, Melvyn A

    2014-01-01

    Patient DF, who developed visual form agnosia following carbon monoxide poisoning, is still able to use vision to adjust the configuration of her grasping hand to the geometry of a goal object. This striking dissociation between perception and action in DF provided a key piece of evidence for the formulation of Goodale and Milner's Two Visual Systems Hypothesis (TVSH). According to the TVSH, the ventral stream plays a critical role in constructing our visual percepts, whereas the dorsal stream mediates the visual control of action, such as visually guided grasping. In this review, we discuss recent studies of DF that provide new insights into the functional organization of the dorsal and ventral streams. We confirm recent evidence that DF has dorsal as well as ventral brain damage - and that her dorsal-stream lesions and surrounding atrophy have increased in size since her first published brain scan. We argue that the damage to DF's dorsal stream explains her deficits in directing actions at targets in the periphery. We then focus on DF's ability to accurately adjust her in-flight hand aperture to changes in the width of goal objects (grip scaling) whose dimensions she cannot explicitly report. An examination of several studies of DF's grip scaling under natural conditions reveals a modest though significant deficit. Importantly, however, she continues to show a robust dissociation between form vision for perception and form vision-for-action. We also review recent studies that explore the role of online visual feedback and terminal haptic feedback in the programming and control of her grasping. These studies make it clear that DF is no more reliant on visual or haptic feedback than are neurologically intact individuals. In short, we argue that her ability to grasp objects depends on visual feedforward processing carried out by visuomotor networks in her dorsal stream that function in the much the same way as they do in neurologically intact individuals. PMID

  4. Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory.

    PubMed

    Witte, Jonathon; Neaton, Jeffrey B; Head-Gordon, Martin

    2016-05-21

    With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions-noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms-with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen's pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems. PMID:27208948

  5. Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

    DOE PAGESBeta

    Naumenko, D.; Pint, B. A.; Quadakkers, W. J.

    2016-05-06

    In memory of John Stringer (1934–2014), one of the leaders in studying the reactive element (RE) effects, this paper reviews the current status of understanding of the effect of RE dopants on high-temperature oxidation behavior, with an emphasis on recent research related to deploying alumina-forming alloys and coatings with optimal performance in commercial systems. Additionally, to the well-known interaction between indigenous sulfur and RE additions, effects have been observed with C, N, and O found in commercial alloys and coatings. While there are many similarities between alumina-forming alloys and coatings, the latter bring additional complicating factors such as the effectsmore » of O incorporation during thermal spraying MCrAlY coatings, coating roughness, and heat treatments that must be considered in optimizing the beneficial dopant addition. We can see analogies between RE effects in alloys and in the substrates beneath diffusion M–Al coatings. Recently, there has been more interest in the influence of mixed oxidant environments, since these may modify the manifestation of the RE effect. Some thoughts are provided on optimizing the RE benefit and modeling oxidation of RE-doped alloys.« less

  6. Design of compact LED free-form optical system for aeronautical illumination.

    PubMed

    Cheng, Haobo; Xu, Chunyun; Jing, Xiaoli; Tam, Hon-Yuen

    2015-09-01

    A type of runway centerline light is designed for the application of light-emitting diode (LED) aeronautical illumination. A total internal reflection collimating lens and an integrated prism are designed, respectively, to meet the intensity distribution of International Convention on Civil Aviation (ICAO) regulations. The principle of geometric optics is adopted to construct the free-form surfaces of a collimating lens, which is simple. Different variations are used in the process of free-form surface calculation. An integrated prism with a diffuser is used for uniformly diffusing rays and then decreasing the central maximum intensity to avoid glare. The structure of the optical system is compact. Computer simulation results show that an optical efficiency of 79.2% is achieved for a 1  mm×1  mm LED source. Tolerance analysis is carried out to determine tolerance limits of manufacture and installation errors. To verify the optical performance of the proposed runway centerline light, the practical illumination distribution is measured by using Cree XP-E2 LED, which can comply with ICAO regulations. PMID:26368886

  7. Is there a connection between fragility of glass forming systems and dynamic heterogeneity/cooperativity?

    SciTech Connect

    Hong, L; Novikov, V. N.; Sokolov, Alexei P

    2011-01-01

    Although fragility of glass forming liquids is traditionally related to cooperativity in molecular motion, the connection between those parameters remains unclear. In this paper we present the estimates of cooperativity (heterogeneity) length scale obtained from the boson peak spectra. We demonstrate that agrees well with the dynamic heterogeneity length scale for the structural relaxation estimated by 4- dimensional NMR, justifying the use of . Presented analysis of large number of materials reveals no clear correlation between and fragility. However, there is a strong correlation between the cooperativity volume 3 and the activation volume measured at Tg. This observation suggests that only the volume (pressure) dependence of structural relaxation time correlates directly with the cooperativity size. However, the pure thermal (energetic) contribution to the structural relaxation, the so-called isochoric fragility, exhibits no correlation to the heterogeneity length scale , or the amount of structural units in 3. The presented results call for a revision of traditional view on the role of cooperativity/heterogeneity in structural relaxation of glass forming systems.

  8. Proposal of a new hydrogen-bonding form to maintain curdlan triple helix.

    PubMed

    Miyoshi, Kentaro; Uezu, Kazuya; Sakurai, Kazuo; Shinkai, Seiji

    2004-06-01

    Curdlan and other beta-1,3-D-glucans form right-handed triple helices, and it has been believed that the intermolecular H-bond is present at the center of the helix to maintain the structure. In this H-bond model, three secondary OH groups form an inequilateral hexagonal shape perpendicular to the helix axis. This hexagonal form seems to be characteristic for beta-1,3-D-glucans and is widely accepted. We carried out MOPAC and ab initio calculations for the curdlan helix, and we propose a new intermolecular H-bonding model. In our model, the H-bonds are formed between the O2-atoms on different x-y planes along the curdlan helix, hence the H-bonds are not perpendicular to the helix axis. The new H-bonds are connected along the helix, traversing three curdlan chains to make a left-handed helix. Therefore, the H-bonding array leads to a reverse helix of the main chain. According to our MOPAC calculation, this model is more stable than the previous one. We believe that the continuous H-bonding array is stabilized by cooperative phenomena in the polymeric system. PMID:17191891

  9. An Analysis of Two Textbooks on the Topic of Intermolecular Forces

    ERIC Educational Resources Information Center

    Tan, Daniel Kim Chwee; Seng, Chan Kim

    2004-01-01

    This paper describes the analysis of two commonly used high school (Grades 11 and 12) chemistry textbooks in Singapore to determine if the content presented in the topic of intermolecular forces is consistent with the concepts and propositional knowledge identified by the authors as essential for the learning and understanding of the topic…

  10. Palladium-Catalyzed Intermolecular Aerobic Annulation of o-Alkenylanilines and Alkynes for Quinoline Synthesis.

    PubMed

    Zheng, Jia; Li, Zun; Huang, Liangbin; Wu, Wanqing; Li, Jianxiao; Jiang, Huanfeng

    2016-08-01

    A new approach to construct 2,3-disubstituted quinolines is described via Pd-catalyzed oxidative cyclization of o-vinylanilines and alkynes with molecular oxygen. This transformation is supposed to undergo intermolecular amination of alkyne, insertion of the olefin, and oxidative cleavage of C-C bond sequence. PMID:27418021

  11. Palladium(0)-Catalyzed Intermolecular Allylic Dearomatization of Indoles by a Formal [4+2] Cycloaddition Reaction.

    PubMed

    Gao, Run-Duo; Xu, Qing-Long; Zhang, Bo; Gu, Yiting; Dai, Li-Xin; You, Shu-Li

    2016-08-01

    Bridged indoline derivatives were synthesized by an intermolecular Pd-catalyzed allylic dearomatization reaction of substituted indoles. The reaction between indoles and allyl carbonates bearing a nucleophilic alcohol side-chain proceeds in a cascade fashion, providing bridged indolines in excellent enantioselectivity. PMID:27321285

  12. Copper-catalyzed intermolecular chloroazidation of α,β-unsaturated amides.

    PubMed

    Chen, Long; Xing, Haotian; Zhang, Huaibin; Jiang, Zhong-Xing; Yang, Zhigang

    2016-08-21

    A highly practical copper-catalyzed intermolecular chloroazidation of α,β-unsaturated amides has been described, giving a series of azidochlorides in good-to-excellent yields. The stable azidoiodine(iii) reagent and SOCl2 were used as azide and chlorine sources, respectively. The synthetic applications of this protocol were also explored by a variety of synthetically useful transformations. PMID:27462802

  13. Rhodium(i)-catalysed intermolecular alkyne insertion into (2-pyridylmethylene)cyclobutenes.

    PubMed

    Matsuda, Takanori; Matsumoto, Takeshi

    2016-06-14

    Cyclobutenes with 2-pyridylmethylene groups at the 3 position underwent an intermolecular alkyne insertion reaction in the presence of a rhodium(i) catalyst at 170 °C to afford substituted benzenes. Among the different 2-pyridylmethylene groups examined, 3-methyl-2-pyridyl derivatives showed superior activity and readily coupled with various alkynes, including sterically demanding, heteroaromatic and terminal alkynes. PMID:27193826

  14. Investigation of intermolecular interactions between fluorene-based conjugated polymers using the dispersion-corrected DFT

    NASA Astrophysics Data System (ADS)

    Ayoub, Sarah; Lagowski, Jolanta B.

    2015-03-01

    Alternating triphenylamine-fluorene, TPAFn (n=1-3), and fluorene-oxadiazole OxFn (n=1-3) conjugated copolymers are important components of novel high-efficiency multi-layer organic light-emitting diodes (OLEDs). In this work, we investigate the intermolecular interactions between the various combinations of monomers of OxFn-TPAFn (n=1-3) copolymers using the dispersion-corrected density functional theory (B97D) method. The monomer combinations are taken with and without the presence of long alkyl chains in order to study the effect of side-chains on the polymer backbone intermolecular interactions. The dispersion effect is studied by comparing the structures of the interacting monomers with those in vacuum. In addition, we calculate intermolecular distances, energy gaps and binding energies of monomer dimers corresponding to different pairings of OxFn-TPAFn (n=1-3) monomers. Our results show that the combination of OxF3-TPAF2 monomers exhibites the highest binding energy, closest intermolecular distance, and the best matching of chain lengths amongst all of the combinations of OxFn-TPAFn (n=1-3) monomers. Experiments have shown that OxF3-TPAF2 combination gives the best performance for OLEDS made of OxF-TPAF polymer layers.

  15. Intermolecular forces and nonbonded interactions: Superoperator nonlinear time-dependent density-functional-theory response approach

    SciTech Connect

    Harbola, Upendra; Mukamel, Shaul

    2004-11-01

    Electrostatic and dispersive interactions of polarizable molecules are expressed in terms of generalized (nonretarded) charge-density response functions of the isolated molecules, which in turn are expanded using the collective electronic oscillator (CEO) eigenmodes of linearized time-dependent density-functional theory. Closed expressions for the intermolecular energy are derived to sixth order in charge fluctuation amplitudes.

  16. Using Molecular Dynamics Simulation to Reinforce Student Understanding of Intermolecular Forces

    ERIC Educational Resources Information Center

    Burkholder, Phillip R.; Purser, Gordon H.; Cole, Renee S.

    2008-01-01

    Intermolecular forces play an important role in many aspects of chemistry ranging from inorganic to biological chemistry. These forces dictate molecular conformation, species aggregation (including self-assembly), trends in solubility and boiling points, adsorption characteristics, viscosity, phase changes, surface tension, capillary action, vapor…

  17. Salting Effects as an Illustration of the Relative Strength of Intermolecular Forces

    ERIC Educational Resources Information Center

    Person, Eric C.; Golden, Donnie R.; Royce, Brenda R.

    2010-01-01

    This quick and inexpensive demonstration of the salting of an alcohol out of an aqueous solution illustrates the impact of intermolecular forces on solubility using materials familiar to many students. Ammonium sulfate (fertilizer) is added to an aqueous 35% solution of isopropyl alcohol (rubbing alcohol and water) containing food coloring as a…

  18. Intermolecular Cyclopropanation of Styrenes Using Iodine and Visible Light via Carbon-Iodine Bond Cleavage.

    PubMed

    Usami, Kaoru; Nagasawa, Yoshitomo; Yamaguchi, Eiji; Tada, Norihiro; Itoh, Akichika

    2016-01-01

    The intermolecular cyclopropanation of aromatic olefins with activated methylene compounds using iodine and visible light irradiation was described. This reaction proceeds under rare-metal-free conditions. Styrenes with various substituted groups (alkyl and electron-withdrawing groups) provided corresponding cyclopropanes in moderate to good yields. PMID:26654114

  19. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-01

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  20. THE INTERACTION OF PARAMAGNETIC RELAXATION REAGENTS WITH INTRA- AND INTERMOLECULAR HYDROGEN BONDED PHENOLS

    EPA Science Inventory

    Intermolecular electron-nuclear 13-C relaxation times (T(1)sup e's) from solutions containing the paramagnetic relaxation reagent (PARR), Cr(acac)3, used in conjunction with 13-C T(1)'s in diamagnetic solutions (intramolecular 13-C - (1)H dipolar T(1)'s) provide a significant inc...

  1. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view

    SciTech Connect

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-28

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  2. Electronic structures of intermolecular hydrogen bond contacts with solute in aqueous solution: glycine as a working prototype.

    PubMed

    Meng, Lingbiao; Wu, Weidong; Lin, Zijing

    2016-06-21

    The intermolecular hydrogen bond (H-bond) interactions play vital roles in many biological systems. Despite continued interest, the nature of their electronic structures has remained elusive. Based on the unique features of aqueous solution, a simple model depicting the H-bond electronic states by orbital hybridizations is developed. The model is demonstrated by reproducing the experimental IR data and yielding favorable solute-solvent interactions for the prototype glycine. The H-bond state for solute H, O and N atoms is found to be characterized by sp(1), sp(2), and sp(3) hybridizations, respectively. The model provides a new way for probing the intricate solute-solvent contacts. PMID:27243041

  3. Theoretical study of intermolecular interactions in CB4H8-HOX (X=F, Cl, Br, I) complexes.

    PubMed

    Derikvand, Zohreh; Zabardasti, Abedien; Azadbakht, Azadeh

    2015-11-01

    The molecular aggregation based on intermolecular interactions between CB4H8 and HOX (X=F, Cl, Br and I) with particular emphasis on their bonding characteristics have been investigated using second order Moller-Plesset perturbation (MP2) method with aug-cc-pVDZ basis set. Different kinds of interactions including hydrogen bond (HB; H⋯O, XH; H⋯X), dihydrogen bond (DiHB; H⋯H) and non-classical B-B⋯H interactions were found between CB4H8 and HOX molecules. The structures of complexes have been analyzed using AIM and natural bond orbital methodologies. Good correlations have been found between the interaction energies (SE), the second-order perturbation energies E((2)), and the charge transfer qCT in the studied systems. PMID:26103431

  4. On the Shape of Meissner Solutions to a Limiting Form of Ginzburg-Landau Systems

    NASA Astrophysics Data System (ADS)

    Xiang, Xingfei

    2016-07-01

    In this paper we study a semilinear system involving the curl operator, which is a limiting form of the Ginzburg-Landau model for superconductors in R^3 for a large value of the Ginzburg-Landau parameter. We consider the locations of the maximum points of the magnitude of solutions, which are associated with the nucleation of instability of the Meissner state for superconductors when the applied magnetic field is increased in the transition between the Meissner state and the vortex state. For small penetration depth, we prove that the location is not only determined by the tangential component of the applied magnetic field, but also by the normal curvatures of the boundary in some directions. This improves the result obtained by Bates and Pan in Commun. Math. Phys. 276, 571-610 (2007). We also show that the solutions decay exponentially in the normal direction away from the boundary if the penetration depth is small.

  5. A coupling model for analyzing dynamical behaviors of an electromagnetic forming system

    SciTech Connect

    Bendjima, B.; Srairi, K.; Feliachi, M.

    1997-03-01

    A coupling model for analyzing dynamical behaviors of an electromagnetic forming system consisting of the expansion of a metallic cylinder by means of an internal solenoidal coil is presented. The two equations governing transient magnetic field and dynamic plastic deformation are solved simultaneously by using finite element and Runge-Kutta methods respectively. The electromotive force due to the deformation is considered. Owing to the fact that the mechanical configuration changes during motion, a suitable technique to avoid introduction of speed term as well as the remesh generation at each time step is proposed. Eddy currents, magnetic force density, radial displacement and velocity of the cylinder are calculated. The numerical results are in good agreement with measurements.

  6. Impact of crystalline form changing on behavior of microcapsules prepared from three-component gel system.

    PubMed

    Fenyvesi, Zsófia; Ashour, Khaled Omaru A; Zelkó, Romána; Müller, Ulrich; Antal, István; Klebovich, Imre; Marton, Sylvia

    2010-12-01

    In this paper, the effect of anhydrous-monohydrate process-induced transformation of theophylline was examined in microcapsules produced by in situ gelation method using sodium alginate, hydroxypropylmethylcellulose and hydroxyethylcellulose. Films produced from gel were applied to characterize the changes by NIR spectroscopy, X-ray, DSC method and stereomicroscopy because it is easier to study that in films in the case of gel systems used in situ gelation process. The properties of end-product are influenced by the swelling ability, equilibrium water uptake, release profile and encapsulation efficiency. Water penetration and drug release were evaluated by Davidson-Peppas and Korsmeyer-Peppas models. The ex tempore formed monohydrate crystals were smaller and built into the matrix structure in a greater extent. Increased drug release, matrix erosion and diffuse reflectance values at 1470 and 1950 nm were observed added theophylline later into the gel because of developing a denser structure. PMID:19848611

  7. A model system to analyse the ability of human keratinocytes to form hair follicles.

    PubMed

    Thangapazham, Rajesh L; Klover, Peter; Li, Shaowei; Wang, Ji-An; Sperling, Leonard; Darling, Thomas N

    2014-06-01

    Earlier studies showed that dermal cells lose trichogenic capacity with passage, but studies on the effect of keratinocyte passage on human hair follicle neogenesis and graft quality have been hampered by the lack of a suitable model system. We recently documented human hair follicle neogenesis in grafted dermal-epidermal composites, and in the present study, we determined the effects of keratinocyte passage on hair follicle neogenesis. Dermal equivalents were made with cultured human dermal papilla cells and were overlaid with either primary or passaged human keratinocytes to form dermal-epidermal composites; these were then grafted onto immunodeficient mice. Superior hair follicle neogenesis was observed using early keratinocyte cultures. Characteristics such as formation of hair shafts and sebaceous glands, presence of hair follicles with features of anagen or telogen follicles, and reproducible hair and skin function parameters make this model a tool to study human hair follicle neogenesis and development. PMID:24758480

  8. Molecular cooperativity in the dynamics of glass-forming systems: A new insight

    NASA Astrophysics Data System (ADS)

    Hong, L.; Gujrati, P. D.; Novikov, V. N.; Sokolov, A. P.

    2009-11-01

    The mechanism behind the steep slowing down of molecular motions upon approaching the glass transition remains a great puzzle. Most of the theories relate this mechanism to the cooperativity in molecular motion. In this work, we estimate the length scale of molecular cooperativity ξ for many glass-forming systems from the collective vibrations (the so-called boson peak). The obtained values agree well with the dynamic heterogeneity length scale estimated using four-dimensional NMR. We demonstrate that ξ directly correlates to the dependence of the structural relaxation on volume. This dependence presents only one part of the mechanism of slowing down the structural relaxation. Our analysis reveals that another part, the purely thermal variation in the structural relaxation (at constant volume), does not have a direct correlation with molecular cooperativity. These results call for a conceptually new approach to the analysis of the mechanism of the glass transition and to the role of molecular cooperativity.

  9. Frontier orbital symmetry control of intermolecular electron transfer

    SciTech Connect

    Stevens, B.

    1991-09-01

    This report contains sections describing the selection of electron donor-acceptor systems, the synthesis and photophysical properties of linked electron-donor-acceptor systems, the estimation of photoinduced charge-separation rate constants from fluorescence quenching data, and radical ion-pair recombination by picosecond transient absorption spectroscopy. 9 refs., 1 fig., 7 tabs.

  10. An altered form of pp60/sup c-src/ is expressed primarily in the central nervous system

    SciTech Connect

    Le Beau, J.M.; Wiestler, O.D.; Walter, G.

    1987-11-01

    The expression of two forms of pp60/sup c-scr/, pp60 and pp60/sup +/, was measured in the central nervous system (CNS) and the peripheral nervous system. Both forms were expressed in the CNS, whereas only pp60 was primarily detected in the peripheral nervous system. Our findings suggest that pp60/sup +/ may play a role in events important to the CNS.

  11. Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

    PubMed Central

    2015-01-01

    We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product

  12. Cross-dehydrogenative coupling for the intermolecular C-O bond formation.

    PubMed

    Krylov, Igor B; Vil', Vera A; Terent'ev, Alexander O

    2015-01-01

    The present review summarizes primary publications on the cross-dehydrogenative C-O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C-O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C-O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C-H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C-O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C-H activation processes involving intermolecular C-O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

  13. Energy Decomposition Analysis with a Stable Charge-Transfer Term for Interpreting Intermolecular Interactions.

    PubMed

    Lao, Ka Un; Herbert, John M

    2016-06-14

    Many schemes for decomposing quantum-chemical calculations of intermolecular interaction energies into physically meaningful components can be found in the literature, but the definition of the charge-transfer (CT) contribution has proven particularly vexing to define in a satisfactory way and typically depends strongly on the choice of basis set. This is problematic, especially in cases of dative bonding and for open-shell complexes involving cation radicals, for which one might expect significant CT. Here, we analyze CT interactions predicted by several popular energy decomposition analyses and ultimately recommend the definition afforded by constrained density functional theory (cDFT), as it is scarcely dependent on basis set and provides results that are in accord with chemical intuition in simple cases, and in quantitative agreement with experimental estimates of the CT energy, where available. For open-shell complexes, the cDFT approach affords CT energies that are in line with trends expected based on ionization potentials and electron affinities whereas some other definitions afford unreasonably large CT energies in large-gap systems, which are sometimes artificially offset by underestimation of van der Waals interactions by density functional theory. Our recommended energy decomposition analysis is a composite approach, in which cDFT is used to define the CT component of the interaction energy and symmetry-adapted perturbation theory (SAPT) defines the electrostatic, polarization, Pauli repulsion, and van der Waals contributions. SAPT/cDFT provides a stable and physically motivated energy decomposition that, when combined with a new implementation of open-shell SAPT, can be applied to supramolecular complexes involving molecules, ions, and/or radicals. PMID:27049750

  14. Cross-dehydrogenative coupling for the intermolecular C–O bond formation

    PubMed Central

    Krylov, Igor B; Vil’, Vera A

    2015-01-01

    Summary The present review summarizes primary publications on the cross-dehydrogenative C–O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C–O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C–O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C–H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C–O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C–H activation processes involving intermolecular C–O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

  15. Efficacy of Various Chemical Disinfectants on Biofilms Formed in Spacecraft Potable Water System Component

    NASA Technical Reports Server (NTRS)

    Wong, Willy; Garcia, Veronica; Castro, Victoria; Ott, Mark; Duane

    2009-01-01

    As the provision of potable water is critical for successful habitation of the International Space Station (ISS), life support systems were installed in December 2008 to recycle both humidity from the atmosphere and urine to conserve available water in the vehicle. Pre-consumption testing from the dispensing needle at the Potable Water Dispenser (PWD) indicated that bacterial concentrations exceeded the current ISS specifications of 50 colony forming units (CFU) per ml. Subsequent investigations revealed that a corrugated stainless steel flex hose upstream of the dispensing needle in the PWD was filled with non-sterile water and left at room temperature for over one month before launch. To simulate biofilm formation that was suspected in the flight system, sterile flex hoses were seeded with a consortium of bacterial isolates previously recovered from other ISS water systems, which included Ralstonia pickettii, Burkholderia multivorans, Caulobacter vibrioides., and Cupriavidus pauculus. After 5 days of incubation, these hoses were challenged with various chemical disinfectants including hydrogen peroxide, colloidal silver, and buffered pH solutions to determine the ability of the disinfectants to decrease and maintain bacterial concentrations below ISS specifications. Disinfection efficacy over time was measured by collecting daily heterotrophic plate counts following exposure to the disinfectants. A single flush with either 6% hydrogen peroxide solution or a mixture of 3% hydrogen peroxide and 400 ppb colloidal silver effectively reduced the bacterial concentrations to less than 1 CFU/ml for a period of up to 2 months. Testing results indicated that hydrogen peroxide and mixtures of hydrogen peroxide and colloidal silver have tremendous potential as alternative disinfectants for ISS water systems.

  16. Intermolecular forces in acetonitrile + ethanol binary liquid mixtures

    NASA Astrophysics Data System (ADS)

    Elangovan, A.; Shanmugam, R.; Arivazhagan, G.; Mahendraprabu, A.; Karthick, N. K.

    2015-10-01

    FTIR spectral measurements have been carried out on the binary mixtures of acetonitrile with ethanol at 1:0 (acetonitrile:ethanol), 1:1, 1:2, 1:3 and 0:1 at room temperature. DFT and isosurface calculations have been performed. The acetonitrile + ethanol binary mixtures consist of 1:1, 1:2, 1:3 and 1:4 complexes formed through both the red and blue shifting H-bonds. Inter as well as intra molecular forces are found to exist in 1:3 and 1:4 complexes.

  17. Effects of Extreme Monsoon Precipitation on River Systems Form And Function, an Early Eocene Perspective

    NASA Astrophysics Data System (ADS)

    Plink-Bjorklund, P.; Birgenheier, L.

    2013-12-01

    Here we document effects of extreme monsoon precipitation on river systems with mountainous drainage basin. We discuss the effects of individual extreme monsoon seasons, as well as long-term changes in Earth surface system's form and function. The dataset spans across 1000 m of stratigraphy across ca 200 km of Paleocene and Early Eocene river deposits. The excessive 3-dimensional outcrops, combined with our new Carbon isotope, ichnological and paleosols record allow reconstruction of long-term river system's evolution during the Paleocene-Eocene Thermal Maximum (PETM) ca 56 million years ago, the transient global warming events during Early Eocene Climate Optimum (EECO) ca 53 to 51.5 million years ago, as well as the effects of highly peaked precipitation events during single monsoon seasons. On the single season scale, the increase in precipitation peakedness causes high discharge flooding events that remove large quantities of sediment from the drainage basin, due to stream erosion and landslide initiation. The initiation of landslides is especially significant, as the drainage basin is of high gradient, the monsoon intensification is accompanied by significant vegetation decline, as the monsoon cycle changes to multi-year droughts interrupted by extreme monsoon precipitation. These large discharge floods laden with sediment cause rapid deposition from high-velocity currents that resemble megaflood deposits in that they are dominated by high-velocity and high deposition rate sedimentary structures and thick simple depositional packages (unit bars). Such high deposition rates cause locally rapid channel bed aggradation and thus increase frequency of channel avulsions and cause catastrophic high-discharge terrestrial flooding events across the river basin. On long time scales, fluvial megafan systems, similar to those, e.g. in the Himalayan foreland, developed across the ca 200 km wide river basin, causing significant sediment aggradation and a landscape with high

  18. Did the Solar system form in a sequential triggered star formation event?

    NASA Astrophysics Data System (ADS)

    Parker, Richard J.; Dale, James E.

    2016-02-01

    The presence and abundance of the short-lived radioisotopes (SLRs) 26Al and 60Fe during the formation of the Solar system is difficult to explain unless the Sun formed in the vicinity of one or more massive star(s) that exploded as supernovae. Two different scenarios have been proposed to explain the delivery of SLRs to the protosolar nebula: (i) direct pollution of the protosolar disc by supernova ejecta, and (ii) the formation of the Sun in a sequential star formation event in which supernovae shockwaves trigger further star formation which is enriched in SLRs. The sequentially triggered model has been suggested as being more astrophysically likely than the direct pollution scenario. In this paper, we investigate this claim by analysing a combination of N-body and smoothed particle hydrodynamics simulations of star formation. We find that sequential star formation would result in large age spreads (or even bi-modal age distributions for spatially coincident events) due to the dynamical relaxation of the first star formation event(s). Secondly, we discuss the probability of triggering spatially and temporally discrete populations of stars and find this to be only possible in very contrived situations. Taken together, these results suggest that the formation of the Solar system in a triggered star formation event is as improbable, if not more so, than the direct pollution of the protosolar disc by a supernova.

  19. Coarse-grained models of stripe forming systems: Phase diagrams, anomalies, and scaling hypothesis

    NASA Astrophysics Data System (ADS)

    Mendoza-Coto, Alejandro; Stariolo, Daniel A.

    2012-11-01

    Two coarse-grained models which capture some universal characteristics of stripe forming systems are studied. At high temperatures, the structure factors of both models attain their maxima on a circle in reciprocal space, as a consequence of generic isotropic competing interactions. Although this is known to lead to some universal properties, we show that the phase diagrams have important differences, which are a consequence of the particular k⃗ dependence of the fluctuation spectrum in each model. The phase diagrams are computed in a mean field approximation and also after inclusion of small fluctuations, which are shown to modify drastically the mean field behavior. Observables like the modulation length and magnetization profiles are computed for the whole temperature range accessible to both models and some important differences in behavior are observed. A stripe compression modulus is computed, showing an anomalous behavior with temperature as recently reported in related models. Also, a recently proposed scaling hypothesis for modulated systems is tested and found to be valid for both models studied.

  20. Sorption of nonionic organic compounds in soil-water systems containing a micelle-forming surfactant

    SciTech Connect

    Sun, S.; Inskeep, W.P.; Boyd, S.A. |

    1994-12-31

    The solubility enhancement of nonionic organic compounds (NOCs) by surfactants may represent an important tool in chemical and biological remediation of contaminated soils. In aqueous systems, the presence of dissolved surfactant emulsions or micelles may enhance the solubility of NOCs by acting as a hydrophobic partitioning phase for the NOCs. However, most environmental remediation efforts involve soil-water or sediment-water systems, where surfactant molecules may also interact with the solid phase. An understanding of the effect of surfactants on the sorption and distribution of NOCs in soil or sediment environments will provide an essential basis for utilizing surfactants in environmental remediation. In this study, the authors examined the effect of a micelle-forming surfactant (Triton X-100) on the sorption of 2,2{prime},4,4{prime},5,5{prime}-PCB, 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (p,p{prime}-DDT) and 1,2,4-trichlorobenzene (1,2,4-TCB). A conceptual model, which accurately describes the functional dependence of K* on Triton X-100 concentration, was developed based on the partition coefficients of these NOCs by soil, soil-surfactant, surfactant monomer and surfactant micelle phases. This model can be further modified to provide quantitative prediction of K* of a given NOC at different surfactant concentrations.

  1. Virtual photon exchange, intermolecular interactions and optical response functions

    NASA Astrophysics Data System (ADS)

    Salam, A.

    2015-11-01

    According to molecular quantum electrodynamics, coupling between material particles occurs due to an exchange of one or more virtual photons. In this work, the relationship between polarisability and hyperpolarisability tensors of atoms and molecules that feature in linear and nonlinear optical processes, and their analytically continued form in the complex frequency domain that appear in formulae describing fundamental inter-particle interactions, is studied. Examples involving a single virtual photon exchange, which are linearly proportional to electric dipole moments at each centre, include the electrostatic energy and the resonant transfer of excitation energy. The Casimir-Polder dispersion potential, and its discriminatory counterpart applicable to coupled chiral molecules, are used to illustrate response properties depending on the exchange of two virtual photons. Meanwhile, the energy shift between two hyperpolarisable species, a higher order discriminatory contribution to the dispersion potential, is employed to represent forces arising from the three virtual photon exchange. It is shown that for energy shifts that are quadratic or bilinear or cubic in the transition dipole moment, it is necessary to account for all two- and three-photon optical processes, such as absorption, emission and linear and nonlinear scattering of light in order to arrive at the correct form of the molecular response tensor.

  2. Characterization of Microemulsion Systems Formed by a Mixed 1,3-Dioxolane Ethoxylate / Octyl Glucoside Surfactant System

    SciTech Connect

    Alkhatib, Mayson H; Hayes, Douglas G; Urban, Volker S

    2009-01-01

    The phase behavior of microemulsion systems containing water (or 1.0 wt% NaCl{sub aq}), isooctane, and the binary surfactant system consisting of n-octyl-{beta}-D-glucopyranoside, C{sub 8}{beta}G{sub 1}, and the acid-cleavable alkyl ethoxylate, 4-CH{sub 3}O (CH{sub 2}CH{sub 2}O){sub 7.2}, 2-(CH{sub 2}){sub 12}CH{sub 3}, 2-(CH{sub 2})CH{sub 3}, 1,3-dioxolane, or 'cyclic ketal' ('CK-2,13'), was determined. Large temperature-insensitive one, two, and three-phase microemulsion-phase regions were obtained when equal masses of the two surfactants were employed, suggesting that C{sub 8}{beta}G{sub 1} reduces the temperature sensitivity of CK-2,13's ethoxylate group. Addition of C{sub 8}{beta}G{sub 1} to CK-2,13 greatly improves the latter's low efficiency, evidenced by the formation of a three-phase microemulsion system for surfactant concentrations at low fractions of total surfactants for systems with equal mass ratios of water to oil and CK-2,13 to C{sub 8}{beta}G{sub 1}. Analysis of the phase diagrams also suggests that CK-2,13 and C{sub 8}{beta}G{sub 1} impart hydrophobic and hydrophilic character, respectively, to the surfactant mixture, and that addition of salt further increases the hydrophilicity of C{sub 8}{beta}G{sub 1}, presumably because of the salting-in of the latter. Analysis of small-angle neutron scattering data revealed that the mixed surfactant system formed spherical oil-in-water microemulsions, and that increasing the CK-2,13 fraction among the surfactants reduced the critical microemulsion concentration but slightly increased the nanodroplet size.

  3. The origins of intra- and inter-molecular vibrational couplings: A case study of H2O-Ar on full and reduced-dimensional potential energy surface.

    PubMed

    Hou, Dan; Ma, Yong-Tao; Zhang, Xiao-Long; Li, Hui

    2016-01-01

    The origin and strength of intra- and inter-molecular vibrational coupling is difficult to probe by direct experimental observations. However, explicitly including or not including some specific intramolecular vibrational modes to study intermolecular interaction provides a precise theoretical way to examine the effects of anharmonic coupling between modes. In this work, a full-dimension intra- and inter-molecular ab initio potential energy surface (PES) for H2O-Ar, which explicitly incorporates interdependence on the intramolecular (Q1,  Q2,  Q3) normal-mode coordinates of the H2O monomer, has been calculated. In addition, four analytic vibrational-quantum-state-specific PESs are obtained by least-squares fitting vibrationally averaged interaction energies for the (v1,  v2,  v3) =  (0,  0,  0), (0,  0,  1), (1,  0,  0), (0,  1,  0) states of H2O to the three-dimensional Morse/long-range potential function. Each vibrationally averaged PES fitted to 442 points has root-mean-square (rms) deviation smaller than 0.15 cm(-1), and required only 58 parameters. With the 3D PESs of H2O-Ar dimer system, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels. This showed that the resulting vibrationally averaged PESs provide good representations of the experimental infrared data, with rms discrepancies smaller than 0.02 cm(-1) for all three rotational branches of the asymmetric stretch fundamental transitions. The infrared band origin shifts associated with three fundamental bands of H2O in H2O-Ar complex are predicted for the first time and are found to be in good agreement with the (extrapolated) experimental values. Upon introduction of additional intramolecular degrees of freedom into the intermolecular potential energy surface, there is clear spectroscopic evidence of intra- and intermolecular vibrational couplings. PMID:26747800

  4. Optical BEAMTAP beam-forming and jammer-nulling system for broadband phased-array antennas.

    PubMed

    Kriehn, G; Kiruluta, A; Silveira, P E; Weaver, S; Kraut, S; Wagner, K; Weverka, R T; Griffiths, L

    2000-01-10

    We present an approach to receive-mode broadband beam forming and jammer nulling for large adaptive antenna arrays as well as its efficient and compact optical implementation. This broadband efficient adaptive method for true-time-delay array processing (BEAMTAP) algorithm decreases the number of tapped delay lines required for processing an N-element phased-array antenna from N to only 2, producing an enormous savings in delay-line hardware (especially for large broadband arrays) while still providing the full NM degrees of freedom of a conventional N-element time-delay-and-sum beam former that requires N tapped delay lines with M taps each. This allows the system to adapt fully and optimally to an arbitrarily complex spatiotemporal signal environment that can contain broadband signals of interest, as well as interference sources and narrow-band and broadband jammers--all of which can arrive from arbitrary angles onto an arbitrarily shaped array--thus enabling a variety of applications in radar, sonar, and communication. This algorithm is an excellent match with the capabilities of radio frequency (rf) photonic systems, as it uses a coherent optically modulated fiber-optic feed network, gratings in a photorefractive crystal as adaptive weights, a traveling-wave detector for generating time delay, and an acousto-optic device to control weight adaptation. Because the number of available adaptive coefficients in a photorefractive crystal is as large as 10(9), these photonic systems can adaptively control arbitrarily large one- or two-dimensional antenna arrays that are well beyond the capabilities of conventional rf and real-time digital signal processing techniques or alternative photonic techniques. PMID:18337889

  5. In-situ forming composite implants for periodontitis treatment: How the formulation determines system performance.

    PubMed

    Do, M P; Neut, C; Metz, H; Delcourt, E; Mäder, K; Siepmann, J; Siepmann, F

    2015-01-01

    Periodontitis is the primary cause of tooth loss in adults and a very wide-spread disease. Recently, composite implants, based on a drug release rate controlling polymer and an adhesive polymer, have been proposed for an efficient local drug treatment. However, the processes involved in implant formation and the control of drug release in these composite systems are complex and the relationships between the systems' composition and the implants' performance are yet unclear. In this study, advanced characterization techniques (e.g., electron paramagnetic resonance, EPR) were applied to better understand the in-situ forming implants based on: (i) different types of poly(lactic-co-glycolic acid) (PLGA) as drug release rate controlling polymers; (ii) hydroxypropyl methylcellulose (HPMC) as adhesive polymer; and (iii) doxycycline or metronidazole as drugs. Interestingly, HPMC addition to shorter chain PLGA slightly slows down drug release, whereas in the case of longer chain PLGA the release rate substantially increases. This opposite impact on drug release was rather surprising, since the only difference in the formulations was the polymer molecular weight of the PLGA. Based on the physico-chemical analyses, the underlying mechanisms could be explained as follows: since longer chain PLGA is more hydrophobic than shorter chain PLGA, the addition of HPMC leads to a much more pronounced facilitation of water penetration into the system (as evidenced by EPR). This and the higher polymer lipophilicity result in more rapid PLGA precipitation and a more porous inner implant structure. Consequently, drug release is accelerated. In contrast, water penetration into formulations based on shorter chain PLGA is rather similar in the presence and absence of HPMC and the resulting implants are much less porous than those based on longer chain PLGA. PMID:25791762

  6. An intermolecular electrostatic interaction controls the prepore-to-pore transition in a cholesterol-dependent cytolysin.

    PubMed

    Wade, Kristin R; Hotze, Eileen M; Kuiper, Michael J; Morton, Craig J; Parker, Michael W; Tweten, Rodney K

    2015-02-17

    β-Barrel pore-forming toxins (βPFTs) form an obligatory oligomeric prepore intermediate before the formation of the β-barrel pore. The molecular components that control the critical prepore-to-pore transition remain unknown for βPFTs. Using the archetype βPFT perfringolysin O, we show that E183 of each monomer within the prepore complex forms an intermolecular electrostatic interaction with K336 of the adjacent monomer on completion of the prepore complex. The signal generated throughout the prepore complex by this interaction irrevocably commits it to the formation of the membrane-inserted giant β-barrel pore. This interaction supplies the free energy to overcome the energy barrier (determined here to be ∼ 19 kcal/mol) to the prepore-to-pore transition by the coordinated disruption of a critical interface within each monomer. These studies provide the first insight to our knowledge into the molecular mechanism that controls the prepore-to-pore transition for a βPFT. PMID:25646411

  7. Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

    SciTech Connect

    Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

    2014-08-14

    The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X-(H2O), X = F, Cl, Br, I, and alkali metal-water, M+(H2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits to the ab initio data that are between one and two orders of magnitude better in the χ2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.

  8. Intramolecular photo-switching and intermolecular energy transfer as primary photoevents in photoreceptive processes: The case of Euglena gracilis

    SciTech Connect

    Mercatelli, Raffaella; Quercioli, Franco; Barsanti, Laura; Evangelista, Valter; Coltelli, Primo; Passarelli, Vincenzo; Frassanito, Anna Maria; Gualtieri, Paolo

    2009-07-24

    In this paper we report the results of measurements performed by FLIM on the photoreceptor of Euglenagracilis. This organelle consists of optically bistable proteins, characterized by two thermally stable isomeric forms: A{sub 498,} non fluorescent and B{sub 462}, fluorescent. Our data indicate that the primary photoevent of Euglena photoreception upon photon absorption consists of two contemporaneous different phenomena: an intramolecular photo-switch (i.e., A{sub 498} becomes B{sub 462}), and a intermolecular and unidirectional Forster-type energy transfer. During the FRET process, the fluorescent B{sub 462} form acts as donor for the non-fluorescent A{sub 498} form of the protein nearby, which acts as acceptor. We hypothesize that in nature these phenomena follow each other with a domino progression along the orderly organized and closely packed proteins in the photoreceptor layer(s), modulating the isomeric composition of the photoreceptive protein pool. This mechanism guarantees that few photons are sufficient to produce a signal detectable by the cell.

  9. A novel bioprinting method and system for forming hybrid tissue engineering constructs.

    PubMed

    Shanjani, Y; Pan, C C; Elomaa, L; Yang, Y

    2015-01-01

    Three dimensional (3D) bioprinting is a promising approach to form tissue engineering constructs (TECs) via positioning biomaterials, growth factors, and cells with controlled spatial distribution due to its layer-by-layer manufacturing nature. Hybrid TECs composed of relatively rigid porous scaffolds for structural and mechanical integrity and soft hydrogels for cell- and growth factor-loading have a tremendous potential to tissue regeneration under mechanical loading. However, despite excessive progress in the field, the current 3D bioprinting techniques and systems fall short in integration of such soft and rigid multifunctional components. Here we present a novel 3D hybrid bioprinting technology (Hybprinter) and its capability enabling integration of soft and rigid components for TECs. Hybprinter employs digital light processing-based stereolithography (DLP-SLA) and molten material extrusion techniques for soft and rigid materials, respectively. In this study, poly-ethylene glycol diacrylate (PEGDA) and poly-(ε-caprolactone) (PCL) were used as a model material for soft hydrogel and rigid scaffold, respectively. It was shown that geometrical accuracy, swelling ratio and mechanical properties of the hydrogel component can be tailored by DLP-SLA module. We have demonstrated the printability of variety of complex hybrid construct designs using Hybprinter technology and characterized the mechanical properties and functionality of such constructs. The compressive mechanical stiffness of a hybrid construct (90% hydrogel) was significantly higher than hydrogel itself (∼6 MPa versus 100 kPa). In addition, viability of cells incorporated within the bioprinted hybrid constructs was determined approximately 90%. Furthermore, a functionality of a hybrid construct composed of porous scaffold with an embedded hydrogel conduit was characterized for vascularized tissue engineering applications. High material diffusion and high cell viability in about 2.5 mm distance

  10. Intermolecular interactions of lysobisphosphatidic acid with phosphatidylcholine in mixed bilayers.

    PubMed

    Holopainen, Juha M; Söderlund, Tim; Alakoskela, Juha-Matti; Säily, Matti; Eriksson, Ove; Kinnunen, Paavo K J

    2005-01-01

    Lysobisphosphatidic acid (LBPA) can be regarded to represent a unique derivative of phosphatidylglycerol. This lipid is highly enriched in late endosomes where it can comprise up to 10-15 mol% of all lipids and in these membranes, LBPA appears to be segregated into microdomains. We studied the thermotropic behavior of pure dioleoyl-LBPA mono- and bilayers using Langmuir-lipid monolayers, electron microscopy, differential scanning calorimetry (DSC), and fluorescence spectroscopy. LBPA formed metastable, liquid-expanded monolayers at an air/buffer interface, and its compression isotherms lacked any indication for structural phase transitions. Neat LBPA formed multilamellar vesicles with no structural transitions or phase transitions between 10 and 80 degrees C at a pH range of 3.0-7.4. We then proceeded to study mixed LBPA/dipalmitoylphosphatidylcholine (DPPC) bilayers by DSC and fluorescence spectroscopy. Incorporating increasing amounts of LBPA (up to X(LBPA) (molar fraction)=0.10) decreased the co-operativity of the main transition for DPPC, and a decrease in the main phase transition as well as pretransition temperature of DPPC was observed yet with no effect on the enthalpy of this transition. In keeping with the DSC data for DPPC, 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC)/LBPA mixed bilayers were more fluid, and no evidence for lateral phase segregation was observed. These results were confirmed using fluorescence microscopy of Langmuir-lipid films composed of POPC and LBPA up to X(LBPA)=0.50 with no evidence for lateral phase separation. As late endosomes are eminently acidic, we examined the effect of lowering pH on lateral organization of mixed PC/LBPA bilayers by DSC and fluorescence spectroscopy. Even at pH 3.0, we find no evidence of LBPA-induced microdomain formation at LBPA contents found in cellular organelles. PMID:15589226

  11. Helping Students Assess the Relative Importance of Different Intermolecular Interactions

    ERIC Educational Resources Information Center

    Jasien, Paul G.

    2008-01-01

    A semi-quantitative model has been developed to estimate the relative effects of dispersion, dipole-dipole interactions, and H-bonding on the normal boiling points ("T[subscript b]") for a subset of simple organic systems. The model is based upon a statistical analysis using multiple linear regression on a series of straight-chain organic…

  12. The Factor Structure of the BASC-2 Behavioral and Emotional Screening System Teacher Form, Child/Adolescent

    ERIC Educational Resources Information Center

    Dever, Bridget V.; Mays, Kristen L.; Kamphaus, Randy W.; Dowdy, Erin

    2012-01-01

    The BASC-2 Behavioral and Emotional Screening System Teacher, Child/Adolescent Form (BESS Teacher Form C/A; Kamphaus & Reynolds, 2007) is a brief teacher-report rating scale designed to identify students who are at-risk for behavioral and emotional problems. The aim of this study was to describe the latent dimensions that underlie the responses to…

  13. Attractivity of the Ginzburg-Landau mode distribution for a pattern forming system with marginally stable long modes

    NASA Astrophysics Data System (ADS)

    Düll, Wolf-Patrick; Kashani, Kourosh Sanei; Schneider, Guido; Zimmermann, Dominik

    2016-07-01

    The mathematical theory of the description of pattern forming systems close to the first instability via the Ginzburg-Landau equation is based on approximation and attractivity results. This theory allowed to prove global existence results and upper semicontinuity of attractors for classical hydrodynamical stability problems such as the Couette-Taylor problem. Recently, approximation results for the Ginzburg-Landau approximation for pattern forming systems with marginally stable long modes, such as the Bénard-Marangoni system, have been shown. It is the purpose of this paper to prove the second fundamental property, namely the attractivity of the Ginzburg-Landau mode distribution, for such systems.

  14. Circulating colony-forming units of granulocytes and monocytes/macrophages in systemic lupus erythematosus.

    PubMed Central

    López-Karpovitch, X; Cardiel, M; Cardenas, R; Piedras, J; Alarcón-Segovia, D

    1989-01-01

    In systemic lupus erythematosus (SLE) patients, in vitro bone marrow (BM) colony-forming units of granulocytes and monocytes/macrophages (CFU-GM) are decreased, suggesting that granulomonopoietic failure may play an important role in the mechanism of peripheral blood (PB) depletion of neutrophils and monocytes. No information concerning CFU-GM in PB of patients with SLE is available. The present study was undertaken in order to determine whether SLE itself and the inactive or active stage of disease would modify the number of GFU-GM in PB samples from 20 treatment-free SLE women, 12 inactive and eight active. CFU-GM growth was significantly decreased in both inactive (P = 0.018) and active (P = 0.008) SLE patients as compared with controls (n = 8). The difference in CFU-GM growth between SLE groups was not significant. These results indicate that the number of circulating CFU-GM is significantly reduced in patients with SLE regardless of disease activity or remission. PMID:2766577

  15. Droplet-based microfluidic system to form and separate multicellular spheroids using magnetic nanoparticles.

    PubMed

    Yoon, Sungjun; Kim, Jeong Ah; Lee, Seung Hwan; Kim, Minsoo; Park, Tai Hyun

    2013-04-21

    The importance of creating a three-dimensional (3-D) multicellular spheroid has recently been gaining attention due to the limitations of monolayer cell culture to precisely mimic in vivo structure and cellular interactions. Due to this emerging interest, researchers have utilized new tools, such as microfluidic devices, that allow high-throughput and precise size control to produce multicellular spheroids. We have developed a droplet-based microfluidic system that can encapsulate both cells and magnetic nanoparticles within alginate beads to mimic the function of a multicellular tumor spheroid. Cells were entrapped within the alginate beads along with magnetic nanoparticles, and the beads of a relatively uniform size (diameters of 85% of the beads were 170-190 μm) were formed in the oil phase. These beads were passed through parallel streamlines of oil and culture medium, where the beads were magnetically transferred into the medium phase from the oil phase using an external magnetic force. This microfluidic chip eliminates additional steps for collecting the spheroids from the oil phase and transferring them to culture medium. Ultimately, the overall spheroid formation process can be achieved on a single microchip. PMID:23426090

  16. Method and system for constructing a rechargeable battery and battery structures formed with the method

    DOEpatents

    Hobson, David O.; Snyder, Jr., William B.

    1995-01-01

    A method and system for manufacturing a thin-film battery and a battery structure formed with the method utilizes a plurality of deposition stations at which thin battery component films are built up in sequence upon a web-like substrate as the substrate is automatically moved through the stations. At an initial station, cathode and anode current collector film sections are deposited upon the substrate, and at another station, a thin cathode film is deposited upon the substrate so to overlie part of the cathode current collector section. At another station, a thin electrolyte film is deposited upon so as to overlie the cathode film and part of the anode current collector film, at yet another station, a thin lithium film is deposited upon so as to overlie the electrolyte film and an additional part of the anode current collector film. Such a method accommodates the winding of a layup of battery components into a spiral configuration to provide a thin-film, high capacity battery and also accommodates the build up of thin film battery components onto a substrate surface having any of a number of shapes.

  17. [Relationship between the oxidation-reduction system of astrocytes with production of active forms of oxygen].

    PubMed

    Semenkova, G N; Kvacheva, Z B; Obydennikova, S V; Cherenkevich, S N; Titov, L P

    1998-01-01

    Cells of neuroglia--the astrocytes are of interest from the point of view of their participation in phagocytosis. Phagocyte ability to generate active oxygen forms (AOF) as used as the basic criterion of the estimation of their functional activity. For the purpose to clear up molecular and cellular mechanisms of phagocytosis a study of astrocyte redox-systems, participating in production of AOF, was undertaken. Registration of AOF in astrocytes was carried out using a method of luminol-dependent chemiluminescence. Primary culture of guinea pig astrocytes was used. Spontaneous chemiluminescence of low intensity was found for the astrocytes at the presence of luminol. The destruction of the cells was accompanied by a significant growth of the intensity of spontaneous chemiluminescence. Suspension of endocutosis inductors, particle of latex and phytohemagglutinin, added to astrocytes did not result in formation of AOF, characteristic for other cells, possessing phagocytosis. It was established, that addition of hydrogen peroxide destroys astrocytes at the presence of luminol and gives rise to the emission. Chemiluminescence was not observed in similar experiments with intact cells. A conclusion was made that inside astrocytes there are structures, which show peroxidase-like activity. PMID:9848214

  18. Solute diffusion through fibrotic tissue formed around protective cage system for implantable devices.

    PubMed

    Prihandana, Gunawan Setia; Ito, Hikaru; Tanimura, Kohei; Yagi, Hiroshi; Hori, Yuki; Soykan, Orhan; Sudo, Ryo; Miki, Norihisa

    2015-08-01

    This article presents the concept of an implantable cage system that can house and protect implanted biomedical sensing and therapeutic devices in the body. Cylinder-shaped cages made of porous polyvinyl alcohol (PVA) sheets with an 80-µm pore size and/or stainless steel meshes with 0.54-mm openings were implanted subcutaneously in the dorsal region of rats for 5 weeks. Analysis of the explanted cages showed the formation of fibrosis tissue around the cages. PVA cages had fibrotic tissue growing mostly along the outer surface of cages, while stainless steel cages had fibrotic tissue growing into the inside surface of the cage structure, due to the larger porosity of the stainless steel meshes. As the detection of target molecules with short time lags for biosensors and mass transport with low diffusion resistance into and out of certain therapeutic devices are critical for the success of such devices, we examined whether the fibrous tissue formed around the cages were permeable to molecules of our interest. For that purpose, bath diffusion and microfluidic chamber diffusion experiments using solutions containing the target molecules were performed. Diffusion of sodium, potassium and urea through the fibrosis tissue was confirmed, thus suggesting the potential of these cylindrical cages surrounded by fibrosis tissue to successfully encase implantable sensors and therapeutic apparatus. PMID:25303239

  19. Atom depth analysis delineates mechanisms of protein intermolecular interactions

    SciTech Connect

    Alocci, Davide; Bernini, Andrea; Niccolai, Neri

    2013-07-12

    Highlights: •3D atom depth analysis is proposed to identify different layers in protein structures. •Amino acid contents for each layers have been analyzed for a large protein dataset. •Charged amino acids in the most external layer are present at very different extents. •Atom depth indexes of K residues reflect their side chains flexibility. •Mobile surface charges can be responsible for long range protein–protein recognition. -- Abstract: The systematic analysis of amino acid distribution, performed inside a large set of resolved protein structures, sheds light on possible mechanisms driving non random protein–protein approaches. Protein Data Bank entries have been selected using as filters a series of restrictions ensuring that the shape of protein surface is not modified by interactions with large or small ligands. 3D atom depth has been evaluated for all the atoms of the 2,410 selected structures. The amino acid relative population in each of the structural layers formed by grouping atoms on the basis of their calculated depths, has been evaluated. We have identified seven structural layers, the inner ones reproducing the core of proteins and the outer one incorporating their most protruding moieties. Quantitative analysis of amino acid contents of structural layers identified, as expected, different behaviors. Atoms of Q, R, K, N, D residues are increasingly more abundant in going from core to surfaces. An opposite trend is observed for V, I, L, A, C, and G. An intermediate behavior is exhibited by P, S, T, M, W, H, F and Y. The outer structural layer hosts predominantly E and K residues whose charged moieties, protruding from outer regions of the protein surface, reorient free from steric hindrances, determining specific electrodynamics maps. This feature may represent a protein signature for long distance effects, driving the formation of encounter complexes and the eventual short distance approaches that are required for protein

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

    SciTech Connect

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

    2014-10-07

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

  1. Mechanochemical mechanism for fast reaction of metastable intermolecular composites based on dispersion of liquid metal

    NASA Astrophysics Data System (ADS)

    Levitas, Valery I.; Asay, Blaine W.; Son, Steven F.; Pantoya, Michelle

    2007-04-01

    An unexpected mechanism for fast reaction of Al nanoparticles covered by a thin oxide shell during fast heating is proposed and justified theoretically and experimentally. For nanoparticles, the melting of Al occurs before the oxide fracture. The volume change due to melting induces pressures of 1-2 GPa and causes dynamic spallation of the shell. The unbalanced pressure between the Al core and the exposed surface creates an unloading wave with high tensile pressures resulting in dispersion of atomic scale liquid Al clusters. These clusters fly at high velocity and their reaction is not limited by diffusion (this is the opposite of traditional mechanisms for micron particles and for nanoparticles at slow heating). Physical parameters controlling the melt dispersion mechanism are found by our analysis. In addition to an explanation of the extremely short reaction time, the following correspondence between our theory and experiments are obtained: (a) For the particle radius below some critical value, the flame propagation rate and the ignition time delay are independent of the radius; (b) damage of the oxide shell suppresses the melt dispersion mechanism and promotes the traditional diffusive oxidation mechanism; (c) nanoflakes react more like micron size (rather than nanosize) spherical particles. The reasons why the melt dispersion mechanism cannot operate for the micron particles or slow heating of nanoparticles are determined. Methods to promote the melt dispersion mechanism, to expand it to micron particles, and to improve efficiency of energetic metastable intermolecular composites are formulated. In particular, the following could promote the melt dispersion mechanism in micron particles: (a) Increasing the temperature at which the initial oxide shell is formed; (b) creating initial porosity in the Al; (c) mixing of the Al with a material with a low (even negative) thermal expansion coefficient or with a phase transformation accompanied by a volume reduction

  2. Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides.

    PubMed

    Batrice, Rami J; Kefalidis, Christos E; Maron, Laurent; Eisen, Moris S

    2016-02-24

    The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ(2)-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle. PMID:26844823

  3. Three-dimensional structures formed by a robotic and meltblowing integrated system

    NASA Astrophysics Data System (ADS)

    Velu, Yogeshwar Karunakaran

    Meltblown nonwovens have been produced as 2D web structures for a variety of end uses. Investigation into the development of 3D structures, has led to the integration of meltblown and robotic technology to form the Robotic Fiber Assembly and Control System. The effects of various process parameters including the fiber stream approach angle and the curvature of the collecting surface on the structural properties of the webs such as the diameter and orientation distribution of the fibers and the pore size distribution on the webs has been investigated. The interrelationships between these structural parameters have been explored and a statistical model developed. Orientation distribution, and the fiber diameter distribution of the webs were measured on image analysis software, while the pore size distribution was measured using equipment developed on the basis of capillary flow technique. SAS was used to develop the correlations between the structural parameters of the web. In general, all the webs show a larger percentage of fibers orienting in the machine direction (MD). The webs with finer fiber diameter produced webs with smaller pore diameter. The take-up speed of the collector had a significant influence on the orientation and diameters of the fibers in the web. Finer fibers were formed which are more oriented in the machine direction as the take-up speed of the collecting surface increased resulting in the formation of a web which has pores with finer diameter. A decrease in the polymer throughput demonstrated a decrease in the fiber diameter, the pore diameter and the basis weights of the webs. The resulting webs also produced pores that are of finer diameter. Lower attenuating air pressures produced larger diameter fibers. The average pore diameter of the analyzed meltblown fabrics decreased significantly when the attenuating air pressure was increased. Increasing the die to collector distance (DCD) shows a decrease in the percentage of fibers that are

  4. Changes of microstructure characteristics and intermolecular interactions of preserved egg white gel during pickling.

    PubMed

    Zhao, Yan; Chen, Zhangyi; Li, Jianke; Xu, Mingsheng; Shao, Yaoyao; Tu, Yonggang

    2016-07-15

    Changes in gel microstructure characteristics and in intermolecular interactions of preserved egg whites during pickling were investigated. Spin-spin relaxation times of preserved egg whites significantly decreased in the first 8 days and remained unchanged after the 16th day. SEM images revealed a three-dimensional gel network, interwoven with a loose linear fibrous mesh structure. The protein gel mesh structure became more regular, smaller, and compacted with pickling time. Free sulfhydryl contents in the egg whites increased significantly, while total sulfhydryl contents dramatically decreased during pickling. The primary intermolecular forces in the preserved egg white gels were ionic and disulfide bonds. Secondary forces included hydrophobic interaction and relatively few hydrogen bonds. During the first 8 days, the proportion of ionic bonds sharply decreased, and that of disulfide bonds increased over the first 24 days. PMID:26948621

  5. Intramolecular and Intermolecular Interactions in Hybrid Organic-Inorganic Alucone Films Grown by Molecular Layer Deposition.

    PubMed

    Park, Yi-Seul; Kim, Hyein; Cho, Boram; Lee, Chaeyun; Choi, Sung-Eun; Sung, Myung Mo; Lee, Jin Seok

    2016-07-13

    Investigation of molecular interactions in polymeric films is crucial for understanding and engineering multiscale physical phenomena correlated to device function and performance, but this often involves a compromise between theoretical and experimental data, because of poor film uniformity. Here, we report the intramolecular and intermolecular interactions inside the ultrathin and conformal hybrid organic-inorganic alucone films grown by molecular layer deposition, based on sequential and self-limiting surface reactions. Varying the carbon chain length of organic precursors, which affects their molecular flexibility, caused intramolecular interactions such as double reactions by bending of the molecular backbone, resulting in formation of hole vacancies in the films. Furthermore, intermolecular interactions in alucone polymeric films are dependent on the thermal kinetics of molecules, leading to binding failures and cross-linking at low and high growth temperatures, respectively. We illustrate these key interactions and identify molecular geometries and potential energies by density functional theory calculations. PMID:27314844

  6. Influence of intermolecular potentials on rarefied gas flows: Fast spectral solutions of the Boltzmann equation

    NASA Astrophysics Data System (ADS)

    Wu, Lei; Liu, Haihu; Zhang, Yonghao; Reese, Jason M.

    2015-08-01

    The Boltzmann equation with an arbitrary intermolecular potential is solved by the fast spectral method. As examples, noble gases described by the Lennard-Jones potential are considered. The accuracy of the method is assessed by comparing both transport coefficients with variational solutions and mass/heat flow rates in Poiseuille/thermal transpiration flows with results from the discrete velocity method. The fast spectral method is then applied to Fourier and Couette flows between two parallel plates, and the influence of the intermolecular potential on various flow properties is investigated. It is found that for gas flows with the same rarefaction parameter, differences in the heat flux in Fourier flow and the shear stress in Couette flow are small. However, differences in other quantities such as density, temperature, and velocity can be very large.

  7. Controlled electrical doping of organic semiconductors: a combined intra- and intermolecular perspective from first principles.

    PubMed

    Joo, Bora; Kim, Eung-Gun

    2016-07-21

    The process of introducing extra charge carriers into organic semiconductors, or simply molecular doping, takes place via intermolecular charge transfer from the donor to the acceptor molecule. Using density functional theory calculations on diverse donor-acceptor pairs, we show that there are two modes of charge transfer; in one, charge transfer is controlled by the sign and in the other, by the magnitude of the donor HOMO-acceptor LUMO level offset. Despite doping being an intermolecular process, the identification of the transfer modes requires a full account of intramolecular geometric changes during charge transfer. We further show that the degree of charge transfer can be represented entirely by the reorganization energy, a common measure of geometric changes, of either the donor or the acceptor. PMID:27314750

  8. Optical Activity Enhanced by Strong Inter-molecular Coupling in Planar Chiral Metamaterials

    PubMed Central

    Kim, Teun-Teun; Oh, Sang Soon; Park, Hyun-Sung; Zhao, Rongkuo; Kim, Seong-Han; Choi, Wonjune; Min, Bumki; Hess, Ortwin

    2014-01-01

    The polarization of light can be rotated in materials with an absence of molecular or structural mirror symmetry. While this rotating ability is normally rather weak in naturally occurring chiral materials, artificial chiral metamaterials have demonstrated extraordinary rotational ability by engineering intra-molecular couplings. However, while in general, chiral metamaterials can exhibit strong rotatory power at or around resonances, they convert linearly polarized waves into elliptically polarized ones. Here, we demonstrate that strong inter-molecular coupling through a small gap between adjacent chiral metamolecules can lead to a broadband enhanced rotating ability with pure rotation of linearly polarized electromagnetic waves. Strong inter-molecular coupling leads to nearly identical behaviour in magnitude, but engenders substantial difference in phase between transmitted left and right-handed waves. PMID:25209452

  9. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    NASA Astrophysics Data System (ADS)

    Chavda, Bhavin R.; Gandhi, Sahaj A.; Dubey, Rahul P.; Patel, Urmila H.; Barot, Vijay M.

    2016-05-01

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb -London -Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

  10. Intermolecular vibrational frequencies of the C-bonded CO2sbnd CO dimer and observation of Hesbnd CO2sbnd CO trimers

    NASA Astrophysics Data System (ADS)

    Barclay, A. J.; Sheybani-Deloui, S.; Michaelian, K. H.; McKellar, A. R. W.; Moazzen-Ahmadi, N.

    2016-05-01

    Infrared spectra of the CO2sbnd CO dimer are observed in the carbon monoxide CO stretch region (≈2150 cm-1). Combination bands yield the first experimental determinations of intermolecular mode frequencies for the planar T-shaped C-bonded form ('isomer 1'): 24.34 cm-1 for the in-plane CO rock and 43.96 cm-1 for the out-of-plane CO rock. These values are significantly higher than the analogous modes of the O-bonded form ('isomer 2'), previously determined to be 14.19 and 22.68 cm-1, respectively. New results are also reported for both isomers of the 12C18O2-substituted form of the dimer. Weak 'satellite bands' observed for both isomers are tentatively assigned to the trimer Hesbnd CO2sbnd CO.

  11. Influence of intermolecular forces at critical-point wedge filling

    NASA Astrophysics Data System (ADS)

    Malijevský, Alexandr; Parry, Andrew O.

    2016-04-01

    We use microscopic density functional theory to study filling transitions in systems with long-ranged wall-fluid and short-ranged fluid-fluid forces occurring in a right-angle wedge. By changing the strength of the wall-fluid interaction we can induce both wetting and filling transitions over a wide range of temperatures and study the order of these transitions. At low temperatures we find that both wetting and filling transitions are first order in keeping with predictions of simple local effective Hamiltonian models. However close to the bulk critical point the filling transition is observed to be continuous even though the wetting transition remains first order and the wetting binding potential still exhibits a small activation barrier. The critical singularities for adsorption for the continuous filling transitions depend on whether retarded or nonretarded wall-fluid forces are present and are in excellent agreement with predictions of effective Hamiltonian theory even though the change in the order of the transition was not anticipated.

  12. The structure and intermolecular forces of DNA condensates

    PubMed Central

    Yoo, Jejoong; Aksimentiev, Aleksei

    2016-01-01

    Spontaneous assembly of DNA molecules into compact structures is ubiquitous in biological systems. Experiment has shown that polycations can turn electrostatic self-repulsion of DNA into attraction, yet the physical mechanism of DNA condensation has remained elusive. Here, we report the results of atomistic molecular dynamics simulations that elucidated the microscopic structure of dense DNA assemblies and the physics of interactions that makes such assemblies possible. Reproducing the setup of the DNA condensation experiments, we measured the internal pressure of DNA arrays as a function of the DNA–DNA distance, showing a quantitative agreement between the results of our simulations and the experimental data. Analysis of the MD trajectories determined the DNA–DNA force in a DNA condensate to be pairwise, the DNA condensation to be driven by electrostatics of polycations and not hydration, and the concentration of bridging cations, not adsorbed cations, to determine the magnitude and the sign of the DNA–DNA force. Finally, our simulations quantitatively characterized the orientational correlations of DNA in DNA arrays as well as diffusive motion of DNA and cations. PMID:26883635

  13. The structure and intermolecular forces of DNA condensates.

    PubMed

    Yoo, Jejoong; Aksimentiev, Aleksei

    2016-03-18

    Spontaneous assembly of DNA molecules into compact structures is ubiquitous in biological systems. Experiment has shown that polycations can turn electrostatic self-repulsion of DNA into attraction, yet the physical mechanism of DNA condensation has remained elusive. Here, we report the results of atomistic molecular dynamics simulations that elucidated the microscopic structure of dense DNA assemblies and the physics of interactions that makes such assemblies possible. Reproducing the setup of the DNA condensation experiments, we measured the internal pressure of DNA arrays as a function of the DNA-DNA distance, showing a quantitative agreement between the results of our simulations and the experimental data. Analysis of the MD trajectories determined the DNA-DNA force in a DNA condensate to be pairwise, the DNA condensation to be driven by electrostatics of polycations and not hydration, and the concentration of bridging cations, not adsorbed cations, to determine the magnitude and the sign of the DNA-DNA force. Finally, our simulations quantitatively characterized the orientational correlations of DNA in DNA arrays as well as diffusive motion of DNA and cations. PMID:26883635

  14. Computation of Normal Forms of Bogdanov-Takens Singularities for High Dimensional Nonlinear Systems

    SciTech Connect

    Chen Shuping; Zhang Wei; Qian Youhua

    2010-05-21

    A new computation of the normal forms of Bogdanov-Takens singularities is developed in this paper. In the theoretical model for the nonplanar nonlinear oscillation of a cantilever beam, the computation method is applied to compute the coefficients of the normal forms for the case of one non-semisimple double zero and a pair of pure imaginary eigenvalues.

  15. Metal-free intermolecular formal cycloadditions enable an orthogonal access to nitrogen heterocycles

    PubMed Central

    Xie, Lan-Gui; Niyomchon, Supaporn; Mota, Antonio J.; González, Leticia; Maulide, Nuno

    2016-01-01

    Nitrogen-containing heteroaromatic cores are ubiquitous building blocks in organic chemistry. Herein, we present a family of metal-free intermolecular formal cycloaddition reactions that enable highly selective and orthogonal access to isoquinolines and pyrimidines at will. Applications of the products are complemented by a density functional theory mechanistic analysis that pinpoints the crucial factors responsible for the selectivity observed, including stoichiometry and the nature of the heteroalkyne. PMID:26975182

  16. Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

    PubMed Central

    Hemric, Brett N

    2016-01-01

    Summary This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates. PMID:26877805

  17. Estimation of Some Parameters from Morse-Morse-Spline-Van Der Waals Intermolecular Potential

    SciTech Connect

    Coroiu, I.

    2007-04-23

    Some parameters such as transport cross-sections and isotopic thermal diffusion factor have been calculated from an improved intermolecular potential, Morse-Morse-Spline-van der Waals (MMSV) potential proposed by R.A. Aziz et al. The treatment was completely classical and no corrections for quantum effects were made. The results would be employed for isotope separations of different spherical and quasi-spherical molecules.

  18. Enantioselective Intermolecular Cyclopropanations for the Synthesis of Chiral Pyrimidine Carbocyclic Nucleosides.

    PubMed

    Xie, Ming-Sheng; Zhou, Peng; Niu, Hong-Ying; Qu, Gui-Rong; Guo, Hai-Ming

    2016-09-01

    A direct route to chiral cyclopropylpyrimidine carbocyclic nucleoside analogues has been reported via highly enantioselective intermolecular cyclopropanation reactions of N1-vinylpyrimidines with α-diazoesters. With chiral ruthenium(II)-phenyloxazoline complex (2 mol %) as the catalyst, cyclopropyl pyrimidine nucleoside analogues could be obtained in good yields (71-96% yields) with high levels of diastereo- and enantioselectivities (10:1 to >20:1 dr and 96-99% ee) in 1 min. PMID:27526779

  19. Intermolecular electronic coupling in organic molecular thin films measured by temperature modulation spectroscopy

    SciTech Connect

    Yadav, Abhishek; Jin, Y; Chan, P. K. L.; Shtein, Max; Pipe, Kevin P.

    2010-01-01

    Temperature modulation spectroscopy is used to obtain the temperature dependences of oscillator strength, exciton transition energy, and line width for a copper phthalocyanine thin film. With increasing temperature, the oscillator strength exhibits a pronounced decrease for charge transfer (CT) excitons, making this technique suitable for differentiating exciton types. From the measured magnitude and temperature dependence of the CT oscillator strength, we obtain estimates for the intermolecular electronic coupling and its exponential decay coefficient.

  20. Carbon dioxide hydrate phase equilibrium and cage occupancy calculations using ab initio intermolecular potentials.

    PubMed

    Velaga, Srinath C; Anderson, Brian J

    2014-01-16

    Gas hydrate deposits are receiving increased attention as potential locations for CO2 sequestration, with CO2 replacing the methane that is recovered as an energy source. In this scenario, it is very important to correctly characterize the cage occupancies of CO2 to correctly assess the sequestration potential as well as the methane recoverability. In order to predict accurate cage occupancies, the guest–host interaction potential must be represented properly. Earlier, these potential parameters were obtained by fitting to experimental equilibrium data and these fitted parameters do not match with those obtained by second virial coefficient or gas viscosity data. Ab initio quantum mechanical calculations provide an independent means to directly obtain accurate intermolecular potentials. A potential energy surface (PES) between H2O and CO2 was computed at the MP2/aug-cc-pVTZ level and corrected for basis set superposition error (BSSE), an error caused due to the lower basis set, by using the half counterpoise method. Intermolecular potentials were obtained by fitting Exponential-6 and Lennard-Jones 6-12 models to the ab initio PES, correcting for many-body interactions. We denoted this model as the “VAS” model. Reference parameters for structure I carbon dioxide hydrate were calculated using the VAS model (site–site ab initio intermolecular potentials) as Δμ(w)(0) = 1206 ± 2 J/mol and ΔH(w)(0) = 1260 ± 12 J/mol. With these reference parameters and the VAS model, pure CO2 hydrate equilibrium pressure was predicted with an average absolute deviation of less than 3.2% from the experimental data. Predictions of the small cage occupancy ranged from 32 to 51%, and the large cage is more than 98% occupied. The intermolecular potentials were also tested by calculating the pure CO2 density and diffusion of CO2 in water using molecular dynamics simulations. PMID:24328234

  1. Temperature-dependent intermolecular force measurement of poly(N-isopropylacrylamide) grafted surface with protein.

    PubMed

    Cho, Eun Chul; Kim, Yong Deuk; Cho, Kilwon

    2005-06-15

    We have investigated the temperature dependence of the intermolecular force between poly(N-isopropylacrylamide) (PNiPAM) grafted surface and bovine serum albumin (BSA) in phosphate buffer (pH 7.4) using atomic force microscopy at the nanonewton scale. These observations show that the interaction force is nearly zero below the phase transition temperature of PNiPAM and that it increases steeply during the phase transition. Since the PNiPAM chains are grafted onto the aminosilane (gamma-aminopropyltriethoxysilane)-treated silicon wafer, we measured the force-distance curve of BSA-immobilized tips for the bare and the aminosilane-treated silicon wafer. These surfaces show no temperature dependence and their values are different from those of the PNiPAM-grafted surfaces at 30 degrees C. The results indicate that the measured adhesion force is between the PNiPAM-grafted surface and the BSA-immobilized tip. Our studies on the intermolecular force between other surfaces (CH(3)- and COOH-terminated self-assembled monolayers) and the BSA-immobilized tip indicate that the variation in the intermolecular force between the PNiPAM surface and BSA with temperature can be attributed to the changes in the properties of the PNiPAM chains. From consideration of the PNiPAM phase transition mechanism, it is speculated that the intermolecular force between the PNiPAM-grafted surface and BSA would be affected by changes in the arrangement of the bound water molecules around the PNiPAM chain and by changes in the conformation (i.e., in the chain mobility) of the PNiPAM chain during the phase transition. PMID:15897061

  2. Cupric-Superoxo Mediated Inter-Molecular C-H Activation Chemistry

    PubMed Central

    Peterson, Ryan L.; Himes, Richard A.; Kotani, Hiroaki; Suenobu, Tomoyoshi; Tian, Li; Siegler, Maxime A.; Solomon, Edward I.; Fukuzumi, Shunichi; Karlin, Kenneth D.

    2011-01-01

    A new cupric-superoxo complex [LCuII(O2•−)]+, which possesses particularly strong O–O and Cu–O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicate a first-order dependence on both the Cu-complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases. PMID:21265534

  3. Pigment Spectra and Intermolecular Interaction Potentials in Glasses and Proteins

    PubMed Central

    Renge, I.; van Grondelle, R.; Dekker, J. P.

    2007-01-01

    A model is proposed for chromophore optical spectra in solids over a wide range of temperatures and pressures. Inhomogeneous band shapes and their pressure dependence, as well as baric shift coefficients of spectral lines, selected by the frequency, were derived using Lennard-Jones potentials of the ground and excited states. Quadratic electron-phonon coupling constants, describing the thermal shift and broadening of zero-phonon lines, were also calculated. Experimentally, thermal shift and broadening of spectral holes were studied between 5 and 40 K for a synthetic pigment, chlorin, embedded in polymer hosts. The baric effects on holes were determined by applying hydrostatic He gas pressure up to 200 bar, at 6 K. Absorption spectra of pheophytin a, chlorophyll a, and β-carotene in polymers and plant photosystem II CP47 complex were measured between 5 (or 77) and 300 K, and subject to Voigtian deconvolution. A narrowing of inhomogeneous bandwidth with increasing temperature, predicted on the basis of hole behavior, was observed as the shrinking of Gaussian spectral component. The Lorentzian broadening was ascribed to optical dephasing up to 300 K in transitions with weak to moderate linear electron-phonon coupling strength. The thermal broadening is purely Gaussian in multiphonon transitions (S2 band of β-carotene, Soret bands of tetrapyrrolic pigments), and the Lorentz process appears to be suppressed, indicating a lack of exponential dephasing. Density, polarity, polarizability, compressibility, and other local parameters of the pigment binding sites in biologically relevant systems can be deduced from spectroscopic data, provided that sufficient background information is available. PMID:17557783

  4. Predetermined embryonic glial cells form the distinct glial sheaths of the Drosophila peripheral nervous system

    PubMed Central

    von Hilchen, Christian M.; Bustos, Álvaro E.; Giangrande, Angela; Technau, Gerhard M.; Altenhein, Benjamin

    2013-01-01

    One of the numerous functions of glial cells in Drosophila is the ensheathment of neurons to isolate them from the potassium-rich haemolymph, thereby establishing the blood-brain barrier. Peripheral nerves of flies are surrounded by three distinct glial cell types. Although all embryonic peripheral glia (ePG) have been identified on a single-cell level, their contribution to the three glial sheaths is not known. We used the Flybow system to label and identify each individual ePG in the living embryo and followed them into third instar larva. We demonstrate that all ePG persist until the end of larval development and some even to adulthood. We uncover the origin of all three glial sheaths and describe the larval differentiation of each peripheral glial cell in detail. Interestingly, just one ePG (ePG2) exhibits mitotic activity during larval stages, giving rise to up to 30 glial cells along a single peripheral nerve tract forming the outermost perineurial layer. The unique mitotic ability of ePG2 and the layer affiliation of additional cells were confirmed by in vivo ablation experiments and layer-specific block of cell cycle progression. The number of cells generated by this glial progenitor and hence the control of perineurial hyperplasia correlate with the length of the abdominal nerves. By contrast, the wrapping and subperineurial glia layers show enormous hypertrophy in response to larval growth. This characterisation of the embryonic origin and development of each glial sheath will facilitate functional studies, as they can now be addressed distinctively and genetically manipulated in the embryo. PMID:23903191

  5. 49 CFR Appendix H to Part 40 - DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 1 2014-10-01 2014-10-01 false DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form H Appendix H to Part 40 Transportation Office of the Secretary..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS)...

  6. 49 CFR Appendix H to Part 40 - DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 1 2013-10-01 2013-10-01 false DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form H Appendix H to Part 40 Transportation Office of the Secretary..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS)...

  7. 49 CFR Appendix H to Part 40 - DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 1 2012-10-01 2012-10-01 false DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form H Appendix H to Part 40 Transportation Office of the Secretary..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS)...

  8. 49 CFR Appendix H to Part 40 - DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 1 2011-10-01 2011-10-01 false DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form H Appendix H to Part 40 Transportation Office of the Secretary..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS)...

  9. Tracking the energy input form the magnetosphere to the ionosphere-thermosphere system

    NASA Astrophysics Data System (ADS)

    Zesta, E.; Connor, H.; Shi, Y.; Raeder, J.; Fedrizzi, M.; Fuller-Rowell, T. J.; Codrescu, M.

    2014-12-01

    During geomagnetically active times, the ionosphere - thermosphere (IT) system is strongly affected by magnetospheric energy that comes in the form of auroral particle precipitation and Poynting flux. This ultimately results in the increase of the thermospheric mass density, a critical parameter not only for determining and predicting air drag on satellites, but also for understanding the solar wind - magnetosphere- IT coupling. We use observations and model simulations to explore when, where and how energy transfers from the solar wind through the magnetosphere and is deposited into the IT system during solar wind disturbances. We observe and simulate dynamic pressure impacts on the magnetosphere and a magnetic storm main phase. We use thermospheric density observations from the CHAMP and GRACE satellites and Poynting flux measurements from Defense Meteorological Satellite Platform (DMSP) satellites. We show that the thermosphere density as well as the downward Poynting flux intensified shortly after (within ~20 min) the sudden enhancement of the solar wind dynamic pressure mostly in the dayside auroral zone and polar cap regions with the peaks in the vicinity of the cusp. Simulations from the two-way coupled OpenGGCM-CTIM magnetosphere-ionosphere-thermosphere model show that the ionospheric Joule heating also increases abruptly along with the sudden enhancement of the dynamic pressure in the same regions. The modeling results show that the pair of high-latitude localized cusp field-aligned currents (FACs) are intensified and extended azimuthally as a result of the enhanced dayside high-latitude reconnection caused by the sudden increase of the solar wind dynamic pressure. They are likely the source of the enhanced Joule heating and the ensuing thermospheric heating in that region. We also look at the first hours of a magnetic storm main phase where the picture is significantly more complex, but Poynting flux and thermospheric density first enhance at polar

  10. 15N fractionation in star-forming regions and Solar System objects

    NASA Astrophysics Data System (ADS)

    Wirström, Eva; Milam, Stefanie; Adande, Gilles; Charnley, Steven B.; Cordiner, Martin A.

    2015-08-01

    A central issue for understanding the formation and evolution of matter in the early Solar System is the relationship between the chemical composition of star-forming interstellar clouds and that of primitive Solar System materials. The pristine molecular content of comets, interplanetary dust particles and carbonaceous chondrites show significant bulk nitrogen isotopic fractionation relative to the solar value, 14N/15N ~ 440. In addition, high spatial resolution measurements in primitive materials locally show even more extreme enhancements of 14N/15N < 100.The coherent 15N enrichment in comets from different formation zones suggests that these isotopic enhancements are remnants of the interstellar chemistry in the natal molecular cloud core and the outer protosolar nebula. Indeed, early chemical models of gas-phase ion-molecule nitrogen fractionation showed that HCN and HNC (nitriles) can hold significant 15N enrichments in cold dark clouds where CO is depleted onto dust grains. In addition, 15N fractionation in nitriles and amines (NH2, NH3) follow different chemical pathways. More recently we have shown that once the spin-state dependence in rates of reactions with H2 is included in the models, amines can either be enhanced or depleted in 15N, depending on the core’s evolutionary stage. Observed 15N fractionation in amines and nitriles therefore cannot be expected to be the same, instead their ratio is a potential chemical clock.Observations of molecular isotope ratios in dark cores are challenging. Limited published results in general show higher 15N/14N ratios in HCN and HNC than ammonia, but more measurements are necessary to confirm these trends. We will present recent results from our ongoing observing campaign of 14N/15N isotopic ratios in HCN, HNC and NH3 in dense cores and protostars which seem consistent with significant fractionation in nitriles as compared to other molecules in each object. The few 14N/15N ratios observed in N2H+ are similar to

  11. Hydrogeochemistry Of A Modern Dolomite-Forming Lagoon System, Cabo Frio-RJ, Brazil

    NASA Astrophysics Data System (ADS)

    Moreira, N. F.; Walter, L. M.

    2004-12-01

    Two hypersaline, dolomite-forming lagoons near Cabo Frio, Brazil, and associated ground- and surface waters were sampled in a comparative sediment and fluid geochemical (solutes, stable isotopes) investigation. Although microbial mediation via sulfate reducers has been invoked to explain dolomite formation in these lagoons, we showed that dolomites are associated with sulfide oxidation (Moreira et al., 2004). Sulfide oxidation is thought to promote dolomite formation by causing undersaturation for competing carbonate phases such as Mg-calcite. Herein, we consider the larger hydrogeologic and temporal setting to further elucidate hydrogeochemical and geochemical constraints on rates and mechanisms of dolomite formation in the two lagoons. The lagoons, Brejo do Espinho (BE) and Lagoa Vermelha (LV), are shallow marginal marine systems flanked by quartz sand dunes separating them from Atlantic open seawater to the south and from Araruama lagoon, a large, hypersaline water body, to the north. In both lagoons, about 1 m of high Mg-calcite and dolomite mud has accumulated over the last 5,000 years on an underlying aquifer composed of highly permeable, quartz-rich coquinas. BE has a proximal relation to recharge from Araruama lagoon, while LV is more closely associated with meteoric recharge from lacustrine and riverine systems. BE is shallower, at 0.5 m water depth, than LV (2 m), permitting BE waters to remain oxic. Oxygen isotope values and chloride mass balances of pore waters and of fluids sampled from shallow ground water wells identify the different water and solute sources the lagoons. BE overlying brines and pore waters appear to be produced by evapoconcentration of Araruama source brines and meteoric precipitation. In contrast, LV derives from evapoconcentrated seawater mixed with regional lake and ground water sources. We envision a scenario in which dense, Mg-SO4-rich brines from Araruama migrate along a permeable flowpath in limited contact with the atmosphere

  12. Effect of intermolecular potential on compressible Couette flow in slip and transitional regimes

    NASA Astrophysics Data System (ADS)

    Weaver, Andrew B.; Venkattraman, A.; Alexeenko, Alina A.

    2014-10-01

    The effect of intermolecular potentials on compressible, planar flow in slip and transitional regimes is investigated using the direct simulation Monte Carlo method. Two intermolecular interaction models, the variable hard sphere (VHS) and the Lennard-Jones (LJ) models, are first compared for subsonic and supersonic Couette flows of argon at temperatures of 40, 273, and 1,000 K, and then for Couette flows in the transitional regime ranging from Knudsen numbers (Kn) of 0.0051 to 1. The binary scattering model for elastic scattering using the Lennard-Jones (LJ) intermolecular potential proposed recently [A. Venkattraman and A. Alexeenko, "Binary scattering model for Lennard-Jones potential: Transport coefficients and collision integrals for non-equilibrium gas flow simulations," Phys. Fluids 24, 027101 (2012)] is shown to accurately reproduce both the theoretical collision frequency in an equilibrium gas as well as the theoretical viscosity variation with temperature. The use of a repulsive-attractive instead of a purely repulsive potential is found to be most important in the continuum and slip regimes as well as in flows with large temperature variations. Differences in shear stress of up to 28% between the VHS and LJ models is observed at Kn=0.0051 and is attributed to differences in collision frequencies, ultimately affecting velocity gradients at the wall. For Kn=1 where the Knudsen layer expands the entire domain, the effect of the larger collision frequency in the LJ model relative to VHS diminishes, and a 7% difference in shear stress is observed.

  13. Intermolecular interactions in multi-component crystals of acridinone/thioacridinone derivatives: Structural and energetics investigations

    NASA Astrophysics Data System (ADS)

    Wera, Michał; Storoniak, Piotr; Trzybiński, Damian; Zadykowicz, Beata

    2016-12-01

    A single crystal X-ray analysis of two multi-component crystals consisting of an acridinone/thioacridinone moiety and a solvent moiety - water and ammonia (1 and 2), respectively, was carried out to determine the crystal structures of obtained crystals. A theoretical approach was undertaken - using the DFT method, lattice energies calculations and Hirshfeld surfaces (HS) - to qualitatively and quantitatively assess the intermolecular interactions within the crystal. HS analysis was showed that the H⋯H, C⋯H/H⋯C and C⋯C contacts for both structures (altogether 81.6% of total Hirshfeld surface area for 1 and 79.3% for 2) and the O⋯H/H⋯O (14.3%) for 1 and the S⋯H/H⋯S (15.2%) contacts for 2 were the characteristic intermolecular contacts in the related crystal structures. Using a computational methods were confirmed that the main contribution to the stabilization of the crystal lattice of compound 1 comes from the Coulombic interactions, whereas in compound 2 electrostatic and van der Waals appear to have similar contribution to the crystal lattice energy. Theoretical calculations of the investigated compounds have also allowed to determine the energy of a single specific intermolecular interaction.

  14. Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining

    PubMed Central

    Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L.; Tomkinson, Alan E.; Tainer, John A.; Ellenberger, Tom

    2015-01-01

    Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. PMID:26130724

  15. Relativistic effects in the intermolecular interaction-induced nuclear magnetic resonance parameters of xenon dimer.

    PubMed

    Hanni, Matti; Lantto, Perttu; Ilias, Miroslav; Jensen, Hans Jorgen Aagaard; Vaara, Juha

    2007-10-28

    Relativistic effects on the (129)Xe nuclear magnetic resonance shielding and (131)Xe nuclear quadrupole coupling (NQC) tensors are examined in the weakly bound Xe(2) system at different levels of theory including the relativistic four-component Dirac-Hartree-Fock (DHF) method. The intermolecular interaction-induced binary chemical shift delta, the anisotropy of the shielding tensor Deltasigma, and the NQC constant along the internuclear axis chi( parallel) are calculated as a function of the internuclear distance. DHF shielding calculations are carried out using gauge-including atomic orbitals. For comparison, the full leading-order one-electron Breit-Pauli perturbation theory (BPPT) is applied using a common gauge origin. Electron correlation effects are studied at the nonrelativistic (NR) coupled-cluster singles and doubles with perturbational triples [CCSD(T)] level of theory. The fully relativistic second-order Moller-Plesset many-body perturbation (DMP2) theory is used to examine the cross coupling between correlation and relativity on NQC. The same is investigated for delta and Deltasigma by BPPT with a density functional theory model. A semiquantitative agreement between the BPPT and DHF binary property curves is obtained for delta and Deltasigma in Xe(2). For these properties, the currently most complete theoretical description is obtained by a piecewise approximation where the uncorrelated relativistic DHF results obtained close to the basis-set limit are corrected, on the one hand, for NR correlation effects and, on the other hand, for the BPPT-based cross coupling of relativity and correlation. For chi( parallel), the fully relativistic DMP2 results obtain a correction for NR correlation effects beyond MP2. The computed temperature dependence of the second virial coefficient of the (129)Xe nuclear shielding is compared to experiment in Xe gas. Our best results, obtained with the piecewise approximation for the binary chemical shift combined with the

  16. Simulations of the THz spectrum of liquid water incorporating the effects of intermolecular charge fluxes through hydrogen bonds

    SciTech Connect

    Torii, Hajime

    2015-12-31

    The intensity of the band at ∼200 cm{sup −1} (∼6 THz) in the Terahertz spectrum of liquid water mainly arises from the modulations of the extent of intermolecular charge transfer through hydrogen bonds, called intermolecular charge fluxes, occurring upon molecular translations along the O…H hydrogen bonds. To obtain reasonable spectral profiles from simulations, it is necessary to effectively incorporate the effects of those intermolecular charge fluxes, but apparently it is not possible by simple classical molecular dynamics simulations with fixed atomic partial charges even if they are amended by molecular induced dipoles due to intermolecular electrostatic interactions. The present paper shows how we can do reasonably correct spectral simulations, without resorting to fully ab initio molecular dynamics.

  17. Solid-state NMR identification and quantification of newly formed aluminosilicate phases in weathered kaolinite systems.

    PubMed

    Crosson, Garry S; Choi, Sunkyung; Chorover, Jon; Amistadi, Mary Kay; O'Day, Peggy A; Mueller, Karl T

    2006-01-19

    The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3-, 1 mol kg-1 of OH-, and pH approximately 13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10(-3), 10(-4), and 10(-5) molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10(-5) m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10(-3) m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and

  18. Solid-State NMR Identification and Quantification of Newly Formed Aluminosilicate Phases in Weathered Kaolinite Systems

    SciTech Connect

    Crosson, Garry S.; Choi, Sunkyung; Chorover, Jon; Amistadi, Mary K.; O'Day, Peggy A.; Mueller, Karl T.

    2006-01-19

    The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3 -, 1 mol kg-1 of OH-, and pH ~13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10-3, 10-4, and 10-5 molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10-5 m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10-3 m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and the quantitative

  19. Different temporal structure for form versus surface cortical color systems--evidence from chromatic non-linear VEP.

    PubMed

    Crewther, David P; Crewther, Sheila G

    2010-01-01

    Physiological studies of color processing have typically measured responses to spatially varying chromatic stimuli such as gratings, while psychophysical studies of color include color naming, color and light, as well as spatial and temporal chromatic sensitivities. This raises the question of whether we have one or several cortical color processing systems. Here we show from non-linear analysis of human visual evoked potentials (VEP) the presence of distinct and independent temporal signatures for form and surface color processing. Surface color stimuli produced most power in the second order Wiener kernel, indicative of a slowly recovering neural system, while chromatic form stimulation produced most power in the first order kernel (showing rapid recovery). We find end-spectral saturation-dependent signals, easily separable from achromatic signals for surface color stimuli. However physiological responses to form color stimuli, though varying somewhat with saturation, showed similar waveform components. Lastly, the spectral dependence of surface and form color VEP was different, with the surface color responses almost vanishing with yellow-grey isoluminant stimulation whereas the form color VEP shows robust recordable signals across all hues. Thus, surface and form colored stimuli engage different neural systems within cortex, pointing to the need to establish their relative contributions under the diverse chromatic stimulus conditions used in the literature. PMID:21187960

  20. Form feature and tolerance transfer from a 3D model to a setup planning system

    SciTech Connect

    Zhang, Hong-Chao; Zhou, Feng; Kuo, Tsai-Chi; Huang, S.H.

    1996-12-31

    Currently, most CAD systems, even the feature-based design systems which were developed for the need of CAPP, cannot provide exact information of an object (e.g., dimensions and tolerances). Some feature-based design systems can provide product data directly or indirectly; however, most CAPP systems still does not have interface with those CAD systems. The product data required by these CAPP systems usually has a specific format. In the CAPP system, it is essential for setup planning to ensure the precision of machining processes. Therefore, it is necessary to develop an interface with CAD models that the part data file can be obtained directly from CAD representation. This paper proposes an approach to integrate the setup planning system with a feature-based CAD system. By using an object-oriented approach - Product Data Translator (PDT), the compute-automated extraction of geometry and complete tolerance information is achieved; and the automated generation of tool approach direction was developed.