Science.gov

Sample records for intermolecular systems formed

  1. Inter-molecular crosslinking activity is engendered by the dimeric form of transglutaminase 2.

    PubMed

    Kim, Nayeon; Lee, Won-Kyu; Lee, Seon-Hyeong; Jin, Kyeong Sik; Kim, Kyung-Hee; Lee, Younho; Song, Minsoo; Kim, Soo-Youl

    2017-03-01

    Transglutaminase 2 (TGase 2) catalyzes a crosslink between protein bound-glutamine and -lysine. We proposed the mechanism of TGase 2 activation depends on conformation change from unfolded monomer to unfolded dimer. We found that TGase 2 has temperature-sensitive conformation change system at 30 °C. Small-angle X-ray scattering analysis showed that the enzyme was maintained as an unfolded monomer at temperatures below 30 °C, but changed to an unfolded dimer at over 30 °C. Mass analysis revealed that the C-terminus of TGase 2 was the critical region for dimerization. Furthermore, this conformational switch creates new biochemical reactivity that catalyzed inter-molecular crosslink at above 30 °C as an unfolded dimer of TGase 2 while catalyzed intra-molecular crosslink at below 30 °C as an unfolded monomer of TGase 2. The mechanism of TGase 2 activation depends on temperature-sensitive conformation change from unfolded monomer to unfolded dimer at over 30 °C. Furthermore, inter-molecular crosslinking activity is generated by the dimeric form of TGase 2. TGase 2 switches its conformation from a monomer to a dimer following a change in temperature, which engendered unique catalytic function of enzyme as inter-molecular crosslinking activity with calcium.

  2. Glass-Forming Tendency of Molecular Liquids and the Strength of the Intermolecular Attractions

    PubMed Central

    Koperwas, Kajetan; Adrjanowicz, Karolina; Wojnarowska, Zaneta; Jedrzejowska, Agnieszka; Knapik, Justyna; Paluch, Marian

    2016-01-01

    When we cool down a liquid below the melting temperature, it can either crystallize or become supercooled, and then form a disordered solid called glass. Understanding what makes a liquid to crystallize readily in one case and form a stable glass in another is a fundamental problem in science and technology. Here we show that the crystallization/glass-forming tendencies of the molecular liquids might be correlated with the strength of the intermolecular attractions, as determined from the combined experimental and computer simulation studies. We use van der Waals bonded propylene carbonate and its less polar structural analog 3-methyl-cyclopentanone to show that the enhancement of the dipole-dipole forces brings about the better glass-forming ability of the sample when cooling from the melt. Our finding was rationalized by the mismatch between the optimal temperature range for the nucleation and crystal growth, as obtained for a modeled Lennard-Jones system with explicitly enhanced or weakened attractive part of the intermolecular 6–12 potential. PMID:27883011

  3. Glass-Forming Tendency of Molecular Liquids and the Strength of the Intermolecular Attractions

    NASA Astrophysics Data System (ADS)

    Koperwas, Kajetan; Adrjanowicz, Karolina; Wojnarowska, Zaneta; Jedrzejowska, Agnieszka; Knapik, Justyna; Paluch, Marian

    2016-11-01

    When we cool down a liquid below the melting temperature, it can either crystallize or become supercooled, and then form a disordered solid called glass. Understanding what makes a liquid to crystallize readily in one case and form a stable glass in another is a fundamental problem in science and technology. Here we show that the crystallization/glass-forming tendencies of the molecular liquids might be correlated with the strength of the intermolecular attractions, as determined from the combined experimental and computer simulation studies. We use van der Waals bonded propylene carbonate and its less polar structural analog 3-methyl-cyclopentanone to show that the enhancement of the dipole-dipole forces brings about the better glass-forming ability of the sample when cooling from the melt. Our finding was rationalized by the mismatch between the optimal temperature range for the nucleation and crystal growth, as obtained for a modeled Lennard-Jones system with explicitly enhanced or weakened attractive part of the intermolecular 6–12 potential.

  4. Rattusin structure reveals a novel defensin scaffold formed by intermolecular disulfide exchanges

    PubMed Central

    Min, Hye Jung; Yun, Hyosuk; Ji, Sehyeon; Rajasekaran, Ganesan; Kim, Jae Il; Kim, Jeong-Sun; Shin, Song Yub; Lee, Chul Won

    2017-01-01

    Defensin peptides are essential for innate immunity in humans and other living systems, as they provide protection against infectious pathogens and regulate the immune response. Here, we report the solution structure of rattusin (RTSN), an α-defensin-related peptide, which revealed a novel C2-symmetric disulfide-linked dimeric structure. RTSN was synthesized by solid-phase peptide synthesis (SPPS) and refolded by air oxidation in vitro. Dimerization of the refolded RTSN (r-RTSN) resulted from five intermolecular disulfide (SS) bond exchanges formed by ten cysteines within two protomer chains. The SS bond pairings of r-RTSN were determined by mass analysis of peptide fragments cleaved by trypsin digestion. In addition to mass analysis, nuclear magnetic resonance (NMR) experiments for a C15S mutant and r-RTSN confirmed that the intermolecular SS bond structure of r-RTSN showed an I-V’, II-IV’, III-III’, IV-II’, V-I’ arrangement. The overall structure of r-RTSN exhibited a cylindrical array, similar to that of β-sandwich folds, with a highly basic surface. Furthermore, fluorescence spectroscopy results suggest that r-RTSN exerts bactericidal activity by damaging membrane integrity. Collectively, these results provide a novel structural scaffold for designing highly potent peptide-based antibiotics suitable for use under various physiological conditions. PMID:28345637

  5. Evaluation of intermolecular forces in a circulating system.

    PubMed

    Guo, Qiuquan; Liu, Mei; Yang, Jun

    2011-11-01

    Intercellular interactions, which are mediated by a variety of complex intercellular molecules through the processes of formation and dissociation of molecular bonds, play a critical role in regulating cellular functions in biological systems. Various approaches are applied to evaluate intercellular or molecular bonding forces. To quantify the intermolecular interaction forces, flow chamber has become a meaningful technique as it can ultimately mimic the cellular microenvironment in vivo under physiological flow conditions. Hydrodynamic forces are usually used to predict the intercellular forces down to the single molecular level. However, results show that only using hydrodynamic force will overestimate up to 30% of the receptor-ligand strength when the non-specific forces such as Derjaguin-Landau-Verway-Overbeek (DLVO) forces become un-neglected. Due to the nature of high ion concentration in the physiological condition, electrostatic force is largely screened which will cause DLVO force unbalanced. In this study, we propose to take account of the DLVO force, including van der Waals (VDW) force and electrostatic force, to predict the intermolecular forces of a cell doublet and cell-substrate model in a circulating system. Results also show that the DLVO force has a nonlinear effect as the cell-cell or cell-substrate distance changes. In addition, we used the framework of high accuracy hydrodynamic theories proved in colloidal systems. It is concluded that DLVO force could not be ignored in quantitative studies of molecular interaction forces in circulating system. More accurate prediction of intercellular forces needs to take account of both hydrodynamic force and DLVO force.

  6. Electronic Structure Theory for Radicaloid Systems and Intermolecular Interactions

    NASA Astrophysics Data System (ADS)

    Kurlancheek, Westin

    associated with unrestriction. Second, the relaxed density matrix itself fails to be N-representable, with natural orbital occupation numbers less than zero and greater than one. Therefore, it is desirable to use a method that is not dependent on the inverse of the Hessian like orbital optimized MP2 (O2). Another system which requires the use of orbital optimization is a neutral soliton on a polyacetylene chain. In this system, the Hartree-Fock reference suffers from severe spin-polarization making the wavefunction physically unreasonable unless a very sophisticated treatment of electron correlation is used to correct this problem. Originally, it was found that computationally expensive methods like CCSD(T) and CASSCF could adequately describe small model chain but not the full system. The O2 method is found to be an dramatic improvement over traditional MP2 which can be feasibly applied to polyenyl chains long enough to characterize the soliton. It is also discovered that density functionals are generally inadequate in describing the half-width of the soliton. Finally, the last chapter takes a slightly different perspective and focuses on the addition of correlation energy to a successful energy decomposition analysis based on absolutely localized molecular orbitals. It is discovered that the resulting new method can adequately describe systems with dispersive intermolecular interactions and large amounts of charge transfer. This scheme is then applied to the water dimer systems and it is found that all of the intermolecular interactions similar in size with the electrostatic interaction being the largest and the dispersive interaction being the smallest. This method is also contrasted with other EDA schemes.

  7. Crystallographic Structure, Intermolecular Packing Energetics, Crystal Morphology and Surface Chemistry of Salmeterol Xinafoate (Form I).

    PubMed

    Moldovan, Alexandru A; Rosbottom, Ian; Ramachandran, Vasuki; Pask, Christopher M; Olomukhoro, Oboroghene; Roberts, Kevin J

    2017-03-01

    Single crystals of salmeterol xinafoate (form I), prepared from slow cooled supersaturated propan-2-ol solutions, crystallize in a triclinic P1¯ symmetry with 2 closely related independent salt pairs within the asymmetric unit, with an approximately double-unit cell volume compared with the previously published crystal structure. Synthonic analysis of the bulk intermolecular packing confirms the similarity in packing energetics between the 2 salt pairs. The strongest synthons, as expected, are dominated by coulombic interactions. Morphologic prediction reveals a plate-like morphology, dominated by the {001}, {010}, and {100} surfaces, consistent with experimentally grown crystals. Although surface chemistry of the slow-growing {001} face comprises large sterically hindering phenyl groups, although weaker coulombic interactions still prevail from the alcohol group present on the phenyl and hydroxymethyl groups. The surface chemistry of the faster growing {010} and {100} faces are dominated by the significantly stronger cation/anion interactions occurring between the carboxylate and protonated secondary ammonium ion groups. The importance of understanding the cohesive and adhesive nature of the crystal surfaces of an active pharmaceutical ingredient, with respect to their interaction with other active pharmaceutical ingredient crystals and how that may affect formulation design, is highlighted.

  8. 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.

  9. Dielectric spectroscopy investigation of ion-containing and intermolecular hydrogen-bonded polymer systems

    NASA Astrophysics Data System (ADS)

    Atorngitjawat, Pornpen

    Ion-containing and intermolecular hydrogen-bonded polymers are used widely in a variety of industrial and commercial applications, from food packaging to battery electrolytes to pharmaceuticals. Yet the dynamics of these polymers, which are both complex and important to the application, are poorly understood. This thesis provides the first systematic study of the dynamics of several ion-containing and intermolecular hydrogen-bonded polymers by broadband dielectric relaxation spectroscopy. The systems under consideration include sulfonated polystyrene (SPS) in acid (SPS-H) and neutralized forms, and mixtures of poly(2-vinylpyridine) (P2VPy) with lithium perchlorate (LiClO4) and low molecular weight phenolic molecules. Dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, small-angle X-ray scattering and wide-angle X-ray diffraction were employed in a complementary role. Multiple relaxations were generally observed at high temperatures. For SPS ionomers, the segmental process, Maxwell-Wagner-Sillars interfacial polarization, and electrode polarization were detected. Three relaxations were also found in spectra of SPS-H, attributed to the segmental process, hydrogen bond association/dissociation, and electrode polarization. Three dielectric relaxations above the segmental process were observed for P2VPy-LiClO4 mixtures: ion-mode relaxation, slow hindered segmental relaxation and electrode polarization. However, only electrode polarization was observed above the segmental relaxation for all P2VPy--small phenolic molecule mixtures, except P2VPy + 10 mol% 2,3,3,4,4,5-hexahydroxybenzophenone. This mixture exhibited an additional relaxation due to Maxwell-Wagner-Sillars interfacial polarization, arising from the existence of phase-separated complexes within the P2VPy matrix. Sub-Tg local relaxations were suppressed by ionic intermolecular interactions for SPS ionomers and P2VPy-LiClO4 mixtures. Intermolecular hydrogen

  10. a General Transformation to Canonical Form for Potentials in Pairwise Intermolecular Interactions

    NASA Astrophysics Data System (ADS)

    Walton, Jay R.; Rivera-Rivera, Luis A.; Lucchese, Robert R.; Bevan, John W.

    2015-06-01

    A generalized formulation of explicit transformations is introduced to investigate the concept of a canonical potential in both fundamental chemical and intermolecular bonding. Different classes of representative ground electronic state pairwise interatomic interactions are referenced to a single canonical potential illustrating application of explicit transformations. Specifically, accurately determined potentials of the diatomic molecules H_2, H_2^+, HF, LiH, argon dimer, and one-dimensional dissociative coordinates in Ar-HBr, OC-HF, and OC-Cl_2 are investigated throughout their bound potentials. The advantages of the current formulation for accurately evaluating equilibrium dissociation energies and a fundamentally different unified perspective on nature of intermolecular interactions will be emphasized. In particular, this canonical approach has relevance to previous assertions that there is no very fundamental distinction between van der Waals bonding and covalent bonding or for that matter hydrogen and halogen bonds.

  11. 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.

  12. Pharmaceutical cocrystals, salts and multicomponent systems; intermolecular interactions and property based design.

    PubMed

    Berry, David J; Steed, Jonathan W

    2017-03-23

    As small molecule drugs become harder to develop and less cost effective for patient use, efficient strategies for their property improvement become increasingly important to global health initiatives. Improvements in the physical properties of Active Pharmaceutical Ingredients (APIs), without changes in the covalent chemistry, have long been possible through the application of binary component solids. This was first achieved through the use of pharmaceutical salts, within the last 10-15years with cocrystals and more recently coamorphous systems have also been consciously applied to this problem. In order to rationally discover the best multicomponent phase for drug development, intermolecular interactions need to be considered at all stages of the process. This review highlights the current thinking in this area and the state of the art in: pharmaceutical multicomponent phase design, the intermolecular interactions in these phases, the implications of these interactions on the material properties and the pharmacokinetics in a patient.

  13. New openings for porous systems research from intermolecular double-quantum NMR.

    PubMed

    Capuani, S; Alesiani, M; Branca, R T; Maraviglia, B

    2004-01-01

    It has been recently recognized that residual intermolecular double-quantum coherences (iDQcs) provide a novel contrast mechanism to study heterogeneity in liquid systems. This is of much interest in the field of the physics of matter and biomedicine. Nowadays, literature concerning the behaviour of the iDQc signal originated by highly heterogeneous systems such as fluids in porous media is scarce. In this paper, we report and discuss our principal results about iDQc signal behaviour in confined liquid systems (trabecular bone, travertine, porous standard systems) and also some new results obtained on doped water in glass capillary pipes.

  14. 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.

  15. 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.

  16. 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

    2013-08-02

    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.

  17. Desensitization of metastable intermolecular composites

    SciTech Connect

    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.

  18. 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.

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

    SciTech Connect

    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}{sub 1}) is the measure of the fastest ET rate ({tau}{sub 1}={tau}{sub ET}{sup fast}=(k{sub ET}{sup fast}){sup -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{sub 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}{sub 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{sub A}) is found to be {approx}0.4 for aromatic amines and {approx}0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the {tau}{sub 1} values are seen to increase very sharply. The large difference in the critical x{sub 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

  20. Intermolecular forces.

    PubMed

    Buckingham, A D

    1975-11-06

    The nature of molecular interactions is examined. Intermolecular forces are divided into long-range and short-range components; the former operate at distances where the effects of electron exchange are negligible and decrease as an inverse power of the separation. The long-range interactions may be subdividied into electrostatic, induction and dispersion contributions, where the electrostatic component is the interaction of the permanent charge distributions and the others originate in the fluctuations in the distributions. Typical magnitudes of the various contributions are given. The forces between macroscopic bodies are briefly considered, as are the effects of a medium. Some of the manifestations of molecular interactions are discussed.

  1. 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.

    PubMed

    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/r(m) and ɛ* = V/ɛ, where r(m) is the separation at the minimum and ɛ the well depth, we propose more generalized scalable forms for the commonly used Mie, Lennard-Jones, Morse, and Buckingham exponential-6 potential energy functions. These new generalized forms have an additional parameter from the original forms and revert to the original ones for some choice of that parameter. In this respect, the original forms of those potentials can be considered as special cases of the more general forms that are introduced. We also propose a scalable, non-revertible to the original one, 4-parameter extended Morse potential.

  2. 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.

  3. 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.

  4. 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

    2015-10-05

    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.

  5. The HC fragment of tetanus toxin forms stable, concentration-dependent dimers via an intermolecular disulphide bond.

    PubMed

    Qazi, Omar; Bolgiano, Barbara; Crane, Dennis; Svergun, Dmitri I; Konarev, Petr V; Yao, Zhong-Ping; Robinson, Carol V; Brown, Katherine A; Fairweather, Neil

    2007-01-05

    Protein oligomerisation is a prerequisite for the toxicity of a number of bacterial toxins. Examples include the pore-forming cytotoxin streptolysin O, which oligomerises to form large pores in the membrane and the protective antigen of anthrax toxin, where a heptameric complex is essential for the delivery of lethal factor and edema factor to the cell cytosol. Binding of the clostridial neurotoxins to receptors on neuronal cells is well characterised, but little is known regarding the quaternary structure of these toxins and the role of oligomerisation in the intoxication process. We have investigated the oligomerisation of the receptor binding domain (H(C)) of tetanus toxin, which retains the binding and trafficking properties of the full-length toxin. Electrophoresis, size exclusion chromatography and mass spectrometry were used to demonstrate that H(C) undergoes concentration-dependent oligomerisation in solution. Reducing agents were found to affect H(C) oligomerisation and, using mutagenesis, Cys869 was shown to be essential for this process. Furthermore, the oligomeric state and quaternary structure of H(C) in solution was assessed using synchrotron small-angle X-ray scattering. Ab initio shape analysis and rigid body modelling coupled with mutagenesis data allowed the construction of an unequivocal model of dimeric H(C) in solution. We propose a possible mechanism for H(C) oligomerisation and discuss how this may relate to toxicity.

  6. 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.

  7. An Efficient Method to Evaluate Intermolecular Interaction Energies in Large Systems Using Overlapping Multicenter ONIOM and the Fragment Molecular Orbital Method

    PubMed Central

    Asada, Naoya; Fedorov, Dmitri G.; Kitaura, Kazuo; Nakanishi, Isao; Merz, Kenneth M.

    2012-01-01

    We propose an approach based on the overlapping multicenter ONIOM to evaluate intermolecular interaction energies in large systems and demonstrate its accuracy on several representative systems in the complete basis set limit at the MP2 and CCSD(T) level of theory. In the application to the intermolecular interaction energy between insulin dimer and 4′-hydroxyacetanilide at the MP2/CBS level, we use the fragment molecular orbital method for the calculation of the entire complex assigned to the lowest layer in three-layer ONIOM. The developed method is shown to be efficient and accurate in the evaluation of the protein-ligand interaction energies. PMID:23050059

  8. 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.

  9. 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.

  10. Intramolecular Flexibility of Relatively Rigid Polymers, and Intermolecular Interactions in Ordered Polymer Systems. Part II.

    DTIC Science & Technology

    1981-01-26

    rials, the ordering of the chains, and the mechanical strenth of the resulting films or fibers . The basic goals are thus a molecular understanding of...polymers, cis and trans polybenzoxazoles (PBO) and polybenzothiazoles (PBT), form such phases, and energy calculations were therefore carried out to...Phys., 18, 000 (1981). 2. Phenylene Group Rotations and Nonplanar Conformations in Some Cis and Trans Polybenzoxazoles and Polybenzothiazoles, W. J

  11. Many-body effects in intermolecular forces.

    PubMed

    Elrod, M J; Saykally, R J

    1994-11-01

    The authors provide a review and literature survey of many-body effects in intermolecular forces. Topics include experimental methods, theoretical methods, many-body effects in atomic systems, and many-body effects in aqueous and nonaqueous molecular systems.

  12. The role of intermolecular interactions: studies on model systems for bacterial biofilms.

    PubMed

    Mayer, C; Moritz, R; Kirschner, C; Borchard, W; Maibaum, R; Wingender, J; Flemming, H C

    1999-10-01

    The mechanical stability of biofilms and other microbial aggregates is of great importance for both the maintenance of biofilm processes and the removal of undesired biofilms. The binding forces are weak interactions such as London dispersion forces, electrostatic interactions and hydrogen bonds. In a first attempt to rank their contribution, the viscosity of solutions of extracellular polymeric substances (EPS) from a mucoid strain of Pseudomonas aeruginosa is measured. In order to distinguish the binding forces, substances are chosen which individually address the different types of bonds. Polyacrylic acid is identified as a suitable model system for EPS when molecular interactions are studied. Electrostatic interactions and hydrogen bonds are found to be the dominating forces among macromolecules within the biofilm.

  13. 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.

  14. 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.

  15. 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.

  16. Intermolecular Hydrogen Bonding in Peptide and Modified Jeffamine Organogels

    NASA Astrophysics Data System (ADS)

    Savin, Daniel; Richardson, Adam

    2011-03-01

    In these studies, we present two systems whereby supramolecular assembly results in rigid organogels. First, a series of AB diblock copolymers consisting of poly(Lysine(Z)) (P(Lys(Z)) blocks were synthesized and found to form stable, rigid organogels in THF (ca. 1 - 1.5 wt.% solutions) and chloroform at room temperature. In these systems, the protecting group on the P(Lys) side-chains remains intact and gel formation results from the assembly of the solventphobic P(Lys(Z)) chains through intermolecular beta-sheet formation. The non-peptide block was found to have an effect on organogel properties due to interfacial frustration, which disrupts H-bonding. Second, Jeffamine polymers were modified in a facile way to incorporate intermolecular H-bonding groups to yield networks able to gel various solvents as well as mineral and canola oil. We present the physical and rheological properties of the organogels produced.

  17. Orthogonal adsorption onto nano-graphene oxide using different intermolecular forces for multiplexed delivery.

    PubMed

    Wang, Feng; Liu, Biwu; Ip, Alexander C-F; Liu, Juewen

    2013-08-14

    Nano-graphene oxide can adsorb both doxorubicin and zwitterionic dioleoyl-sn-glycero-3-phosphocholine (DOPC) liposomes in an orthogonal and non-competing manner with high capacities based on different surface and intermolecular forces taking place on the heterogeneous surface of the graphene oxide. The system forms stable colloids, allowing co-delivery of both cargos to cancer cells.

  18. 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

  19. Mapping intermolecular bonding in C₆₀.

    PubMed

    Sundqvist, Bertil

    2014-08-22

    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.

  20. Enthalpies of mixing and intermolecular interactions in the 1-octanol-dimethylformamide system at 298-318 K

    NASA Astrophysics Data System (ADS)

    Smirnova, N. L.; Kustov, A. V.

    2013-05-01

    The heat effects of solution of N,N-dimethylformamide (DMF) and 1-octanol (OctOH) in the DMF (1)-OctOH (2) system are measured over the range of compositions using a variable-temperature isothermal-shell calorimeter at 298, 308, and 318 K. The partial molar enthalpies of the binary mixture components and the enthalpies and heat capacities of mixing are determined. It is found that the amide-alcohol mixing is strongly endothermic and very weakly depends on temperature. The enthalpy and specific heat parameters of binary and ternary interactions between the DMF molecules in OctOH and the OctOH molecules in DMF are determined in terms of the virial expansion technique, and it is shown that the two nonelectrolytes exhibit a tendency to homoassociation.

  1. Direct evaluation of individual hydrogen bond energy in situ in intra- and intermolecular multiple hydrogen bonds system.

    PubMed

    Liu, Cui; Zhao, Dong-Xia; Yang, Zhong-Zhi

    2012-02-05

    The results of evaluating the individual hydrogen bond (H-bond) strength are expected to be helpful for the rational design of new strategies for molecular recognition or supramolecular assemblies. Unfortunately, there is few obvious and unambiguous means of evaluating the energy of a single H-bond within a multiple H-bonds system. We present a local analytic model, ABEEMσπ H-bond energy (HBE) model based on ab initio calculations (MP2) as benchmark, to directly and rapidly evaluate the individual HBE in situ in inter- and intramolecular multiple H-bonds system. This model describes the HBE as the sum of electrostatic and van der Waals (vdW) interactions which all depend upon the geometry and environment, and the ambient environment of H-bond in the model is accounted fairly. Thus, it can fairly consider the cooperative effect and secondary effect. The application range of ABEEMσπ HBE model is rather wide. This work has discussed the individual H-bond in DNA base pair and protein peptide dimers. The results indicate that the interactions among donor H atom, acceptor atom as well as those atoms connected to them with 1,2 or 1,3 relationships are all important for evaluating the HBE, although the interaction between the donor H atom and the acceptor atom is large. Furthermore, our model quantitatively indicates the polarization ability of N, O, and S in a new style, and gives the percentage of the polarization effect in HBE, which can not be given by fixed partial charge force field.

  2. Ladder Forms in Estimation and System Identification.

    DTIC Science & Technology

    1977-01-01

    system identification . Many record applications, such as in geophysical signal processing, high resolution (’maximum entropy’) spectral estimation and speech encoding, justify the interest in these forms. They appear in many contexts, such as scattering and network theory and the theory of orthogonal polynomials. The state-space model ladder realizations are very closely related in (block) Schwarz matrix canonical forms, which generally appear in the context of stability analysis. In fact they are the natural ’stability canonical form’ for

  3. 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…

  4. Perturbation analyses of intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Koyama, Yohei M.; Kobayashi, Tetsuya J.; Ueda, Hiroki R.

    2011-08-01

    Conformational fluctuations of a protein molecule are important to its function, and it is known that environmental molecules, such as water molecules, ions, and ligand molecules, significantly affect the function by changing the conformational fluctuations. However, it is difficult to systematically understand the role of environmental molecules because intermolecular interactions related to the conformational fluctuations are complicated. To identify important intermolecular interactions with regard to the conformational fluctuations, we develop herein (i) distance-independent and (ii) distance-dependent perturbation analyses of the intermolecular interactions. We show that these perturbation analyses can be realized by performing (i) a principal component analysis using conditional expectations of truncated and shifted intermolecular potential energy terms and (ii) a functional principal component analysis using products of intermolecular forces and conditional cumulative densities. We refer to these analyses as intermolecular perturbation analysis (IPA) and distance-dependent intermolecular perturbation analysis (DIPA), respectively. For comparison of the IPA and the DIPA, we apply them to the alanine dipeptide isomerization in explicit water. Although the first IPA principal components discriminate two states (the α state and PPII (polyproline II) + β states) for larger cutoff length, the separation between the PPII state and the β state is unclear in the second IPA principal components. On the other hand, in the large cutoff value, DIPA eigenvalues converge faster than that for IPA and the top two DIPA principal components clearly identify the three states. By using the DIPA biplot, the contributions of the dipeptide-water interactions to each state are analyzed systematically. Since the DIPA improves the state identification and the convergence rate with retaining distance information, we conclude that the DIPA is a more practical method compared with the

  5. Plasma formed ion beam projection lithography system

    DOEpatents

    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.

  6. 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

  7. Form and function in systems neuroscience.

    PubMed

    Kristan, William B; Katz, Paul

    2006-10-10

    'Form follows function' is an architectural philosophy attributed to the great American architect Louis Sullivan, and later taken up by the Bauhaus movement. It stresses that the form of a building should reflect its function. Neuroscientists have used the converse of this dictum to learn the functions of neural circuits, believing that if we study neural architecture, it will lead us to an understanding of how neural systems function. New tools for studying the structure of neural circuits are being developed, so it is important to discuss what the old techniques have taught us about how to derive function from the form of a neural circuit.

  8. 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.

  9. 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.

  10. The intermolecular interaction in D2 - CX4 and O2 - CX4 (X = F, Cl) systems: Molecular beam scattering experiments as a sensitive probe of the selectivity of charge transfer component.

    PubMed

    Cappelletti, David; Falcinelli, Stefano; Pirani, Fernando

    2016-10-07

    Gas phase collisions of a D2 projectile by CF4 and by CCl4 targets have been investigated with the molecular beam technique. The integral cross section, Q, has been measured for both collisional systems in the thermal energy range and oscillations due to the quantum "glory" interference have been resolved in the velocity dependence of Q. The analysis of the measured Q(v) data provided novel information on the anisotropic potential energy surfaces of the studied systems at intermediate and large separation distances. The relative role of the most relevant types of contributions to the global interaction has been characterized. Extending the phenomenology of a weak intermolecular halogen bond, the present work demonstrates that while D2 - CF4 is basically bound through the balance between size (Pauli) repulsion and dispersion attraction, an appreciable intermolecular bond stabilization by charge transfer is operative in D2 - CCl4. We also demonstrated that the present analysis is consistent with that carried out for the F((2)P)-D2 and Cl((2)P)-D2 systems, previously characterized by scattering experiments performed with state-selected halogen atom beams. A detailed comparison of the present and previous results on O2-CF4 and O2-CCl4 systems pinpointed striking differences in the behavior of hydrogen and oxygen molecules when they interact with the same partner, mainly due to the selectivity of the charge transfer component. The present work contributes to cast light on the nature and role of the intermolecular interaction in prototype systems, involving homo-nuclear diatoms and symmetric halogenated molecules.

  11. The intermolecular interaction in D2 - CX4 and O2 - CX4 (X = F, Cl) systems: Molecular beam scattering experiments as a sensitive probe of the selectivity of charge transfer component

    NASA Astrophysics Data System (ADS)

    Cappelletti, David; Falcinelli, Stefano; Pirani, Fernando

    2016-10-01

    Gas phase collisions of a D2 projectile by CF4 and by CCl4 targets have been investigated with the molecular beam technique. The integral cross section, Q, has been measured for both collisional systems in the thermal energy range and oscillations due to the quantum "glory" interference have been resolved in the velocity dependence of Q. The analysis of the measured Q(v) data provided novel information on the anisotropic potential energy surfaces of the studied systems at intermediate and large separation distances. The relative role of the most relevant types of contributions to the global interaction has been characterized. Extending the phenomenology of a weak intermolecular halogen bond, the present work demonstrates that while D2 - CF4 is basically bound through the balance between size (Pauli) repulsion and dispersion attraction, an appreciable intermolecular bond stabilization by charge transfer is operative in D2 - CCl4. We also demonstrated that the present analysis is consistent with that carried out for the F(2P)-D2 and Cl(2P)-D2 systems, previously characterized by scattering experiments performed with state-selected halogen atom beams. A detailed comparison of the present and previous results on O2-CF4 and O2-CCl4 systems pinpointed striking differences in the behavior of hydrogen and oxygen molecules when they interact with the same partner, mainly due to the selectivity of the charge transfer component. The present work contributes to cast light on the nature and role of the intermolecular interaction in prototype systems, involving homo-nuclear diatoms and symmetric halogenated molecules.

  12. In Situ Forming Polymeric Drug Delivery Systems

    PubMed Central

    Madan, M.; Bajaj, A.; Lewis, S.; Udupa, N.; Baig, J. A.

    2009-01-01

    In situ forming polymeric formulations are drug delivery systems that are in sol form before administration in the body, but once administered, undergo gelation in situ, to form a gel. The formation of gels depends on factors like temperature modulation, pH change, presence of ions and ultra violet irradiation, from which the drug gets released in a sustained and controlled manner. Various polymers that are used for the formulation of in situ gels include gellan gum, alginic acid, xyloglucan, pectin, chitosan, poly(DL-lactic acid), poly(DL-lactide-co-glycolide) and poly-caprolactone. The choice of solvents like water, dimethylsulphoxide, N-methyl pyrrolidone, triacetin and 2-pyrrolidone for these formulations depends on the solubility of polymer used. Mainly in situ gels are administered by oral, ocular, rectal, vaginal, injectable and intraperitoneal routes. The in situ gel forming polymeric formulations offer several advantages like sustained and prolonged action in comparison to conventional drug delivery systems. The article presents a detailed review of these types of polymeric systems, their evaluation, advancements and their commercial formulations. From a manufacturing point of view, the production of such devices is less complex and thus lowers the investment and manufacturing cost. PMID:20490289

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

    PubMed

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

    2014-04-11

    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.

  14. 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.

  15. 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…

  16. Intermolecular potentials for hexafluoride gases

    SciTech Connect

    Aziz, R.A. . Dept. of Physics); Taylor, W.L. )

    1989-10-31

    Second virial coefficient and viscosity data were used to evaluate intermolecular potential functions proposed in the literature for SF{sub 6}, UF{sub 6}, and WF{sub 6}. It was found that none of the potentials could predict the properties simultaneously. By suitable adjustment of the repulsive wall, we constructed an inverse power (n{minus}7) potential which correlates second virial coefficient and viscosity data at the same time. The best integer repulsive exponent for SF{sub 6} was found to be n = 40, while that for UF{sub 6} and WF{sub 6} was n = 46. 41 refs., 10 figs., 11 tabs.

  17. 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)....

  18. Some mathematical models of intermolecular autophosphorylation.

    PubMed

    Doherty, Kevin; Meere, Martin; Piiroinen, Petri T

    2015-04-07

    Intermolecular autophosphorylation refers to the process whereby a molecule of an enzyme phosphorylates another molecule of the same enzyme. The enzyme thereby catalyses its own phosphorylation. In the present paper, we develop two generic models of intermolecular autophosphorylation that also include dephosphorylation by a phosphatase of constant concentration. The first of these, a solely time-dependent model, is written as one ordinary differential equation that relies upon mass-action and Michaelis-Menten kinetics. Beginning with the enzyme in its dephosphorylated state, it predicts a lag before the enzyme becomes significantly phosphorylated, for suitable parameter values. It also predicts that there exists a threshold concentration for the phosphorylation of enzyme and that for suitable parameter values, a continuous or discontinuous switch in the phosphorylation of enzyme are possible. The model developed here has the advantage that it is relatively easy to analyse compared with most existing models for autophosphorylation and can qualitatively describe many different systems. We also extend our time-dependent model of autophosphorylation to include a spatial dependence, as well as localised binding reactions. This spatio-temporal model consists of a system of partial differential equations that describe a soluble autophosphorylating enzyme in a spherical geometry. We use the spatio-temporal model to describe the phosphorylation of an enzyme throughout the cell due to an increase in local concentration by binding. Using physically realistic values for model parameters, our results provide a proof-of-concept of the process of activation by local concentration and suggest that, in the presence of a phosphatase, this activation can be irreversible.

  19. 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....

  20. 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....

  1. 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....

  2. 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....

  3. 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....

  4. FormEd: An X Window System application for managing first-order formulas

    SciTech Connect

    Henry, T.L.; McCune, W.W.

    1990-11-01

    FormEd is a window-based program for constructing, displaying, and managing first-order logic formulas. The main motivation for constructing FormEd was the desire to have formulas displayed in a readable, two-dimensional format. Users of FormEd can make two kinds of transformation on formulas: logic transformations, such as negation normal form translation, which preserve the meaning of a formula, and edit transformations, which can be used to make arbitrary changes, such as adding a hypothesis to a subformula. FormEd was written by using the X Window System, Version 11, and code from the theorem prover OTTER. 4 refs.

  5. Intermolecular interaction approach for TADF (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Wong, Ken-Tsung

    2016-09-01

    Materials with thermally activated delayed fluorescence (TADF) have recently emerged as new fluorescent emitters for highly efficient organic light-emitting diodes (OLEDs). Molecule with TADF behavior needs to have a small singlet-triplet energy difference (ΔES-T) that allows the up-conversion from nonradiative triplet state (T1) to radiative singlet state (S1) via reverse intersystem crossing (RISC) process. Generally, molecules with small ΔES-T can be obtained via carefully manipulate the degree of "intramolecular" charge transfer (ICT) between electron-donating and -accepting components, such that the electron exchange energy that contributes to ΔES-T, can be minimized. Alternatively, excited state with small ΔES-T can be feasibly realized via "intermolecular" charge transfer occurring at the interface between spatially separating donor (D) and acceptor (A) molecules. Because the exchange energy decreases as the HOMO-LUMO separation distance increases, theoretically, the intermolecular D/A charge transfer state (or exciplex) should have rather small ΔES-T, leading to efficient TADF. However, it is still a challenge to access highly efficient exciplex systems. This is mainly because exciplex formation is commonly accompanied with a large red shift of emission spectra and long radiative lifetime, which tend to diminish photoluminescence quantum yield (PLQY) as well as electroluminescence (EL) performance. Until now, exciplex-based OLEDs with external quantum efficiency (EQE) above 10% are still limited. By judicious selection of donor and acceptor, the formation of efficient exciplex can be feasibly achieved. In this conference, our recent efforts on highly efficient exciplexes using C3-symmetry triazine acceptors and various donors, and their device characteristics will be presented.

  6. Intermolecular interactions in solid benzene.

    PubMed

    Kearley, G J; Johnson, M R; Tomkinson, J

    2006-01-28

    The lattice dynamics and molecular vibrations of benzene and deuterated benzene crystals are calculated from force constants derived from density-functional theory (DFT) calculations and compared with measured inelastic neutron-scattering spectra. A very small change (0.5%) in lattice parameter is required to obtain real lattice-mode frequencies across the Brillouin zone. There is a strong coupling between wagging and breathing modes away from the zone center. This coupling and sensitivity to cell size arises from two basic interactions. Firstly, comparatively strong interactions that hold the benzene molecules together in layers. These include an intermolecular interaction in which H atoms of one molecule link to the center of the aromatic ring of a neighboring molecule. The layers are held to each other by weaker interactions, which also have components that hold molecules together within a layer. Small changes in the lattice parameters change this second type of interaction and account for the changes to the lattice dynamics. The calculations also reveal a small auxetic effect in that elongation of the crystal along the b axis leads to an increase in internal pressure in the ac plane, that is, elongation in the b direction induces expansion in the a and c directions.

  7. 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.

  8. Probing Intermolecular Coupled Vibrations between Two Molecules

    NASA Astrophysics Data System (ADS)

    Han, Zhumin; Czap, Gregory; Xu, Chen; Chiang, Chi-lun; Yuan, Dingwang; Wu, Ruqian; Ho, W.

    2017-01-01

    Intermolecular interactions can induce energy shifts and coupling of molecular vibrations. However, the detection of intermolecular coupled vibrations has not been reported at the single molecule level. Here we detected an intermolecular coupled vibration between two CO molecules, one on the surface and another on the tip within the gap of a subkelvin scanning tunneling microscope, and analyzed the results by density functional calculations. We attribute the evolution of the energy and intensity of this coupled vibration as a function of tip-sample distance to the tilting and orbital alignment of the two CO molecules.

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

    DOE PAGES

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

    2015-02-19

    Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this study, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field,more » the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (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

  10. 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.

  11. 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

  12. Broadband reconfigurable optical beam-forming systems

    NASA Astrophysics Data System (ADS)

    Toughlian, Edward N.; Zmuda, Henry; Carter, Charity A.

    1994-06-01

    It is shown that by applying spatial frequency dependent optical phase compensation in an optical heterodyne process, variable RF delay can be achieved over a prescribed frequency band. Experimental results that demonstrate the performance of the delay line with regard to both maximum delay and resolution over a broad bandwidth are presented. Additionally, a spatially integrated optical system is proposed for control of phased array antennas, providing mechanical stability, essentially eliminating the drift problems associated with free-space optical systems, and providing high packing density. This approach uses a class of SLM known as a deformable mirror device and leads to a steerable arbitrary antenna radiation pattern of the true time-delay type. Also considered is the ability to utilize the delay line as a general photonic signal processing element in an adaptive (reconfigurable) transversal frequency filter configuration. Such systems are widely applicable in jammer/noise canceling systems, broadband ISDN, spread spectrum secure communications and the like.

  13. Cobalt complex of cinchonine: intermolecular interactions in two crystalline modifications.

    PubMed

    Skórska, Agnieszka; Oleksyn, Barbara J; Sliwiński, Jan

    2002-01-01

    Two crystalline modifications of cinchonine cobalt complex, C19H23Cl3CoN2O, were obtained from mixture of saturated alcohol solutions of CoCl3 x 6H2O and cinchonine. The X-ray structure analysis revealed that the asymmetric unit of one modification, CoCn1, contains only zwitterionic molecules of the complex. In the asymmetric unit of the other, CoCn2, there are two molecules of the title compound and two molecules of ethanol. The influence of the absolute configuration, the CoCl3 coordination with quinoline, and the presence of alcohol molecules on the studied structures was established by comparison of the crystal and molecular structures of both cobalt complexes with the analogous quinine complex and zinc complex of cinchonine. The interactions that dominate in the packing of the molecules in both structures are intermolecular hydrogen bonds. They form characteristic ring systems, depending on the presence of the alcohol molecules. The ring features are also related to the absolute configuration of the alkaloid.

  14. 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

  15. Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

    PubMed Central

    Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

    2016-01-01

    An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

  16. System and method for incremental forming

    DOEpatents

    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.

  17. Efficient activation of a visible light-activatable CA4 prodrug through intermolecular photo-unclick chemistry in mitochondria.

    PubMed

    Bio, Moses; Rajaputra, Pallavi; Lim, Irene; Thapa, Pritam; Tienabeso, Bomaonye; Hurst, Robert E; You, Youngjae

    2017-02-07

    Photo-unclick chemistry mediates visible and near IR-controlled drug release via a singlet oxygen (SO)-cleavable linker. Due to the limited diffusion distance of SO in biological systems, a photosensitizer and the SO-cleavable linker have been conjugated in one molecule or mixed in nano-drug delivery systems. In this communication, we demonstrate a new strategy to activate prodrugs with photo-unclick chemistry in an intermolecular fashion using an SO-cleavable CA4 prodrug and a mitochondria-specific photosensitizer, protoporphyrin IX, formed from prodrug hexyl-5-aminolevulinate.

  18. 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.

  19. 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.

  20. 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

  1. On Goursat Normal Forms, Prolongations, and Control Systems

    DTIC Science & Technology

    2007-11-02

    form, we also show how the exact linearization conditions for control systems can be restated in the language of Pfaffian systems. In addition, we give...area. We show that all of the main results in exact linearization of nonlinear systems can be restated in terms of exterior differential systems, and...to Goursat form can be specialized to give conditions for exact linearization . Theorem 6. Exact Linearization [5]. If a control system I defined

  2. Density functional calculation of intermolecular potentials.

    PubMed

    Nyeland, Carl

    2011-06-30

    Calculations of intermolecular potentials following the density functional theory (DFT) turn out to be very complicated without using some appropriate approximations. Most often the following three approximations have been considered. In one approximation the disturbed charge distributions during collisions are reduced to sums of undisturbed charge distributions from the colliding species. In another approximation, the so-called local density approximation (LDA), one neglects the fact that the intermolecular potentials that depend on charge densities also depend on gradients in the densities. In a third approximation one assumes that the intermolecular potential can be considered as a sum of two terms: a term for the long-range geometry and a term for the short-range geometry. In this Article the three approximations mentioned will be discussed for numerical accuracy for calculations of potentials between inert gas atoms and for calculations of potentials between surfaces and inert gas atoms. In the discussion a few other approximations will be mentioned too.

  3. Tooth form design supporting system in module design

    NASA Astrophysics Data System (ADS)

    Nagasawa, Junji; Namiki, Ryou; Tanaka, Souichi; Aoyama, Shigeru

    A lot of time was spent in designing the tooth form because there was no Computer Aided Design (CAD) system suitable for designing the tooth form of gears. A CAD system to support the tooth form design to promote efficiency of the tooth form design of gears for a wristwatch was developed. This system can perform calculation of torque transmission factor of gears, automatic drawing of tooth form drawing, and engagement simulation, and by utilizing this system the tooth form can be designed in less than one fourth of the time required by the conventional method. The characteristics of the system used to calculate the torque transmission factor of a pair of gears are summarized and the displayed results are shown.

  4. Influence of intermolecular interactions on magnetic observables

    NASA Astrophysics Data System (ADS)

    Schnack, Jürgen

    2016-02-01

    Very often it is an implied paradigm of molecular magnetism that magnetic molecules in a crystal interact so weakly that measurements of dc magnetic observables reflect ensemble properties of single molecules. But the number of cases where the assumption of virtually noninteracting molecules does not hold grows steadily. A deviation from the noninteracting case can especially clearly be seen in clusters with antiferromagnetic couplings, where steps of the low-temperature magnetization curve are smeared out with increasing intermolecular interaction. In this investigation we demonstrate with examples in one, two, and three space dimensions how intermolecular interactions influence typical magnetic observables such as magnetization, susceptibility, and specific heat.

  5. 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…

  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. 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

  8. Investigation on intermolecular interaction between two solutes where one solute occurs in two states

    NASA Astrophysics Data System (ADS)

    Kang, Xiaoyan; He, Anqi; Guo, Ran; Chen, Jing; Zhai, Yanjun; Xu, Yizhuang; Noda, Isao; Wu, Jinguang

    2016-11-01

    The spectral behavior of a pair of 2D asynchronous spectra generated by using the double asynchronous orthogonal sample design (DAOSD) approach on a chemical system is investigated. Two solutes (P and Q) are dissolved in the solution and intermolecular interaction between P and Q is characterized. In this particular system, P occurs in two exchangeable states when it is dissolved in the solutions. Results on mathematical analysis and computer simulation demonstrated that interference unrelated to the intermolecular interaction can be completely removed. Hence the resultant 2D asynchronous spectra generated by using the DAOSD approach can reflect intermolecular interaction reliably. Moreover, properties of cross peaks in different regions of the pair of asynchronous spectra are discussed. In our previous works, cross peaks generated by using the DAOSD and relevant techniques reflect variations on peak position, bandwidth or absorptivity of the characteristic peaks of solutes caused by intermolecular interaction. However, we find that cross peak can still be produced even if intermolecular interaction do not bring about any changes on the characteristic peaks of solutes. Mathematical analysis demonstrates that cross peaks are related to the variations of chemical systems caused by intermolecular interaction at a network level.

  9. 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

  10. 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.

  11. Intermolecular Slip Mechanism in Tropocollagen Nanofibrils

    DTIC Science & Technology

    2009-01-01

    Imperfecta or Ehlers - Danlos Syndrome. REPORT DOCUMENTATION PAGE (SF298) (Continuation Sheet) Continuation for Block 13 ARO Report Number Intermolecular slip...our studies could advance our knowledge of mechan- isms underlying important collagen-related diseases like Osteogenesis Imperfecta or Ehlers - Danlos

  12. Catalytic intermolecular alkene oxyamination with nitrenes.

    PubMed

    Dequirez, Geoffroy; Ciesielski, Jennifer; Retailleau, Pascal; Dauban, Philippe

    2014-07-14

    The Rh(II)-catalyzed intermolecular addition of nitrenes to aromatic and aliphatic alkenes provides vicinal amino alcohols with yields of up to 95 % and complete regioselectivity. This 1,2-oxyamination reaction involves the formation of an aziridine intermediate that undergoes in situ ring opening. The latter is induced by the Rh-bound nitrene that behaves as a Lewis acid.

  13. 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.

  14. Altering intra- to inter-molecular hydrogen bonding by dimethylsulfoxide: A TDDFT study of charge transfer for coumarin 343

    NASA Astrophysics Data System (ADS)

    Liu, Xiaochun; Yin, Hang; Li, Hui; Shi, Ying

    2017-04-01

    DFT and TDDFT methods were carried out to investigate the influences of intramolecular and intermolecular hydrogen bonding on excited state charge transfer for coumarin 343 (C343). Intramolecular hydrogen bonding is formed between carboxylic acid group and carbonyl group in C343 monomer. However, in dimethylsulfoxide (DMSO) solution, DMSO 'opens up' the intramolecular hydrogen bonding and forms solute-solvent intermolecular hydrogen bonded C343-DMSO complex. Analysis of frontier molecular orbitals reveals that intramolecular charge transfer (ICT) occurs in the first excited state both for C343 monomer and complex. The results of optimized geometric structures indicate that the intramolecular hydrogen bonding interaction is strengthened while the intermolecular hydrogen bonding is weakened in excited state, which is confirmed again by monitoring the shifts of characteristic peaks of infrared spectra. We demonstrated that DMSO solvent can not only break the intramolecular hydrogen bonding to form intermolecular hydrogen bonding with C343 but also alter the mechanism of excited state hydrogen bonding strengthening.

  15. 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

  16. Effects of intermolecular interaction on inelastic electron tunneling spectra

    NASA Astrophysics Data System (ADS)

    Kula, Mathias; Luo, Yi

    2008-02-01

    We have examined the effects of intermolecular interactions on the inelastic electron tunneling spectroscopy (IETS) of model systems: a pair of benzenethiol or a pair of benzenedithiol sandwiched between gold electrodes. The dependence of the IETS on the mutual position of and distance between the paired molecules has been predicted and discussed in detailed. It is shown that, although in most cases, there are clear spectral fingerprints present which allow identification of the actual structures of the molecules inside the junction. Caution must be exercised since some characteristic lines can disappear at certain symmetries. The importance of theoretical simulation is emphasized.

  17. Intermolecular Michael reactions: a computational investigation.

    PubMed

    Kwan, Eugene E; Evans, David A

    2010-11-19

    Computational studies have suggested that η(3)-lithium enolates in which the cation is partially bound to both carbon and oxygen may be important reactive intermediates. DFT calculations are used to demonstrate that explicitly solvated acetone enolates are largely O-bound. With this premise in mind, the stereochemical course of intermolecular Michael additions is examined. The results are generally consistent with what is observed experimentally and the model advanced by Heathcock and co-workers.

  18. Rational targeting of subclasses of intermolecular interactions: elimination of nonspecific binding for analyte sensing.

    PubMed

    Lane, Jordan S; Richens, Joanna L; Vere, Kelly-Ann; O'Shea, Paul

    2014-08-12

    The ability to target and control intermolecular interactions is crucial in the development of several different technologies. Here we offer a tool to rationally design liquid media systems that can modulate specific intermolecular interactions. This has broad implications in deciphering the nature of intermolecular forces in complex solutions and offers insight into the forces that govern both specific and nonspecific binding in a given system. Nonspecific binding still continues to be a problem when dealing with analyte detection across a range of different detection technologies. Here, we exemplify the problem of nonspecific binding on model membrane systems and when dealing with low-abundance protein detection on commercially available SPR technology. A range of different soluble reagents that target specific subclasses of intermolecular interactions have been tested and optimized to virtually eliminate nonspecific binding while leaving specific interactions unperturbed. Thiocyanate ions are used to target nonpolar interactions, and small reagents such as glycylglycylglycine are used to modulate the dielectric constant, which targets charge-charge and dipole interactions. We show that with rational design and careful modulation these reagents offer a step forward in dissecting the intermolecular forces that govern binding, alongside offering nonspecific binding elimination in detection systems.

  19. An isotopic mass effect on the intermolecular potential

    SciTech Connect

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

    2015-09-28

    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 paper, 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. Finally, the analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologue thermodynamics.

  20. 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

  1. Experimental and computational investigation of intermolecular interactions in cyclopentanone with methanol mixture

    NASA Astrophysics Data System (ADS)

    Zhang, Yu-Feng; Huang, Rong-Yi; Wang, Jun-Wei; Geng, Tong-Mou; Zhao, Shun-Ping; Wu, Gen-Hua

    2014-09-01

    In this Letter, excess molar volumes, refractive index deviations, Raman spectra and quantum-chemical calculations have been used to explore the underlying intermolecular interactions in the binary mixture containing cyclopentanone (CPN) and methanol. The experimental data reveal that the 1:1 (Ia) and 1:2 (Ib) cross-associations between CPN and methanol are formed in the studied binary mixture. This result has been further corroborated via theoretical calculations. In addition, the observed 1747 and 1732 cm-1 bands can be assigned to the Cdbnd O stretching vibrations of the intermolecular cross-associations Ia and Ib, respectively, in distinct contradiction with the previous explanations.

  2. 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.

  3. Beam-Forming Concentrating Solar Thermal Array Power Systems

    NASA Technical Reports Server (NTRS)

    Cwik, Thomas A. (Inventor); Dimotakis, Paul E. (Inventor); Hoppe, Daniel J. (Inventor)

    2016-01-01

    The present invention relates to concentrating solar-power systems and, more particularly, beam-forming concentrating solar thermal array power systems. A solar thermal array power system is provided, including a plurality of solar concentrators arranged in pods. Each solar concentrator includes a solar collector, one or more beam-forming elements, and one or more beam-steering elements. The solar collector is dimensioned to collect and divert incoming rays of sunlight. The beam-forming elements intercept the diverted rays of sunlight, and are shaped to concentrate the rays of sunlight into a beam. The steering elements are shaped, dimensioned, positioned, and/or oriented to deflect the beam toward a beam output path. The beams from the concentrators are converted to heat at a receiver, and the heat may be temporarily stored or directly used to generate electricity.

  4. Sources of Chaos in Planetary Systems Formed Through Numerical Methods

    NASA Astrophysics Data System (ADS)

    Clement, Matthew S.

    2017-01-01

    The formation of the solar system’s terrestrial planets has been numerically modeled in countless works, and many other studies have been devoted to char- acterizing our modern planets’ chaotic dynamical state. However, it is still not known whether our planets fragile chaotic state is an expected outcome of terrestrial planet accretion. We use a large suite of numerical simulations to present a detailed analysis and characterization of the dynamical chaos in 145 different systems produced via terrestrial planet formation in Kaib & Cowan (2015). These systems were created in the presence of a fully formed Jupiter and Saturn, using a variety of different initial conditions. We provide the first analysis of the dynamical states of fully evolved (4.5 Gyr) planetary systems formed using numerical simulations. We find that dynamical chaos is preva- lent in roughly half of the systems, with the largest source of the chaos being perturbations from Jupiter. Chaos is most prevalent in systems that form 4 or 5 terrestrial planets. Additionally, an eccentric Jupiter and Saturn is shown to enhance the prevalence of chaos in systems. Furthermore, systems with a center of mass highly concentrated between 0.8-1.2 AU generally prove to be less chaotic than systems with more exotic mass distributions. Through the process of evolving systems to the current epoch, we show that late instabilities are quite common in our systems. Of greatest interest, many of the sources of chaos observed in our own solar system (such as the secularly driven chaos between Mercury and Jupiter) are shown to be common outcomes of terrestrial planetary formation. Thus, the solar system’s marginally stable, chaotic state may naturally arise from the process of terrestrial planet formation.

  5. 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.

  6. NMR detection of intermolecular interaction sites in the dimeric 5'-leader of the HIV-1 genome.

    PubMed

    Keane, Sarah C; Van, Verna; Frank, Heather M; Sciandra, Carly A; McCowin, Sayo; Santos, Justin; Heng, Xiao; Summers, Michael F

    2016-11-15

    HIV type-1 (HIV-1) contains a pseudodiploid RNA genome that is selected for packaging and maintained in virions as a noncovalently linked dimer. Genome dimerization is mediated by conserved elements within the 5'-leader of the RNA, including a palindromic dimer initiation signal (DIS) that has been proposed to form kissing hairpin and/or extended duplex intermolecular contacts. Here, we have applied a (2)H-edited NMR approach to directly probe for intermolecular interactions in the full-length, dimeric HIV-1 5'-leader (688 nucleotides; 230 kDa). The interface is extensive and includes DIS:DIS base pairing in an extended duplex state as well as intermolecular pairing between elements of the upstream Unique-5' (U5) sequence and those near the gag start site (AUG). Other pseudopalindromic regions of the leader, including the transcription activation (TAR), polyadenylation (PolyA), and primer binding (PBS) elements, do not participate in intermolecular base pairing. Using a (2)H-edited one-dimensional NMR approach, we also show that the extended interface structure forms on a time scale similar to that of overall RNA dimerization. Our studies indicate that a kissing dimer-mediated structure, if formed, exists only transiently and readily converts to the extended interface structure, even in the absence of the HIV-1 nucleocapsid protein or other RNA chaperones.

  7. Dissecting Anion Effects in Gold(I)-Catalyzed Intermolecular Cycloadditions

    PubMed Central

    Homs, Anna; Obradors, Carla; Lebœuf, David; Echavarren, Antonio M

    2014-01-01

    From a series of gold complexes of the type [t-BuXPhosAu(MeCN)]X (X=anion), the best results in intermolecular gold(I)-catalyzed reactions are obtained with the complex with the bulky and soft anion BAr4F− [BAr4F−=3,5-bis(trifluoromethyl)phenylborate] improving the original protocols by 10–30% yield. A kinetic study on the [2+2] cycloaddition reaction of alkynes with alkenes is consistent with an scenario in which the rate-determining step is the ligand exchange to generate the (η2-phenylacetylene)gold(I) complex. We have studied in detail the subtle differences that can be attributed to the anion in this formation, which result in a substantial decrease in the formation of unproductive σ,π-(alkyne)digold(I) complexes by destabilizing the conjugated acid formed. PMID:26190958

  8. VSCF calculations for the intra- and intermolecular vibrational modes of the water dimer and its isotopologs

    NASA Astrophysics Data System (ADS)

    Monteiro, João G. S.; Barbosa, André G. H.

    2016-11-01

    In this work we show how the VSCF method may be successfully used to describe all fundamental vibrational transitions of several isotopologs of water dimer. By expressing the normal mode displacements in terms of appropriate delocalized internal coordinates we are able to minimize the mode-mode coupling in the PES and thus yield PT2-VSCF frequencies in good agreement with the experiment. The use of curvilinear normal modes is of paramount importance to describe vibrational transitions of the very soft intermolecular modes. Within our approach the maximum calculated error for the (H2O)2 intermolecular frequencies are reduced from 311 cm-1 (Cartesian normal modes) to just 56 cm-1 (curvilinear normal modes). Plots of the diagonal intermolecular potential and of the vibrational wave function illustrate the remarkable effect of different coordinate systems. In conclusion, our PT2-VSCF calculations provide a fair anharmonic description of the fundamental transitions of water dimers.

  9. 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

  10. Invited article: Digital beam-forming imaging riometer systems.

    PubMed

    Honary, Farideh; Marple, Steve R; Barratt, Keith; Chapman, Peter; Grill, Martin; Nielsen, Erling

    2011-03-01

    The design and operation of a new generation of digital imaging riometer systems developed by Lancaster University are presented. In the heart of the digital imaging riometer is a field-programmable gate array (FPGA), which is used for the digital signal processing and digital beam forming, completely replacing the analog Butler matrices which have been used in previous designs. The reconfigurable nature of the FPGA has been exploited to produce tools for remote system testing and diagnosis which have proven extremely useful for operation in remote locations such as the Arctic and Antarctic. Different FPGA programs enable different instrument configurations, including a 4 × 4 antenna filled array (producing 4 × 4 beams), an 8 × 8 antenna filled array (producing 7 × 7 beams), and a Mills cross system utilizing 63 antennas producing 556 usable beams. The concept of using a Mills cross antenna array for riometry has been successfully demonstrated for the first time. The digital beam forming has been validated by comparing the received signal power from cosmic radio sources with results predicted from the theoretical beam radiation pattern. The performances of four digital imaging riometer systems are compared against each other and a traditional imaging riometer utilizing analog Butler matrices. The comparison shows that digital imaging riometer systems, with independent receivers for each antenna, can obtain much better measurement precision for filled arrays or much higher spatial resolution for the Mills cross configuration when compared to existing imaging riometer systems.

  11. Emulsion forming drug delivery system for lipophilic drugs.

    PubMed

    Wadhwa, Jyoti; Nair, Anroop; Kumria, Rachna

    2012-01-01

    In the recent years, there is a growing interest in the lipid-based formulations for delivery of lipophilic drugs. Due to their potential as therapeutic agents, preferably these lipid soluble drugs are incorporated into inert lipid carriers such as oils, surfactant dispersions, emulsions, liposomes etc. Among them, emulsion forming drug delivery systems appear to be a unique and industrially feasible approach to overcome the problem of low oral bioavailability associated with the BCS class II drugs. Self-emulsifying formulations are ideally isotropic mixtures of oils, surfactants and co-solvents that emulsify to form fine oil in water emulsions when introduced in aqueous media. Fine oil droplets would pass rapidly from stomach and promote wide distribution of drug throughout the GI tract, thereby overcome the slow dissolution step typically observed with solid dosage forms. Recent advances in drug carrier technologies have promulgated the development of novel drug carriers such as control release self-emulsifying pellets, microspheres, tablets, capsules etc. that have boosted the use of "self-emulsification" in drug delivery. This article reviews the different types of formulations and excipients used in emulsion forming drug delivery system to enhance the bioavailability of lipophilic drugs.

  12. Embedding the Form Generator in a Content Management System

    NASA Astrophysics Data System (ADS)

    Delgado, A.; Wicenec, A.; Delmotte, N.; Tejero, A.

    2008-08-01

    Given the tremendous amount of data generated by ESO's telescopes and the rapid evolution of the World Wide Web, the ESO archive web interface needs to offer more flexible services and advanced functionalities to a growing community of users all over the world. To achieve this endeavour, a query form generator is being developed inside a Content Management System. We present here a progress report.

  13. Bistability Controlled by Convection in a Pattern-Forming System

    NASA Astrophysics Data System (ADS)

    Marsal, Nicolas; Weicker, Lionel; Wolfersberger, Delphine; Sciamanna, Marc

    2017-01-01

    We analyze the transition from convective to absolute dynamical instabilities in a nonlinear optical system forming patterns, i.e., a photorefractive crystal in a single feedback configuration. We demonstrate that the convective regime is directly related to the bistability area in which the homogeneous steady state coexists with a pattern solution. Outside this domain, the system exhibits either a homogeneous steady state or an absolute dynamical regime. We evidence that the bistability area can be greatly increased by adjusting the mirror tilt angle and/or by applying an external background illumination on the photorefractive crystal.

  14. Ultrasonic and IR study of intermolecular association through hydrogen bonding in ternary liquid mixtures.

    PubMed

    Awasthi, Aashees; Shukla, J P

    2003-08-01

    Complex formation in ternary liquid mixtures of dimethylsulfoxide (DMSO) with phenol and o-cresol in carbontetrachloride has been studied by measuring ultrasonic velocity at 2 MHz, in the concentration range of 0.019-0.162 (in mole fraction of DMSO) at varying temperatures of 20, 30 and 40 degrees C. Using measured values of ultrasonic velocity, other parameters such as adiabatic compressibility, intermolecular free length, molar sound velocity, molar compressibility, specific acoustic impedance and molar volume have been evaluated. These parameters have been utilized to study the solute-solute interactions in these systems. The ultrasonic velocity shows a maxima and adiabatic compressibility a corresponding minima as a function of concentration for these mixtures. The results indicate the occurrence of complex formation between unlike molecules through intermolecular hydrogen bonding between oxygen atom of DMSO molecule and hydrogen atom of phenol and o-cresol molecules. The excess values of adiabatic compressibility and intermolecular free length have also been evaluated. The variation of both these parameters with concentration also indicates the possibility of the complex formation in these systems. Further, to investigate the presence of O-HO bond complexes and the strength of molecular association with concentrations, the infrared spectra of both the systems, DMSO-phenol and DMSO-o-cresol, have been recorded for various concentrations at room temperature (20 degrees C). The results obtained using infrared spectroscopy for both the systems also support the occurrence of complex formation through intermolecular hydrogen bonding in these ternary liquid mixtures.

  15. 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.

  16. 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.

  17. Thermodynamic curvature for attractive and repulsive intermolecular forces.

    PubMed

    May, Helge-Otmar; Mausbach, Peter; Ruppeiner, George

    2013-09-01

    The thermodynamic curvature scalar R for the Lennard-Jones system is evaluated in phase space, including vapor, liquid, and solid state. We paid special attention to the investigation of R along vapor-liquid, liquid-solid, and vapor-solid equilibria. Because R is a measure of interaction strength, we traced out the line R=0 dividing the phase space into regions with effectively attractive (R<0) or repulsive (R>0) interactions. Furthermore, we analyzed the dependence of R on the strength of attraction applying a perturbation ansatz proposed by Weeks-Chandler-Anderson. Our results show clearly a transition from R>0 (for poorly repulsive interaction) to R<0 when loading attraction in the intermolecular potential.

  18. 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

  19. The B-box module of CYLD is responsible for its intermolecular interaction and cytoplasmic localization.

    PubMed

    Xie, Songbo; Chen, Miao; Gao, Siqi; Zhong, Tao; Zhou, Peng; Li, Dengwen; Zhou, Jun; Gao, Jinmin; Liu, Min

    2017-02-07

    The tumor suppressor protein cylindromatosis (CYLD), as a microtubule-associated deubiquitinase, plays a pivotal role in a wide range of cellular activities, including innate immunity, cell division, and ciliogenesis. Structural characterization reveals a small zinc-binding B-box inserted within the ubiquitin specific protease (USP) domain of CYLD; however, the exact role for this module remains yet to be elucidated. Here we identify a critical role for the B-box in facilitating the intermolecular interaction and subcellular localization of CYLD. By co-immunoprecipitation assays we uncover that CYLD has the ability to form an intermolecular complex. Native gel electrophoresis analysis and pull down assays show that the USP domain of CYLD is essential for its intermolecular interaction. Further investigation reveals that deletion of the B-box from the USP domain disrupts the intermolecular interaction of CYLD. Importantly, although loss of the B-box has no obvious effect on the deubiquitinase activity of CYLD, it abolishes the USP domain-mediated retention of CYLD in the cytoplasm. Collectively, these data demonstrate an important role for the B-box module of CYLD in mediating its assembly and subcellular distribution, which might be related to the functions of CYLD in various biological processes.

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

    PubMed

    Jarvis, Samuel Paul

    2015-08-21

    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.

  1. 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

  2. An isotopic mass effect on the intermolecular potential

    DOE PAGES

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

    2015-09-28

    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 paper, 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. Finally, the analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologuemore » thermodynamics.« less

  3. 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.

  4. 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.

  5. Intermolecular potential functions from spectroscopic properties of weakly bound complexes

    SciTech Connect

    Muenter, J.S.

    1992-01-01

    Goal is to consolidate the information from high resolution spectroscopy of weakly bound cluster molecules through a theoretical model of intermolecular potential energy surfaces. The ability to construct analytic intermolecular potential functions that accurately predict the interaction energy between small molecules will have a major impact in chemistry, biochemistry, and biology. This document presents the evolution and capabilities of a potential function model developed here, and then describes plans for future developments and applications. This potential energy surface (PES) model was first used on (HCCH){sub 2}, (CO{sub 2}){sub 2}, HCCH - CO{sub 2}; it had to be modified to work with HX dimers and CO{sub 2}-HX complexes. Potential functions have been calculated for 15 different molecular complexes containing 7 different monomer molecules. Current questions, logical extensions and new applications of the model are discussed. The questions are those raised by changing the repulsion and dispersion terms. A major extension of the PES model will be the inclusion of induction effects. Projects in progress include PES calculations on (HCCH){sub 3}, CO{sub 2} containing complexes, (HX){sub 2}, HX - CO{sub 2}, CO{sub 2} - CO, (CO{sub 2}){sub 3}, and (OCS){sub 2}. The first PES calculation for a nonlinear molecule will be for water and ammonia complexes. Possible long-term applications for biological molecules are discussed. Differences between computer programs used for molecular mechanics and dynamics in biological systems are discussed, as is the problem of errors. 12 figs, 74 refs. (DLC)

  6. 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.

  7. High-frequency intermolecular homologous recombination during herpes simplex virus-mediated plasmid DNA replication.

    PubMed

    Fu, Xinping; Wang, Hua; Zhang, Xiaoliu

    2002-06-01

    Homologous recombination is a prominent feature of herpes simplex virus (HSV) type 1 DNA replication. This has been demonstrated and traditionally studied in experimental settings where repeated sequences are present or are being introduced into a single molecule for subsequent genome isomerization. In the present study, we have designed a pair of unique HSV amplicon plasmids to examine in detail intermolecular homologous recombination (IM-HR) between these amplicon plasmids during HSV-mediated DNA replication. Our data show that IM-HR occurred at a very high frequency: up to 60% of the amplicon concatemers retrieved from virion particles underwent intermolecular homologous recombination. Such a high frequency of IM-HR required that both plasmids be replicated by HSV-mediated replication, as IM-HR events were not detected when either one or both plasmids were replicated by simian virus 40-mediated DNA replication, even with the presence of HSV infection. In addition, the majority of the homologous recombination events resulted in sequence replacement or targeted gene repair, while the minority resulted in sequence insertion. These findings imply that frequent intermolecular homologous recombination may contribute directly to HSV genome isomerization. In addition, HSV-mediated amplicon replication may be an attractive model for studying intermolecular homologous recombination mechanisms in general in a mammalian system. In this regard, the knowledge obtained from such a study may facilitate the development of better strategies for targeted gene correction for gene therapy purposes.

  8. 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.

  9. A Catalytic, Brønsted Base Strategy for Intermolecular Allylic C—H Amination

    PubMed Central

    Reed, Sean A.; Mazzotti, Anthony R.; White, M. Christina

    2009-01-01

    A Brønsted base activation mode for oxidative, Pd(II)/sulfoxide catalyzed, intermolecular C—H allylic amination is reported. N,N-diisopropylethylamine was found to promote amination of unactivated terminal olefins, forming the corresponding linear allylic amine products with high levels of stereo-, regio-, and chemoselectivity. The predictable and high selectivity of this C—H oxidation method enables late-stage incorporation of nitrogen into advanced synthetic intermediates and natural products. PMID:19645492

  10. Chemotaxis and Autotaxis in Biofilm-Forming Systems

    NASA Astrophysics Data System (ADS)

    Strain, Shinji; Bienvenu, Samuel; Thatcher, Travis; Cooley, Benjamin; Gordon, Vernita

    2011-03-01

    Biofilms are multicellular, surface-bound communities of interacting unicellular organisms. In the initial stages of biofilm formation, discrete cells populate the surface and eventually form microcolonies (dense surface-bound clusters of cells). How much these microcolonies arise from clonal growth and how much they arise from attraction and active motility of non-clonal cells is not well-understood. One potentially important form of attraction is autotaxis, movement of cells toward like cells. Another is chemotaxis, movement of cells toward an attractive chemical, which could act to concentrate cells with no direct intercellular interaction. While both autotaxis and chemotaxis have been studied for three-dimensional, swimming, dense bacterial systems, they remain largely unstudied in sparse, surface-bound populations that initiate biofilms. Using microscopy and automated tracking and analysis algorithms, we will study how bacteria respond to each other and to chemoattractants, in a spatially-dependent manner. We will determine how variations in neighbor density and arrangement stimulate changes in the motility of E. coli and P. aeruginosa cells on a surface.

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. From intra- to inter-molecular hydrogen bonds with the surroundings: steady-state and time-resolved behaviours.

    PubMed

    Alarcos, Noemí; Gutiérrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

    2015-07-01

    We report on the photodynamics of 2-(2'-hydroxyphenyl)benzoxazole (HBO), compared to its amino derivatives, 6-amino-2-(2'-hydroxypheny)benzoxazole (6A-HBO) and 5-amino-2-(2'-hydroxypheny)benzoxazole (5A-HBO) in N,N-dimethylformamide (DMF) solutions. HBO at S0 shows a reversible deprotonation reaction leading to the production of anionic forms. However, for 6A-HBO and 5A-HBO, DMF containing KOH is necessary to produce the anions. Excited HBO in DMF exhibits intra- as well as inter-molecular proton transfer (ESIPT and ESPT) reactions. With excitation at 330 nm, we observed the open-enol, anti-enol and keto forms with different emission and lifetimes (620 ps, 1.5 ns, and 74 ps, respectively), while with the excitation at 433 nm, only the anionic species emission was detected (3.7 ns). Contrary to HBO, 6A-HBO and 5A-HBO do not exhibit any proton transfer process, and only the emissions of the open-enol charge-transferred forms (open-ECT) were observed, which are comparable to those of their methylated derivatives (6A-MBO and 5A-MBO). Femtosecond studies of 6A-MBO and 6A-HBO in DMF indicate that an intramolecular charge-transfer (ICT) reaction (∼80 fs) and solvent relaxation process (2 ps) take place at S1. Remarkably, the photoinduced breaking of the intramolecular hydrogen bond of 6A-HBO and the formation of an intermolecular hydrogen bond with DMF molecules occurs in 80 ps, while for 5A-HBO, this process occurs in less than 10 ps. In this study, we have demonstrated that the presence and position of the amino group in the HBO framework change both the S0 and S1 behaviours of the intramolecular H-bonds; a result which might be useful for the design and better understanding of supramolecular systems based on intra- and intermolecular H-bonds.

  17. A pneumatic transfer system for special form {sup 252}Cf

    SciTech Connect

    Gehrke, R.J.; Berry, S.M.; Grafwallner, E.G.; Hoggan, J.M.

    1996-09-01

    A pneumatic transfer system has been developed for use with series 100 Special Form {sup 252}Cf. It was developed to reduce the exposure to personnel handling sources of {sup 252}Cf with masses up to 150 {micro}g by permitting remotely activated two-way transfer between the storage container and the irradiation position. The pneumatic transfer system also permits transfers for reproducible repetitive irradiation periods. In addition to the storage container equipped with quick-release fittings, the transfer system consists of an irradiation station, a control box with momentary contact switches to activate the air-pressure control valves and indicators to identify the location of the source, and connecting air hose and electrical wire. A source of 20 psig air and 110 volt electrical power are required for operation of the transfer system which can be easily moved and set up by one individual in 5 to 10 minutes. Tests have shown that rarely does a source become lodged in the transfer tubing, but two methods have been developed to handle incomplete transfers of the {sup 252}Cf source. The first method consists of closing one air vent to allow a pressure impulse to propel the source to the opposite side. The second method applies to those {sup 252}Cf capsules with a threaded or tapped end to which a small ferromagnetic piece can be attached; an incompletely transferred source in the transfer tube can then be guided to a position of safety by surrounding the transfer tubing containing the capsule with a horseshoe magnet attached to the end of a long pole.

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

    PubMed

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

    2016-01-05

    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.

  19. Form and toxicity of copper released into marine systems from ...

    EPA Pesticide Factsheets

    The fate and effects of pristine engineered nanomaterials (ENMs) in simplified systems have been widely studied; however, little is known about the potential release and impact of ENMs from consumer goods, especially lumber that has been treated with micronized copper. Micronized copper solutions contain copper complexes predominately in the 10-700 nm size range, and are used in lumber to prevent microbial degradation and fouling. In this work, the goal was to determine the rate, concentration, and form of copper released from commercially available pressure treated lumber samples (blocks and sawdust) exposed to an aqueous system. Lumber tested included Southern Yellow Pine (SYP) treated with micronized copper azole (MCA) at 0.96 and 2.4 Kg/m3, alkaline copper quaternary (ACQ) at 0.30 and 9.6 Kg/m3, and chromated copper arsenate (CCA) at 40 Kg/m3. Of the different chemical treatments, only MCA included nano- and micro-sized copper complexes. The experimental system included wood cubes cut from the outer 2 cm surface of the lumber or the equivalent mass (4 g) of sawdust submerged in 250 mL of media (0, 1, 10, and 30 ppt filtered natural seawater) in polyethylene bottles, and mixed on a shaker table at 120 rpm. Water samples were taken at 8 hours, and on days 1, 2, 7, 14, and 28 for the blocks and days 1, 2, 3, 7, 17, and 28 for the sawdust. Subsamples included unfiltered water (defined as 0.45 µm - filtered water for the sawdust), and water filtered through a 0.

  20. Synthesis and intermolecular interactions of N-benzylidenetyramines

    NASA Astrophysics Data System (ADS)

    Maldonado, Mauricio; Pérez-Redondo, Adrián; Quevedo, Rodolfo

    2017-01-01

    In this paper, the synthesis and intermolecular interactions between N-benzylidenetyramine molecules were investigated. The crystal structure of N-(4-nitrobenzylidene)tyramine shows a molecular organization in zigzag chains with intermolecular O-H⋯N hydrogen bonds between the azomethine and phenolic hydroxyl groups. Those chains are held together by C-H⋯O hydrogen bonds to generate layers, which are connected by C-H⋯O, π⋯π and NO2⋯π interactions.

  1. Intermolecular forces between the motor protein and the filament.

    PubMed

    Suda, H; Taylor, T W

    1993-03-07

    Intermolecular forces between motor proteins and filaments were evaluated on the basis of the experimental data of an in vitro motility assay by considering the molecular friction in the movement system. The molecular friction was caused by a different mechanism from that of the hydrodynamic drag. However, the molecular frictional forces apparently gave the same expression as the hydrodynamic frictional forces. The resulting equation was very effective in examining the physical properties of the weak interaction in the dynein-microtubules system from basic experiments carried out by Vale et al. (1989). From careful analysis of their experimental data, it was concluded that the hydrodynamic friction was not dominant, even in the weak binding state. The electrostatic interaction between dynein-heads and microtubules in the weak binding state was analyzed by applying the DLVO (Derjaguin-Landau-Verway-Overbeek) theory in colloid science through the ionic dependence of one-dimensional diffusion. The interacting distance between charges which took part in the weak adhesion was estimated to be 3 nm. In the present study, the molecular mechanism of the sliding velocity was also investigated for the myosin-actin filaments and the kinesin-microtubules systems by fitting the ATP-dependence and the ionic dependence in ATP-driven active sliding.

  2. 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.

  3. Investigation of intermolecular interactions in perylene films on Au(111) by infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Ding, Li; Schulz, Philip; Farahzadi, Azadeh; Shportko, Kostiantyn V.; Wuttig, Matthias

    2012-02-01

    Intermolecular interactions in crystalline perylene films on Au(111) have been investigated by Fourier transform infrared spectroscopy. Dimer modes of vibrations are observed in the crystalline film, in contrast to the monomer modes found for isolated perylene molecules. These dimers are formed via hydrogen bonding in the sandwich herringbone structure of the crystalline α-phase. Davydov splitting of both the monomer and the dimer modes is observed due to resonance dynamic intermolecular interaction. The splitting of monomer modes into three distinct vibrations and the occurrence of the dimer modes confirm that the film crystallizes in the α phase, which is in line with the x-ray diffraction results. The frequency shift and band broadening at elevated temperature have been attributed to the cubic and quartic anharmonic interactions.

  4. 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).

  5. Pediatric Scleroderma –Systemic and Localized Forms

    PubMed Central

    Torok, Kathryn S.

    2012-01-01

    Synopsis statement Pediatric scleroderma includes two major groups of clinical entities, systemic sclerosis (SSc) and localized scleroderma (LS). Although both share a common pathophysiology, with an initial inflammatory phase associated with endothelial activation, and a later fibrotic phase evidenced by collagenization of tissue and appreciable skin thickness, their clinical manifestations differ. LS is typically confined to the skin and underlying subcutis, and though not fatal like SSc, up to a quarter of the patients may have extracutaneous disease manifestations, such as arthritis and uveitis. While any organ may be affected in SSc, vascular (Raynaud’s phenomenon), cutaneous (skin thickening), GI, pulmonary and musculoskeletal involvement are most commonly seen in children. Auto-antibody profiles in childhood onset SSc can assist in predicting internal organ involvement. Treatment for both forms of scleroderma targets the active inflammatory stage and halts disease progression; however, progress still needs to be made towards the development of a more effective anti-fibrotic therapy to help reverse disease damage. PMID:22560576

  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. Theory of specific heat in glass-forming systems

    NASA Astrophysics Data System (ADS)

    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

  8. NMR detection of intermolecular interaction sites in the dimeric 5′-leader of the HIV-1 genome

    PubMed Central

    Keane, Sarah C.; Van, Verna; Frank, Heather M.; Sciandra, Carly A.; McCowin, Sayo; Santos, Justin; Heng, Xiao; Summers, Michael F.

    2016-01-01

    HIV type-1 (HIV-1) contains a pseudodiploid RNA genome that is selected for packaging and maintained in virions as a noncovalently linked dimer. Genome dimerization is mediated by conserved elements within the 5′-leader of the RNA, including a palindromic dimer initiation signal (DIS) that has been proposed to form kissing hairpin and/or extended duplex intermolecular contacts. Here, we have applied a 2H-edited NMR approach to directly probe for intermolecular interactions in the full-length, dimeric HIV-1 5′-leader (688 nucleotides; 230 kDa). The interface is extensive and includes DIS:DIS base pairing in an extended duplex state as well as intermolecular pairing between elements of the upstream Unique-5′ (U5) sequence and those near the gag start site (AUG). Other pseudopalindromic regions of the leader, including the transcription activation (TAR), polyadenylation (PolyA), and primer binding (PBS) elements, do not participate in intermolecular base pairing. Using a 2H-edited one-dimensional NMR approach, we also show that the extended interface structure forms on a time scale similar to that of overall RNA dimerization. Our studies indicate that a kissing dimer-mediated structure, if formed, exists only transiently and readily converts to the extended interface structure, even in the absence of the HIV-1 nucleocapsid protein or other RNA chaperones. PMID:27791166

  9. 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.

  10. 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.

  11. Data assimilation and determining forms for weakly damped, dispersive systems

    NASA Astrophysics Data System (ADS)

    Sadigov, Tural

    In this work, we show that the global attractor of the 1D damped, driven, nonlinear Schrodinger equations (NLS) is embedded in the long-time dynamics of a determining form. The determining form for the NLS is an ordinary differential equation in a space of trajectories X = Cb 1(R,PmH2) where Pm is the L2-projector onto the span of the ?rst m Fourier modes. Similarly, we also find a determining form for the damped, driven Korteweg de-Vries equations (KdV). This time, the determining form for the KdV is an ordinary differential equation in a space of trajectories X = Cb 1(R,PmH2). In both cases, there is a one-to-one identi?cation with the trajectories in the global attractor of the underlying equations and the steady states of the determining form for the that equation. The determining form for both of these equations is dv(s, t)/ dt= - sup{s∈R} |v( s, t) - PmW (v( s, t))|2(v(s, t) - Pmu* (s, t)), where v( s) ∈ X, u* is a steady state of the underlying equation and W is a special map from X to a different Banach space which contains the relation between the underlying partial differential equation and the determining form. Additionally, we prove that the determining modes property holds for both of these equations. We give an improved estimate for the number of the determining modes for the NLS and we give an estimate for the number of determining modes for the KdV. Moreover, we give a continuous data assimilation algorithm via feedback control approach for the NLS and the KdV using only definitely many modes. The NLS and the KdV equations are ius + uxx + |u|2u + gammau = f, (NLS) us + uux + uxxx + gamma u = f, (KdV) respectively. We prove the following theorem: Theorem. Let u be a solution of the following equation us = F( u), with an initial data u(s 0), where the above equation is either (NLS) or (KdV), and let w be the solution of the corresponding data assimilation equation ws = F(w) - micro Pm(w - u), with an arbitrary initial data w(s0). For micro large

  12. 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.

  13. Heterotetrameric forms of human phenylalanine hydroxylase: co-expression of wild-type and mutant forms in a bicistronic system.

    PubMed

    Leandro, João; Leandro, Paula; Flatmark, Torgeir

    2011-05-01

    Hybrid forms of human phenylalanine hydroxylase (hPAH) mutants have been found to present catalytic activities lower than predicted from the individual recombinant forms, indicating that interallelic complementation could be a major determinant of the metabolic phenotype of compound heterozygous phenylketonuric (PKU) patients. To provide a molecular explanation for interallelic complementation we have here developed a bicistronic expression system and a purification strategy to obtain isolated hPAH heteromeric forms. On co-expression of WT-hPAH (~50% tetramer; ~10% dimer) and the N- and C-terminally truncated form ΔN102/ΔC24-hPAH (~80% dimer) no heterodimers were recovered. Moreover, by co-expression of WT-hPAH and the N-terminally truncated form ΔN102-hPAH (~95% tetramer), heterotetramers, as a result of an assembly of two different homodimers, were isolated. The recovered (WT)/(ΔN102)-hPAH heterotetramers revealed a catalytic activity deviating significantly from that calculated by averaging the respective recombinant homotetrameric forms. The heterotetramer assembly also results in conformational changes in the WT-hPAH protomer, as detected by trypsin limited proteolysis. The finding that the presence of two homodimers with different kinetic parameters influences the properties of the resulting heterotetrameric protein indicates that the dimers exhibit interactions which are transmitted across the assembled tetramer. The bicistronic expression system developed here allowed the isolation of hybrid forms that exhibit negative interallelic complementation, and may represent a model system for studying the molecular pathogenic mechanisms of PAH gene mutations in compound heterozygous PKU patients, providing the rationale to understand the observed inconsistencies both in genotype/phenotype correlations and in the response to BH(4) supplementation.

  14. Forming design teams to develop healthcare information systems.

    PubMed

    Saleem, Naveed; Jones, Donald R; Van Tran, Hien; Moses, Beulah

    2006-01-01

    Healthcare information systems are assuming an increasingly critical role in providing quality patient care in an effective and efficient manner. However, the success of these systems in achieving these goals remains a lingering concern. Consequently, investigating and devising strategies to enhance the likelihood of success of a healthcare information system continues to draw research interest. One strategy recommended by both researchers and practitioners alike is the participation of the target users in the design and development of the information system. However, practical considerations mandate representative, rather than universal, participation of users. Unfortunately, the information systems literature offers few guidelines for selecting user representatives to serve on a design team. This lack of guidelines easily results in system designers talking with the wrong users or managers assigning the wrong users to the design team. On the basis of the theoretical paradigms underlying the user participation and design team concepts, the authors examined and derived user characteristics that are considered the most critical criteria for selecting user members of a design team. They then report on a field survey they conducted to validate the derived criteria in healthcare information systems context. The authors conclude that the system-related functional expertise should be the primary criterion employed to select healthcare personnel to participate in system design and development. Other criteria, such as users' communication skills, computing backgrounds, and personality traits, should be given secondary considerations. Ignoring these guidelines can render user participation superfluous, resulting in system failures.

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

    PubMed

    Renaud, Nicolas; Grozema, Ferdinand C

    2015-02-05

    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.

  16. The intermolecular hydrogen-hydrogen structure of chain-molecule liquids from neutron diffraction

    NASA Astrophysics Data System (ADS)

    Londono, J. D.; Annis, B. K.; Turner, J. Z.; Soper, A. K.

    1994-11-01

    Neutron diffraction isotopic substitution experiments on liquid n-decane (C10H22) and n-eicosane (C20H42) are described. The intermolecular H-H structure function hHH(Q) and the intermolecular H-H correlation function ginterHH(r) are obtained without recourse to models of the intramolecular structure. The structure of the ginterHH(r) found at 2.5, 5.0, and 7.0 Å corresponds to different shells in the H-H pair correlation function. In addition, ginterHH(r)<1 for a considerable range, due to the screening of intermolecular correlations by intramolecular correlations. This ``correlation hole'' effect is accentuated by extrapolation of the structure functions to the expected infinite wavelength limit, and shows good agreement with values determined from small-angle neutron scattering (SANS) data. All of these features are in good agreement with the results of molecular dynamics simulations for the closely related system C13H28.

  17. Highly enantioselective and anti-diastereoselective catalytic intermolecular glyoxylate-ene reactions: effect of the geometrical isomers of alkenes.

    PubMed

    Zhang, Xiang; Wang, Min; Ding, Ran; Xu, Yun-He; Loh, Teck-Peng

    2015-06-05

    An efficient method for the synthesis of homoallylic alcohols with high enantioselectivities and anti-diastereoselectivities via an In(III)-catalyzed intermolecular glyoxylate-ene reaction has been developed. The geometrical isomers of alkenes were shown to have different reactivities. Only the isomers of the alkenes having a proton β-cis to the substituent reacted in this catalytic system.

  18. 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.

  19. Isotopic enrichment of forming planetary systems from supernova pollution

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    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 disc 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 discs 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Novel RNA modifications in the nervous system: form and function.

    PubMed

    Satterlee, John S; Basanta-Sanchez, Maria; Blanco, Sandra; Li, Jin Billy; Meyer, Kate; Pollock, Jonathan; Sadri-Vakili, Ghazaleh; Rybak-Wolf, Agnieszka

    2014-11-12

    Modified RNA molecules have recently been shown to regulate nervous system functions. This mini-review and associated mini-symposium provide an overview of the types and known functions of novel modified RNAs in the nervous system, including covalently modified RNAs, edited RNAs, and circular RNAs. We discuss basic molecular mechanisms involving RNA modifications as well as the impact of modified RNAs and their regulation on neuronal processes and disorders, including neural fate specification, intellectual disability, neurodegeneration, dopamine neuron function, and substance use disorders.

  5. 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.

  6. ORGANIC CHEMISTRY. Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes.

    PubMed

    Hoyt, Jordan M; Schmidt, Valerie A; Tondreau, Aaron M; Chirik, Paul J

    2015-08-28

    Cycloadditions, such as the [4+2] Diels-Alder reaction to form six-membered rings, are among the most powerful and widely used methods in synthetic chemistry. The analogous [2+2] alkene cycloaddition to synthesize cyclobutanes is kinetically accessible by photochemical methods, but the substrate scope and functional group tolerance are limited. Here, we report iron-catalyzed intermolecular [2+2] cycloaddition of unactivated alkenes and cross cycloaddition of alkenes and dienes as regio- and stereoselective routes to cyclobutanes. Through rational ligand design, development of this base metal-catalyzed method expands the chemical space accessible from abundant hydrocarbon feedstocks.

  7. Vibrational Circular Dichroism (VCD) Reveals Subtle Conformational Aspects and Intermolecular Interactions in the Carnitine Family.

    PubMed

    Mazzeo, Giuseppe; Abbate, Sergio; Longhi, Giovanna; Castiglioni, Ettore; Villani, Claudio

    2015-12-01

    Vibrational circular dichroism spectra (VCD) in the mid-IR region and electronic circular dichroism (ECD) spectra for three carnitine derivatives in the form of hydrochloride salts were recorded in deuterated methanol solutions. Density Functional Theory calculations help one to understand the significance of the observed VCD bands. VCD and ECD spectra are informative about the absolute configuration of the molecule, but VCD data reveal also some conformational aspects in the N,N,N-trimethyl moiety and inform us about intermolecular interactions gained from the carbonyl stretching region for the acyl substituted carnitines.

  8. 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.

  9. 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.

  10. 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.

  11. 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…

  12. Connecting Protein Structure to Intermolecular Interactions: A Computer Modeling Laboratory

    ERIC Educational Resources Information Center

    Abualia, Mohammed; Schroeder, Lianne; Garcia, Megan; Daubenmire, Patrick L.; Wink, Donald J.; Clark, Ginevra A.

    2016-01-01

    An understanding of protein folding relies on a solid foundation of a number of critical chemical concepts, such as molecular structure, intra-/intermolecular interactions, and relating structure to function. Recent reports show that students struggle on all levels to achieve these understandings and use them in meaningful ways. Further, several…

  13. 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…

  14. Intermolecular atom-atom bonds in crystals - a chemical perspective.

    PubMed

    Thakur, Tejender S; Dubey, Ritesh; Desiraju, Gautam R

    2015-03-01

    Short atom-atom distances between molecules are almost always indicative of specific intermolecular bonding. These distances may be used to assess the significance of all hydrogen bonds, including the C-H⋯O and even weaker C-H⋯F varieties.

  15. Information systems form large part of strategic plan.

    PubMed

    Landis, D

    1991-02-01

    Strategic planning is often a low priority for community hospitals because it is often too impractical. The difference for Ed McFall, chief information officer at Pitt County Memorial Hospital (PCMH) in Greenville, N.C., is that his hospital's and affiliated medical school's information systems plans work.

  16. 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.

  17. 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.

  18. Rodlike localized structure in isotropic pattern-forming systems.

    PubMed

    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.

  19. Divergent dynamics and the Kauzmann temperature in glass forming systems

    PubMed Central

    Martinez-Garcia, Julio Cesar; Rzoska, Sylwester J.; Drzozd-Rzoska, Aleksandra; Martinez-Garcia, Jorge; Mauro, John C.

    2014-01-01

    In the last decade the challenging analysis of previtreous behavior of relaxation time (τ(T)) in ultraviscous low molecular weight liquids led to the conceptual shift of the glass transition physics toward theories not predicting a “finite-temperature” divergence. This “breakthrough” experimental finding was strengthened by the discovery that “dynamic” (i.e. from τ(T) fitting) and “thermodynamic” estimations of the “ideal glass” (Kauzmann) temperature do not match, what in fact questioned its existence. In this report, due to the novel way of analysis based on the transformation of τ(T) experimental data to the activation energy temperature index form, the clear prevalence of the “finite-temperature” divergence is proved. The obtained “dynamic” singular temperatures clearly coincide with “thermodynamic” estimations of the Kauzmann temperature, thus solving also the second mystery. The comprehensive picture was obtained due to the analysis of 55 experimental data-sets, ranging from low molecular weight liquids and polymers to liquid crystal and plastic crystals. PMID:24895028

  20. 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.

  1. Global feedback control for pattern-forming systems.

    PubMed

    Stanton, L G; Golovin, A A

    2007-09-01

    Global feedback control of pattern formation in a wide class of systems described by the Swift-Hohenberg (SH) equation is investigated theoretically, by means of stability analysis and numerical simulations. Two cases are considered: (i) feedback control of the competition between hexagon and roll patterns described by a supercritical SH equation, and (ii) the use of feedback control to suppress the blowup in a system described by a subcritical SH equation. In case (i), it is shown that feedback control can change the hexagon and roll stability regions in the parameter space as well as cause a transition from up to down hexagons and stabilize a skewed (mixed-mode) hexagonal pattern. In case (ii), it is demonstrated that feedback control can suppress blowup and lead to the formation of spatially localized patterns in the weakly nonlinear regime. The effects of a delayed feedback are also investigated for both cases, and it is shown that delay can induce temporal oscillations as well as blowup.

  2. 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

  3. Intermolecular forces: a solution to dispersion interactions.

    PubMed

    Shimizu, Ken D

    2013-12-01

    London dispersion forces have been cited as an important factor in protein folding, drug–receptor interactions, and catalyst selectivities. However, careful analysis of a model system finds that the dispersion interactions are only minor contributors to the formation of complexes in solution.

  4. Intermolecular forces and scaling relations between heterogeneous macromolecular surfaces

    NASA Astrophysics Data System (ADS)

    Rosenberg, Kenneth J.

    Most theories regarding the behavior of intermolecular forces assume perfectly smooth surfaces with well-defined chemical and material properties. In this thesis, three separate systems are studied to explore the accuracy of this assumption in very different situations. In the first system, the effects of milli-molar amounts of dissolved gas (the amount typically present in normal atmospheric conditions) have been studied at a pristine oil/water interface. It was found that the removal of the dissolved gas significantly increased the lifetime of the oil droplets, effectively reducing the long-range hydrophobic attractive force present under standard conditions. In the second system, the effect of varying normal and lateral roughness of solid surfaces in understanding the long-range steric forces and shorter-range adhesive (van der Waals) forces are studied. Various techniques to reproducibly control and vary the roughness were developed for a number of different types of polymeric surfaces. A strong correlation between the roughness and the repulsive steric force was observed for randomly rough surfaces. Similar scaling relations between the roughness and the magnitude of the adhesive force were measured. Friction measurements between these surfaces show that even a few nanometers of roughness significantly reduces the critical shear stress required to initiate sliding. However, the coefficient of friction was relatively unaffected by the range of roughness considered, in agreement with the macroscopic Amontons' law. The third and final system dealt with the properties of adsorbed layers of polyampholytes (containing both positively and negatively charged groups), as opposed to the more common classes of neutral polymers or polyelectrolytes. These measurements took advantage of a naturally occurring family of proteins (a class of polyampholytes), known as tau, which exist in six different well-defined lengths and charge densities. Force measurements were made with

  5. Tuning intermolecular non-covalent interactions for nanowires of organic semiconductors.

    PubMed

    Jiang, Lang; Gao, Jianhua; Fu, Yanyan; Dong, Huanli; Zhao, Huaping; Li, Hongxiang; Tang, Qingxin; Chen, Keqiu; Hu, Wenping

    2010-12-01

    Anthracene and its derivatives are used to demonstrate a simple way to cast assemble nanowires of organic semiconductors with tuning of intermolecular non-covalent interactions by molecular design. The tuning of intermolecular interactions could be achieved by (i) decreasing intermolecular hydrophobic interactions by linking hydrophilic side chains to anthracene rings, (ii) increasing intermolecular interaction for self-assembly with the assistance of hydrogen bonds, and (iii) enhancing molecular π-π interaction by increasing the conjugated dimension of the compounds.

  6. Tuning intermolecular non-covalent interactions for nanowires of organic semiconductors

    NASA Astrophysics Data System (ADS)

    Jiang, Lang; Gao, Jianhua; Fu, Yanyan; Dong, Huanli; Zhao, Huaping; Li, Hongxiang; Tang, Qingxin; Chen, Keqiu; Hu, Wenping

    2010-12-01

    Anthracene and its derivatives are used to demonstrate a simple way to cast assemble nanowires of organic semiconductors with tuning of intermolecular non-covalent interactions by molecular design. The tuning of intermolecular interactions could be achieved by (i) decreasing intermolecular hydrophobic interactions by linking hydrophilic side chains to anthracene rings, (ii) increasing intermolecular interaction for self-assembly with the assistance of hydrogen bonds, and (iii) enhancing molecular π-π interaction by increasing the conjugated dimension of the compounds.

  7. Microwave Imaging Radar Reflectometer System Utilizing Digital Beam Forming

    NASA Astrophysics Data System (ADS)

    Hu, Fengqi; Li, Meijiao; Domier, Calvin W.; Liu, Xiaoguang; Luhmann, Neville C., Jr.

    2016-10-01

    Microwave Imaging Reflectometry is a radar-like technique developed to measure the electron density fluctuations in fusion plasmas. Phased Antenna Arrays can serve as electronically controlled ``lenses'' that can generate the required wavefronts by phase shifting and amplitude scaling, which is being realized in the digital domain with higher flexibility and faster processing speed. In the transmitter, the resolution of the phase control is 1.4 degrees and the amplitude control is 0.5 dB/ step. A V-band double-sided, printed bow tie antenna which exhibits 49% bandwidth (46 - 76 GHz) is employed. The antenna is fed by a microstrip transmission line for easy impedance matching. The simple structure and the small antenna are suitable for low cost fabrication, easy circuit integration, and phased antenna array multi-frequency applications. In the receiver part, a sub-array of 32 channels with 200 mil spacing is used to collect the scattered reflected signal from one unit spot on the plasma cutoff surface. Pre-amplification is used to control the noise level of the system and wire bondable components are used to accommodate the small spacing between each channel. After down converting, base band signals are digitized and processed in an FPGA module. U.S. Department of Energy Grant No. DE-FG02-99ER54531.

  8. Magneto-dielectric effects induced by optically-generated intermolecular charge-transfer states in organic semiconducting materials.

    PubMed

    Zang, Huidong; Yan, Liang; Li, Mingxing; He, Lei; Gai, Zheng; Ivanov, Ilia; Wang, Min; Chiang, Long; Urbas, Augustine; Hu, Bin

    2013-10-02

    Traditionally, magneto-dielectric effects have been developed by combining ferroelectric and magnetic materials. Here, we show a magneto-dielectric effect from optically-generated intermolecular charge-transfer states in an organic semiconducting donor:acceptor (PVK:TCNB) system. We observe in magnetic field effects of photoluminescence that a magnetic field can change singlet/triplet population ratio in intermolecular charge-transfer states. Furthermore, our theoretical analysis and experimental evidence indicate that the singlets and triplets in charge-transfer states have stronger and weaker electrical polarizations, respectively. Therefore, the observed magneto-dielectric effect can be attributed to magnetically-dependent singlet/triplet ratio in intermolecular charge-transfer states. In principle, a magneto-dielectric effect can be generated through two different channels based on magneto-polarization and magneto-current effects when the singlet/triplet ratio in intermolecular charge-transfer states is changed by a magnetic field. We find, from the simulation of dielectric effects, that magneto-polarization and magneto-current effects play primary and secondary roles in the generation of magneto-dielectric effect.

  9. 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.

  10. Foot-and-mouth disease virus leader proteinase: structural insights into the mechanism of intermolecular cleavage.

    PubMed

    Steinberger, Jutta; Grishkovskaya, Irina; Cencic, Regina; Juliano, Luiz; Juliano, Maria A; Skern, Tim

    2014-11-01

    Translation of foot-and-mouth disease virus RNA initiates at one of two start codons leading to the synthesis of two forms of leader proteinase L(pro) (Lab(pro) and Lb(pro)). These forms free themselves from the viral polyprotein by intra- and intermolecular self-processing and subsequently cleave the cellular eukaryotic initiation factor (eIF) 4 G. During infection, Lb(pro) removes six residues from its own C-terminus, generating sLb(pro). We present the structure of sLb(pro) bound to the inhibitor E64-R-P-NH2, illustrating how sLb(pro) can cleave between Lys/Gly and Gly/Arg pairs. In intermolecular cleavage on polyprotein substrates, Lb(pro) was unaffected by P1 or P1' substitutions and processed a substrate containing nine eIF4GI cleavage site residues whereas sLb(pro) failed to cleave the eIF4GI containing substrate and cleaved appreciably more slowly on mutated substrates. Introduction of 70 eIF4GI residues bearing the Lb(pro) binding site restored cleavage. These data imply that Lb(pro) and sLb(pro) may have different functions in infected cells.

  11. 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.

  12. 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.

  13. Correlated and cooperative motions in segmental relaxation: Influence of constitutive unit weight and intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Rijal, Bidur; Soto Puente, Jorge Arturo; Atawa, Bienvenu; Delbreilh, Laurent; Fatyeyeva, Kateryna; Saiter, Allisson; Dargent, Eric

    2016-12-01

    This work clarifies the notion of correlated and cooperative motions appearing during the α-relaxation process through the role of the molecular weight of the constitutive units and of the interchain dipolar interactions. By studying amorphous copolymers of poly(ethylene-co-vinyl acetate) with different vinyl acetate contents, we show that the correlated motions are not sensitive to the interchain dipolar interactions, in contrast to the cooperative motions, which increase with a strengthening of the intermolecular interactions for this sample family. Concerning the influence of the molecular weight m0, the notion of "correlated motions" seems to be equivalent to the notion of "cooperative motions" only for low m0 systems.

  14. Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

    PubMed Central

    Rubina, Marina; Sherrill, William M; Barkov, Alexey Yu

    2014-01-01

    Summary A novel class of chiral phosphanyl-oxazoline (PHOX) ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands. PMID:25161709

  15. 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.

  16. 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.

  17. Calciate-mediated intermolecular hydroamination of diphenylbutadiyne with secondary anilines.

    PubMed

    Glock, Carsten; Görls, Helmar; Westerhausen, Matthias

    2012-07-18

    Calciate-mediated intermolecular hydroamination of diphenylbutadiyne with N-phenyl and N-isopropyl-substituted anilines yields E- and Z-isomers of the corresponding 1-anilino-1,4-diphenylbut-1-ene-3-yne. In the case of HNPh(2) solely heterobimetallic K(2)Ca(NPh(2))(4) is able to effectively catalyze this hydroamination reaction in tetrahydrofuran at elevated temperatures.

  18. 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.

  19. A new criterion for bar-forming instability in rapidly rotating gaseous and stellar systems. 2: Nonaxisymmetric form

    NASA Technical Reports Server (NTRS)

    Christodoulou, Dimitris M.; Shlosman, Isaac; Tohline, Joel E.

    1995-01-01

    We have previously introduced the parameter alpha as an indicator of stability to m = 2 nonaxisymmetric modes in rotating, self-gravitating, axisymmetric, gaseous (alpha less than or approximately equal to 0.34) and stellar (alpha less than or approximately equal to 0.25) systems. This parameter can be written as alpha = (ft/2)(exp 1/2), where t is defined as T/(absolute value of W), T is the total rotational kinetic energy, W is the total gravitational potential energy, and f is a function characteristic of the topology/connectedness and the geometric shape of a system. In this paper, we extend the stability criterion to nonaxisymmetric equilibrium systems by determining empirically the appropriate form of the function f for ellipsoids and elliptical disks and cylinders. We test the validity of this extension of the stability indicator alpha by considering its predictions for previously published, gaseous and stellar, nonaxisymmetric models. The formulation and critical values account accurately for the stability properties of m =2 modes in gaseous Riemann S-type ellipsoids (including the Jacobi and Dedekind ellipsoids) and elliptical Riemann disks as well as in stellar elliptical Freeman disks and cylinders: all these systems are dynamically stable except the stellar elliptical Freeman disks that exhibit a relatively small region of m = 2 dynamical instability. A partial disagreement in the case of stellar Freeman ellipsoids in maximum rotation may be due to the fact that the region of instability has not been previously determined with sufficient accuracy.

  20. A new criterion for bar-forming instability in rapidly rotating gaseous and stellar systems. 1: Axisymmetric form

    NASA Technical Reports Server (NTRS)

    Christodoulou, Dimitris M.; Shlosman, Isaac; Tohline, Joel E.

    1995-01-01

    We analyze previous results on the stability of uniformly and differentialy rotating, self-gravitating, gaseous and stellar, axisymmetric systems to derive a new stability criterion for the appearance of torodial, m = 2 intermediate or I-modes and bar modes. In the process, we demonstrate that the bar modes in stellar systems and the m = 2 I-modes in gaseous systems have many common physical characteristics and only one substantial difference: because of the anisotropy of the stress tensor, dynamical instability sets in at lower rotation in stellar systems. This difference is reflected also in the new stability criterion. The new stability parameter alpha equals (T(sub J))/(absolute value of W) is formulated first for uniformly rotating systems and is based on the angular momentum content rather than on the energy content of a system. (T(sub J) is defined as ((L)(Omega(sub J)))/2; L is the total angular momentum; Omega(sub J) is the Jeans frequency introduced by self-gravity; and W is the total gravitational potential energy.) For stability of stellar systems alpha less than or equal to 0.254-0.258 while alpha less than or equal to 0.341-0.354 for stability of gaseous systems. For uniform rotation, one can write alpha = ((ft)/2)(exp 1/2), where t is defined as T/(absolute value of W), T is the total kinetic energy due to rotation, and f is a function characteristic of the topology/connectedness and the geometric shape of a system. Equivalently, alpha equals t/(chi), where chi is defined as Omega/Omega(sub J) and Omega is the rotation frequency. Using these forms, alpha can be extended to and calculated for a variety of differentially rotating, gaseous and stellar, axisymmetric disk and spheroidal models whose equilibrium structures and stability characteristics are known. In this paper, we also estimate alpha for gaseous torodial models and for stellar disk systems embedded in an inert or responsive 'halo.' We find that the new stability criterion holds equally

  1. 78 FR 5477 - Agency Information Collection Activities: InfoPass System, No Form Number; Extension, Without...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-01-25

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: InfoPass... Collection. (2) Title of the Form/Collection: InfoPass System. (3) Agency form number, if any, and the.... The InfoPass system allows an applicant or petitioner to schedule an interview appointment with...

  2. 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…

  3. 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.

  4. Curcumin amorphous solid dispersions: the influence of intra and intermolecular bonding on physical stability.

    PubMed

    Wegiel, Lindsay A; Zhao, Yuhong; Mauer, Lisa J; Edgar, Kevin J; Taylor, Lynne S

    2014-12-01

    We have investigated the physical stability of amorphous curcumin dispersions and the role of curcumin-polymer intermolecular interactions in delaying crystallization. Curcumin is an interesting model compound as it forms both intra and intermolecular hydrogen bonds in the crystal. A structurally diverse set of amorphous dispersion polymers was investigated; poly(vinylpyrrolidone), Eudragit E100, carboxymethyl cellulose acetate butyrate, hydroxypropyl methyl cellulose (HPMC) and HPMC-acetate succinate. Mid-infrared spectroscopy was used to determine and quantify the extent of curcumin-polymer interactions. Physical stability under different environmental conditions was monitored by powder X-ray diffraction. Curcumin chemical stability was monitored by UV-Vis spectroscopy. Isolation of stable amorphous curcumin was difficult in the absence of polymers. Polymers proved to be effective curcumin crystallization inhibitors enabling the production of amorphous solid dispersions; however, the polymers showed very different abilities to inhibit crystallization during long-term storage. Curcumin intramolecular hydrogen bonding reduced the extent of its hydrogen bonding with polymers; hence most polymers were not highly effective crystallization inhibitors. Overall, polymers proved to be crystallization inhibitors, but inhibition was limited due to the intramolecular hydrogen bonding in curcumin, which leads to a decrease in the ability of the polymers to interact at a molecular level.

  5. 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.

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

    PubMed

    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 N-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 N-H···S hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

  7. 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.

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

    PubMed

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2014-06-05

    In the present work, the experimental and theoretical vibrational spectra of 5-hydroxymethyluracil were investigated. The FT-IR (4000-400cm(-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 NH stretching modes shifted to lower frequencies, while its in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular NH⋯O hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

  9. Intermolecular Singlet and Triplet Exciton Transfer Integrals from Many-Body Green's Functions Theory.

    PubMed

    Wehner, Jens; Baumeier, Björn

    2017-03-08

    A general approach to determine orientation and distance-dependent effective intermolecular exciton transfer integrals from many-body Green's functions theory is presented. On the basis of the GW approximation and the Bethe-Salpeter equation (BSE), a projection technique is employed to obtain the excitonic coupling by forming the expectation value of a supramolecular BSE Hamiltonian with electron-hole wave functions for excitations localized on two separated chromophores. Within this approach, accounting for the effects of coupling mediated by intermolecular charge transfer (CT) excitations is possible via perturbation theory or a reduction technique. Application to model configurations of pyrene dimers shows an accurate description of short-range exchange and long-range Coulomb interactions for the coupling of singlet and triplet excitons. Computational parameters, such as the choice of the exchange-correlation functional in the density-functional theory (DFT) calculations that underly the GW-BSE steps and the convergence with the number of included CT excitations, are scrutinized. Finally, an optimal strategy is derived for simulations of full large-scale morphologies by benchmarking various approximations using pairs of dicyanovinyl end-capped oligothiophenes (DCV5T), which are used as donor material in state-of-the-art organic solar cells.

  10. Weak intermolecular interactions in 11-chloro-2,3,4,5-tetrahydro-1H-cyclohepta[b]quinoline.

    PubMed

    Novaković, Sladjana B; Vitorović-Todorović, Maja D; Bogdanović, Goran A; Drakulić, Branko J

    2008-09-01

    The title compound, C(14)H(14)ClN, is a chloro analogue of tacrine, an acetylcholinesterase inhibitor. The compound comprises a seven-membered alicyclic ring whose CH donor groups are engaged in extensive intermolecular interactions. The important feature of this crystal structure is that, regardless of the presence of two typical hydrogen-bonding acceptors, viz. chlorine and nitrogen, the corresponding C-H...Cl and C-H...N interactions take no significant role in crystal stabilization. The molecules form dimers through pi-pi interactions with an interplanar distance between interacting pyridine rings of 3.576 (1) A. Within the dimers, the molecules are additionally interconnected by four C-H...pi interactions. The dimers arrange into regular columns via further intermolecular C-H...pi interactions.

  11. Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic molecules probed by the methods of vibrational spectroscopy.

    PubMed

    Semenov, M A; Blyzniuk, Iu N; Bolbukh, T V; Shestopalova, A V; Evstigneev, M P; Maleev, V Ya

    2012-09-01

    By the methods of vibrational spectroscopy (Infrared and Raman) the investigation of the hetero-association of biologically active aromatic compounds: flavin-mononucleotide (FMN), ethidium bromide (EB) and proflavine (PRF) was performed in aqueous solutions. It was shown that between the functional groups (CO and NH(2)) the intermolecular hydrogen bonds are formed in the hetero-complexes FMN-EB and FMN-PRF, additionally stabilizing these structures. An estimation of the enthalpy of Н-bonding obtained from experimental shifts of carbonyl vibrational frequencies has shown that the H-bonds do not dominate in the magnitude of experimentally measured total enthalpy of the hetero-association reactions. The main stabilization is likely due to intermolecular interactions of the molecules in these complexes and their interaction with water environment.

  12. Intermolecular hydrogen bonds in hetero-complexes of biologically active aromatic molecules probed by the methods of vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    Semenov, M. A.; Blyzniuk, Iu. N.; Bolbukh, T. V.; Shestopalova, A. V.; Evstigneev, M. P.; Maleev, V. Ya.

    2012-09-01

    By the methods of vibrational spectroscopy (Infrared and Raman) the investigation of the hetero-association of biologically active aromatic compounds: flavin-mononucleotide (FMN), ethidium bromide (EB) and proflavine (PRF) was performed in aqueous solutions. It was shown that between the functional groups (Cdbnd O and NH2) the intermolecular hydrogen bonds are formed in the hetero-complexes FMN-EB and FMN-PRF, additionally stabilizing these structures. An estimation of the enthalpy of Н-bonding obtained from experimental shifts of carbonyl vibrational frequencies has shown that the H-bonds do not dominate in the magnitude of experimentally measured total enthalpy of the hetero-association reactions. The main stabilization is likely due to intermolecular interactions of the molecules in these complexes and their interaction with water environment.

  13. From H2+ to the multidimensional potential of the intermolecular interaction Ar·HBr: A canonical approach

    NASA Astrophysics Data System (ADS)

    Walton, Jay R.; Rivera-Rivera, Luis A.; Lucchese, Robert R.; Bevan, John W.

    2015-10-01

    A proof-of-concept for the accurate generation of multidimensional intermolecular interaction potentials is demonstrated. The basis for evaluating this application is the available very accurate 3-D morphed potential of Ar·HBr. Starting from the well-defined potential of the simplest molecule, the diatomic H2+, a recently developed 1-D canonical potential is used with selected 2-D polyatomic data to generate the adiabatic intermolecular interaction potential in Ar·HBr, with HBr in the vibrational ground state. This represents the first application of canonical transformations to a higher vibrationally dimensional molecular system, in this case, Ar·HBr. Results indicate intrinsic bonding characteristics inherent to both systems.

  14. 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.

  15. 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.

  16. 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

  17. INTERMOLECULAR FORCES IN ASSOCIATION OF PURINES WITH POLYBENZENOID HYDROCARBONS.

    PubMed

    PULLMAN, B; CLAVERIE, P; CAILLET, J

    1965-03-12

    The interactions in solution between purine or pyrimidine bases and polybenzenoid aromatic hydrocarbons probably consist in a vertical, stacking-type physical association. By molecular orbital calculations the role of the Van der Waals-London intermolecular forces in these interactions is determined. The electrostatic dipole-dipole forces are negligible, the polarization (or induction) dipole-induced dipole forces are contributory, but most important are the dispersion (or fluctuation) forces. This loose, physical type of interaction should not show any specificity with respect to the carcinogenic activity of the hydrocarbons.

  18. 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.

  19. 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…

  20. CCR Certification Form for Wyoming or EPA R8 Tribal Community Water Systems

    EPA Pesticide Factsheets

    The CCR Certification Form can be used to certify that community water systems in Wyoming or on Tribal Lands in EPA Region 8 have completed and distributed their annual Consumer Confidence Report (CCR) or water quality report.

  1. 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

  2. Intermolecular hydrogen bonding in chlorine dioxide photochemistry: A time-resolved resonance Raman study

    NASA Astrophysics Data System (ADS)

    Philpott, Matthew P.; Hayes, Sophia C.; Thomsen, Carsten L.; Reid, Philip J.

    2001-01-01

    The geminate-recombination and vibrational-relaxation dynamics of chlorine dioxide (OClO) dissolved in ethanol and 2,2,2-trifluoroethanol (TFE) are investigated using time-resolved resonance Raman spectroscopy. Stokes spectra are measured as a function of time following photoexcitation using degenerate pump and probe wavelengths of 398 nm. For OClO dissolved in ethanol, subpicosecond geminate recombination occurs resulting in the reformation of ground-state OClO with a quantum yield of 0.5±0.1. Following recombination, intermolecular-vibrational relaxation of OClO occurs with a time constant of 31±10 ps. For OClO dissolved in TFE, recombination occurs with a time constant of 1.8±0.8 ps and a quantum yield of only 0.3±0.1. The intermolecular-vibrational-relaxation time constant of OClO in TFE is 79±27 ps. The reduced geminate-recombination quantum yield, delayed recombination, and slower vibrational relaxation for OClO in TFE is interpreted in terms of greater self-association of the solvent. Degenerate pump-probe experiments are also presented that demonstrate decay of the Cl-solvent charge-transfer complex on the ˜1-ns time scale in ethanol and TFE. This time is significantly longer than the abstraction times observed for other systems demonstrating that Cl hydrogen abstraction from alcohols occurs in the presence of a significant energy barrier.

  3. Free-form surface measuring method based on optical theodolite measuring system

    NASA Astrophysics Data System (ADS)

    Yu, Caili

    2012-10-01

    The measurement for single-point coordinate, length and large-dimension curved surface in industrial measurement can be achieved through forward intersection measurement by the theodolite measuring system composed of several optical theodolites and one computer. The measuring principle of flexible large-dimension three-coordinate measuring system made up of multiple (above two) optical theodolites and composition and functions of the system have been introduced in this paper. Especially for measurement of curved surface, 3D measured data of spatial free-form surface is acquired through the theodolite measuring system and the CAD model is formed through surface fitting to directly generate CAM processing data.

  4. Crystallization force--a density functional theory concept for revealing intermolecular interactions and molecular packing in organic crystals.

    PubMed

    Li, Tonglei; Ayers, Paul W; Liu, Shubin; Swadley, Matthew J; Aubrey-Medendorp, Clare

    2009-01-01

    Organic molecules are prone to polymorphic formation in the solid state due to the rich diversity of functional groups that results in comparable intermolecular interactions, which can be greatly affected by the selection of solvent and other crystallization conditions. Intermolecular interactions are typically weak forces, such as van der Waals and stronger short-range ones including hydrogen bonding, that are believed to determine the packing of organic molecules during the crystal-growth process. A different packing of the same molecules leads to the formation of a new crystal structure. To disclose the underlying causes that drive the molecule to have various packing motifs in the solid state, an electronic concept or function within the framework of conceptual density functional theory has been developed, namely, crystallization force. The concept aims to describe the local change in electronic structure as a result of the self-assembly process of crystallization and may likely quantify the locality of intermolecular interactions that directs the molecular packing in a crystal. To assess the applicability of the concept, 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile, so-called ROY, which is known to have the largest number of solved polymorphs, has been examined. Electronic calculations were conducted on the seven available crystal structures as well as on the single molecule. The electronic structures were analyzed and crystallization force values were obtained. The results indicate that the crystallization forces are able to reveal intermolecular interactions in the crystals, in particular, the close contacts that are formed between molecules. Strong correlations exist between the total crystallization force and lattice energy of a crystal structure, further suggesting the underlying connection between the crystallization force and molecular packing.

  5. 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.

  6. Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Moldt, Thomas; Gahl, Cornelius; Weinelt, Martin; Draxl, Claudia

    2016-12-01

    In a joint theoretical and experimental work, the optical properties of azobenzene-functionalized self-assembled monolayers (SAMs) are studied at different molecular packing densities. Our results, based on density-functional and many-body perturbation theory, as well as on differential reflectance (DR) spectroscopy, shed light on the microscopic mechanisms ruling photo-absorption in these systems. While the optical excitations are intrinsically excitonic in nature, regardless of the molecular concentration, in densely packed SAMs intermolecular coupling and local-field effects are responsible for a sizable weakening of the exciton binding strength. Through a detailed analysis of the character of the electron-hole pairs, we show that distinct excitations involved in the photo-isomerization at low molecular concentrations are dramatically broadened by intermolecular interactions. Spectral shifts in the calculated DR spectra are in good agreement with the experimental results. Our findings represent an important step forward to rationalize the excited-state properties of these complex materials.

  7. 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.

  8. Intermolecular interactions and the thermodynamic properties of supercritical fluids

    NASA Astrophysics Data System (ADS)

    Yigzawe, Tesfaye M.; Sadus, Richard J.

    2013-05-01

    The role of different contributions to intermolecular interactions on the thermodynamic properties of supercritical fluids is investigated. Molecular dynamics simulation results are reported for the energy, pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound of fluids interacting via both the Lennard-Jones and Weeks-Chandler-Andersen potentials. These properties were obtained for a wide range of temperatures, pressures, and densities. For each thermodynamic property, an excess value is determined to distinguish between attraction and repulsion. It is found that the contributions of intermolecular interactions have varying effects depending on the thermodynamic property. The maxima exhibited by the isochoric and isobaric heat capacities, isothermal compressibilities, and thermal expansion coefficient are attributed to interactions in the Lennard-Jones well. Repulsion is required to obtain physically realistic speeds of sound and both repulsion and attraction are necessary to observe a Joule-Thomson inversion curve. Significantly, both maxima and minima are observed for the isobaric and isochoric heat capacities of the supercritical Lennard-Jones fluid. It is postulated that the loci of these maxima and minima converge to a common point via the same power law relationship as the phase coexistence curve with an exponent of β = 0.32. This provides an explanation for the terminal isobaric heat capacity maximum in supercritical fluids.

  9. Hybrid materials from intermolecular associations between cationic lipid and polymers.

    PubMed

    Pereira, Edla M A; Kosaka, Priscila M; Rosa, Heloísa; Vieira, Débora B; Kawano, Yoshio; Petri, Denise F S; Carmona-Ribeiro, Ana M

    2008-08-07

    Intermolecular associations between a cationic lipid and two model polymers were evaluated from preparation and characterization of hybrid thin films cast on silicon wafers. The novel materials were prepared by spin-coating of a chloroformic solution of lipid and polymer on silicon wafer. Polymers tested for miscibility with the cationic lipid dioctadecyldimethylammonium bromide (DODAB) were polystyrene (PS) and poly(methyl methacrylate) (PMMA). The films thus obtained were characterized by ellipsometry, wettability, optical and atomic force microscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and activity against Escherichia coli. Whereas intermolecular ion-dipole interactions were available for the PMMA-DODAB interacting pair producing smooth PMMA-DODAB films, the absence of such interactions for PS-DODAB films caused lipid segregation, poor film stability (detachment from the silicon wafer) and large rugosity. In addition, the well-established but still remarkable antimicrobial DODAB properties were transferred to the novel hybrid PMMA/DODAB coating, which is demonstrated to be highly effective against E. coli.

  10. 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

  11. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    DOE PAGES

    Hathwar, Venkatesha R.; Sist, Mattia; Jørgensen, Mads R. V.; ...

    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. 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.

  13. Cooperative control design for non-holonomic chained-form systems

    NASA Astrophysics Data System (ADS)

    Cao, Ke-Cai; Jiang, Bin; Chen, YangQuan

    2015-07-01

    Consensus and formation control problems for multiple non-holonomic chained-form systems are solved in this paper. For consensus problem, based on cascaded structure of the chained-form systems, it amounts to solving two consensus subproblems of two linear subsystems transformed from the original system. With the obtained consensus protocols and the method of virtual structure, decentralised formation controllers can then be designed. According to different desired motion patterns of the entire group, both the formation tracking and formation stabilisation problems can be considered. The significance of this paper lies in adapting theories from non-autonomous cascaded systems for cooperative control design for non-holonomic chained-form systems. A unique feature of our proposed solution is that all states can be cooperatively controlled to achieve the desired references for non-holonomic chained-form system. Simulation results are included to illustrate the effectiveness of the proposed methods in solving cooperative control problems of non-holonomic chained-form systems.

  14. The rotational spectrum, geometry, and intermolecular force constant of the heterodimer of hydrogen cyanide and fluoroform

    NASA Astrophysics Data System (ADS)

    Goodwin, Elizabeth J.; Legon, A. C.

    1986-02-01

    The ground-state rotational spectra of six isotopic species of an intermolecular complex formed by hydrogen cyanide and fluoroform have been measured using the pulsed-nozzle, Fourier-transform microwave technique. The rotational constant B0, the centrifugal distortion constants DJ,DJK,HJ, HJK, and HKJ, and, where appropriate, the nuclear quadrupole coupling constants χ(14N) and χ(D) have been determined for each of the species HC14NṡṡṡHCF3, DC14NṡṡṡHCF3, HC14ṡṡṡDCF3, HC15NṡṡṡHCF3, HC15NṡṡṡDCF3, and DC15NṡṡṡHCF3. For HC14NṡṡṡHCF3 the values are as follows: B0=1151.2991(4) MHz, DJ=1.91(1) kHz, DJK=282.75(6) kHz, HJ=-0.1(1) Hz, HJK=44.3(5) Hz, HKJ=53(5) Hz, and χ(14N)=3.948(8) MHz. The form of the spectra and magnitudes of the rotational constants allow the conclusion that the geometry of the complex is of C3V symmetry with the nuclei in the order HCNṡṡṡHCF3 and lead to r(NṡṡṡC)=3.489(2) Å for HCF3 species but 3.483(1) Å for DCF3 species. The intermolecular stretching force constant determined from DJ is kσ=3.52 N m-1.

  15. [Intermolecular hydrogen bond between protein and flavonoid and its contribution to the stability of the flavonoids].

    PubMed

    Fang, Ru; Leng, Xiao-jing; Wu, Xia; Li, Qi; Hao, Rui-fang; Ren, Fa-zheng; Jing, Hao

    2012-01-01

    The interactions between three proteins (BSA, lysozyme and myoglobin) and three flavonoids (quercetin, kaempferol and rutin) were analyzed, using three-dimensional fluorescence spectrometry in combination with UV-Vis spectrometry and Fourier transform infrared (FTIR) spectroscopy. The stabilities of unbound flavonoids and protein-bound flavonoids were compared. The correlation between the interaction and stability was analyzed. The results showed that the hydrophobic interaction was the main binding code in all proteins and flavonoids systems. However, the hydrogen bond has been involved merely in the BSA system. The stability of all three flavonoids (quercetin, kaempferol and rutin) was improved by BSA. There was a great correlation between the hydrogen bonding and the stability of the flavonoids in the presence of BSA. It suggested that the protection of BSA on the flavonoids was due to the intermolecular hydrogen bonding between BSA and flavonoid, and the stronger hydrogen bonding resulted in more protection.

  16. 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.

  17. Programmable display of DNA-protein chimeras for controlling cell-hydrogel interactions via reversible intermolecular hybridization.

    PubMed

    Zhang, Zhaoyang; Li, Shihui; Chen, Niancao; Yang, Cheng; Wang, Yong

    2013-04-08

    Extensive studies have been recently carried out to achieve dynamic control of cell-material interactions primarily through physicochemical stimulation. The purpose of this study was to apply reversible intermolecular hybridization to program cell-hydrogel interactions in physiological conditions based on DNA-antibody chimeras and complementary oligonucleotides. The results showed that DNA oligonucleotides could be captured to and released from the immobilizing DNA-functionalized hydrogels with high specificity via DNA hybridization. Accordingly, DNA-antibody chimeras were captured to the hydrogels, successfully inducing specific cell attachment. The cell attachment to the hydrogels reached the plateau at approximately half an hour after the functionalized hydrogels and the cells were incubated together. The attached cells were rapidly released from the bound hydrogels when triggering complementary oligonucleotides were introduced to the system. However, the capability of the triggering complementary oligonucleotides in releasing cells was affected by the length of intermolecular hybridization. The length needed to be at least more than 20 base pairs in the current experimental setting. Notably, because the procedure of intermolecular hybridization did not involve any harsh condition, the released cells maintained the same viability as that of the cultured cells. The functionalized hydrogels also exhibited the potential to catch and release cells repeatedly. Therefore, this study demonstrates that it is promising to regulate cell-material interactions dynamically through the DNA-programmed display of DNA-protein chimeras.

  18. 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.

  19. 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.

  20. 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.

  1. Correlations of life form, pollination mode and sexual system in aquatic angiosperms.

    PubMed

    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.

  2. 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

  3. Genetically engineered photoinducible homodimerization system with improved dimer-forming efficiency.

    PubMed

    Nihongaki, Yuta; Suzuki, Hideyuki; Kawano, Fuun; Sato, Moritoshi

    2014-03-21

    Vivid (VVD) is a photoreceptor derived from Neurospora Crassa that rapidly forms a homodimer in response to blue light. Although VVD has several advantages over other photoreceptors as photoinducible homodimerization system, VVD has a critical limitation in its low dimer-forming efficiency. To overcome this limitation of wild-type VVD, here we conduct site-directed saturation mutagenesis in the homodimer interface of VVD. We have found that the Ile52Cys mutation of VVD (VVD-52C) substantially improves its homodimer-forming efficiency up to 180%. We have demonstrated the utility of VVD-52C for making a light-inducible gene expression system more robust. In addition, using VVD-52C, we have developed photoactivatable caspase-9, which enables optical control of apoptosis of mammalian cells. The present genetically engineered photoinducible homodimerization system can provide a powerful tool to optically control a broad range of molecular processes in the cell.

  4. Semiclassical form factor for spectral and matrix element fluctuations of multidimensional chaotic systems.

    PubMed

    Turek, Marko; Spehner, Dominique; Müller, Sebastian; Richter, Klaus

    2005-01-01

    We present a semiclassical calculation of the generalized form factor Kab(tau) which characterizes the fluctuations of matrix elements of the operators a and b in the eigenbasis of the Hamiltonian of a chaotic system. Our approach is based on some recently developed techniques for the spectral form factor of systems with hyperbolic and ergodic underlying classical dynamics and f = 2 degrees of freedom, that allow us to go beyond the diagonal approximation. First we extend these techniques to systems with f > 2. Then we use these results to calculate Kab(tau). We show that the dependence on the rescaled time tau (time in units of the Heisenberg time) is universal for both the spectral and the generalized form factor. Furthermore, we derive a relation between Kab(tau) and the classical time-correlation function of the Weyl symbols of a and b.

  5. Adaptive Fuzzy Tracking Control for a Class of MIMO Nonlinear Systems in Nonstrict-Feedback Form.

    PubMed

    Chen, Bing; Lin, Chong; Liu, Xiaoping; Liu, Kefu

    2015-12-01

    This paper focuses on the problem of fuzzy adaptive control for a class of multiinput and multioutput (MIMO) nonlinear systems in nonstrict-feedback form, which contains the strict-feedback form as a special case. By the condition of variable partition, a new fuzzy adaptive backstepping is proposed for such a class of nonlinear MIMO systems. The suggested fuzzy adaptive controller guarantees that the proposed control scheme can guarantee that all the signals in the closed-loop system are semi-globally uniformly ultimately bounded and the tracking errors eventually converge to a small neighborhood around the origin. The main advantage of this paper is that a control approach is systematically derived for nonlinear systems with strong interconnected terms which are the functions of all states of the whole system. Simulation results further illustrate the effectiveness of the suggested approach.

  6. 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.

  7. Testing electronic structure methods for describing intermolecular H...H interactions in supramolecular chemistry.

    PubMed

    Casadesús, Ricard; Moreno, Miquel; González-Lafont, Angels; Lluch, José M; Repasky, Matthew P

    2004-01-15

    In this article a wide variety of computational approaches (molecular mechanics force fields, semiempirical formalisms, and hybrid methods, namely ONIOM calculations) have been used to calculate the energy and geometry of the supramolecular system 2-(2'-hydroxyphenyl)-4-methyloxazole (HPMO) encapsulated in beta-cyclodextrin (beta-CD). The main objective of the present study has been to examine the performance of these computational methods when describing the short range H. H intermolecular interactions between guest (HPMO) and host (beta-CD) molecules. The analyzed molecular mechanics methods do not provide unphysical short H...H contacts, but it is obvious that their applicability to the study of supramolecular systems is rather limited. For the semiempirical methods, MNDO is found to generate more reliable geometries than AM1, PM3 and the two recently developed schemes PDDG/MNDO and PDDG/PM3. MNDO results only give one slightly short H...H distance, whereas the NDDO formalisms with modifications of the Core Repulsion Function (CRF) via Gaussians exhibit a large number of short to very short and unphysical H...H intermolecular distances. In contrast, the PM5 method, which is the successor to PM3, gives very promising results. Our ONIOM calculations indicate that the unphysical optimized geometries from PM3 are retained when this semiempirical method is used as the low level layer in a QM:QM formulation. On the other hand, ab initio methods involving good enough basis sets, at least for the high level layer in a hybrid ONIOM calculation, behave well, but they may be too expensive in practice for most supramolecular chemistry applications. Finally, the performance of the evaluated computational methods has also been tested by evaluating the energetic difference between the two most stable conformations of the host(beta-CD)-guest(HPMO) system.

  8. Multi-referenced excited states and intermolecular forces from the anti-Hermitian contracted Schrodinger equation

    NASA Astrophysics Data System (ADS)

    Sturm, Erica J.

    Strong correlation due to multi-referenced electronic states of quantum chemical systems are crucial for a proper understanding of important phenomena including excited states, bond breakage and formation, singlet fission and biological transport. By solving for the 2-electron reduced density matrix (2-RDM) directly via the anti-Hermitian contracted Schrodinger equation (ACSE) we provide a balanced treatment of single and multi-referenced correlation effects without utilizing the N-electron wave function. This significantly reduces the computational expense while still maintaining near full configuration interaction accuracy when available. When provided with an initial 2-RDM guess from an active-space multi-configuration self consistent field wave function the ACSE scales as [special characters omitted] where ra is the number of active molecular orbitals (MOs) and ra is the number of external MOs. This work demonstrates the energetic accuracy of ACSE calculations with several small multi-referenced systems and presents a novel approach for investigating intermolecular interactions, using a simple dimer test case. In this monomer-optimized basis set approach we compute each monomer's properties in isolation and obtain a set of natural orbitals that best describe the monomer. We then remove or truncate orbitals deemed excessive as a function of occupation number, defining a monomer molecular orbital basis uniquely suited to that monomer. Combining two such monomers yields a super-system expressed in the monomer basis which we then rotate to a dimer basis at a desired geometry before creating a new initial 2-RDM for the final optimization by an ACSE calculation. It is found that the intermolecular properties calculated in this fashion from larger atomic basis sets maintain their high accuracy but at a fraction of the computational cost. Furthermore this basis set optimization is free of basis set superposition error, circumventing the need for an expensive

  9. Intermolecular potential energy surface for CS2 dimer.

    PubMed

    Farrokhpour, Hossein; Mombeini, Zainab; Namazian, Mansoor; Coote, Michelle L

    2011-04-15

    A new four-dimensional intermolecular potential energy surface for CS(2) dimer is obtained by ab initio calculation of the interaction energies for a range of configurations and center-of-mass separation distances for the first time. The calculations were performed using the supermolecular approach at the Møller-Plesset second-order perturbation (MP2) level of theory with the augmented correlation consistent basis sets (aug-cc-pVxZ, x = D, T) and corrected for the basis-set superposition error using the full counterpoise correction method. A two-point extrapolation method was used to extrapolate the calculated energy points to the complete basis set limit. The effect of using the higher levels of theory, quadratic configuration interaction containing single, double, and perturbative triple excitations QCISD(T) and coupled cluster singles, doubles and perturbative triples excitations CCSD(T), on the shape of potential energy surface was investigated. It is shown that the MP2 level of theory apparently performs extremely poorly for describing the intermolecular potential energy surface, overestimating the total energy by a factor of nearly 1.73 in comparison with the QCISD(T) and CCSD(T) values. The value of isotropic dipole-dipole dispersion coefficient (C(6) ) of CS(2) fluid was obtained from the extrapolated MP2 potential energy surface. The MP2 extrapolated energy points were fitted to well-known analytical potential functions using two different methods to represent the potential energy surface analytically. The most stable configuration of the dimer was determined at R = 6.23 au, α = 90°, β = 90°, and γ = 90°, with a well depth of 3.980 kcal mol(-1) at the MP2 level of theory. Finally, the calculated second virial coefficients were compared with experimental values to test the quality of the presented potential energy surface.

  10. 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.

  11. 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.

  12. Second law considerations in Fourier heat conduction of a lattice chain in relation to intermolecular potentials

    NASA Astrophysics Data System (ADS)

    Jesudason, Christopher G.

    2017-01-01

    Two aspects of conductive heat are focused here (i) the nature of conductive heat, defined as that form of energy that is transferred as a result of a temperature difference and (ii) the nature of the intermolecular potentials that induces both thermal energy flow and the temperature profile at the steady state for a 1-D lattice chain. It is found that the standard presuppositions of people like Benofy and Quay (BQ) following Joseph Fourier do not obtain for at least a certain specified regime of intermolecular potential parameters related to harmonic (quadratic) potentials for nearest neighbor interactions. For these harmonic potentials, it appears from the simulation results that steady state solutions exist utilizing non-synthetic thermostats that couple not just the two particles at the extreme ends of the lattice chain, but to a control volume of N particles located at either ends of the chain that does not accord with the unique analytical solutions that obtains for single particle thermostatting at the ends of the lattice with a different thermostatting algorithm that utilizes coupling coefficients. If the method used here is considered a more "realistic" or feasible model of the physical reality, then a re-evaluation of some aspects of the standard theoretical methodology is warranted since the standard model solution profile does not accord with the simulation temperature profile determined here for this related model. We also note that the sinusoidal temperature profile generated suggests that thermal integrated circuits with several thermal P-N junctions may be constructed, opening a way to create more complex thermal transistor circuits. A stationary principle is proposed for regions that violate the Fourier principle Jq.∇T ≤ 0, where Jq is the heat current vector and T the temperature.

  13. Instructions for the preparation of Resource Allocation Support System (RASS) data forms

    SciTech Connect

    Baldwin, T.E.; Buehring, W.A.; Jusko, M.J.; Keisler, J.M.; Whitfield, R.G.; Wolsko, T.D.

    1994-03-01

    The Resource Allocation Support System (RASS) is a decision-aiding system being developed to assist the US Department of Energy`s Office of Waste Management in program and budget decision making. Information about proposed work, developed by DOE program managers and contractors, comprises what is called the RASS database. A set of data forms and worksheets (paper copies) are provided to record information that will be entered into the RASS database. This report contains instructions for preparing the data forms and worksheets.

  14. Design of a Precast Concrete Stay-in-Place Forming System for Lock Wall Rehabilitation

    DTIC Science & Technology

    1987-07-01

    RE-HABILITATION RESEARCH PROGNtAN ai ,_TECHNICAL REPORT REMR-CS-7 DESIGN OF A PRECAST CONCRETE AD-A 185 0 8 1 STAY-IN-PLACE FORMING SYSTEM FOR LOCK...ie report was prepred: Problem Area Probim Area CS Concrete snd Stee Structures EM Electrical end Mechanical GT Giotechnical El Environmentso Impacts...ment concrete , cracking problems can be eliminated. This report descr-bes the design of such a forming system. A range of design ’alternatives was

  15. Intermolecularly-induced conformational disorder in ferrocene, 1-bromoferrocene and 1,1‧-dibromoferrocene

    NASA Astrophysics Data System (ADS)

    Silva, Patrícia A.; Maria, Teresa M. R.; Nunes, Cláudio M.; Eusébio, Maria Ermelinda S.; Fausto, Rui

    2014-12-01

    Conformational preferences for isolated molecules of ferrocene, 1-bromoferrocene and 1,1‧-dibromoferrocene were obtained by combined use of matrix-isolation infrared spectroscopy and quantum chemical calculations. Monomeric ferrocene and 1-dibromoferrocene were found to exist in a low temperature argon matrix (T = 15 K) exclusively in the eclipsed configuration, which corresponds to their most stable conformation in gas phase. On the other hand, for the neat compounds in crystalline phase, intermolecular interactions induce conformational disorder, leading to presence in the room temperature polymorphic forms of monomeric units with the staggered (or nearly staggered) conformation. 1,1‧-Dibromoferrocene exists in both gas phase and low temperature argon matrix in two conformers of C2 symmetry (C2-I and C2-II), with eclipsed cyclopentadienyl moieties and Br atoms opposed to H atoms. The populations of the two conformers trapped in the as-deposited matrix were found to correspond to those estimated from theory for the room temperature equilibrium gas phase. By increasing the temperature of the matrix (up to 35 K), the gas phase lower energy form (C2-I) converted to the C2-II form. Besides allowing the precise structural and spectroscopic characterization of the two forms, these studies also revealed that the C2-II conformer (having a largest dipole moment) is stabilized in the matrix media, thus becoming more stable than the C2-I form under these conditions. Very interestingly, the room temperature stable polymorph of the compound (Tfus = 325.4 ± 0.1 K) is composed by 1,1‧-dibromoferrocene units exhibiting the C2v symmetry eclipsed conformation with opposed bromine atoms, which for the isolated molecule corresponds to the highest energy conformation along the ring torsional coordinate and is the transition state structure between the two symmetry equivalent C2-II minima. Differential scanning calorimetry, polarized light thermomicroscopy and infrared

  16. 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.

  17. Meeting the Challenge of Intermolecular Gold(I)-Catalyzed Cycloadditions of Alkynes and Allenes

    PubMed Central

    Muratore, Michael E; Homs, Anna; Obradors, Carla; Echavarren, Antonio M

    2014-01-01

    The development of gold(I)-catalyzed intermolecular carbo- and hetero-cycloadditions of alkynes and allenes has been more challenging than their intramolecular counterparts. Here we review, with a mechanistic perspective, the most fundamental intermolecular cycloadditions of alkynes and allenes with alkenes. PMID:25048645

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

    PubMed

    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.

  1. 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.

  2. Intermolecular forces in bovine serum albumin solutions exhibiting solidlike mechanical behaviors.

    PubMed

    Ikeda, S; Nishinari, K

    2000-01-01

    Mechanical properties of bovine serum albumin (BSA) solutions were analyzed to gain information on intermolecular forces that stabilize the system under normal physiological conditions. BSA solutions showed unexpectedly large zero shear viscosity values under steady shear flows but responded like solids to sinusoidal linear strains: the storage shear moduli were always larger than the loss shear moduli in the frequency range 1-100 rad/s. These results suggest that BSA solutions are so-called colloidal crystals in which colloidal particles are ordered in an array due to strong repulsive forces among particles. However, the pair potential between BSA molecules predicted based on the conventional Derjaguin-Landau-Verwey-Overbeek theory failed to explain these remarkable mechanical properties of BSA solutions. Additional repulsive forces other than electrostatic must be introduced to explain stability of BSA aqueous dispersions.

  3. 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.

  4. 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.

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

    PubMed Central

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

    2016-01-01

    CONSPECTUS Rh-carbenes derived from α-diazocarbonyl compounds have found broad utility across a remarkable range of reactivity, including cyclopropanation, cyclopropenation, C–H insertions, heteroatom–H insertions, and ylide forming reactions. However, in contrast to α-aryl or α-vinyl-α-diazocarbonyl compounds, the utility of α-alkyl-α-diazocarbonyl compounds had been moderated by the propensity of such compounds to undergo intramolecular β-hydride migration to give alkene products. Especially challenging had been intermolecular reactions involving α-alkyl-α-diazocarbonyl compounds. PMID:26689221

  6. 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.

  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. Importance of the donor:fullerene intermolecular arrangement for high-efficiency organic photovoltaics.

    PubMed

    Graham, Kenneth R; Cabanetos, Clement; Jahnke, Justin P; Idso, Matthew N; El Labban, Abdulrahman; Ngongang Ndjawa, Guy O; Heumueller, Thomas; Vandewal, Koen; Salleo, Alberto; Chmelka, Bradley F; Amassian, Aram; Beaujuge, Pierre M; McGehee, Michael D

    2014-07-09

    The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) (13)C{(1)H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material

  9. 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.

  10. 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.

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

    PubMed

    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.

  12. A new form measurement system based on subaperture stitching with a line-scanning interferometer

    NASA Astrophysics Data System (ADS)

    Laubach, Sören; Ehret, Gerd; Riebeling, Jörg; Lehmann, Peter

    2016-12-01

    A new optical form measurement system for almost rotational symmetric surfaces has been set up. It is based on an interferometric line sensor applying sinusoidal path length modulation in combination with a movement system. With this system, ring-shaped subapertures of the specimens are measured. The system is especially suitable for measuring spheres and aspheres with a broad range of radii (r>50 mm). The individual subapertures are stitched together to yield the full 3D topography. Because the rotation of the specimen by more than 360° has to yield the same results, inherent consistency tests are possible. Example measurements of a sphere are shown and discussed. Reproducibility measurements for one ring scan performed with the system show a standard deviation of 14 nm. The system can be set up at a moderate price as off-the-shelf mechanical and optoelectronic devices can be used. Future improvements of the system are discussed.

  13. 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.

  14. Selecting a response form for nonverbal persons: Facilitated communication, pointing systems, or sign language?

    PubMed Central

    Sundberg, Mark L.

    1993-01-01

    The three major types of augmentative communication for nonverbal persons consist of writing (or typing), pointing, and signing. These alternative response forms are examined in terms of their advantages and disadvantages for establishing effective verbal behavior. In addition, these systems are examined using the concepts from Skinner's (1957) analysis of verbal behavior (i.e., mand, tact, intraverbal, and autoclitic). The results of this analysis show that sign language has the most advantages and the fewest disadvantages, and more closely parallels speech in terms of the verbal operants. Although, the current trend is to favor facilitated communication (typing) and pointing systems, both of these response forms have several disadvantages that impede the development of the verbal operants. It is suggested that for many nonverbal individuals sign language is a better alternative response form, and has a better chance of improving speech. PMID:22477084

  15. Self-formed cavity quantum electrodynamics in coupled dipole cylindrical-waveguide systems.

    PubMed

    Afshar V, S; Henderson, M R; Greentree, A D; Gibson, B C; Monro, T M

    2014-05-05

    An ideal optical cavity operates by confining light in all three dimensions. We show that a cylindrical waveguide can provide the longitudinal confinement required to form a two dimensional cavity, described here as a self-formed cavity, by locating a dipole, directed along the waveguide, on the interface of the waveguide. The cavity resonance modes lead to peaks in the radiation of the dipole-waveguide system that have no contribution due to the skew rays that exist in longitudinally invariant waveguides and reduce their Q-factor. Using a theoretical model, we evaluate the Q-factor and modal volume of the cavity formed by a dipole-cylindrical-waveguide system and show that such a cavity allows access to both the strong and weak coupling regimes of cavity quantum electrodynamics.

  16. Factor structure of the BASC-2 Behavioral and Emotional Screening System Student Form.

    PubMed

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

    2011-06-01

    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 Personality (BASC-2 SRP; Reynolds & Kamphaus, 2004) using principal component analytic procedures and theoretical considerations. Using 3 samples, the authors conducted exploratory factor analyses (EFA) and confirmatory factor analyses (CFA) to understand the underlying factor structure of the BESS Student Form. The results of the EFA suggested that the SRP contained a 4-factor (i.e., Personal Adjustment, Inattention/Hyperactivity, Internalizing, School Problems) emergent structure, which was supported by CFA in 2 additional samples. Practical and research implications are discussed.

  17. 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…

  18. 77 FR 65898 - Agency Information Collection Activities: InfoPass System, No Form Number; Extension, Without...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-10-31

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: InfoPass...: Extension, Without Change, of a Currently Approved Collection. (2) Title of the Form/Collection: InfoPass... as a brief abstract: Primary: Individuals or households. The InfoPass system allows an applicant...

  19. 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.

  20. 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.

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

    PubMed

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

    2016-01-19

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

  2. Potential mesogens based on pyridine derivatives: The geometric structure, conformational properties and characteristics of intermolecular hydrogen bonds

    NASA Astrophysics Data System (ADS)

    Fedorov, Mikhail S.; Giricheva, Nina I.; Shpilevaya, Kseniya E.; Lapykina, Elena A.; Syrbu, Svetlana A.

    2017-03-01

    Conformational properties of the main part (excluding sbnd OC3H7 radicals) of the p-n-propyloxybenzoic (A1) and p-n-propyloxycinnamic (A2) acids molecules (relating to mesomorphic compounds) as well as p-n-propyloxybenzoic acid pyridine ester (B1) and p-n-propyloxyphenylazopyridine (B2) molecules (relating to non-mesomorphic compounds) were studied by DFT(B3LYP)/cc-pVTZ method. It was shown that the main parts of A1 and A2 acids are rigid. The barrier to internal rotation of pyridine fragment in the B1 and B2 molecules depends on the nature of the bridging group. It was determined that all studied A1⋯B1, A2⋯B1 and A2⋯B2 complexes are characterized by a strong hydrogen bond. The binding energy of complexes (≈14 kcal/mol, with BSSE corrections, DFT(B97D)/6-311++G**) exceeds the energy per hydrogen bond in the corresponding acid dimers (≈10 kcal/mol). The structural non-rigidity of A⋯B complexes is mainly caused by possibility of sbnd OC3H7 radicals internal rotation and A and B molecules rotation about the (H)O⋯N line. The characteristics of intermolecular hydrogen bonds were determined by NBO-analysis. The obtained results indicate that examined complexes correspond to the basic requirements to mesogen molecular forms. The thermodynamic functions of the gas-phase complexation reactions (idealized model of the complexes formation in the condensed state) were calculated. Preliminary studies of mesogen-non-mesogen A1⋯B2 system by differential scanning calorimetry and polarizing optical microscopy, showed that it has mesomorphic properties.

  3. Expression, purification and characterization of inactive and active forms of ERK2 from insect expression system.

    PubMed

    Yan, Kelly; Merritt, Hanne; Crawford, Kenneth; Pardee, Gwynn; Cheng, Jan Marie; Widger, Stephania; Hekmat-Nejad, Mohammad; Zaror, Isabel; Sim, Janet

    2015-06-01

    Extracellular signal-regulated kinase 2 (ERK2) is a serine/threonine protein kinase involved in many cellular programs, such as cell proliferation, differentiation, motility and programed cell-death. It is therefore considered an important target in the treatment of cancer. In an effort to support biochemical screening and small molecule drug discovery, we established a robust system to generate both inactive and active forms of ERK2 using insect expression system. We report here, for the first time, that inactive ERK2 can be expressed and purified with 100% homogeneity in the unphosphorylated form using insect system. This resulted in a significant 20-fold yield improvement compared to that previously reported using bacterial expression system. We also report a newly developed system to generate active ERK2 in insect cells through in vivo co-expression with a constitutively active MEK1 (S218D S222D). Isolated active ERK2 was confirmed to be doubly phosphorylated at the correct sites, T185 and Y187, in the activation loop of ERK2. Both ERK2 forms, inactive and active, were well characterized by biochemical activity assay for their kinase function. Inactive and active ERK2 were the two key reagents that enabled successful high through-put biochemical assay screen and structural drug discovery studies.

  4. Evidence for production of oxidizing radicals by the particulate O-2-forming system from human neutrophils.

    PubMed

    Tauber, A I; Gabig, T G; Babior, B M

    1979-04-01

    The particulate O-2-forming system from human neutrophils was found to oxidize methional and 2-keto-4-methylthiobutyric acid (KMB) to ethylene, indicating the formation by this system of strongly oxidizing radicals. Conforming this interpretation was the observation that ethylene production was inhibited by the radical scavengers benzoate, ethanol, and mannitol. Ethylene production was also sharply reduced by superoxide dismutase, implicatin O-2 as a precursor of oxidizing radicals. In our system catalase only partially inhibited ethylene generation from either methional or KMB, suggesting that oxidizing radicals are generated at least in part by the reacton of O-2 with compounds other than H2O2. We propose that in neutrophils oxidizing radicals are formed in a reaction between O-2 and a peroxide according to the following equation: O-2 + ROOH leads to RO . + OH- + O2, in which ROOH may be hydrogen peroxide, an alkyl peroxide, or an acyl peroxide (i.e., a peroxy acid).

  5. Early Campanian coastal progradational systems and their coal-forming environments, Wyoming to New Mexico

    SciTech Connect

    Marley, W.E.; Flores, R.M.; Ethridge, F.G.; Cavaroc, V.V.

    1985-05-01

    Ammonite zones (Baculites obtusus-Scaphites hippocrepis) in the marine facies associated with the Mesaverde Formation in the Bighorn basin, Wyoming, Star Point Sandstone and Blackhawk Formation in the Wasatch Plateau, Utah, and the Point Lookout Sandstone, Menefee Formation, and Crevasse Canyon Formation in the Gallup coalfield, New Mexico, indicate that these formations were deposited during early Campanian time (80-84 Ma). The coal-forming environments of these early Campanian formations were located landward of wave-reworked coastal sand complexes of progradational systems along the western margin of the Cretaceous seaway from Wyoming to New Mexico. The Mesaverde coals accumulated in swamps of the lower delta plain and coeval interdeltaic strandplain environments. The Star Point-Blackhawk coals accumulated in swamps of the lower delta plains of laterally shifting, prograding deltas and associated barrier ridge plains. The Point Lookout, Menefee, and Crevasse canyon coals formed in swamps of the lower delta plain and infilled lagoons behind barrier islands. Although the common coal-forming environments of these progradational systems are back barrier and delta plain, the former setting was the more conducive for accumulation of thick, laterally extensive coals. Economic coal deposits formed in swamps built on abandoned back-barrier platforms that were free of detrital influx and marine influence. Delta-plain coals tend to be lenticular and laterally discontinuous and thus uneconomic. The early Campanian coal-forming coastal-plain environments are analogous to modern peat-forming environments along the coast of Belize, Central America. Deltaic sediments deposited along the Belize coast by short-headed streams are reworked by waves into coastal barrier systems.

  6. 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.

  7. Glass transition in binary eutectic systems: best glass-forming composition.

    PubMed

    Wang, Li-Min; Li, Zijing; Chen, Zeming; Zhao, Yue; Liu, Riping; Tian, Yongjun

    2010-09-23

    The glass transition and glass-forming ability in a binary eutectic system of methyl o-toluate (MOT) versus methyl p-toluate (MPT) are studied across the whole composition range. The phase diagram is constructed to explore the best glass-forming composition as the characteristic temperatures of the glass transition, crystallization, eutectic, and liquidus are determined. The best vitrification region is found to locate between the eutectic and the midpoint compositions of the eutectic line, indicating a remarkable deviation from the eutectic composition. The compilation of various simple binary eutectic systems covering inorganic, metallic, ionic, and molecular glass-forming liquids reproduces the rule. Kinetics and thermodynamics in binary systems are investigated to associate with the rule. The composition dependence of the structural relaxation time and the kinetic fragility are presented with dielectric measurements. It is found that whereas mixing of binary miscible liquids kinetically favors glass formation, thermodynamic contribution to the deviation of the best glass-forming composition from eutectics is implied.

  8. Two-dimensional infrared spectroscopy of intermolecular hydrogen bonds in the condensed phase.

    PubMed

    Elsaesser, Thomas

    2009-09-15

    Hydrogen bonding plays a key role in the structural, physical, and chemical properties of liquids such as water and in macromolecular structures such as proteins. Vibrational spectroscopy is an important tool for understanding hydrogen bonding because it provides a way to observe local molecular geometries and their interaction with the environment. Linear vibrational spectroscopy has mapped characteristic changes of vibrational spectra and the occurrence of new bands that form upon hydrogen bonding. However, linear vibrational spectroscopy gives very limited insight into ultrafast dynamics of the underlying molecular interactions, such as the motions of hydrogen-bonded groups, energy dissipation and delocalization, and the fluctuations within hydrogen-bonded structures that occur in the ultrafast time domain. Nonlinear vibrational spectroscopy with its femtosecond time resolution can discern these dynamic processes in real time and has emerged as an important tool for unraveling molecular dynamics and for quantifying interactions that govern the vibrational and structural dynamics of hydrogen bonds. This Account reviews recent progress originating from third-order nonlinear methods of coherent multidimensional vibrational spectroscopy. Ultrafast dynamics of intermolecular hydrogen bonds are addressed for a number of prototype systems: hydrogen-bonded carboxylic acid dimers in an aprotic liquid environment, the disordered fluctuating hydrogen-bond network of liquid water, and DNA oligomers interacting with water. Cyclic carboxylic acid dimers display a rich scheme of vibrational couplings, resulting in OH stretching absorption bands with highly complex spectral envelopes. Two-dimensional spectroscopy of acetic acid dimers in a nonpolar liquid environment demonstrates that multiple Fermi resonances of the OH stretching mode with overtones and combination tones of fingerprint vibrations dominate both the 2D and linear absorption spectra. The coupling of the OH

  9. Piecewise smooth dynamical systems: Persistence of periodic solutions and normal forms

    NASA Astrophysics Data System (ADS)

    Gouveia, Márcio R. A.; Llibre, Jaume; Novaes, Douglas D.; Pessoa, Claudio

    2016-04-01

    We consider an n-dimensional piecewise smooth vector field with two zones separated by a hyperplane Σ which admits an invariant hyperplane Ω transversal to Σ containing a period annulus A fulfilled by crossing periodic solutions. For small discontinuous perturbations of these systems we develop a Melnikov-like function to control the persistence of periodic solutions contained in A. When n = 3 we provide normal forms for the piecewise linear case. Finally we apply the Melnikov-like function to study discontinuous perturbations of the given normal forms.

  10. Enhancement of oxygen transfer efficiency in diffused aeration systems using liquid-film-forming apparatus.

    PubMed

    Zhu, H; Imai, T; Tani, K; Ukita, M; Sekine, M; Higuchi, T; Zhang, Z J

    2007-05-01

    Surface transfer and bubble transfer both contribute significantly to oxygen transfer in a diffused aeration system. In the present study, liquid-film-forming apparatus is successfully developed on a laboratory scale to improve considerably the surface transfer via the unique liquid film transfer technique. The experimental results show that the volumetric mass transfer coefficient for liquid-film-forming apparatus alone is found to be as much as 5.3 times higher than that for water surface and that the total volumetric mass transfer coefficient for liquid film aeration system increases by 37 % in comparison with conventional aeration system. Additionally, by tuning finely the structural parameters of the liquid-film-forming apparatus, it can also lead to high dissolved oxygen water with the dissolved oxygen percent saturation greater than 90 %. More importantly, this result is accomplished by simply offering a single-pass aeration at the depth as shallow as 26 cm. As a result, the objective of economical energy consumption in diffused aeration systems can be realized by lowering the aeration depth without sacrificing the aeration efficiency.

  11. Economic consequences of aviation system disruptions: A reduced-form computable general equilibrium analysis

    SciTech Connect

    Chen, Zhenhua; Rose, Adam Z.; Prager, Fynnwin; Chatterjee, Samrat

    2017-01-01

    The state of the art approach to economic consequence analysis (ECA) is computable general equilibrium (CGE) modeling. However, such models contain thousands of equations and cannot readily be incorporated into computerized systems used by policy analysts to yield estimates of economic impacts of various types of transportation system failures due to natural hazards, human related attacks or technological accidents. This paper presents a reduced-form approach to simplify the analytical content of CGE models to make them more transparent and enhance their utilization potential. The reduced-form CGE analysis is conducted by first running simulations one hundred times, varying key parameters, such as magnitude of the initial shock, duration, location, remediation, and resilience, according to a Latin Hypercube sampling procedure. Statistical analysis is then applied to the “synthetic data” results in the form of both ordinary least squares and quantile regression. The analysis yields linear equations that are incorporated into a computerized system and utilized along with Monte Carlo simulation methods for propagating uncertainties in economic consequences. Although our demonstration and discussion focuses on aviation system disruptions caused by terrorist attacks, the approach can be applied to a broad range of threat scenarios.

  12. High pressure rheology of gas hydrate formed from multiphase systems using modified Couette rheometer.

    PubMed

    Pandey, Gaurav; Linga, Praveen; Sangwai, Jitendra S

    2017-02-01

    Conventional rheometers with concentric cylinder geometries do not enhance mixing in situ and thus are not suitable for rheological studies of multiphase systems under high pressure such as gas hydrates. In this study, we demonstrate the use of modified Couette concentric cylinder geometries for high pressure rheological studies during the formation and dissociation of methane hydrate formed from pure water and water-decane systems. Conventional concentric cylinder Couette geometry did not produce any hydrates in situ and thus failed to measure rheological properties during hydrate formation. The modified Couette geometries proposed in this work observed to provide enhanced mixing in situ, thus forming gas hydrate from the gas-water-decane system. This study also nullifies the use of separate external high pressure cell for such measurements. The modified geometry was observed to measure gas hydrate viscosity from an initial condition of 0.001 Pa s to about 25 Pa s. The proposed geometries also possess the capability to measure dynamic viscoelastic properties of hydrate slurries at the end of experiments. The modified geometries could also capture and mimic the viscosity profile during the hydrate dissociation as reported in the literature. The present study acts as a precursor for enhancing our understanding on the rheology of gas hydrate formed from various systems containing promoters and inhibitors in the context of flow assurance.

  13. High pressure rheology of gas hydrate formed from multiphase systems using modified Couette rheometer

    NASA Astrophysics Data System (ADS)

    Pandey, Gaurav; Linga, Praveen; Sangwai, Jitendra S.

    2017-02-01

    Conventional rheometers with concentric cylinder geometries do not enhance mixing in situ and thus are not suitable for rheological studies of multiphase systems under high pressure such as gas hydrates. In this study, we demonstrate the use of modified Couette concentric cylinder geometries for high pressure rheological studies during the formation and dissociation of methane hydrate formed from pure water and water-decane systems. Conventional concentric cylinder Couette geometry did not produce any hydrates in situ and thus failed to measure rheological properties during hydrate formation. The modified Couette geometries proposed in this work observed to provide enhanced mixing in situ, thus forming gas hydrate from the gas-water-decane system. This study also nullifies the use of separate external high pressure cell for such measurements. The modified geometry was observed to measure gas hydrate viscosity from an initial condition of 0.001 Pa s to about 25 Pa s. The proposed geometries also possess the capability to measure dynamic viscoelastic properties of hydrate slurries at the end of experiments. The modified geometries could also capture and mimic the viscosity profile during the hydrate dissociation as reported in the literature. The present study acts as a precursor for enhancing our understanding on the rheology of gas hydrate formed from various systems containing promoters and inhibitors in the context of flow assurance.

  14. Noncovalent Intermolecular Forces in Phycobilisomes of Porphyridium cruentum.

    PubMed

    Zilinskas, B A; Glick, R E

    1981-08-01

    Using sensitized fluorescence as a measure of intactness of phycobilisomes isolated from Porphyridium cruentum, the effects of various environmental perturbations on phycobilisome integrity were investigated. The rate of phycobilisome dissociation in 0.75 ionic strength sodium salts proceeds in the order: SCN(-) > NO(3) (-) > Cl(-) > C(6)H(5)O(7) (3-) > SO(4) (2-) > PO(4) (3-), as predicted from the lyotropic series of anions and their effects on hydrophobic interactions in proteins. Similarly, increasing temperature (to 30 C) and pH values approaching the isoelectric points of the biliproteins stabilize phycobilisomes. Deuterium substitution at exchangeable sites on the phycobiliproteins decreases the rate of phycobilisome dissociation, while substitution at nonexchangeable sites increases rates of dissociation. It is concluded that hydrophobic intermolecular interactions are the most important forces in maintaining the phycobilisome structure. Dispersion forces also seem to contribute to phycobilisome stabilization. The adverse effects of electrostatic repulsion must not be ignored; however, it seems that the requirement of phycobilisomes of high salt concentrations is not simply countershielding of charges on the proteins.

  15. 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.

  16. Phosphite-oxazole/imidazole ligands in asymmetric intermolecular Heck reaction.

    PubMed

    Mazuela, Javier; Tolstoy, Paivi; Pàmies, Oscar; Andersson, Pher G; Diéguez, Montserrat

    2011-02-07

    We describe the application of a new class of ligands--the phosphite-oxazole/imidazole (L1-L5a-g)--in asymmetric intermolecular Pd-catalyzed Heck reactions under thermal and microwave conditions. These ligands combine the advantages of the oxazole/imidazole moiety with those of the phosphite moiety: they are more stable than their oxazoline counterparts, less sensitive to air and other oxidizing agents than phosphines and phosphinites, and easy to synthesize from readily available alcohols. The results indicate that activities, regio- and enantioselectivities, are highly influenced by the type of nitrogen donor group (oxazole or imidazole), the oxazole and biaryl-phosphite substituents and the axial chirality of the biaryl moiety of the ligand. By carefully selecting the ligand components, we achieved high activities, regio- (up to 99%) and enantioselectivities (up to 99%) using several triflate sources. Under microwave-irradiation conditions, reaction times were considerably shorter (from 24 h to 30 min) and regio- and enantioselectivities were still excellent.

  17. 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

    2016-03-11

    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.

  18. 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

  19. 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.

  20. A IR Diode Laser Spectroscopic Study of Adsorption and Intermolecular Interactions on Stepped Metal Surfaces: Carbon Monoxide on Vicinal COPPER(100)

    NASA Astrophysics Data System (ADS)

    Borguet, Eric Urbain

    The kinetics of elementary surface processes, intermolecular interactions and stepped surfaces are intrinsic scientific interest, as well as being important to industrially relevant processes such as catalysis. A novel time-resolved surface sensitive technique, Transient Diode Laser Infrared Reflection-Absorption Spectroscopy, has been developed to investigate adsorption on stepped metal surfaces. The IR spectra display anomalous intensity behavior resulting in a minority step-CO species accounting for a disproportionate fraction of the spectral intensity. A model has been elaborated which successfully accounts for, and simulates, the observed spectra. This enables site specific concentrations to be determined, even in the presence of strong dynamic-dipole coupling. These methods allow the spectroscopy, kinetics and intermolecular interactions of CO on a stepped Cu(100) surface to be probed. In particular, it has been possible to observe a dynamic equilibrium between CO adsorbed at step and terrace sites and to investigate the kinetics of site exchange on this surface. The IR spectra also reveal the nature and range of the intermolecular interactions and the local order which results. The CO/Cu(100) system is characterized by repulsive first and second nearest neighbor interactions. As a consequence, the adsorbates adopt a configuration which maximizes the intermolecular distance. Additionally, a non-resonant, broadband, adsorbate induced change in surface reflectivity is observed both in the IR and visible. This linear dependence of this signal with coverage provides a simple method of determining total adsorbed CO concentration.

  1. An IR diode laser spectroscopic study of adsorption and intermolecular interactions on stepped metal surfaces: CO on vicinal Cu(100). [IR (infrared)

    SciTech Connect

    Borguet, E.R.

    1993-01-01

    The kinetics of elementary surface processes, intermolecular interactions and stepped surfaces are intrinsic scientific interest, as well as being important to industrially relevant processes such as catalysis. A novel time-resolved surface sensitive technique. Transient Diode Laser Infrared Reflection-Absorption Spectroscopy, has been developed to investigate adsorption on stepped metal surfaces. The IR spectra display anomalous intensity behavior resulting in a minority step-CO species accounting for a disporportionate fraction of the spectral intensity. A model has been elaborated which successfully accounts for, and simulates, the observed spectra. This enables site specific concentrations to be determined, even in the presence of strong dynamic-dipole coupling. These methods allow the spectroscopy, kinetics and intermolecular interactions of CO on a stepped Cu(100) surface to be probed. In particular, it has been possible to observe a dynamic equilibrium between CO adsorbed at step and terrace sites and to investigate the kinetics of site exchanges on this surface. The IR spectra also reveal the nature and range of the intermolecular interactions and the local order which results. The CO/Cu(100) system is characterized by repulsive first and second nearest neighbor interactions. As a consequence, the adsorbates adopt a configuration which maximizes the intermolecular distance. Additionally, a non-resonant, broadband, adsorbate induced change in surface reflectivity is observed both in the IR and visible. This linear dependence of this signal with coverage provides a simple method of determining total absorbed CO concentration.

  2. 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.

  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. Accurate description of intermolecular interactions involving ions using symmetry-adapted perturbation theory.

    PubMed

    Lao, Ka Un; Schäffer, Rainer; Jansen, Georg; Herbert, John M

    2015-06-09

    Three new data sets for intermolecular interactions, AHB21 for anion-neutral dimers, CHB6 for cation-neutral dimers, and IL16 for ion pairs, are assembled here, with complete-basis CCSD(T) results for each. These benchmarks are then used to evaluate the accuracy of the single-exchange approximation that is used for exchange energies in symmetry-adapted perturbation theory (SAPT), and the accuracy of SAPT based on wave function and density-functional descriptions of the monomers is evaluated. High-level SAPT calculations afford poor results for these data sets, and this includes the recently proposed "gold", "silver", and "bronze standards" of SAPT, namely, SAPT2+(3)-δMP2/aug-cc-pVTZ, SAPT2+/aug-cc-pVDZ, and sSAPT0/jun-cc-pVDZ, respectively [ Parker , T. M. , et al. , J. Chem. Phys. 2014 , 140 , 094106 ]. Especially poor results are obtained for symmetric shared-proton systems of the form X(-)···H(+)···X(-), for X = F, Cl, or OH. For the anionic data set, the SAPT2+(CCD)-δMP2/aug-cc-pVTZ method exhibits the best performance, with a mean absolute error (MAE) of 0.3 kcal/mol and a maximum error of 0.7 kcal/mol. For the cationic data set, the highest-level SAPT method, SAPT2+3-δMP2/aug-cc-pVQZ, outperforms the rest of the SAPT methods, with a MAE of 0.2 kcal/mol and a maximum error of 0.4 kcal/mol. For the ion-pair data set, the SAPT2+3-δMP2/aug-cc-pVTZ performs the best among all SAPT methods with a MAE of 0.3 kcal/mol and a maximum error of 0.9 kcal/mol. Overall, SAPT2+3-δMP2/aug-cc-pVTZ affords a small and balanced MAE (<0.5 kcal/mol) for all three data sets, with an overall MAE of 0.4 kcal/mol. Despite the breakdown of perturbation theory for ionic systems at short-range, SAPT can still be saved given two corrections: a "δHF" correction, which requires a supermolecular Hartree-Fock calculation to incorporate polarization effects beyond second order, and a "δMP2" correction, which requires a supermolecular MP2 calculation to account for higher

  5. Intramolecular photo-switching and intermolecular energy transfer as primary photoevents in photoreceptive processes: the case of Euglena gracilis.

    PubMed

    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(498,) non fluorescent and B(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(498) becomes B(462)), and a intermolecular and unidirectional Forster-type energy transfer. During the FRET process, the fluorescent B(462) form acts as donor for the non-fluorescent A(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.

  6. 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

  7. Intermolecular proton-transfer in acetic acid clusters induced by vacuum-ultraviolet photoionization

    NASA Astrophysics Data System (ADS)

    Ohta, Keisuke; Matsuda, Yoshiyuki; Mikami, Naohiko; Fujii, Asuka

    2009-11-01

    Infrared (IR) spectroscopy based on vacuum-ultraviolet one-photon ionization detection was carried out to investigate geometric structures of neutral and cationic clusters of acetic acid: (CH3COOH)2, CH3COOH-CH3OH, and CH3COOH-H2O. All the neutral clusters have cyclic-type intermolecular structures, in which acetic acid and solvent molecules act as both hydrogen donors and acceptors, and two hydrogen-bonds are formed. On the other hand, (CH3COOH)2+ and (CH3COOH-CH3OH)+ form proton-transferred structures, where the acetic acid moiety donates the proton to the counter molecule. (CH3COOH-H2O)+ has a non-proton-transferred structure, where CH3COOH+ and H2O are hydrogen-bonded. The origin of these structural differences among the cluster cations is discussed with the relative sizes of the proton affinities of the cluster components and the potential energy curves along the proton-transfer coordinate.

  8. 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.

  9. 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.

  10. Simulated imaging of intermolecular bonds using high throughput real-space density functional calculations

    NASA Astrophysics Data System (ADS)

    Lee, Alex; Kim, Minjung; Chelikowsky, James

    2015-03-01

    Recent experimental noncontact atomic force microscopy (AFM) studies on 8-hydroxyquinoline (8-hq) assemblies have imaged distinct lines between molecules that are thought to represent intermolecular bonding. To aid the interpretation of these images, we calculate simulated AFM images of an 8-hq dimer with a CO functionalized tip using a real-space pseudopotential formalism. We examine the effects of Pauli repulsion and tip probe relaxation as explanations for the enhanced resolution that resolves these intermolecular force lines. Our study aims to compute ab initio real-space images of intermolecular interactions.

  11. Ground state intermolecular proton transfer in the supersystems thymine-(H2O)n and thymine-(CH3OH)n, n = 1,2: a theoretical study.

    PubMed

    Delchev, Vassil B; Shterev, Ivan G

    2009-04-01

    Twelve binary and eight ternary supersystems between thymine and methanol, and water were investigated in the ground state at the B3LYP and MP2 levels of theory using B3LYP/6-311 + + G(d,p) basis functions. The thermodynamics of complex formations and the mechanisms of intermolecular proton transfers were clarified in order to find out the most stable H-boned system. It was established that the energy barriers of the water/methanol-assisted proton transfers are several times lower than those of the intramolecular proton transfers in the DNA/RNA bases. The X-ray powder spectra of thymine, and this precrystallized from water and methanol showed that water molecules are incorporated in the crystal lattice of thymine forming H-bridges between thymine molecules.

  12. 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.

  13. 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.

  14. Student construction of differential length elements in multivariable coordinate systems: A symbolic forms analysis

    NASA Astrophysics Data System (ADS)

    Thompson, John; Schermerhorn, Benjamin

    2017-01-01

    Analysis of properties of physical quantities represented by vector fields often involves symmetries and spatial relationships best expressed in non-Cartesian coordinate systems. Many important quantities are determined by integrals that can involve multivariable vector differential quantities. Four pairs of students in junior-level Electricity and Magnetism (E&M) were interviewed to investigate their understanding of the structure of non-Cartesian coordinate systems and the associated differential elements. Pairs were asked to construct differential length elements for an unconventional spherical coordinate system. In order to explore how student conceptual understanding interacts with their understanding of the specific structures of these expressions, a symbolic forms framework was used. Analysis of student reasoning revealed both known and novel forms as well as the general progression of students--use and combination of symbol templates during the construction process. Each group invoked and combined symbolic forms in a similar sequence. Difficulties with the construction of expressions seem to be related almost exclusively to the conceptual schema (e.g., neglecting the role of projection) rather than with symbol templates. Supported in part by NSF Grant PHY-1405726.

  15. 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).

  16. 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.

  17. Still-Forming Solar System May Have Planets Orbiting Star in Opposite Directions, Astronomers Say

    NASA Astrophysics Data System (ADS)

    2006-02-01

    Astronomers studying a disk of material circling a still-forming star inside our Galaxy have found a tantalizing result -- the inner part of the disk is orbiting the protostar in the opposite direction from the outer part of the disk. Protostar Graphic Disk Around Young Star Rotating in Opposite Directions CREDIT: Bill Saxton, NRAO/AUI/NSF More Graphics "This is the first time anyone has seen anything like this, and it means that the process of forming planets from such disks is more complex than we previously expected," said Anthony Remijan, of the National Radio Astronomy Observatory, who with his colleague Jan M. Hollis, of the NASA Goddard Space Flight Center, used the National Science Foundation's Very Large Array radio telescope to make the discovery. "The solar system that likely will be formed around this star will include planets orbiting in different directions, unlike our own solar system in which all the planets orbit the Sun in the same direction," Hollis explained. Stars and planets, scientists believe, are formed when giant clouds of gas and dust collapse. As the cloud collapses, a flattened, rotating disk of material develops around the young star. This disk provides the material from which planets form. The disk and the resulting planets rotate in the same direction as the original cloud, with the rotation speed increasing closer to the center, much as a spinning figure skater spins faster when they draw their arms inward. If all the material in the star and disk come from the same prestellar cloud, they all will rotate in the same direction. That is the case with our own solar system, in which the planets all orbit the Sun in the same direction as the Sun itself rotates on its axis. In the case of a young star some 500 light-years from Earth in the direction of the constellation Ophiuchus, Remijan and Hollis found the inner and outer parts of the disk rotating in opposite directions. "We think this system may have gotten material from two clouds

  18. 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.

  19. Composition-insensitive highly viscous wormlike micellar solutions formed in anionic and cationic surfactant systems.

    PubMed

    Aramaki, Kenji; Iemoto, Suzuka; Ikeda, Naoaki; Saito, Keitaro

    2010-01-01

    We investigated phase behavior and rheological properties of aqueous micellar phase formed in water/cocoyl glutamate neutralized with triethanol amine (CGT-n)/hexadecyl trimethylammonium salt (CTAB or CTAC) systems, where n is a degree of neutralization. Micellar phase appears in wide composition range with respect to the surfactant mixing fraction in ternary phase diagrams at 25 degrees C. At high mixing fraction of cationic surfactant in the water/CGT-n/CTAB systems, one can observe a highly viscous micellar phase in which worm-like micelles are expected to form. Contrary to conventional systems in which worm-like micelles are formed, the zero-shear viscosity of the micellar solution in the water/CGT-n/CTAB system with n=1.2 increases with the addition of cationic cosurfactant and once decreases after a maximum, then increases again and decreases after the second maximum. At n=1.5 and 2, highly viscous solution is observed in the relatively wide range of surfactant mixing fraction instead of two maxima of the viscosity curve observed at n=1.2. In the case of CTAC instead of CTAB we can observe narrow composition range for the maximum viscosity. Frequency sweep measurements were performed on the highly viscous samples in the water/CGT-1.5/CTAB system. Typical viscoelastic behavior of worm-like micellar solutions is observed; i.e. the curves of storage (G') and loss (G") moduli make a crossover and the data points of G' and G" can be fitted to the Maxwell model. Relaxation time against the mixing fraction of two surfactants behaves similarly to the zero-shear viscosity change, whereas the plateau modulus continuously increases in the plateau region for the zero-shear viscosity curve.

  20. Intra- and intermolecular interaction ECL study of novel ruthenium tris-bipyridyl complexes with different amine reductants.

    PubMed

    Sun, Shiguo; Yang, Yang; Liu, Fengyu; Fan, Jiangli; Peng, Xiaojun; Kehr, Jan; Sun, Licheng

    2009-10-14

    A series of ruthenium(II) tris-bipyridyl complexes covalently linked with different amine reductants such as tripropylamine (TPrA), ethanolamine and diethanolamine for an electrochemiluminescence (ECL) system have been synthesized. Their ECL property at different working electrodes has been studied with and without the presence of TPrA, triethanolamine (TEOA) and 2-(dibutylamino) ethanol (DBAE) as the coreactant, respectively. The results demonstrate that the conjugated ruthenium complex alone can generate ECL through intramolecular interaction at a relatively low concentration, while with intermolecular interaction the ECL intensity increases progressively and becomes increasingly dominant with increasing complex concentration. For the coreactant system ECL, the amine coreactant needed for the conjugate complexes can be significantly lowered in comparison with that of the well known [Ru(bpy)(3)](2+)/TPrA system. One amine substituent is better for the system in order to diminish the steric hindrance, and the intramolecular amine reductant employed should have a similar structure with that of the additive amine coreactant to achieve a good ECL performance, which can pave a new route to further improving the ECL efficiency and increase the sensitivity of detection through combining both intra- and intermolecular interaction.

  1. Effects of intermolecular interactions on the stability of carbon nanotube–gold nanoparticle conjugates in solution

    PubMed Central

    Konczak, Lukasz; Narkiewicz-Michalek, Jolanta; Pastorin, Giorgia; Panczyk, Tomasz

    2016-01-01

    This work deals with the role of intermolecular interactions in the stability of a carbon nanotube (CNT) capped by functionalized gold nanoparticles (AuNPs). The importance of such a system is due to its potential application as a pH-controlled drug carrier. Our preliminary experimental studies showed that fabrication of such a nanobottle/nanocontainer is feasible and it is possible to encapsulate the anticancer drug cisplatin inside the inner space of a CNT and seal its ends by functionalized AuNPs. The expected behavior, that is, detachment of AuNPs at acidic pH and the release of cisplatin, was, however, not observed. On the other hand, our theoretical studies of chemically identical system led to the conclusion that the release of cisplatin at acidic pH should be observed. Therefore, in this work, a deeper theoretical analysis of various factors that could be responsible for the disagreement between experimental and theoretical results were performed. The study found that the major factor is a large dispersion interaction component acting between CNT and AuNP in solution in the case of the experimental system. This factor can be controlled to some extent by tuning the system size or the ratio between AuNP diameter and CNT diameter. Thus, such kind of a pH-sensitive drug carrier is still of great interest, but its structural parameters need to be properly adjusted. PMID:27853368

  2. [Influence of double rice cropping system innovation on paddy soil profile form and soil characteristics].

    PubMed

    Zeng, Xi-Bai; Sun, Nan; Gao, Ju-Sheng; Li, Lian-Fang; Wang, Bo-Ren; Bai, Ling-Yu

    2008-05-01

    Field experiments were conducted on the double rice cropping paddy field in red soil area to evaluate the influence of cropping system innovation on soil profile form and related soil characteristics. Four cropping systems of rice-rice-Chinese Milkvetch (Astragalus sinicus Linn.), forage, paddy-upland rotation, and upland were substituted for the double rice cropping system. The results indicated that compared with those under double rice cropping system, the thickness of cultivated horizon under upland cropping system increased by 4 cm, that of plow pan declined by 2 cm, > 2 mm aggregates in wet-sieved particle-size fractions increased by 6.94%, wet-sieved mean-mass diameter increased by 0.37 mm, contents of humic acid carbon and fulvic acid carbon increased by 0.15 and 0.49 g kg(-1), respectively, and quotient of aggregates water stability was 0.78 times higher. Under paddy-upland rotation, the quotient of aggregates water stability was higher (95.86), while soil nutrient contents changed a little. Under rice-rice-Chinese Milkvetch system, soil organic matter content increased by 1.3 g kg(-1), quotient of aggregates water stability declined by 8.82, but other parameters had less changes. Under forage system, the thickness of cultivated and transitional horizons increased by 2 cm and 9 cm, respectively, quotient of aggregates water stability increased by 1.39, while the contents of soil organic matter and total potassium decreased by 5.6 and 2.8 g kg(-1), respectively. Among all test cropping systems, forage system had the greatest changes in soil characteristics. It was completely feasible to substitute the local double rice cropping system for paddy-upland rotation or upland cropping, particularly in the areas where full irrigation was not available. However, attention should be paid to the decrease of soil potassium content when the cropping system innovation was practiced.

  3. Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

    NASA Astrophysics Data System (ADS)

    Shcherbina, M. A.; Bakirov, A. V.; Yakunin, A. N.; Percec, V.; Beginn, U.; Möller, M.; Chvalun, S. N.

    2012-03-01

    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.

  4. 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.

  5. LED surgical lighting system with multiple free-form surfaces for highly sterile operating theater application.

    PubMed

    Liu, Peng; Zhang, Yaqin; Zheng, Zhenrong; Li, Haifeng; Liu, Xu

    2014-06-01

    Although the ventilation system is widely employed in the operating theater, a strictly sterile surgical environment still cannot be ensured because of laminar disturbance, which is mainly caused by the surgical lighting system. Abandoning traditional products, we propose an LED surgical lighting system, which can alleviate the laminar disturbance and provide an appropriate lighting condition for surgery. It contains a certain amount of LED lens units, which are embedded in the ceiling and arranged around the air supply smallpox. The LED lens unit integrated with an LED light source and a free-form lens is required to produce a uniform circular illumination with a large tolerance to the change of lighting distance. To achieve such a dedicated lens, two free-form refractive surfaces, which are converted into two ordinary differential equations by the design method presented in this paper, are used to deflect the rays. The results show that the LED surgical lighting system can provide an excellent illumination environment for surgery, and, apparently, the laminar disturbance also can be relieved.

  6. 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.

  7. 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.

  8. Competing intermolecular interactions in some 'bridge-flipped' isomeric phenylhydrazones.

    PubMed

    Ojala, William H; Arola, Trina M; Brigino, Ann M; Leavell, Jeremy D; Ojala, Charles R

    2012-07-01

    To examine the roles of competing intermolecular interactions in differentiating the molecular packing arrangements of some isomeric phenylhydrazones from each other, the crystal structures of five nitrile-halogen substituted phenylhydrazones and two nitro-halogen substituted phenylhydrazones have been determined and are described here: (E)-4-cyanobenzaldehyde 4-chlorophenylhydrazone, C(14)H(10)ClN(3), (Ia); (E)-4-cyanobenzaldehyde 4-bromophenylhydrazone, C(14)H(10)BrN(3), (Ib); (E)-4-cyanobenzaldehyde 4-iodophenylhydrazone, C(14)H(10)IN(3), (Ic); (E)-4-bromobenzaldehyde 4-cyanophenylhydrazone, C(14)H(10)BrN(3), (IIb); (E)-4-iodobenzaldehyde 4-cyanophenylhydrazone, C(14)H(10)IN(3), (IIc); (E)-4-chlorobenzaldehyde 4-nitrophenylhydrazone, C(13)H(10)ClN(3)O(2), (III); and (E)-4-nitrobenzaldehyde 4-chlorophenylhydrazone, C(13)H(10)ClN(3)O(2), (IV). Both (Ia) and (Ib) are disordered (less than 7% of the molecules have the minor orientation in each structure). Pairs (Ia)/(Ib) and (IIb)/(IIc), related by a halogen exchange, are isomorphous, but none of the 'bridge-flipped' isomeric pairs, viz. (Ib)/(IIb), (Ic)/(IIc) or (III)/(IV), is isomorphous. In the nitrile-halogen structures (Ia)-(Ic) and (IIb)-(IIc), only the bridge N-H group and not the bridge C-H group acts as a hydrogen-bond donor to the nitrile group, but in the nitro-halogen structures (III) (with Z' = 2) and (IV), both the bridge N-H group and the bridge C-H group interact with the nitro group as hydrogen-bond donors, albeit via different motifs. The occurrence here of the bridge C-H contact with a hydrogen-bond acceptor suggests the possibility that other pairs of `bridge-flipped' isomeric phenylhydrazones may prove to be isomorphous, regardless of the change from isomer to isomer in the position of the N-H group within the bridge.

  9. Hydrogen-Bonding Polarizable Intermolecular Potential Model for Water.

    PubMed

    Jiang, Hao; Moultos, Othonas A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2016-12-08

    A polarizable intermolecular potential model with short-range directional hydrogen-bonding interactions was developed for water. The model has a rigid geometry, with bond lengths and angles set to experimental gas-phase values. Dispersion interactions are represented by the Buckingham potential assigned to the oxygen atom, whereas electrostatic interactions are modeled by Gaussian charges. Polarization is handled by a Drude oscillator site, using a negative Gaussian charge attached to the oxygen atom by a harmonic spring. An explicit hydrogen-bonding term is included in the model to account for the effects of charge transfer. The model parameters were optimized to density, configurational energy, pair correlation function, and the dielectric constant of water under ambient conditions, as well as the minimum gas-phase dimer energy. Molecular dynamics and Gibbs ensemble Monte Carlo simulations were performed to evaluate the new model with respect to the thermodynamic and transport properties over a wide range of temperature and pressure conditions. Good agreement between model predictions and experimental data was found for most of the properties studied. The new model yields better performance relative to the majority of existing models and outperforms the BK3 model, which is one of the best polarizable models, for vapor-liquid equilibrium properties, whereas the new model is not better than the BK3 model for representation of other properties. The model can be efficiently simulated with the thermalized Drude oscillator algorithm, resulting in computational costs only 3 times higher than those of the nonpolarizable TIP4P/2005 model, whereas having significantly improved properties. Because it involves only a single Drude oscillator site, the new model is significantly faster than polarizable models with multiple sites. With the explicit inclusion of hydrogen-bond interactions, the model may provide a better description of the phase behavior of aqueous mixtures.

  10. New Closed-Form of the Largest Eigenvalue PDF for Max-SNR MIMO System Performances

    NASA Astrophysics Data System (ADS)

    Letessier, Jonathan; Vrigneau, Baptiste; Rostaing, Philippe; Burel, Gilles

    Multiple-input multiple-output (MIMO) maximum-SNR (max-SNR) system employs the maximum ratio combiner (MRC) at the receiver side and the maximum ratio transmitter (MRT) at the transmitter side. Its performances highly depend on MIMO channel characteristics, which vary according to both the number of antennas and their distribution between the transmitter and receiver sides. By using the decomposition of the ordered Wishart distribution in the uncorrelated Rayleigh case, we derived a closed-form expression of the largest eigenvalue probability density function (PDF). The final result yields to an expression form of the PDF where polynomials are multiplied by exponentials; it is worth underlining that, though this form had been previously observed for given couples of antennas, to date no formally-written closed-form was available in the literature for an arbitrary couple. Then, this new expression permits one to quickly and easily get the well known largest eigenvalue PDF and use it to determine the binary error probability (BEP) of the max-SNR.

  11. 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.

  12. Intermolecular Forces in Introductory Chemistry Studied by Gas Chromatography, Computer Models, and Viscometry

    NASA Astrophysics Data System (ADS)

    Wedvik, Jonathan C.; McManaman, Charity; Anderson, Janet S.; Carroll, Mary K.

    1998-07-01

    An experiment on intermolecular forces for first-term introductory college chemistry is presented. The experiment integrates traditional viscometry-based measurements with modern chromatographic analysis and use of computer-based molecular models. Students performing gas chromatographic (GC) analyses of mixtures of n-alkanes and samples that simulate crime scene evidence discover that liquid mixtures can be separated rapidly into their components based upon intermolecular forces. Each group of students is given a liquid sample that simulates one collected at an arson scene, and the group is required to determine the identity of the accelerant. Students also examine computer models to better visualize how molecular structure affects intermolecular forces: London forces, dipole-dipole interactions, and hydrogen bonding. The relative viscosities of organic liquids are also measured to relate physical properties to intermolecular forces.

  13. The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding: phosphorylated azoles.

    PubMed

    Chernyshev, Kirill A; Larina, Ludmila I; Chirkina, Elena A; Krivdin, Leonid B

    2012-02-01

    The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding have been investigated in the series of tetracoordinated, pentacoordinated and hexacoordinated N-vinylpyrazoles and intermolecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorous pentachloride both experimentally and theoretically. It was shown that either intramolecular or intermolecular coordination involving phosphorous results in a dramatic (31)P nuclear shielding amounting to approximately 150 ppm on changing the phosphorous coordination number by one. A major importance of solvent effects on (31)P nuclear shielding of intramolecular and intermolecular complexes involving N → P coordination bond has been demonstrated. It was found that the zeroth-order regular approximation-gauge-including atomic orbital-B1PW91/DZP method was sufficiently accurate for the calculation of (31)P NMR chemical shifts, provided relativistic corrections are taken into account, the latter being of crucial importance in the description of (31)P nuclear shielding.

  14. 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)

  15. 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.

  16. Multi-system Nernst-Michaelis-Menten model applied to bioanodes formed from sewage sludge.

    PubMed

    Rimboud, Mickaël; Desmond-Le Quemener, Elie; Erable, Benjamin; Bouchez, Théodore; Bergel, Alain

    2015-11-01

    Bioanodes were formed under constant polarization at -0.2 V/SCE from fermented sewage sludge. Current densities reached were 9.3±1.2 A m(-2) with the whole fermented sludge and 6.2±0.9 A m(-2) with the fermented sludge supernatant. The bioanode kinetics was analysed by differentiating among the contributions of the three redox systems identified by voltammetry. Each system ensured reversible Nernstian electron transfer but around a different central potential. The global overpotential required to reach the maximum current plateau was not imposed by slow electron transfer rates but was due to the potential range covered by the different redox systems. The microbial communities of the three bioanodes were analysed by 16S rRNA gene pyrosequencing. They showed a significant microbial diversity around a core of Desulfuromonadales, the proportion of which was correlated with the electrochemical performance of the bioanodes.

  17. Forming system of strategic innovation management at high-tech engineering enterprises

    NASA Astrophysics Data System (ADS)

    Ergunova, O. T.; Lizunkov, V. G.; Malushko, E. Yu; Marchuk, V. I.; Ignatenko, A. Yu

    2017-02-01

    The article considers the processes of forming the strategic system of innovative activity management at the enterprises of a high-tech mechanical engineering complex (MEC) that are traditionally decisive in shaping the economic base of Russia. The authors proposed a method of designing a strategic system of innovative activity management at the MEC’s enterprises of the region which is based on the consideration of means and opportunities of the enterprise to implement intellectual activity. The proposed methodology and the empirical results constituted a ground for developing a system of strategic innovation management when performing the state-guaranteed order at the hi-tech MEC enterprises. Its implementation will help to reduce the level of uncertainty throughout the entire life cycle of an innovative activity product.

  18. 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.

  19. 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.

  20. Enhanced tunability afforded by aqueous biphasic systems formed by fluorinated ionic liquids and carbohydrates.

    PubMed

    Ferreira, Ana M; Esteves, Pedro D O; Boal-Palheiros, Isabel; Pereiro, Ana B; Rebelo, Luís Paulo N; Freire, Mara G

    2016-02-21

    This work unveils the formation of novel aqueous biphasic systems (ABS) formed by perfluoroalkylsulfonate-based ionic liquids (ILs) and a large number of carbohydrates (monosaccharides, disaccharides and polyols) aiming at establishing more benign alternatives to the salts commonly used. The respective ternary phase diagrams were determined at 298 K. The aptitude of the carbohydrates to induce phase separation closely follows their hydration capability, while the length of the IL cation/anion fluorinated chain also plays a crucial role. Finally, these systems were investigated as liquid-liquid extraction strategies for four food dyes. Single-step extraction efficiencies for the carbohydrate-rich phase up to 94% were obtained. Remarkably and contrarily to the most investigated IL-salt ABS, most dyes preferentially migrate for the most hydrophilic and biocompatible carbohydrate-rich phase - an outstanding advantage when envisaging the products recovery and further use. On the other hand, more hydrophobic dyes preferentially partition to the IL-rich phase, disclosing therefore these novel systems as highly amenable to be tuned by the proper choice of the phase-forming components.

  1. Laser impact assessment in a biofilm-forming bacterium Pseudoalteromonas carrageenovora using a flow cytometric system.

    PubMed

    Nandakumar, Kanavillil; Obika, Hideki; Shinozaki, Tatsuya; Ooie, Toshihiko; Utsumi, Akihiro; Yano, Tetsuo

    2003-05-20

    Impact by pulsed laser irradiations from an Nd:YAG laser on the marine biofilm-forming bacterium Pseudoalteromonas carrageenovora has been studied using a flow cytometric system. The biofilm-forming bacteria in the planktonic state have been irradiated while flowing, and the mortality and bacterial attachment have been determined by exposing TiN coupons in the system. Coupons suspended in the non-irradiated bacterial flow were treated as the control. The fluence used in the study was 0.1 J/cm(2). Three flow rates (14, 28, and 42 cm/min) and two exposure durations (15 and 30 min) were tested. The results showed the increase in bacterial mortality with the decrease in flow rate. The maximum mortality of 27.5% was observed when the flow rate was 14 cm/min. The bacterial attachment increased with the increase in flow rate and exposure duration. The area of bacterial attachment on the experimental coupons exposed to the irradiated sample was significantly lesser than that for the nonirradiated sample. The results thus show in a flowing system, low power pulsed laser irradiations could reduce the bacterial attachment even though it did not cause significant mortality.

  2. 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.

  3. Good's buffers as novel phase-forming components of ionic-liquid-based aqueous biphasic systems.

    PubMed

    Luís, Andreia; Dinis, Teresa B V; Passos, Helena; Taha, Mohamed; Freire, Mara G

    2015-09-15

    Aiming at the development of self-buffering and benign extraction/separation processes, this work reports a novel class of aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and organic biological buffers (Good's buffers, GBs). A large array of ILs and GBs was investigated, revealing than only the more hydrophobic and fluorinated ILs are able to form ABS. For these systems, the phase diagrams, tie-lines, tie-line lengths, and critical points were determined at 25 °C. The ABS were then evaluated as alternative liquid-liquid extraction strategies for two amino acids (L-phenylalanine and L-tryptophan). The single-step extraction efficiencies for the GB-rich phase range between 22.4 and 100.0 % (complete extraction). Contrarily to the most conventional IL-salt ABS, in most of the systems investigated, the amino acids preferentially migrate for the most biocompatible and hydrophilic GB-rich phase. Remarkably, in two of the studied ABS, L-phenylalanine completely partitions to the GB-rich phase while L-tryptophan shows a preferential affinity for the opposite phase. These results show that the extraction efficiencies of similar amino acids can be tailored by the design of the chemical structures of the phase-forming components, creating thus new possibilities for the use of IL-based ABS in biotechnological separations.

  4. Enhanced tunability afforded by aqueous biphasic systems formed by fluorinated ionic liquids and carbohydrates†

    PubMed Central

    Boal-Palheiros, Isabel; Pereiro, Ana B.; Rebelo, Luís Paulo N.; Freire, Mara G.

    2016-01-01

    This work unveils the formation of novel aqueous biphasic systems (ABS) formed by perfluoroalkylsulfonate-based ionic liquids (ILs) and a large number of carbohydrates (monosaccharides, disaccharides and polyols) aiming at establishing more benign alternatives to the salts commonly used. The respective ternary phase diagrams were determined at 298 K. The aptitude of the carbohydrates to induce phase separation closely follows their hydration capability, while the length of the IL cation/anion fluorinated chain also plays a crucial role. Finally, these systems were investigated as liquid–liquid extraction strategies for four food dyes. Single-step extraction efficiencies for the carbohydrate-rich phase up to 94% were obtained. Remarkably and contrarily to the most investigated IL-salt ABS, most dyes preferentially migrate for the most hydrophilic and biocompatible carbohydrate-rich phase – an outstanding advantage when envisaging the products recovery and further use. On the other hand, more hydrophobic dyes preferentially partition to the IL-rich phase, disclosing therefore these novel systems as highly amenable to be tuned by the proper choice of the phase-forming components. PMID:27667966

  5. 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.

  6. Oriented covalent immobilization of antibodies for measurement of intermolecular binding forces between zipper-like contact surfaces of split inteins

    PubMed Central

    Sorci, Mirco; Dassa, Bareket; Liu, Hongwei; Anand, Gaurav; Dutta, Amit K.; Pietrokovski, Shmuel; Belfort, Marlene; Belfort, Georges

    2013-01-01

    In order to measure the intermolecular binding forces between two halves (or partners) of naturally split protein splicing elements called inteins, a novel thiol-hydrazide linker was designed and used to orient immobilized antibodies specific for each partner. Activation of the surfaces was achieved in one step allowing direct force measurements of the formation of a peptide bond catalyzed by the binding of the two partners of the split intein (called protein trans-splicing). Through this binding process, a whole functional intein is formed resulting in subsequent splicing. Atomic force microscopy (AFM) was used to directly measure the split intein partner binding at 1µm/s between native (wild-type) and mixed pairs of C- and N-terminal partners of naturally occurring split inteins from three cyanobacteria. Native and mixed pairs exhibit similar binding forces within the error of the measurement technique (~52 pN). Bioinformatic sequence analysis and computational structural analysis discovered a zipper-like contact between the two partners with electrostatic and non-polar attraction between multiple aligned ion pairs and hydrophobic residues. Also, we tested the Jarzynski’s equality and demonstrated, as expected, that non-equilibrium dissipative measurements obtained here gave larger energies of interaction as compared with those for equilibrium. Hence, AFM coupled with our immobilization strategy and computational studies provides a useful analytical tool for the direct measurement of intermolecular association of split inteins and could be extended to any interacting protein pair. PMID:23679912

  7. Molecular structure and effects of intermolecular hydrogen bonding on the vibrational spectrum of trifluorothymine, an antitumor and antiviral agent.

    PubMed

    Cırak, Cağrı; Koç, Nurettin

    2012-09-01

    In the present work, the experimental and the theoretical vibrational spectra of trifluorothymine were investigated. The FT-IR (400-4000 cm(-1)) and μ-Raman spectra (100-4000 cm(-1)) of trifluorothymine in the solid phase were recorded. The geometric parameters (bond lengths and bond angles) and vibrational frequencies of the title molecule in the ground state were calculated using ab initio Hartree-Fock (HF) method and density functional theory (B3LYP) method with the 6-31++G(d,p) and 6-311++G(d,p) basis sets 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 results found in the literature. Vibrational frequencies were assigned based on the potential energy distribution using the VEDA 4 program. The dimeric form of trifluorothymine was also simulated to evaluate the effect of intermolecular hydrogen bonding on the vibrational frequencies. It was observed that the stretching modes shifted to lower frequencies, while the in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular N-H⋯O hydrogen bonds.

  8. 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.

  9. pH-controlled carbon nanotube aggregation/dispersion based on intermolecular i-motif DNA formation.

    PubMed

    Cheng, Enjun; Yang, Yang; Liu, Dongsheng

    2010-11-01

    In this work, we report a new strategy to manipulate the aggregation and dispersion of carbon nanotube in solution via formation of intermolecular i-motif (four-stranded C-quadruplex) structures in a pH dependent manner. Firstly, single-stranded (ss) DNAs containing two stretches of cytosine (C)-rich domains are covalently linked to carbon nanotubes. At pH 8.0, DNAs are at random coil state, which enhance the dispersion of multi-wall carbon nanotubes (MWNTs) in water; after changing pH to 5.0, the intermolecular i-motif structures formed by the C-rich ssDNAs on neighboring carbon nanotube could drive the MWNTs aggregate. This process is reversible and the transition process has been verified by circular dichroism (CD) spectroscopy, gel electrophoresis and transmission electron microscopy (TEM). Considering the mechanical properties of carbon nanotube, this finding will benefit many application research fields, such as artificial muscle, functional nano-devices and so on.

  10. 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

  11. The preparation and intra- and intermolecular addition reactions of acyclic N-acylimines: application to the synthesis of (+/-)-sertraline.

    PubMed

    DeNinno, M P; Eller, C; Etienne, J B

    2001-10-19

    Intramolecular endo-cyclization reactions of N-acyliminium ions have seen wide application for the synthesis of heterocyclic compounds. The corresponding exocyclic variant, which would provide 1-aminotetralin derivatives, for example, has little precedent. We have discovered that acyclic N-acylcarbamates can be readily reduced to the corresponding N-acylhemiaminal derivatives in high yield using DIBAL as the reducing agent. These intermediates are remarkably stable and, if desired, can be purified and stored. The acyclic N-acylhemiaminals undergo both intra- and intermolecular nucleophilic addition reactions mediated by strong Lewis acids, such as TiCl(4). Diastereoselectivity, induced either by a substituent on the newly formed ring, or by utilizing a chiral ester on the carbamic acid, was disappointingly low. This methodology was successfully applied to the synthesis of the racemic form of the marketed antidepressant sertraline.

  12. Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS (1)H solid-state NMR spectroscopy and GIPAW calculations.

    PubMed

    Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P

    2017-03-02

    Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional (1)H, (13)C and (15)N and two-dimensional (1)H-(13)C and (14)N-(1)H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the (1)H, (13)C and (14)N/(15)N resonances. A two-dimensional (1)H-(1)H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions.

  13. 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

  14. 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

  15. 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.

  16. Challenges in Forming the Solar System's Giant Planet Cores via Pebble Accretion

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Though ~10 M ⊕ 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.

  17. Anti-plasticizing effect of amorphous indomethacin induced by specific intermolecular interactions with PVA copolymer.

    PubMed

    Ueda, Hiroshi; Aikawa, Shohei; Kashima, Yousuke; Kikuchi, Junko; Ida, Yasuo; Tanino, Tadatsugu; Kadota, Kazunori; Tozuka, Yuichi

    2014-09-01

    The mechanism of how poly(vinyl alcohol-co-acrylic acid-co-methyl methacrylate) (PVA copolymer) stabilizes an amorphous drug was investigated. Solid dispersions of PVA copolymer, poly(vinyl pyrrolidone) (PVP), and poly(vinyl pyrrolidone-co-vinyl acetate) (PVPVA) with indomethacin (IMC) were prepared. The glass transition temperature (Tg)-proportion profiles were evaluated by differential scanning calorimetry (DSC). General Tg profiles decreasing with the IMC ratio were observed for IMC-PVP and IMC-PVPVA samples. An interesting antiplasticizing effect of IMC on PVA copolymer was observed; Tg increased up to 20% IMC ratio. Further addition of IMC caused moderate reduction with positive deviation from theoretical values. Specific hydrophilic and hydrophobic interactions between IMC and PVA copolymer were revealed by infrared spectra. The indole amide of IMC played an important role in hydrogen bonding with PVA copolymer, but not with PVP and PVPVA. X-ray diffraction findings and the endotherm on DSC profiles suggested that PVA copolymer could form a semicrystalline structure and a possibility of correlation of the crystallographic nature with its low hygroscopicity was suggested. PVA copolymer was able to prevent crystallization of amorphous IMC through both low hygroscopicity and the formation of a specific intermolecular interaction compared with that with PVP and PVPVA.

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

    PubMed

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

    2010-03-14

    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.

  19. Universal Form of Stochastic Evolution for Slow Variables in Equilibrium Systems

    NASA Astrophysics Data System (ADS)

    Itami, Masato; Sasa, Shin-ichi

    2017-02-01

    Nonlinear, multiplicative Langevin equations for a complete set of slow variables in equilibrium systems are generally derived on the basis of the separation of time scales. The form of the equations is universal and equivalent to that obtained by Green. An equation with a nonlinear friction term for Brownian motion turns out to be an example of the general results. A key method in our derivation is to use different discretization schemes in a path integral formulation and the corresponding Langevin equation, which also leads to a consistent understanding of apparently different expressions for the path integral in previous studies.

  20. Optimization of topical gels with betamethasone dipropionate: selection of gel forming and optimal cosolvent system.

    PubMed

    Băiţan, Mariana; Lionte, Mihaela; Moisuc, Lăcrămioara; Gafiţanu, Eliza

    2011-01-01

    The purpose of these studies was to develop a 0.05% betamethasone gel characterized by physical-chemical stability and good release properties. The preliminary studies were designed to select the gel-forming agents and the excipients compatible with betamethasone dipropionate. In order to formulate a clear gel without particles of drug substances in suspension, a solvent system for the drug substance was selected. The content of drug substance released, the rheological and in vitro release tests were the tools used for the optimal formulation selection. A stable carbomer gel was obtained by solubilization of betamethasone dipropionate in a vehicle composed by 40% PEG 400, 10% ethanol and 5% Transcutol.

  1. Universal Form of Stochastic Evolution for Slow Variables in Equilibrium Systems

    NASA Astrophysics Data System (ADS)

    Itami, Masato; Sasa, Shin-ichi

    2017-04-01

    Nonlinear, multiplicative Langevin equations for a complete set of slow variables in equilibrium systems are generally derived on the basis of the separation of time scales. The form of the equations is universal and equivalent to that obtained by Green. An equation with a nonlinear friction term for Brownian motion turns out to be an example of the general results. A key method in our derivation is to use different discretization schemes in a path integral formulation and the corresponding Langevin equation, which also leads to a consistent understanding of apparently different expressions for the path integral in previous studies.

  2. 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

  3. 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.

  4. Improving activity of minicellulosomes by integration of intra- and intermolecular synergies

    PubMed Central

    2013-01-01

    Background Complete hydrolysis of cellulose to glucose requires the synergistic action of three general types of glycoside hydrolases; endoglucanases, exoglucanases, and cellobiases. Cellulases that are found in Nature vary considerably in their modular diversity and architecture. They include: non-complexed enzymes with single catalytic domains, independent single peptide chains incorporating multiple catalytic modules, and complexed, scaffolded structures, such as the cellulosome. The discovery of the latter two enzyme architectures has led to a generally held hypothesis that these systems take advantage of intramolecular and intermolecular proximity synergies, respectively, to enhance cellulose degradation. We use domain engineering to exploit both of these concepts to improve cellulase activity relative to the activity of mixtures of the separate catalytic domains. Results We show that engineered minicellulosomes can achieve high levels of cellulose conversion on crystalline cellulose by taking advantage of three types of synergism; (1) a complementary synergy produced by interaction of endo- and exo-cellulases, (2) an intramolecular synergy of multiple catalytic modules in a single gene product (this type of synergism being introduced for the first time to minicellulosomes targeting crystalline cellulose), and (3) an intermolecular proximity synergy from the assembly of these cellulases into larger multi-molecular structures called minicellulosomes. The binary minicellulosome constructed in this study consists of an artificial multicatalytic cellulase (CBM4-Ig-GH9-X11-X12-GH8-Doc) and one cellulase with a single catalytic domain (a modified Cel48S with the structure CBM4-Ig-GH48-Doc), connected by a non-catalytic scaffoldin protein. The high level endo-exo synergy and intramolecular synergies within the artificial multifunctional cellulase have been combined with an additional proximity-dependent synergy produced by incorporation into a minicellulosome

  5. Aqueous Two-Phase Systems formed by Biocompatible and Biodegradable Polysaccharides and Acetonitrile.

    PubMed

    de Brito Cardoso, Gustavo; Souza, Isabela Nascimento; Pereira, Matheus M; Freire, Mara G; Soares, Cleide Mara Faria; Lima, Álvaro Silva

    2014-11-05

    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.

  6. 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

  7. 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.

  8. 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

  9. Intermolecular forces in spread phospholipid monolayers at oil/water interfaces.

    PubMed

    Mingins, James; Pethica, Brian A

    2004-08-31

    The lateral intermolecular forces between phospholipids are of particular relevance to the behavior of biomembranes, and have been approached via studies of monolayer isotherms at aqueous interfaces, mostly restricted to air/water (A/W) systems. For thermodynamic properties, the oil/water (O/W) interface has major advantages but is experimentally more difficult and less studied. A comprehensive reanalysis of the available thermodynamic data on spread monolayers of phosphatidyl cholines (PC) and phosphatidyl ethanolamines (PE) at O/W interfaces is conducted to identify the secure key features that will underpin further development of molecular models. Relevant recourse is made to isotherms of single-chain molecules and of mixed monolayers to identify the contributions of chain-chain interactions and interionic forces. The emphasis is on the properties of the phase transitions for a range of oil phases. Apparent published discrepancies in thermodynamic properties are resolved and substantial agreement emerges on the main features of these phospholipid monolayer systems. In compression to low areas, the forces between the zwitterions of like phospholipids are repulsive. The molecular model for phospholipid headgroup interactions developed by Stigter et al. accounts well for the virial coefficients in expanded phospholipid O/W monolayers. Inclusion of the changes in configuration and orientation of the zwitterion headgroups on compression, which are indicated by the surface potentials in the phase transition region, and inclusion of the energy of chain demixing from the oil phase will be required for molecular modeling of the phase transitions.

  10. Photophysical and computational investigation of the intermolecular interactions of pyrene with phenothiazine and promazine

    NASA Astrophysics Data System (ADS)

    Güloğlu, Pınar; Acar, Nursel

    2016-10-01

    The intermolecular interactions between the pyrene (Py) (as acceptor) and phenothiazine (Pheno), promazine (Prom) (as donors) were investigated using UV/Vis absorption and fluorescence spectroscopy. Fluorescence quenching rate constants for Py-Pheno and Py-Prom systems have been calculated approximately 1010 M-1 s-1, indicating diffusion controlled processes. A computational investigation has also been carried out in gas phase at ωB97XD/6-31G(d,p) level. Time-dependent density functional theory (TDDFT) was used to calculate the electronic transitions of molecules at B3LYP/6-311++G(d,p) level. Total electronic energies, complexation energies, free energy differences, excitation wavelengths, and HOMO-LUMO energy gaps are discussed in gas phase. Analyses of first excited singlet states have indicated charge transfers transitions between Py and Pheno, Prom through π-π stacking in gas phase at 433 nm and 466 nm, respectively. Due to its charge transfer character, Py-Pheno and Py-Prom systems seem to be appropriate models to investigate and design photosensitive materials.

  11. 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.

  12. 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

  13. In situ-forming hydrogels--review of temperature-sensitive systems.

    PubMed

    Ruel-Gariépy, Eve; Leroux, Jean-Christophe

    2004-09-01

    In the past few years, an increasing number of in situ-forming systems have been reported in the literature for various biomedical applications, including drug delivery, cell encapsulation, and tissue repair. There are several possible mechanisms that lead to in situ gel formation: solvent exchange, UV-irradiation, ionic cross-linkage, pH change, and temperature modulation. The thermosensitive approach can be advantageous for particular applications as it does not require organic solvents, co-polymerization agents, or an externally applied trigger for gelation. In the last 2 decades, several thermosensitive formulations have been proposed. This manuscript focuses on aqueous polymeric solutions that form implants in situ in response to temperature change, generally from ambient to body temperature. It mainly reviews the characterization and use of polysaccharides, N-isopropylacrylamide copolymers, poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (poloxamer) and its copolymers, poly(ethylene oxide)/(D,L-lactic acid-co-glycolic acid) copolymers, and thermosensitive liposome-based systems.

  14. Pore-forming Activity of the Escherichia coli Type III Secretion System Protein EspD*

    PubMed Central

    Chatterjee, Abhishek; Caballero-Franco, Celia; Bakker, Dannika; Totten, Stephanie; Jardim, Armando

    2015-01-01

    Enterohemorrhagic Escherichia coli is a causative agent of gastrointestinal and diarrheal diseases. Pathogenesis associated with enterohemorrhagic E. coli involves direct delivery of virulence factors from the bacteria into epithelial cell cytosol via a syringe-like organelle known as the type III secretion system. The type III secretion system protein EspD is a critical factor required for formation of a translocation pore on the host cell membrane. Here, we show that recombinant EspD spontaneously integrates into large unilamellar vesicle (LUV) lipid bilayers; however, pore formation required incorporation of anionic phospholipids such as phosphatidylserine and an acidic pH. Leakage assays performed with fluorescent dextrans confirmed that EspD formed a structure with an inner diameter of ∼2.5 nm. Protease mapping indicated that the two transmembrane helical hairpin of EspD penetrated the lipid layer positioning the N- and C-terminal domains on the extralumenal surface of LUVs. Finally, a combination of glutaraldehyde cross-linking and rate zonal centrifugation suggested that EspD in LUV membranes forms an ∼280–320-kDa oligomeric structure consisting of ∼6–7 subunits. PMID:26324713

  15. 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.

  16. Injectable long-acting in situ forming systems for Radix Ophiopogonis polysaccharide.

    PubMed

    Shi, XiaoLi; Lin, Xiao; Yao, ChunXia; Shen, Lan; Feng, Yi

    2015-01-01

    In the area of injectable long-acting formulations, the in situ forming system (ISFS) is an attractive alternative for its various superiorities. In this study, both hydrophilic and hydrophobic in situ forming systems, using Poloxamer and sucrose acetate isobutyrate (SAIB) or poly(D,L-lactide-co-glycolide) copolymer (PLGA) as carrier, respectively, were investigated for Radix Ophiopogonis polysaccharide (ROP), a natural anti-myocardial ischemic fructan. A reasonable and applicable range of formulations were selected from each carrier for in vivo study by investigating their rheological property. The results from in vivo evaluation show that relatively promising sustained behaviors were achieved by formulations 24% P407/10% P188, 40% PLGA30k/NMP, and 30% PLGA50k/NMP. Significant differences of drug release kinetics were observed between in situ thermally-induced Poloxamer-based hydrogels and in situ solvent exchange-induced hydrophobic PLGA depots. This suggests that different ISFS could be chosen to provide different application purpose for polysaccharide drugs. In the case of ROP, Poloxamer-based ISFS is promising for short-term acute therapies; however, PLGA-based ISFS might be promising for long-term precaution or/and cure of myocardial ischemia.

  17. 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

    ... required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... Associations § 249.821 Form PILOT, information required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this chapter. This form shall be used by all...

  18. NOISE AND HYSTERESIS IN CHARGED STRIPE, CHECKERBOARD, AND CLUMP FORMING SYSTEMS

    SciTech Connect

    Reichhardt, Charles; Reichhardt, Cynthia J.; Bishop, Alan R.

    2007-05-07

    We numerically examine noise fluctuations and hysteresis phenomena in charged systems that form stripe, labyrinth or clump patterns. It is believed that charge inhomogeneities of this type arise in two-dimensional (2D) quantum hall systems and in electron crystal structures in high temperature superconductors, while related patterns appear in manganites and type-I superconductors. Recent noise and transport experiments in twodimensional electron gases and high temperature superconducting samples revealed both 1/ fα. noise signatures and hysteretic phenomena. Using numerical simulations we show that 1/ fα. noise fluctuations and hysteresis are generic features that occur in charge systems which undergo a type of phase separation that results in stripes, clumps, checkerboards, or other inhomogeneous patterns. We find that these systems exhibit 1/ fα. fluctuations with 1.2 < α < 1.8, rather than simple 1/ f or 1/ f 2 fluctuations. We also propose that the 2D metal insulator transition may be associated with a clump electron glass phase rather than a Wigner glass phase.

  19. 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.

  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. In situ gel-forming AP-57 peptide delivery system for cutaneous wound healing.

    PubMed

    Li, Xiaoling; Fan, Rangrang; Tong, Aiping; Yang, Meijia; Deng, Jiaojiao; Zhou, Liangxue; Zhang, Xiaoning; Guo, Gang

    2015-11-10

    In situ gel-forming system as local drug delivery system in dermal traumas has generated a great interest. Accumulating evidence shows that antimicrobial peptides play pivotal roles in the process of wound healing. Here in this study, to explore the potential application of antimicrobial peptide in wound healing, biodegradable poly(L-lactic acid)-Pluronic L35-poly(L-lactic acid) (PLLA-L35-PLLA) was developed at first. Then based on this polymer, an injectable in situ gel-forming system composed of human antimicrobial peptides 57 (AP-57) loaded nanoparticles and thermosensitive hydrogel was prepared and applied for cutaneous wound healing. AP-57 peptides were enclosed with biocompatible nanoparticles (AP-57-NPs) with high drug loading and encapsulation efficiency. AP-57-NPs were further encapsulated in a thermosensitive hydrogel (AP-57-NPs-H) to facilitate its application in cutaneous wound repair. As a result, AP-57-NPs-H released AP-57 in an extended period and exhibited quite low cytotoxicity and high anti-oxidant activity in vitro. Moreover, AP-57-NPs-H was free-flowing liquid at room temperature, and can form non-flowing gel without any crosslink agent upon applied on the wounds. In vivo wound healing assay using full-thickness dermal defect model of SD rats indicated that AP-57-NPs-H could significantly promote wound healing. At day 14 after operation, AP-57-NPs-H treated group showed nearly complete wound closure of 96.78 ± 3.12%, whereas NS, NPs-H and AP-57-NPs group recovered by about 68.78 ± 4.93%, 81.96 ± 3.26% and 87.80 ± 4.62%, respectively. Histopathological examination suggested that AP-57-NPs-H could promote cutaneous wound healing through enhancing granulation tissue formation, increasing collagen deposition and promoting angiogenesis in the wound tissue. Therefore, AP-57-NPs-H might have potential application in wound healing.

  2. Adsorption kinetics and intermolecular interactions of CO adsorbed on Cu(100) by transient laser reflection-absorption spectroscopy

    SciTech Connect

    Borguet, E.; Dai, H.L.

    1993-12-31

    IR and visible transient laser spectroscopic techniques have been developed to probe adsorption/desorption kinetics and intermolecular interactions of the CO/Cu(100) system. Vibrational spectroscopy, in general, can provide information about the nature of species adsorbed on surfaces e.g. chemical identity, site, orientation and concentration. In the presence of a few percent of CO adsorbed at step/defect sites, the spectra of the CO adsorbed on the terrace sites are greatly perturbed through dynamic-dipole coupling. This perturbation depends strongly on the intermolecular distance and the short-range order of the adsorbates. An analysis of this dynamic-dipole coupling reveals that the local arrangement of adsorbates is dominant by repulsive nearest-neighbor interactions. Successful modeling of the observed lineshapes allows the populations at each site to be determined at all coverages. The authors have also observed non-resonant adsorbate induced changes in both the IR and visible reflectance for a number of different adsorbates. This provides a simple and sensitive optical means of studying adsorption and desorption kinetics.

  3. Controlled transition dipole alignment of energy donor and energy acceptor molecules in doped organic crystals, and the effect on intermolecular Förster energy transfer.

    PubMed

    Wang, Huan; Yue, Bailing; Xie, Zengqi; Gao, Bingrong; Xu, Yuanxiang; Liu, Linlin; Sun, Hongbo; Ma, Yuguang

    2013-03-14

    The orientation factor κ(2) ranging from 0 to 4, which depends on the relative orientation of the transition dipoles of the energy donor (D) and the energy acceptor (A) in space, is one of the pivotal factors deciding the efficiency and directionality of resonance energy transfer (RET) in a D-A molecular system. In this work, tetracene (Tc) and pentacene (Pc) are successfully doped in a trans-1,4-distyrylbenzene (DSB) crystalline lattice to form definite D-A mutually perpendicular transition dipole orientations. The cross D-A dipole arrangement results in an extremely small orientation factor, which is about two orders smaller than that in the disordered films. The energy transfer properties from the host (DSB) to the guest (Tc/Pc) were investigated in detail by steady-state as well as time-resolved fluorescence spectroscopy. Our experimental research results show that the small value of κ(2) allows less or partial energy transfer from the host (DSB) to the guest (Tc) in a wide range of guest concentration, with the Förster distance of around 1.5 nm. By controlling the doping concentrations in the Tc and Pc doubly doped DSB crystals, we demonstrate, as an example, for the first time the application of the restricted energy transfer by D-A cross transition dipole arrangement for preparation of a large-size, white-emissive organic crystal with the CIE coordinates of (0.36, 0.37) approaching an ideal white light. In contrast, Tc is also doped in an anthracene crystalline lattice to form head-to-tail D-A transition dipole alignment, which is proved to be highly effective to promote the intermolecular energy transfer. In this doped system, the orientation factor is relatively large and the Förster distance is around 7 nm.

  4. An automated framework for NMR resonance assignment through simultaneous slice picking and spin system forming.

    PubMed

    Abbas, Ahmed; Guo, Xianrong; Jing, Bing-Yi; Gao, Xin

    2014-06-01

    Despite significant advances in automated nuclear magnetic resonance-based protein structure determination, the high numbers of false positives and false negatives among the peaks selected by fully automated methods remain a problem. These false positives and negatives impair the performance of resonance assignment methods. One of the main reasons for this problem is that the computational research community often considers peak picking and resonance assignment to be two separate problems, whereas spectroscopists use expert knowledge to pick peaks and assign their resonances at the same time. We propose a novel framework that simultaneously conducts slice picking and spin system forming, an essential step in resonance assignment. Our framework then employs a genetic algorithm, directed by both connectivity information and amino acid typing information from the spin systems, to assign the spin systems to residues. The inputs to our framework can be as few as two commonly used spectra, i.e., CBCA(CO)NH and HNCACB. Different from the existing peak picking and resonance assignment methods that treat peaks as the units, our method is based on 'slices', which are one-dimensional vectors in three-dimensional spectra that correspond to certain ([Formula: see text]) values. Experimental results on both benchmark simulated data sets and four real protein data sets demonstrate that our method significantly outperforms the state-of-the-art methods while using a less number of spectra than those methods. Our method is freely available at http://sfb.kaust.edu.sa/Pages/Software.aspx.

  5. The Two Visual Systems Hypothesis: New Challenges and Insights from Visual form Agnosic Patient DF

    PubMed Central

    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

  6. X-filtering for a range of coupling constants: application to the detection of intermolecular NOEs

    NASA Astrophysics Data System (ADS)

    Zangger, Klaus; Oberer, Monika; Keller, Walter; Sterk, Heinz

    2003-02-01

    A new method for heteronuclear X-filtering is presented, which relies on repetitive applications of 90°( 1H)-τ(1/4 1J HC)-180°( 1H, 13C)-τ(1/4 1J HC)-90°( 1H, 13C)- PFG building blocks employing gradient-mediated suppression of magnetization built up for directly heteronuclear coupled protons. Thereby, a range of heteronuclear coupling constants can be suppressed by varying the delays of scalar coupling evolution both within and between individual transients. To achieve efficient destruction of 13C-coupled protons in macromolecular systems, the scalar coupling evolution delays were optimized using simulated annealing by including transverse relaxation effects. With a combination of regular hard pulses, delays and pulsed field gradients only, this method yields sufficient X-filtering to allow the observation of intermolecular nuclear overhauser effects in a molecular complex consisting of a 13C, 15N double-labeled, and an unlabeled protein. This is achieved by exciting magnetization of 12C- and 14N-bound protons and detecting 13C-bound 1H magnetization in a 3D 13C-filtered, 13C-edited NOESY-HSQC experiment. The method is tested on the 18 kDa homodimeric bacterial antidote ParD.

  7. Modeling and simulation of magnetic resonance imaging based on intermolecular multiple quantum coherences

    NASA Astrophysics Data System (ADS)

    Cai, Congbo; Dong, Jiyang; Cai, Shuhui; Cheng, En; Chen, Zhong

    2006-11-01

    Intermolecular multiple quantum coherences (iMQCs) have many potential applications since they can provide interaction information between different molecules within the range of dipolar correlation distance, and can provide new contrast in magnetic resonance imaging (MRI). Because of the non-localized property of dipolar field, and the non-linear property of the Bloch equations incorporating the dipolar field term, the evolution behavior of iMQC is difficult to deduce strictly in many cases. In such cases, simulation studies are very important. Simulation results can not only give a guide to optimize experimental conditions, but also help analyze unexpected experimental results. Based on our product operator matrix and the K-space method for dipolar field calculation, the MRI simulation software was constructed, running on Windows operation system. The non-linear Bloch equations are calculated by a fifth-order Cash-Karp Runge-Kutta formulism. Computational time can be efficiently reduced by separating the effects of chemical shifts and strong gradient field. Using this software, simulation of different kinds of complex MRI sequences can be done conveniently and quickly on general personal computers. Some examples were given. The results were discussed.

  8. 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.

  9. Study of Self Assembly Systems Formed by Malic Acid and Alkyloxy Benzoic Acids

    NASA Astrophysics Data System (ADS)

    Vijayakumar, Vellalapalayam Nallagounder; Madhu Mohan, Mathukumalli Lakshmi Narayana

    2010-12-01

    Self assembly systems formed by malic acid and alkyloxy benzoic acids are characterized. The ferroelectric ingredient malic acid formed double hydrogen bond with p-n-alkyloxy benzoic acids. Various hydrogen bonded complexes have been synthesized with malic acid and pentyl to dodecyloxy benzoic acid, respectively. Fourier transformation infrared (FTIR) studies confirm the hydrogen bond formation. Polarizing optical microscopic (POM) studies revealed the textural information while the transition and enthalpy values are calculated from differential scanning calorimetry (DSC) studies. A phase diagram has been constructed from the POMand DSC studies. A new smectic ordering, smectic X*, has been identified which exhibits a finger print type texture. This phase has been characterized by POM, DSC, helix, and tilt angle studies. The transition from traditional cholesteric to smectic X* phase is observed to be first order. The tilt angle data in this phase has been fitted to a power law and the temperature variation of the tilt angle follows mean field theory predictions. The results of FTIR, POM, DSC, tilt angle, and helicoidal studies are discussed.

  10. 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.

  11. Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

    DOE PAGES

    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

  12. Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

    SciTech Connect

    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 effects 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.

  13. Carboxylated and Uncarboxylated Forms of Osteocalcin Directly Modulate the Glucose Transport System and Inflammation in Adipocytes

    PubMed Central

    Hill, H. S.; Grams, J.; Walton, R. G.; Liu, J.; Moellering, D. R.; Garvey, W. T.

    2017-01-01

    Osteocalcin is secreted by osteoblasts and improves insulin sensitivity in vivo, although mechanisms remain unclear. We tested the hypothesis that osteocalcin directly modulates cell biology in insulin-targeted peripheral tissues. In L-6 myocytes, osteocalcin stimulated glucose transport both in the absence (basal) and presence of insulin. Similarly, in primary cultured adipocytes, both carboxylated and uncarboxylated osteocalcin increased basal and insulin-stimulated glucose transport as well as insulin sensitivity. Osteocalcin also increased basal and insulin-stimulated glucose oxidation, though there was no effect on fatty acid synthesis or lipolysis. In primary-cultured adipocytes, both forms of osteocalcin suppressed secretion of tumor necrosis factor alpha into the media; however, only carboxylated osteocalcin suppressed interleukin 6 release, and neither form of osteocalcin modulated monocyte chemoattractant protein-1 secretion. Both carboxylated and uncarboxylated osteocalcin increased secretion of adiponectin and the anti-inflammatory cytokine interleukin 10. In conclusion, both carboxylated and uncarboxylated osteocalcin directly increase glucose transport in adipocytes and muscle cells, while suppressing proinflammatory cytokine secretion and stimulating interleukin 10 and adiponectin release. Thus, these results provide a mechanism for the insulin-sensitizing effects of osteocalcin and help elucidate the role that bone plays in regulating systemic metabolism. PMID:24554534

  14. Dosage Form Developments of Nanosuspension Drug Delivery System for Oral Administration Route.

    PubMed

    Chen, Ang; Shi, Ye; Yan, Zhiqiang; Hao, Hongxun; Zhang, Yong; Zhong, Jian; Hou, Huiming

    2015-01-01

    A large amount of new drug candidates are practically insoluble in aqueous solvents and are even simultaneously poorly soluble in organic solvents. Nanosuspension drug delivery system (DDS) was firstly developed in 1994 and has attracted more and more attention as a formation solution for the poorly soluble drugs. By nansizing the poorly soluble drugs, nanosuspensions have several outstanding advantages for drug delivery. Among many administration routes of drug delivery, oral administration is the most preferred route due to its advantages such as ease of ingestion, versatility to accommodate various types of drug candidates, low production cost, high safety, good patient compliance, and pain avoidance. Current marketed pharmaceutical nanosuspension DDS products are mostly for oral administration. This review is to systematically summarize the nanosuspension DDS dosage form developments of poorly soluble drugs for oral administration use.

  15. On the Shape of Meissner Solutions to a Limiting Form of Ginzburg-Landau Systems

    NASA Astrophysics Data System (ADS)

    Xiang, Xingfei

    2016-12-01

    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.

  16. Quantitative theory of a relaxation function in a glass-forming system.

    PubMed

    Lerner, Edan; Procaccia, Itamar

    2008-08-01

    We present a quantitative theory for a relaxation function in a simple glass-forming model (binary mixture of particles with different interaction parameters). It is shown that the slowing down is caused by the competition between locally favored regions (clusters) that are long-lived but each of which relaxes as a simple function of time. Without the clusters, the relaxation of the background is simply determined by one typical length, which we deduce from an elementary statistical mechanical argument. The total relaxation function (which depends on time in a nontrivial manner) is quantitatively determined as a weighted sum over the clusters and the background. The "fragility" in this system can be understood quantitatively since it is determined by the temperature dependence of the number fractions of the locally favored regions.

  17. 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.

  18. High-resolution absorptive intermolecular multiple-quantum coherence NMR spectroscopy under inhomogeneous fields

    NASA Astrophysics Data System (ADS)

    Lin, Meijin; Lin, Yanqin; Chen, Xi; Cai, Shuhui; Chen, Zhong

    2012-01-01

    Intermolecular multiple-quantum coherence (iMQC) is capable of improving NMR spectral resolution using a 2D shearing manipulation method. A pulse sequence termed CT-iDH, which combines intermolecular double-quantum filter (iDQF) with a modified constant-time (CT) scheme, is designed to achieve fast acquisition of high-resolution intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) spectra without strong coupling artifacts. Furthermore, double-absorption lineshapes are first realized in 2D intermolecular multi-quantum coherences (iMQCs) spectra under inhomogeneous fields through a combination of iZQC and iDQC signals to double the resolution without loss of sensitivity. Theoretically the spectral linewidth can be further reduced by half compared to original iMQC high-resolution spectra. Several experiments were performed to test the feasibility of the new method and the improvements are evaluated quantitatively. The study suggests potential applications for in vivo spectroscopy.

  19. 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.

  20. 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

  1. A triple protostar system formed via fragmentation of a gravitationally unstable disk.

    PubMed

    Tobin, John J; Kratter, Kaitlin M; Persson, Magnus V; Looney, Leslie W; Dunham, Michael M; Segura-Cox, Dominique; Li, Zhi-Yun; Chandler, Claire J; Sadavoy, Sarah I; Harris, Robert J; Melis, Carl; Pérez, Laura M

    2016-10-27

    Binary and multiple star systems are a frequent outcome of the star formation process and as a result almost half of all stars with masses similar to that of the Sun have at least one companion star. Theoretical studies indicate that there are two main pathways that can operate concurrently to form binary/multiple star systems: large-scale fragmentation of turbulent gas cores and filaments or smaller-scale fragmentation of a massive protostellar disk due to gravitational instability. Observational evidence for turbulent fragmentation on scales of more than 1,000 astronomical units has recently emerged. Previous evidence for disk fragmentation was limited to inferences based on the separations of more-evolved pre-main sequence and protostellar multiple systems. The triple protostar system L1448 IRS3B is an ideal system with which to search for evidence of disk fragmentation as it is in an early phase of the star formation process, it is likely to be less than 150,000 years old and all of the protostars in the system are separated by less than 200 astronomical units. Here we report observations of dust and molecular gas emission that reveal a disk with a spiral structure surrounding the three protostars. Two protostars near the centre of the disk are separated by 61 astronomical units and a tertiary protostar is coincident with a spiral arm in the outer disk at a separation of 183 astronomical units. The inferred mass of the central pair of protostellar objects is approximately one solar mass, while the disk surrounding the three protostars has a total mass of around 0.30 solar masses. The tertiary protostar itself has a minimum mass of about 0.085 solar masses. We demonstrate that the disk around L1448 IRS3B appears susceptible to disk fragmentation at radii between 150 and 320 astronomical units, overlapping with the location of the tertiary protostar. This is consistent with models for a protostellar disk that has recently undergone gravitational instability

  2. A triple protostar system formed via fragmentation of a gravitationally unstable disk

    NASA Astrophysics Data System (ADS)

    Tobin, John J.; Kratter, Kaitlin M.; Persson, Magnus V.; Looney, Leslie W.; Dunham, Michael M.; Segura-Cox, Dominique; Li, Zhi-Yun; Chandler, Claire J.; Sadavoy, Sarah I.; Harris, Robert J.; Melis, Carl; Pérez, Laura M.

    2016-10-01

    Binary and multiple star systems are a frequent outcome of the star formation process and as a result almost half of all stars with masses similar to that of the Sun have at least one companion star. Theoretical studies indicate that there are two main pathways that can operate concurrently to form binary/multiple star systems: large-scale fragmentation of turbulent gas cores and filaments or smaller-scale fragmentation of a massive protostellar disk due to gravitational instability. Observational evidence for turbulent fragmentation on scales of more than 1,000 astronomical units has recently emerged. Previous evidence for disk fragmentation was limited to inferences based on the separations of more-evolved pre-main sequence and protostellar multiple systems. The triple protostar system L1448 IRS3B is an ideal system with which to search for evidence of disk fragmentation as it is in an early phase of the star formation process, it is likely to be less than 150,000 years old and all of the protostars in the system are separated by less than 200 astronomical units. Here we report observations of dust and molecular gas emission that reveal a disk with a spiral structure surrounding the three protostars. Two protostars near the centre of the disk are separated by 61 astronomical units and a tertiary protostar is coincident with a spiral arm in the outer disk at a separation of 183 astronomical units. The inferred mass of the central pair of protostellar objects is approximately one solar mass, while the disk surrounding the three protostars has a total mass of around 0.30 solar masses. The tertiary protostar itself has a minimum mass of about 0.085 solar masses. We demonstrate that the disk around L1448 IRS3B appears susceptible to disk fragmentation at radii between 150 and 320 astronomical units, overlapping with the location of the tertiary protostar. This is consistent with models for a protostellar disk that has recently undergone gravitational instability

  3. 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.

  4. Re-forming medical delivery systems: economic organization and dynamics of regional planning and managed competition.

    PubMed

    Perkins, B B

    1999-01-01

    This paper compares structural components of medical delivery in two major systemwide reform strategies in the United States. Commonly portrayed in terms of opposing ideologies of planning vs. market reform, regional organization and managed competition have promoted similar structural elements and geographic configurations. They both support growth of institution-based specialized teams and hospital consolidation. They both differentiate hospital care into vertically integrated levels, and develop regions as the key production and market area for organized delivery systems. System-wide management or regulation in each has tried to control allocation of resources, capital investment, and competition. Developed in the context of large-scale industrial production, these components have inherent economic dynamics and together they shape the market structure of medical care. The final section briefly considers the locus of power in the two reform approaches and the implication for choosing mechanisms of reform. It also notes that despite their rhetoric, the two strategies do not shape their services according to information about population benefit. The conclusion points out that the commonalities in structure and power demonstrate the dominance of economic organization in medical reform and contribute to the wide acceptance of this business form of organization as an international model.

  5. A biorelevant in vitro release/permeation system for oral transmucosal dosage forms.

    PubMed

    Delvadia, Poonam R; Barr, William H; Karnes, H Thomas

    2012-07-01

    This research describes the development and validation of a biorelevant in vitro release/permeation system to predict the in vivo performance of oral transmucosal dosage forms. The system is a biorelevant bidirectional transmucosal apparatus which allows better simulation of oral cavity physiological variables in comparison to compendial dissolution apparatuses and therefore may be a better predictor of in vivo behavior. The feasibility of the bidirectional apparatus was studied using smokeless tobacco (snus) as a model oral transmucosal product. In this research, nicotine release and permeation was investigated from commercially available snus using a modified USP IV flow-through apparatus, a commercially available vertical diffusion cell and a fabricated novel bidirectional transmucosal apparatus. The percent nicotine released/permeated was utilized as an input function for the prediction of in vivo plasma nicotine profiles by back calculation based on the Wagner-Nelson method. The prediction errors in C(max) and AUC(0-∞) with the USP IV flow-through device, vertical diffusion cell and novel apparatus were 4.03, 22.85 and 1.59 and -5.85, 5.85 and -9.27% respectively. This work demonstrated the suitability of the novel bidirectional transmucosal apparatus for predicting the in vivo behavior of oral transmucosal products.

  6. 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.

  7. Waterhole form and process in the anastomosing channel system of Cooper Creek, Australia

    NASA Astrophysics Data System (ADS)

    Knighton, A. David; Nanson, Gerald C.

    2000-10-01

    One of the most distinctive features of Cooper Creek's anastomosing channel system is the preponderance of waterholes, enlarged segments of channel ranging in length from 100 m to over 20 km. Enlargement occurs in both the width and depth dimensions to give bankfull cross-sectional areas four to eight times the average size of individual anastomosing channels. The anastomosing system is cut into a floodplain of subtle relief but depths of incision can be highly variable, giving rise to changes in the degree of anastomosis as different sets of channels are activated during the filling stage of a flood. Also, cross-sectional form and bed topography can vary markedly over short channel distances, which has implications for local flow conditions and erosive potential. Hydraulic geometry analyses suggest that cross-sectional area adjusts much more readily than velocity to increasing discharge in waterholes, particularly if there is limited lateral confinement. Consequently, velocities tend to be rather modest across a wide spectrum of flows, with average values rarely reaching 1 m s -1. Nevertheless, observations made during a 1:20-year flood reveal a deeply penetrative band of relatively high velocity in one waterhole, suggesting that localized values of bed shear could be quite large even when sectional averages are moderate. Waterholes appear to be a product of the present regime, since they concentrate flow from both feeder channels and the floodplain during flood discharges. In several respects they resemble chains-of-ponds morphology [Eyles, R.J., 1977. Birchams Creek: the transition from a chain of ponds to a gully. Aust. Geogr. Stud. 15, 146-157.], and could represent the discontinuous sections of a present-day channel, which cannot be maintained in that form over its entire length. That the one waterhole to accommodate the entire cross-valley flow at bankfull stage (Meringhina Waterhole) has cross-sectional dimensions similar to those predicted by appropriate

  8. Distributive Fluvial Systems of the Chaco Plain - Satellite Image Assessment of Fluvial Form and Facies Distributions

    NASA Astrophysics Data System (ADS)

    Weissmann, G. S.; Hartley, A. J.; Scuderi, L.; Bhattacharyya, P.; Buehler, H.; Leleu, S.; Mather, A.

    2009-12-01

    Distributive fluvial systems (DFS) dominate fluvial deposition inside modern continental sedimentary basins and are particularly extensive in modern foreland basins. The largest of these DFS are found in the Chaco Plain, Andean Foreland Basin, South America. We use published literature, field and satellite data (Landsat, Modis, and SRTM) to construct preliminary hypotheses about the geomorphic form and fluvial facies distributions on the DFSs in this basin. The Pilcomayo River DFS extends over 700 km from apex to toe. The river enters the DFS apex as a large braided river with a bankfull channel width of 2500 m. Gravels and cobbles occur in terraces cut through the apex. At ~70-km downstream the bankfull channel width is ~2000 m and the channel is dominated by fine sand with cut banks 2-3 m high. The proximal channel belt is surrounded by floodplain sediments, however many sandy abandoned channel belts are present across the DFS, indicating a mobile channel system. Abandoned channels have a similar form to the modern channel, with minor reworking by underfit meandering streams. At ~75-km downfan, the river system diminishes in size (bankfull channel width up to 2 km but generally <1.5 km) and becomes increasingly sinuous in planform. This point appears to serve as a node for a series of recently abandoned meander belts and splays associated with discrete channels surrounded by floodplain material. At 100 km downstream the planform is highly sinuous and bankfull width has decreased to 1500 m or less. Downstream of this area abandoned meander belts dominate along the flanks of the modern channel with oxbow lakes present adjacent to the active channel. At 150 km downstream the bankfull channel belt width is 500 m or less and the river bifurcates into splays and multiple active channels which extend downstream for a further 200 km. Vegetation maps derived from Modis imagery indicate an increase in tree density around the DFS at this elevation (230 m). Along the distal

  9. Localization of the dominant non-enzymatic intermolecular cross-linking sites on fibrous collagen.

    PubMed

    Chiue, Hiroko; Yamazoye, Tsutako; Matsumura, Sueo

    2015-06-05

    Previous studies have shown that fibrous collagen undergoes intermolecular cross-linking at multiple sites of the elongated triple-helical regions among adjacent juxtaposed collagen molecules on incubation with a very high concentration of reducing sugar such as 200 mM ribose, and the similarity of the changes in its physicochemical properties to that of senescent collagen aged in vivo has been emphasized. In the present study, however, it was found that when incubated with less than 30 mM ribose, fibrous collagen underwent intermolecular cross-linking primarily between the telopeptide region of a collagen molecule and the triple-helical region of another adjacent collagen molecule, and intermolecular cross-linking between the triple-helical regions of adjacent collagen molecules was very small. Physiological significance of the previous studies thus needs to be reevaluated.

  10. Definition and computation of intermolecular contact in liquids using additively weighted Voronoi tessellation.

    PubMed

    Isele-Holder, Rolf E; Rabideau, Brooks D; Ismail, Ahmed E

    2012-05-10

    We present a definition of intermolecular surface contact by applying weighted Voronoi tessellations to configurations of various organic liquids and water obtained from molecular dynamics simulations. This definition of surface contact is used to link the COSMO-RS model and molecular dynamics simulations. We demonstrate that additively weighted tessellation is the superior tessellation type to define intermolecular surface contact. Furthermore, we fit a set of weights for the elements C, H, O, N, F, and S for this tessellation type to obtain optimal agreement between the models. We use these radii to successfully predict contact statistics for compounds that were excluded from the fit and mixtures. The observed agreement between contact statistics from COSMO-RS and molecular dynamics simulations confirms the capability of the presented method to describe intermolecular contact. Furthermore, we observe that increasing polarity of the surfaces of the examined molecules leads to weaker agreement in the contact statistics. This is especially pronounced for pure water.

  11. 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.

  12. Optical BEAMTAP Beam-Forming and Jammer-Nulling System for Broadband Phased-Array Antennas

    NASA Astrophysics Data System (ADS)

    Kriehn, Gregory; Kiruluta, Andrew; Silveira, Paulo E. X.; Weaver, Sam; Kraut, Shawn; Wagner, Kelvin; Weverka, R. Ted; Griffiths, Lloyd

    2000-01-01

    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.

  13. 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.

  14. 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.

  15. 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

    ... 17 Commodity and Securities Exchanges 4 2014-04-01 2014-04-01 false Form PILOT, information required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... Associations § 249.821 Form PILOT, information required of self-regulatory organizations operating...

  16. 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

    ... 17 Commodity and Securities Exchanges 3 2011-04-01 2011-04-01 false Form PILOT, information required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... Associations § 249.821 Form PILOT, information required of self-regulatory organizations operating...

  17. 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

    ... 17 Commodity and Securities Exchanges 3 2013-04-01 2013-04-01 false Form PILOT, information required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... Associations § 249.821 Form PILOT, information required of self-regulatory organizations operating...

  18. 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

    ... 17 Commodity and Securities Exchanges 3 2012-04-01 2012-04-01 false Form PILOT, information required of self-regulatory organizations operating pilot trading systems pursuant to § 240.19b-5 of this... Associations § 249.821 Form PILOT, information required of self-regulatory organizations operating...

  19. 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…

  20. 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.

  1. Intermolecular associations in an equimolar formamide-water solution based on neutron scattering and DFT calculations.

    PubMed

    Abdelmoulahi, Hafedh; Ghalla, Houcine; Nasr, Salah; Darpentigny, Jacques; Bellissent-Funel, Marie-Claire

    2016-10-07

    In the present work, we have investigated the intermolecular associations of formamide with water in an equimolar formamide-water solution (FA-Water) by means of neutron scattering in combination with density functional theory calculations. The neutron scattering data were analyzed to deduce the structure factor SM(q) and the intermolecular pair correlation function gL(r). By considering different hydrogen bonded FA-Water associations, it has been shown that some of them describe well the local order in the solution. Natural bond orbital and atoms in molecules analyses have been performed to give more insight into the properties of hydrogen bonds involved in the more probable models.

  2. 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.

  3. Generalized spin-ratio scaled MP2 method for accurate prediction of intermolecular interactions for neutral and ionic species

    NASA Astrophysics Data System (ADS)

    Tan, Samuel; Barrera Acevedo, Santiago; Izgorodina, Ekaterina I.

    2017-02-01

    The accurate calculation of intermolecular interactions is important to our understanding of properties in large molecular systems. The high computational cost of the current "gold standard" method, coupled cluster with singles and doubles and perturbative triples (CCSD(T), limits its application to small- to medium-sized systems. Second-order Møller-Plesset perturbation (MP2) theory is a cheaper alternative for larger systems, although at the expense of its decreased accuracy, especially when treating van der Waals complexes. In this study, a new modification of the spin-component scaled MP2 method was proposed for a wide range of intermolecular complexes including two well-known datasets, S22 and S66, and a large dataset of ionic liquids consisting of 174 single ion pairs, IL174. It was found that the spin ratio, ɛΔ s=E/INT O SEIN T S S , calculated as the ratio of the opposite-spin component to the same-spin component of the interaction correlation energy fell in the range of 0.1 and 1.6, in contrast to the range of 3-4 usually observed for the ratio of absolute correlation energy, ɛs=E/OSES S , in individual molecules. Scaled coefficients were found to become negative when the spin ratio fell in close proximity to 1.0, and therefore, the studied intermolecular complexes were divided into two groups: (1) complexes with ɛΔ s< 1 and (2) complexes with ɛΔ s≥ 1 . A separate set of coefficients was obtained for both groups. Exclusion of counterpoise correction during scaling was found to produce superior results due to decreased error. Among a series of Dunning's basis sets, cc-pVTZ and cc-pVQZ were found to be the best performing ones, with a mean absolute error of 1.4 kJ mol-1 and maximum errors below 6.2 kJ mol-1. The new modification, spin-ratio scaled second-order Møller-Plesset perturbation, treats both dispersion-driven and hydrogen-bonded complexes equally well, thus validating its robustness with respect to the interaction type ranging from ionic

  4. Sol-forming oil-displacing system intended to enhance oil recovery from deposits with difficult-to-recover reserves

    NASA Astrophysics Data System (ADS)

    Kozlov, V. V.; Altunina, L. K.; Stasyeva, L. A.; Kuvshinov, V. A.

    2016-11-01

    The paper presents the results of laboratory tests of the sol-forming NINKA®-Z system intended to enhance oil recovery from deposits with difficult-to-recover reserves. The kinetic and rheological features of solation in the oil-displacing system have been investigated. A physical modeling of the oil displacement process was carried out under the conditions of a heterogeneous reservoir at a low temperature using the sol-forming NINKA®-Z system. The investigations have proved its high efficiency, and the system was recommended for pilot tests.

  5. Holographic metasurface systems for beam-forming and imaging (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Smith, David R.

    2016-09-01

    Metamaterials offer an alternative perspective for the design of new materials and devices. The advantage of the metamaterial description is that certain device solutions can more easily be recognized. Here, we discuss broadly the impact of the metamaterial design philosophy on quasi-optical apertures based on patterned holographic metasurfaces. In a guided wave format, in which radiating complementary metamaterial irises are patterned on the upper plate of a microstrip or parallel plate waveguide, the reference wave is equivalent to the guided wave and the entire structure becomes a compact, efficient holographic, aperture antenna. We have developed a millimeter-wave imaging system that makes use of a set of complementary metamaterial waveguide panels to form a frequency-diverse aperture. In this context, the metamaterial aperture produces a complex radiation pattern that varies spatially as a function of the driving frequency; a frequency sweep over a selected bandwidth thus illuminates a region of space with a set of distinct radiation patterns. Collecting the returned signal reflected by illuminated objects within the scene, a set of measurements can be made from which an image of the scene can be reconstructed. This imaging application provides a useful example of the introduction, integration and optimization of a metamaterial aperture into a complete system, where all other aspects of the system—including algorithms, calibration, software and electronics—must be tailored for the particulars of the metamaterial component. As metamaterials transition from science to technology, these aspects may prove just as challenging and interesting as the underlying metamaterial components.

  6. Sparse electrocardiogram signals recovery based on solving a row echelon-like form of system.

    PubMed

    Cai, Pingmei; Wang, Guinan; Yu, Shiwei; Zhang, Hongjuan; Ding, Shuxue; Wu, Zikai

    2016-02-01

    The study of biology and medicine in a noise environment is an evolving direction in biological data analysis. Among these studies, analysis of electrocardiogram (ECG) signals in a noise environment is a challenging direction in personalized medicine. Due to its periodic characteristic, ECG signal can be roughly regarded as sparse biomedical signals. This study proposes a two-stage recovery algorithm for sparse biomedical signals in time domain. In the first stage, the concentration subspaces are found in advance. Then by exploiting these subspaces, the mixing matrix is estimated accurately. In the second stage, based on the number of active sources at each time point, the time points are divided into different layers. Next, by constructing some transformation matrices, these time points form a row echelon-like system. After that, the sources at each layer can be solved out explicitly by corresponding matrix operations. It is noting that all these operations are conducted under a weak sparse condition that the number of active sources is less than the number of observations. Experimental results show that the proposed method has a better performance for sparse ECG signal recovery problem.

  7. 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.

  8. Development and evaluation of in situ gel-forming system for sustained delivery of insulin.

    PubMed

    Dhawan, Sanju; Kapil, Rishi; Kapoor, Deepak N

    2011-03-01

    Phase-sensitive in situ gel-forming controlled release formulations of insulin were prepared using poly(lactide-co-glycolide) and a solvent system consisting of various proportions of benzyl benzoate and benzyl alcohol. The in vitro release samples of formulations were assayed for insulin content by enzyme linked immunosorbent assay. Sodium dodecyl sulfate polyacrylamide gel electrophoresis and circular dichroism spectroscopy studies of released insulin confirmed its conformational stability. The stability of insulin in the formulation was assessed using Fourier transform infrared spectroscopy. Rheological properties of the formulations, assessed under isothermal conditions, showed dilatant behavior of all the formulations. In vivo studies were carried out on the optimized formulations vis-à-vis pure insulin in mice and blood glucose levels were monitored for 15 days. Mean percentage reduction in blood glucose levels was calculated in all the animals and the results analyzed using ANOVA. The studies construed better pharmacodynamic response for the two optimized formulations in controlling the blood glucose levels vis-à-vis routine once-a-day administration of insulin. The subcutaneous tissues, further subjected to scanning electron microscopy studies and histopathological examinations, ascertained the biocompatibility of the formulation.

  9. Development and evaluation of in situ gel forming system for sustained delivery of cyclosporine.

    PubMed

    Dhawan, Sanju; Kapil, Rishi; Kapoor, Deepak N; Kumar, Manoj

    2009-10-01

    Phase-sensitive in situ gel forming controlled release formulations of cyclosporine were prepared using poly (lactide-co-glycolide) and a solvent system consisting of various proportions of benzyl benzoate and benzyl alcohol. Uniformity of content of cyclosporine in the formulation and in vitro release samples was determined by radio immune assay (RIA). FTIR and CD spectroscopy ratified the conformational stability of cyclosporine in the formulation and in vitro release samples, respectively. Rheological properties of the formulations, assessed under isothermal conditions, showed dilatant behavior of all the formulations. In vivo studies were carried out on the optimized formulations vis-à-vis pure cyclosporine in rats and drug levels were monitored for 13 days. Mean plasma concentration of cyclosporine was calculated for all the animals and pharmacokinetic parameters were determined using Win NonLin software. The studies construed better regulation of plasma drug levels with the optimized formulation vis-à-vis routine once-a-day administration of cyclosporine. The subcutaneous tissues, further subjected to histopathological examinations ascertained the biocompatibility of the formulation.

  10. 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.

  11. Ependymal cells of chordate larvae are stem-like cells that form the adult nervous system.

    PubMed

    Horie, Takeo; Shinki, Ryoko; Ogura, Yosuke; Kusakabe, Takehiro G; Satoh, Nori; Sasakura, Yasunori

    2011-01-27

    In ascidian tunicates, the metamorphic transition from larva to adult is accompanied by dynamic changes in the body plan. For instance, the central nervous system (CNS) is subjected to extensive rearrangement because its regulating larval organs are lost and new adult organs are created. To understand how the adult CNS is reconstructed, we traced the fate of larval CNS cells during ascidian metamorphosis by using transgenic animals and imaging technologies with photoconvertible fluorescent proteins. Here we show that most parts of the ascidian larval CNS, except for the tail nerve cord, are maintained during metamorphosis and recruited to form the adult CNS. We also show that most of the larval neurons disappear and only a subset of cholinergic motor neurons and glutamatergic neurons are retained. Finally, we demonstrate that ependymal cells of the larval CNS contribute to the construction of the adult CNS and that some differentiate into neurons in the adult CNS. An unexpected role of ependymal cells highlighted by this study is that they serve as neural stem-like cells to reconstruct the adult nervous network during chordate metamorphosis. Consequently, the plasticity of non-neuronal ependymal cells and neuronal cells in chordates should be re-examined by future studies.

  12. A proposal for a drug product Manufacturing Classification System (MCS) for oral solid dosage forms.

    PubMed

    Leane, Michael; Pitt, Kendal; Reynolds, Gavin

    2015-01-01

    This paper proposes the development of a drug product Manufacturing Classification System (MCS) based on processing route. It summarizes conclusions from a dedicated APS conference and subsequent discussion within APS focus groups and the MCS working party. The MCS is intended as a tool for pharmaceutical scientists to rank the feasibility of different processing routes for the manufacture of oral solid dosage forms, based on selected properties of the API and the needs of the formulation. It has many applications in pharmaceutical development, in particular, it will provide a common understanding of risk by defining what the "right particles" are, enable the selection of the best process, and aid subsequent transfer to manufacturing. The ultimate aim is one of prediction of product developability and processability based upon previous experience. This paper is intended to stimulate contribution from a broad range of stakeholders to develop the MCS concept further and apply it to practice. In particular, opinions are sought on what API properties are important when selecting or modifying materials to enable an efficient and robust pharmaceutical manufacturing process. Feedback can be given by replying to our dedicated e-mail address (mcs@apsgb.org); completing the survey on our LinkedIn site; or by attending one of our planned conference roundtable sessions.

  13. Hydrogen bonding: part 78. Ab initio molecular orbital study of intra- and intermolecular hydrogen bonding in choline and betaine and their compounds with HF and H 2O

    NASA Astrophysics Data System (ADS)

    Harmon, K. M.; Avci, G. F.; Madeira, S. L.; Mounts, P. A.; Thiel, A. C.

    2001-10-01

    We previously prepared several compounds of the zwitterions [(CH 3) 3NCH 2CH 2O] 0 (deprotonated choline, herein named cholaine) and [(CH 3) 3NCH 2CO 2] 0 (betaine) and proposed structures based on infrared spectroscopy. We now examine these compounds with use of ab initio molecular orbital methods to further elucidate possible structure. These calculations demonstrate that: (1) cholaine and betaine both have internal CHO hydrogen bonds, and these are retained in some form in all other compounds. (2) Cholaine hydrate and hydrofluoride and betaine hydrofluoride monomers have covalent three-center hydrogen bonds between H 2O or HF and negative zwitterion oxygen, and additional CHX hydrogen bonds to H 2O oxygen or HF fluorine. (3) Cholaine monohydrate and cholaine hydrofluoride monohydrate form dimers of Ci symmetry which contain planar C2 h (H 2O·O) 2 and (HOH·F) 2 clusters. (4) Cholaine hydrofluoride forms head-to-tail dimers bound by intermolecular CHX hydrogen bonds; this arrangement could lead to extended linear structures in the solid state. (5) Betaine hydrofluoride, in contrast, forms a tightly bound discrete dimeric unit in which two molecules join in a head-to-head manner held together by five intermolecular hydrogen bonds and by the mutual proximities of negative fluorides to positive nitrogens.

  14. Studies on tolfenamic acid-chitosan intermolecular interactions: effect of pH, polymer concentration and molecular weight.

    PubMed

    Ahmed, Sofia; Sheraz, Muhammad Ali; Rehman, Ihtesham Ur

    2013-06-01

    Solid-state properties of tolfenamic acid (TA) and its complexes with chitosan (CT) have been studied. Effect of medium pH, molecular weight of polymer and its different concentrations on these TA-CT complexes were studied in detail. Low and medium molecular weight CT have been used in different ratios at pH ranging from 4 to 6 and freeze-drying technique has been employed to modify the appearance of crystalline TA. Physical properties of the formed complexes have been studied by employing X-ray diffraction, differential scanning calorimetry and scanning electron microscopy; chemical structure has been studied using Fourier transform infrared spectroscopy. The results showed that both forms of the polymer exhibited complete conversion in 1:8 ratio at pH 4, 1:4 at pH 5 and 1:1 at pH 6 indicating a marked effect of pH on drug-polymer complexation. The percent crystallinity calculations indicated low molecular weight CT slightly more effective than the other form. No changes in the complexes have been observed during the 12 week storage under controlled conditions. Both forms of CT at different pH values indicated retardation of recrystallization in TA during cooling of the melt from 1:1 ratios exhibiting formation of strong intermolecular hydrogen bonding between the drug and the polymer.

  15. Intermolecular vibrations and vibrational dynamics of a phenol⋯methanol binary complex studied by LIF spectroscopy

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, Deb Pratim; Biswas, Souvick; Chakraborty, Tapas

    2017-04-01

    Low-frequency intermolecular vibrations in S0 and S1 states of p-fluorophenol (pFP) methanol binary complex have been studied using laser induced fluorescence (LIF) spectroscopy in a supersonic jet expansion. Vibrational fundamentals of five such modes show up in fluorescence excitation (FE) spectrum, and corresponding ground state frequencies are obtained measuring disperse fluorescence (DF) spectra. Signatures of strong coupling between the hydrogen bond stretching fundamental (σ01) and a ring mode of pFP moiety in S1 state are revealed. In comparison with the analogous pFP-water complex, the present system displays very low threshold (∼170 cm-1) for vibrational energy relaxation in S1 state.

  16. Tandem intermolecular Suzuki coupling/intramolecular vinyl triflate-arene coupling.

    PubMed

    Willis, Michael C; Claverie, Christelle K; Mahon, Mary F

    2002-04-21

    Treatment of a benzyl substituted meso-ditriflate with boronic acids in the presence of palladium acetate, triphenylphosphine and caesium fluoride results in intermolecular Suzuki coupling followed by vinyl triflate-arene cyclisation to provide, in high yields, single regioisomers of tricyclic-carbocycles.

  17. Selective intermolecular amination of C-H bonds at tertiary carbon centers.

    PubMed

    Roizen, Jennifer L; Zalatan, David N; Du Bois, J

    2013-10-18

    C-H insertion: A method for intermolecular amination of tertiary CH bonds is described that uses limiting amounts of substrate and a convenient phenol-derived nitrogen source. Structure-selectivity and mechanistic studies suggest that steric interaction between the substrate and active oxidant is the principal determinant of product selectivity.

  18. 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…

  19. Intermolecular C-H Quaternary Alkylation of Aniline Derivatives Induced by Visible-Light Photoredox Catalysis.

    PubMed

    Cheng, Jie; Deng, Xia; Wang, Guoqiang; Li, Ying; Cheng, Xu; Li, Guigen

    2016-09-16

    The intermolecular direct C-H alkylation of aniline derivatives with α-bromo ketones to build a quaternary carbon center was reported with a visible-light catalysis procedure. The reaction covers a variety of functional groups with good to excellent yields. A regioselectivity favoring the ortho position for the amine group was observed and investigated with Fukui indices and spectral methods.

  20. 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…

  1. Head-to-tail intermolecular hydrogen bonding of OH and NH groups with fluoride.

    PubMed

    Ashokkumar, Pichandi; Ramakrishnan, Vayalakkavoor T; Ramamurthy, Perumal

    2011-02-07

    To explore the anion-recognition ability of the phenolic hydroxyl group and the amino hydrogen, we synthesized three different acridinedione (ADD) based anion receptors, 1, 2 and 3, having OH, NH, and combination of OH and NH groups, respectively. Absorption, emission and (1)H NMR spectral studies revealed that receptor 1, having only a phenolic OH group, shows selective deprotonation of the hydroxyl proton towards F(-), which results in an "ON-OFF"-type signal in the fluorescence spectral studies. Receptor 2, which only has an amino hydrogen, also shows deprotonation of the amino hydrogen with F(-), whereas receptor 3 (having both OH and NH groups) shows head-to-tail intermolecular hydrogen bonding of OH and NH groups with F(-) prior to deprotonation. The observation of hydrogen bonding of the OH and NH groups in a combined solution of 1 and 2 with F(-) in a head-to-tail hetero-intermolecular fashion, and the absence of head-to-head and tail-to-tail intermolecular hydrogen bonding in 1 and 2 with F(-), prove that the difference in the acidity of the OH and NH protons leads to the formation of an intermolecular hydrogen-bonding complex with F(-) prior to deprotonation. The presence of this hydrogen-bonding complex was confirmed by absorption spectroscopy, 3D emission contour studies, and (1)H NMR titration.

  2. 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.

  3. 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…

  4. Enhancing intermolecular benzoyl-transfer reactivity in crystals by growing a "reactive" metastable polymorph by using a chiral additive.

    PubMed

    Murali, Chebrolu; Shashidhar, Mysore S; Gonnade, Rajesh G; Bhadbhade, Mohan M

    2009-01-01

    Racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate, which normally crystallizes in a monoclinic form (form I, space group P2(1)/n) could be persuaded to crystallize out as a metastable polymorph (form II, space group C2/c) by using a small amount of either D- or L- 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoformate as an additive in the crystallization medium. The structurally similar enantiomeric additive was chosen by the scrutiny of previous experimental results on the crystallization of racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate. Form II crystals can be thermally transformed to form I crystals at about 145 degrees C. The relative organization of the molecules in these dimorphs vary slightly in terms of the helical assembly of molecules, that is, electrophile (El)...nucleophile (Nu) and C-H...pi interactions, but these minor variations have a profound effect on the facility and specificity of benzoyl-group-transfer reactivity in the two crystal forms. While form II crystals undergo a clean intermolecular benzoyl-group-transfer reaction, form I crystals are less reactive and undergo non-specific benzoyl-group transfer leading to a mixture of products. The role played by the additive in fine-tuning small changes that are required in the molecular packing opens up the possibility of creating new polymorphs that show varied physical and chemical properties. Crystals of D-2,6-di-O-benzoyl-myo-inositol-1,3,5-orthoformate (additive) did not show facile benzoyl-group-transfer reactivity (in contrast to the corresponding racemic compound) due to the lack of proper juxtaposition and assembly of molecules.

  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

    ..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS) Data... 49 Transportation 1 2010-10-01 2010-10-01 false DOT Drug and Alcohol Testing Management Information System (MIS) Data Collection Form H Appendix H to Part 40 Transportation Office of the...

  6. 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

    ..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS) Data... 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...

  7. 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

    ..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS) Data... 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...

  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

    ..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS) Data... 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...

  9. 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

    ..., App. H Appendix H to Part 40—DOT Drug and Alcohol Testing Management Information System (MIS) Data... 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...

  10. Abundances in Star-forming Galaxies and Damped Lyman Alpha Systems

    NASA Astrophysics Data System (ADS)

    Schulte-Ladbeck, R.; Rao, S. M.; Hopkins, A. M.; König, B.; Turnshek, D. A.; Miller, C. J.; Vanden Berk, D.

    2004-12-01

    Our knowledge about the chemical properties of galaxies is based on measurements of emission lines from photo-ionized gas. The abundances of galaxies at high-z are inferred using absorption lines arising in neutral gas in Damped Lyman Alpha (DLA) systems. Do the results of emission and absorption experiments agree in cases of nearby star-forming galaxies (SFGs) causing DLAs? Schulte-Ladbeck et al. (2004a) examined the z=0.009 DLA/SFG SBS 1543+593. We derived [O/H]II=-0.54. The bright QSO HS 1543+5921 intercepts the disk at small impact parameter. We found a lower limit, [O/H]I>-2.14, using HST archival spectra. New HST observations by Bowen et al. are analyzed to yield a S abundance of [S/H]I=-0.54. Using S as a proxy for O this suggests [O/H]I=[O/H]II (or 0.29xsolar) for one genuine DLA. To investigate additional SFG/QSO pairs, we used the CMU-Pitt Value Added Catalog to assemble from the SDSS DR1 a database of about 13,000 SFGs with 0< z <0.36 (Schulte-Ladbeck 2004b). We applied the strong-line indices of Pettini & Pagel (2004), derived O/HII for all objects, and a median O/HII ratio of 0.74xsolar with a SIQR of 0.19. An O/H vs. z diagram is constructed by augmenting these data to z≈5 with O/HI ratios for DLAs (Prochaska et al. 2003). We matched our SFG catalog against the SDSS QSO catalog, then used the HST archive to determine the HI column densities and limits on O/HI for these SFGs. The results are discussed using the O/H vs. redshift diagram. We acknowledge support of HST archival funding to program ID 10282.

  11. Predetermined embryonic glial cells form the distinct glial sheaths of the Drosophila peripheral nervous system.

    PubMed

    von Hilchen, Christian M; Bustos, Alvaro E; Giangrande, Angela; Technau, Gerhard M; Altenhein, Benjamin

    2013-09-01

    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.

  12. 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

  13. The L723 Low-Mass Star Forming Protostellar System: Resolving a Double Core

    NASA Astrophysics Data System (ADS)

    Girart, J. M.; Rao, R.; Estalella, R.

    2009-03-01

    We present 1.35 mm Submillimeter Array (SMA) observations around the low-mass Class 0 source IRAS 19156+1906, at the center of the LDN 723 (L723) dark cloud. We detected emission from dust as well as emission from H2CO 30,3-20,2, DCN 3-2, and CN 2-1 lines, which arise from two cores, SMA 1 and SMA 2, separated by 2farcs9 (880 AU in projected distance). SMA 2 is associated with the previously detected source VLA 2. Weak SiO 5-4 emission is detected, possibly tracing a region of interaction between the dense envelope and the outflow. We modeled the dust and H2CO emission from the two cores. The results from the modeling show that the cores have similar physical properties (density and temperature distribution) but that SMA 2 has a larger p-H2CO abundance (by a factor of 3-10) than SMA 1. The p-H2CO abundances' findings are compatible with the value of the outer part of the circumstellar envelopes associated with Class 0 sources. SMA 2 is harboring an active multiple low-mass protostellar system and powering at least one molecular outflow. In contrast, there are no known signs of outflow activity toward SMA 1. This suggests that SMA 2 is more evolved than SMA 1. The kinematics of the two sources show marginal evidence of infall and rotation motions. The mass detected by the SMA observation, which trace scales of lsim1000 AU, is only a small fraction of the mass contained in the large-scale molecular envelope, which suggests that L723 is still in a very early phase of star formation. Despite the apparent quiescent nature of the L723, fragmentation is occurring at the center of the cloud at different scales. Thus, at sime1000 AU, the cloud has fragmented in two cores: SMA 1 and SMA 2. At the same time, at least one of these cores, SMA 2, has undergone additional fragmentation at scales of sime150 AU, forming a multiple stellar system.

  14. Model intermolecular potentials and virial coefficients determined from the speed of sound

    NASA Astrophysics Data System (ADS)

    Trusler, J. P. M.; Wakeham, W. A.; Zarari, M. P.

    A simple procedure is given for determining model two- and three-body intermolecular potential energy functions from precise measurements of the speed of sound in the gas phase. The method is applied to the pure gases argon, methane and nitrogen and results are considered for propane and the mixture (methane + propane) obtained recently by similar methods. For the pair potential, the four-parameter model proposed by Maitland and Smith is used while the consequences of three-body forces were generally assumed to be represented adequately by the triple-dipole dispersion potential of Axilrod and Teller. The effect of including additional dispersion and exchange terms in the three-body potential was investigated for argon; each of these terms is significant but their effect on the third virial coefficient may be absorbed accurately in an effective triple-dipole potential. Three or, in some cases, all four of the parameters in the pair potential were optimized, together with the triple-dipole dispersion coefficient, in fits to the acoustic data. Ordinary second and third virial coefficients have been calculated from the model potential and the former are shown to be in excellent agreement with directly measured values. In the case of the third virial coefficient, some small discrepancies are noted; the resolution of these differences could have important implications for our understanding of many-body forces. The values of the dilute-gas viscosity predicted by the model pair potentials are examined also and, in the case of argon, found to be in good agreement with experimental values; for the other systems differences of several per cent were noted.

  15. 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

  16. Photo-induced spin transition of Iron(III) compounds with pi-pi intermolecular interactions.

    PubMed

    Hayami, Shinya; Hiki, Kenji; Kawahara, Takayoshi; Maeda, Yonezo; Urakami, Daisuke; Inoue, Katsuya; Ohama, Mitsuo; Kawata, Satoshi; Sato, Osamu

    2009-01-01

    Iron(III) spin-crossover compounds [Fe(pap)(2)]ClO(4) (1), [Fe(pap)(2)]BF(4) (2), [Fe(pap)(2)]PF(6) (3), [Fe(qsal)(2)]NCS (4), and [Fe(qsal)(2)]NCSe (5) (Hpap=2-(2-pyridylmethyleneamino)phenol and Hqsal=2-[(8-quinolinylimino)methyl]phenol) were prepared and their spin-transition properties investigated by magnetic susceptibility and Mössbauer spectroscopy measurements. The iron(III) compounds exhibited spin transition with thermal hysteresis. Single crystals of the iron(III) compounds were obtained as suitable solvent adducts for X-ray analysis, and structures in high-spin (HS) and low-spin (LS) states were revealed. Light-induced excited-spin-state trapping (LIESST) effects of the iron(III) compounds were induced by light irradiation at 532 nm for 1-3 and at 800 nm for 4 and 5. The activation energy E(a) and the low-temperature tunneling rate k(HL)(T-->0) of iron(III) LIESST compound 1 were estimated to be 1079 cm(-1) and 2.4x10(-8) s(-1), respectively, by HS-->LS relaxation experiments. The Huang-Rhys factor S of 1 was also estimated to be 50, which was similar to that expected for iron(II) complexes. It is thought that the slow relaxation in iron(III) systems is achieved by the large structural distortion between HS and LS states. Introduction of strong intermolecular interactions, such as pi-pi stacking, can also play an important role in the relaxation behavior, because it can enhance the structural distortion of the LIESST complex.

  17. Coherent-form energy conservation relation for the elastic scattering of a guided mode in a symmetric scattering system.

    PubMed

    Liu, Haitao

    2013-10-07

    We propose a coherent-form energy conservation relation (ECR) that is generally valid for the elastic transmission and reflection of a guided mode in a symmetric scattering system. In contrast with the classical incoherent-form ECR, |τ|2 + |ρ|2≤1 with τ and ρ denoting the elastic transmission and reflection coefficients of a guided mode, the coherent-form ECR is expressed as |τ + ρ|≤1, which imposes a constraint on a coherent superposition of the transmitted and reflected modes. The coherent-form ECR is rigorously demonstrated and is numerically tested by considering different types of modes in various scattering systems. Further discussions with the scattering matrix formalism indicate that two coherent-form ECRs, |τ + ρ|≤1 and |τ-ρ|≤1, along with the classical ECR |τ|2 + |ρ|2≤1 constitute a complete description of the energy conservation for the elastic scattering of a guided mode in a symmetric scattering system. The coherent-form ECR provides a common tool in terms of energy transfer for understanding and analyzing the scattering dynamics in currently interested scattering systems.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. The proteolytic system of pineapple stems revisited: Purification and characterization of multiple catalytically active forms.

    PubMed

    Matagne, André; Bolle, Laetitia; El Mahyaoui, Rachida; Baeyens-Volant, Danielle; Azarkan, Mohamed

    2017-02-23

    Crude pineapple proteases extract (aka stem bromelain; EC 3.4.22.4) is an important proteolytic mixture that contains enzymes belonging to the cysteine proteases of the papain family. Numerous studies have been reported aiming at the fractionation and characterization of the many molecular species present in the extract, but more efforts are still required to obtain sufficient quantities of the various purified protease forms for detailed physicochemical, enzymatic and structural characterization. In this work, we describe an efficient strategy towards the purification of at least eight enzymatic forms. Thus, following rapid fractionation on a SP-Sepharose FF column, two sub-populations with proteolytic activity were obtained: the unbound (termed acidic) and bound (termed basic) bromelain fractions. Following reversible modification with monomethoxypolyethylene glycol (mPEG), both fractions were further separated on Q-Sepharose FF and SP-Sepharose FF, respectively. This procedure yielded highly purified molecular species, all titrating ca. 1 mol of thiol group per mole of enzyme, with distinct biochemical properties. N-terminal sequencing allowed identifying at least eight forms with proteolytic activity. The basic fraction contained previously identified species, i.e. basic bromelain forms 1 and 2, ananain forms 1 and 2, and comosain (MEROPS identifier: C01.027). Furthermore, a new proteolytic species, showing similarities with basic bomelain forms 1 and 2, was discovered and termed bromelain form 3. The two remaining species were found in the acidic bromelain fraction and were arbitrarily named acidic bromelain forms 1 and 2. Both, acidic bromelain forms 1, 2 and basic bromelain forms 1, 2 and 3 are glycosylated, while ananain forms 1 and 2, and comosain are not. The eight protease forms display different amidase activities against the various substrates tested, namely small synthetic chromogenic compounds (DL-BAPNA and Boc-Ala-Ala-Gly-pNA), fluorogenic compounds

  3. 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

  4. 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

  5. Different temporal structure for form versus surface cortical color systems--evidence from chromatic non-linear VEP.

    PubMed

    Crewther, David P; Crewther, Sheila G

    2010-12-20

    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.

  6. 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…

  7. Intermolecular potential functions from spectroscopic properties of weakly bound complexes. Third progress report, July 1, 1991--June 30, 1992

    SciTech Connect

    Muenter, J.S.

    1992-08-01

    Goal is to consolidate the information from high resolution spectroscopy of weakly bound cluster molecules through a theoretical model of intermolecular potential energy surfaces. The ability to construct analytic intermolecular potential functions that accurately predict the interaction energy between small molecules will have a major impact in chemistry, biochemistry, and biology. This document presents the evolution and capabilities of a potential function model developed here, and then describes plans for future developments and applications. This potential energy surface (PES) model was first used on (HCCH){sub 2}, (CO{sub 2}){sub 2}, HCCH - CO{sub 2}; it had to be modified to work with HX dimers and CO{sub 2}-HX complexes. Potential functions have been calculated for 15 different molecular complexes containing 7 different monomer molecules. Current questions, logical extensions and new applications of the model are discussed. The questions are those raised by changing the repulsion and dispersion terms. A major extension of the PES model will be the inclusion of induction effects. Projects in progress include PES calculations on (HCCH){sub 3}, CO{sub 2} containing complexes, (HX){sub 2}, HX - CO{sub 2}, CO{sub 2} - CO, (CO{sub 2}){sub 3}, and (OCS){sub 2}. The first PES calculation for a nonlinear molecule will be for water and ammonia complexes. Possible long-term applications for biological molecules are discussed. Differences between computer programs used for molecular mechanics and dynamics in biological systems are discussed, as is the problem of errors. 12 figs, 74 refs. (DLC)

  8. Newly formed minerals of the Fe-P-S system in Kolyma fulgurite

    NASA Astrophysics Data System (ADS)

    Plyashkevich, A. A.; Minyuk, P. S.; Subbotnikova, T. V.; Alshevsky, A. V.

    2016-04-01

    Newly obtained data from microscopic, geochemical, and thermomagnetic studies of the large Kolyma fulgurite are presented here: the fulgurite was formed in the Holocene as a result of lightning affected black shale alluvium. The composition is very close to that of glass formed from a melt. The glass has elevated concentrations of Y, Zr, Nb, and REEs. The newly formed mineral phases have been identified: those are Al-Si glass, α-cristobalite, moissanite, native iron with a phosphorus admixture, nickel-less shreibersite (?), troilite, and possibly cohenite. The formation of these minerals is related to the melt fractionation and the effects of element concentration and segregation of ore components under conditions of the rock melting caused by the effect of high-energy plasma (lightning strike).

  9. Halistaurin, phialidin and modified forms of aequorin as Ca2+ indicator in biological systems.

    PubMed Central

    Shimomura, O; Shimomura, A

    1985-01-01

    Two kinds of aequorin-type photoproteins, i.e., halistaurin and phialidin, and four kinds of modified forms of aequorin, i.e., products of acetylation, ethoxycarbonylation, fluorescamine-modification and fluorescein labelling, were prepared. The modified forms of aequorin were more sensitive to Ca2+ than was aequorin in their Ca2+-triggered luminescence reactions, whereas halistaurin and phialidin were less sensitive. The emission maxima of luminescence were all within a wavelength range 450-464 nm, except for fluorescein-labelled aequorin, which emitted yellowish light (lambda max. 520 nm). A new technique of measuring Ca2+ concentration is suggested. PMID:4026808

  10. An Analysis of Ill-Formed Input in Natural Language Queries to Document Retrieval Systems.

    ERIC Educational Resources Information Center

    Young, Charlene W.; And Others

    1991-01-01

    Describes a study conducted at the University of South Carolina that examined the frequency of occurrence of several types of errors in a sample of natural language queries submitted by users requesting online searches in information retrieval systems. Implications for system design are suggested, including parsing systems. (28 references) (LRW)

  11. 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.

  12. 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

  13. Exponents in Lifetime and Power Spectral Density Forms in Self-Organized Critical Systems

    DTIC Science & Technology

    1994-08-01

    exponentially cutoff power laws. For example, the behavior of real sandpiles (ref 3) and the Barkhausen effect (ref 4) indicate that the distributions...are cut off, but the ý,est form is not obvious. The distribution of lifetimes in the Barkhausen effect in three ferromagnetic metals (Metglas 2605S

  14. On-line Technology Information System (OTIS): Solid Waste Management Technology Information Form (SWM TIF)

    NASA Technical Reports Server (NTRS)

    Levri, Julie A.; Boulanger, Richard; Hogan, John A.; Rodriguez, Luis

    2003-01-01

    Contents include the following: What is OTIS? OTIS use. Proposed implementation method. Development history of the Solid Waste Management (SWM) Technology Information Form (TIF) and OTIS. Current development state of the SWM TIF and OTIS. Data collection approach. Information categories. Critiques/questions/feedback.

  15. A lithologic data-recording form for a computer-based well-data system

    USGS Publications Warehouse

    Conley, C.D.; Hea, J.P.

    1972-01-01

    Well-data files maintained by petroleum companies and service companies are important sources of data for exploration geologists. To make these data readily accessible and useful for computer studies, three preliminary steps are necessary: (1) systematic data gathering and recording, (2) storage for ready retrieval, and (3) preparation of analysis programs. One important source of geologic data is lithologic descriptions of well cuttings and cores. The practical lithologic data-recording form described here is used routinely at the well site and in the laboratory. It is designed in an 80-column format and uses codes for lithologic characteristics, porosity, and hydrocarbon shows, and forms part of an integrated well-data file. This datarecording form has the advantages that descriptions are made according to a standardized format convenient to use at the well site, and the data are subsequently available in raw form relatively free from interpretive bias. A library of analysis and display programs can be assembled for utilization of the data. ?? 1972 Plenum Publishing Corporation.

  16. Individualized Testing System: Performance Checks, ISCS Level III, WW-CP Form A.

    ERIC Educational Resources Information Center

    Hathway, James A., Ed.

    This is one form of three performance checks booklets (A, B, and C) for two texts of Level III of the Intermediate Science Curriculum Study (ISCS). These two texts are Winds and Weather (WW), and Crusty Problems (CP). The 12 performance checks booklets for Level III are considered one of four major subdivisions of a set of individualized…

  17. Individualized Testing System: Performance Checks, ISCS Level III, WW-CP Form C.

    ERIC Educational Resources Information Center

    Hathway, James A., Ed.

    This is one form of three performance checks booklets (A, B, and C) for two texts of Level III of the Intermediate Science Curriculum Study (ISCS). These two texts are Winds and Weather (WW), and Crusty Problems (CP). The 12 performance checks booklets for Level III are considered one of four subdivisions of a set of individualized evaluation…

  18. Individualized Testing System: Performance Checks, ISCS Level III, WW-CP Form B.

    ERIC Educational Resources Information Center

    Hathway, James A., Ed.

    This is one form of three performance checks booklets (A, B, and C) for two texts of Level III of the Intermediate Science Curriculum Study (ISCS). These two texts are Winds and Weather (WW), and Crusty Problems (CP). The 12 performance checks booklets for Level III are considered one of four major subdivisions of a set of individualized…

  19. Density functional theory study of self-association of N-methylformamide and its effect on intramolecular and intermolecular geometrical parameters and the cis/trans population.

    PubMed

    García Martínez, A; Teso Vilar, E; García Fraile, A; Martínez-Ruiz, P

    2006-06-21

    The single-point total energy (E) of several acyclic and cyclic oligomers of N-methylformamide (NMF) was computed by the first time without any geometrical restriction, using the B3LYP6-31G* method of the density functional theory in order to determine the effect of self-association on intramolecular geometrical parameters of cis- and trans-NMF, the intermolecular distances of the hydrogen-bonding chains formed by NMF as well as intermolecular association energies including counterpoise corrections. It is concluded that liquid NMF exists mainly as polymers formed by self-association of trans-NMF units, whereas the cis-NMF isomer occurs as isolated units inserted along the chains. These computational results are in accordance with the experimentally determined predominance (ca. 90%) of trans-NMF population by means of (1)H- NMR and other spectroscopic techniques, but in severe contradiction with a recent interpretation of x-ray diffraction data on liquid NMF, postulating a cyclic trimer of cis-NMF (c-C(3)) as the predominating species. The counterpoise-corrected values of the association energy, DeltaE(CP), calculated for cyclic oligomers, increase with the polymerization degree (n) revealing a high grade of cooperative effect for amidic hydrogen-bonded chains. Noteworthy, the difference between the DeltaE(CP) values of the cyclic cis- and trans-homooligomers of NMF is positive for n=2 and 3 but negative for n > or =4.

  20. Technology maturation project on optimization of sheet metal forming of aluminum for use in transportation systems: Final project report

    SciTech Connect

    Johnson, K.I.; Smith, M.T.; Lavender, C.A.; Khalell, M.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 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; 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.

  1. Joint Tactical Radio System Handheld, Manpack, and Small Form Fit Radios (JTRS HMS)

    DTIC Science & Technology

    2015-12-01

    waveforms: SRW, Single Channel Ground and Airborne Radio System, satellite communication, and Mobile-User Objective System. The Manpack Radio is utilized...2015 SAR March 21, 2016 18:21:36 UNCLASSIFIED 6 Executive Summary HMS is structured as a single acquisition program. The program completed the EMD...include: SRW, Single Channel Ground and Airborne Radio System (Army managed waveform), Satellite Communications (Army managed waveform), and Mobile

  2. Multiple-access phased array antenna simulator for a digital beam forming system investigation

    NASA Technical Reports Server (NTRS)

    Kerczewski, Robert J.; Yu, John; Walton, Joanne C.; Perl, Thomas D.; Andro, Monty; Alexovich, Robert E.

    1992-01-01

    Future versions of data relay satellite systems are currently being planned by NASA. Being given consideration for implementation are on-board digital beamforming techniques which will allow multiple users to simultaneously access a single S-band phased array antenna system. To investigate the potential performance of such a system, a laboratory simulator has been developed at NASA's Lewis Research Center. This paper describes the system simulator, and in particular, the requirements, design, and performance of a key subsystem, the phased array antenna simulator, which provides realistic inputs to the digital processor including multiple signals, noise, and nonlinearities.

  3. Mucoadhesive system formed by liquid crystals for buccal administration of poly(hexamethylene biguanide) hydrochloride.

    PubMed

    Souza, Carla; Watanabe, Evandro; Borgheti-Cardoso, Livia Neves; De Abreu Fantini, Márcia Carvalho; Lara, Marilisa Guimarães

    2014-12-01

    Antimicrobial approaches are valuable in controlling the development of buccal diseases, but some antibacterial agents have a short duration of activity. Therefore, the development of prolonged delivery systems would be advantageous. Liquid crystalline systems comprising monoolein (GMO)/water have been considered to be a potential vehicle to deliver drugs to the buccal mucosa because of the phase properties that allow for controlled drug release as well as its mucoadhesive properties. Therefore, the aim of this study was to develop a GMO/water system for the slow release of poly(hexamethylene biguanide) hydrochloride (PHMB) on the buccal mucosa and test the properties of this system with regard to swelling, release profile, antimicrobial activity, and strength of mucoadhesion, with the overall goal of treating buccal infections. The tested systems were capable of modulating drug release, which is controlled by diffusion of the drug throughout the system. Furthermore, PHMB appeared to improve the mucoadhesive properties of the system and may synergistically act with the drug to promote antimicrobial activity against S. mutas and C. albicans, indicating that liquid crystals may be suitable for the administration of PHMB on the buccal mucosa. Therefore, this system could be proposed as a novel system for mucoadhesive drug delivery.

  4. Multiple-access phased array antenna simulator for a digital beam-forming system investigation

    NASA Technical Reports Server (NTRS)

    Kerczewski, Robert J.; Yu, John; Walton, Joanne C.; Perl, Thomas D.; Andro, Monty; Alexovich, Robert E.

    1992-01-01

    Future versions of data relay satellite systems are currently being planned by NASA. Being given consideration for implementation are on-board digital beamforming techniques which will allow multiple users to simultaneously access a single S-band phased array antenna system. To investigate the potential performance of such a system, a laboratory simulator has been developed at NASA's Lewis Research Center. This paper describes the system simulator, and in particular, the requirements, design and performance of a key subsystem, the phased array antenna simulator, which provides realistic inputs to the digital processor including multiple signals, noise, and nonlinearities.

  5. Design of output feedback consensus controllers for nonlinear sampled-data multi-agent systems of strict-feedback form

    NASA Astrophysics Data System (ADS)

    Katayama, Hitoshi

    2014-09-01

    Design of reduced-order observer-based output feedback consensus controllers for nonlinear sampled-data multi-agent systems of strict-feedback form is considered based on nonlinear sampled-data control and consensus control theories. As a practical application of the proposed design method, output feedback consensus control for sampled-data fully actuated ships is also discussed.

  6. Experience of Forming Professional and Communicative Competency of Future Social Workers in Education Systems of Western European Countries

    ERIC Educational Resources Information Center

    Baranyuk, Vita

    2015-01-01

    The article analyzes the experience of forming professional and communicative competency of future social workers in the education systems of Western European countries, in particular, France, Germany and Switzerland. On the basis of generalization of the studied data it has been found out that each country has its own techniques of forming…

  7. Comparison between Synthesized Lead Particles and Lead Solids Formed on Surfaces in Real Drinking Water Distribution Systems

    EPA Science Inventory

    The objective of this work is to compare the properties of lead solids formed during bench-scale precipitation experiments to solids found on lead pipe removed from real drinking water distribution systems and metal coupons used in pilot scale corrosion testing. Specifically, so...

  8. Rationalising polymer selection for supersaturated film forming systems produced by an aerosol spray for the transdermal delivery of methylphenidate.

    PubMed

    Edwards, A; Qi, S; Liu, F; Brown, M B; McAuley, W J

    2017-05-01

    Film forming systems offer a number of advantages for topical and transdermal drug delivery, in particular enabling production of a supersaturated state which can greatly improve drug absorption and bioavailability. However the suitability of individual film forming polymers to stabilise the supersaturated state and optimise delivery of drugs is not well understood. This study reports the use of differential scanning calorimetry (DSC) to measure the solubility of methylphenidate both as the free base and as the hydrochloride salt in two polymethacrylate copolymers, Eudragit RS (EuRS) and Eudragit E (EuE) and relates this to the ability of films formed using these polymers to deliver methylphenidate across a model membrane. EuRS provided greater methylphenidate delivery when the drug was formulated as the free base in comparison EuE because the lower solubility of the drug in EuRS provided a higher degree of drug saturation in the polymeric film. In contrast EuE provided greater delivery of methylphenidate hydrochloride as EuRS could not prevent its crystallisation from a supersaturated state. Methylphenidate flux across the membrane could be directly related to degree of saturation of the drug in the film formulation as estimated by the drug solubility in the individual polymers demonstrating the importance of drug solubility in the polymer included in film forming systems for topical/transdermal drug delivery. In addition DSC has been demonstrated to be a useful tool for determining the solubility of drugs in polymers used in film forming systems and the approaches outlined here are likely to be useful for predicting the suitability of polymers for particular drugs in film forming transdermal drug delivery systems.

  9. Coupled effects of substrate adhesion and intermolecular forces on polymer thin film glass-transition behavior.

    PubMed

    Xia, Wenjie; Keten, Sinan

    2013-10-15

    Intermolecular noncovalent forces between polymer chains influence the mobility and glass-transition temperature (Tg), where weaker interchain interactions, all else being the same, typically results in lower bulk polymer Tg. Using molecular dynamics simulations, here we show that this relation can become invalid for supported ultrathin films when the substrate-polymer interaction is extremely strong and the polymer-polymer interactions are much weaker. This contrasting trend is found to be due to a more pronounced substrate-induced appreciation of the film Tg for polymers with weaker intermolecular interactions and low bulk Tg. We show that optimizing this coupling between substrate adhesion and bulk Tg maximizes thin film Tg, paving the way for tuning film properties through interface nanoengineering.

  10. Intermolecular potential and second virial coefficient of the water-nitrogen complex.

    PubMed

    Tulegenov, Akyl S; Wheatley, Richard J; Hodges, Matthew P; Harvey, Allan H

    2007-03-07

    The authors construct a rigid-body (five-dimensional) potential energy surface for the water-nitrogen complex using the systematic intermolecular potential extrapolation routine. The intermolecular potential is then extrapolated to the limit of a complete basis set. An analytic fit of this surface is obtained, and, using this, the global minimum energy is found. The minimum is located in an arrangement in which N2 is near the H atom of H2O, almost collinear with the OH bond. The best estimate of the binding energy is 441 cm-1 (1 cm-1 approximately 1.986 43x10(-23) J). The extrapolated potential is then used to calculate the second cross virial coefficient over a wide temperature range (100-3000 K). These calculated second virial coefficients are generally consistent with experimental data, but for the most part the former have smaller uncertainties.

  11. 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.

  12. Investigation of intermolecular double-quantum off-resonance longitudinal relaxation in the tilted rotating frame

    NASA Astrophysics Data System (ADS)

    Cai, Honghao; Zheng, Bingwen; Ke, Hanping; Chen, Zhong

    2015-11-01

    A modified correlation spectroscopy revamped by asymmetric z-gradients echo detection (CRAZED) sequence was applied to investigate the behavior of intermolecular double-quantum longitudinal relaxation processes in the tilted rotating frame. Theoretical formalism based on dipolar field theory was presented in detail. Spectroscopic measurements and quantitative analysis demonstrated that the signal intensities and intermolecular double-quantum off-resonance longitudinal relaxation time in the rotating frame (T1ρ, DQC eff) are inversely correlated with the tilt angle (θ), while positively correlated with the effective frequency of spin-locking field (ωe). Magnetic resonance imaging experiments of an agarose phantom also prove the validity of the theoretical analysis and demonstrated the feasibility of imaging based on T1ρ, DQC eff . The rotating-frame double-quantum relaxation measurements are useful for probing slow-motion molecules and this study provides the guidance for optimization of the spin-lock experiments.

  13. Synthesis of Waste Form in the Gd-Fe-Al-Ni-Mn-Cr-O System

    SciTech Connect

    Chae, S.C.; Jang, Y.N.; Bae, I.K.; Ryu, K.W.

    2006-07-01

    Poly-phase waste form which was the mixture of Gd{sub 3}Fe{sub 2}Al{sub 3}O{sub 12} and (Ni{sub x}Mn{sub 1-x})(Fe{sub y}Cr{sub 1-y}){sub 2}O{sub 4} was synthesized. Also, we are intended to examine phase relation and physicochemical properties of coexisted phases in the compositions and to confirm accommodation relation of elements and phases. Two types of phase series were observed: Garnet-perovskite-spinel and Garnet-spinel. The compositions of garnets and spinels were nonstoichiometric, and especially, this poly-phase ceramics may be in a good waste form. The excessive Gd in garnets indicated the immobilization of higher content of actinides. The nonstoichiometric compositions of garnet and spinel were attributed to the formation of perovskite in that perovskite contained Gd, Fe and Al from garnet and Cr from spinel. (authors)

  14. Analyzing dynamic performance of power systems over parameter space using the method of normal forms of vector fields

    NASA Astrophysics Data System (ADS)

    Zhu, Songzhe

    Today's power systems have become more and more stressed due to the high utilization of available facilities. The complex dynamic behavior of large stressed power systems following disturbances can not be fully explained with present tools, such as linear eigen-analysis tools and nonlinear time-domain simulation methods. This research work applies a nonlinear analytical tool, the method of normal forms of vector fields, to help understand the complex transient oscillations in stressed power systems. The method of normal forms is a well-known mathematical tool to study systems of differential equations. The basic idea is to simplify the dynamical system by a sequence of nonlinear coordinate transformations. If there is no resonance in the system, then the nonlinear vector field can be turned into a linear one by the transformations. Previous work applied the second-order normal form transformation under non-resonance condition to power system dynamical equations. The nonlinear interaction among the fundamental modes was investigated. Based on these efforts, this work extends the application of normal forms to evaluate the dynamic performance of power systems taking into account changing operation conditions. As the resonance and near-resonance could occur in parameter space, a new normal form transformation under second order resonance condition is derived. The analysis shows that the high nonlinearity resulting from the resonance and near-resonance among poorly damped oscillatory modes and control modes is detrimental to the system performance. An approach to determine the resonance and near-resonance regions in parameter space is developed. The modes contributing to the detrimental behavior associated with the near-resonance region are identified by a procedure based on certain modal interaction indices. The state variables showing detrimental behavior are then determined using nonlinear participation factors. The accuracy of the prediction is verified by

  15. System and method for forming synthetic protein crystals to determine the conformational structure by crystallography

    DOEpatents

    Craig, George D.; Glass, Robert; Rupp, Bernhard

    1997-01-01

    A method for forming synthetic crystals of proteins in a carrier fluid by use of the dipole moments of protein macromolecules that self-align in the Helmholtz layer adjacent to an electrode. The voltage gradients of such layers easily exceed 10.sup.6 V/m. The synthetic protein crystals are subjected to x-ray crystallography to determine the conformational structure of the protein involved.

  16. System and method for forming synthetic protein crystals to determine the conformational structure by crystallography

    DOEpatents

    Craig, G.D.; Glass, R.; Rupp, B.

    1997-01-28

    A method is disclosed for forming synthetic crystals of proteins in a carrier fluid by use of the dipole moments of protein macromolecules that self-align in the Helmholtz layer adjacent to an electrode. The voltage gradients of such layers easily exceed 10{sup 6}V/m. The synthetic protein crystals are subjected to x-ray crystallography to determine the conformational structure of the protein involved. 2 figs.

  17. Quantum systems with effective and time-dependent masses: form-preserving transformations and reality conditions

    NASA Astrophysics Data System (ADS)

    Schulze-Halberg, Axel

    2005-12-01

    We study the time-dependent Schrödinger equation (TDSE) with an effective (position-dependent) mass, relevant in the context of transport phenomena in semiconductors. The most general form-preserving transformation between two TDSEs with different effective masses is derived. A condition guaranteeing the reality of the potential in the transformed TDSE is obtained. To ensure maximal generality, the mass in the TDSE is allowed to depend on time also.

  18. 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

  19. 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.

  20. 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.