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Sample records for intermolecular transfer integral

  1. Intermolecular transfer integrals for organic molecular materials: can basis set convergence be achieved?

    NASA Astrophysics Data System (ADS)

    Huang, Jingsong; Kertesz, Miklos

    2004-05-01

    Intermolecular transfer integrals, and associated band-structures of organic molecular materials can be calculated through a dimer approach. Extensive numerical studies are performed on an ethylene π-dimer to investigate the basis sets dependence of transfer integrals. Convergence of calculated transfer integrals is achieved with respect to both Gaussian and plane-wave basis sets, provided the same level of theory is used. Effects of diffuse and polarization Gaussian functions on transfer integrals are identified. Comparison of experimental and theoretical values of transfer integrals of the TTF-TCNQ charge transfer salt is also presented.

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

    PubMed

    Huang, Jingsong; Kertesz, Miklos

    2005-06-15

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

  3. Frontier orbital symmetry control of intermolecular electron transfer

    SciTech Connect

    Stevens, B.

    1990-11-01

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

  4. Fluorescence photoactivation by intermolecular proton transfer.

    PubMed

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

    2012-10-11

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

  5. 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.

  6. 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.

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

    SciTech Connect

    Stevens, B.

    1997-07-01

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

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

    SciTech Connect

    Kato, Nobuhiko; Ida, Tomonori; Endo, Kazunaka

    2004-04-30

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

  9. Intermolecular nonradiative energy transfer in clusters with plasmonic nanoparticles

    NASA Astrophysics Data System (ADS)

    Kucherenko, M. G.; Stepanov, V. N.; Kruchinin, N. Yu.

    2015-01-01

    The influence of carbon (fullerenes, nanotubes) and metal (Ni, Co, Cu, Ag) nanoparticles on the nonradiative electronic excitation energy transfer between the molecules of organic dyes (acrylic orange as a donor and Nile blue as an acceptor) in alcohol solutions of polyvinylbutyral is studied. It is found that, at particular concentrations of the mixture components, plasmonic nanoparticles affect the nonradiative electronic excitation energy transfer, which is manifested in an increase in the intensity of sensitized fluorescence of acceptors with simultaneous quenching of the fluorescence of donors. A very simple model is proposed to illustrate the observed redistribution of luminescence intensity between the spectral bands of the general spectrum. Molecular-dynamic calculations of the structure of nanocomposites performed for the same purpose confirmed the formation of associated molecular plasmonic complexes fixed by macrochain links.

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

    SciTech Connect

    Wayner, P.C. Jr.

    1999-10-01

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

  11. Nonresonant and resonant mode-specific intermolecular vibrational energy transfers in electrolyte aqueous solutions.

    PubMed

    Bian, Hongtao; Chen, Hailong; Li, Jiebo; Wen, Xiewen; Zheng, Junrong

    2011-10-27

    The donor/acceptor energy mismatch and vibrational coupling strength dependences of interionic vibrational energy transfer kinetics in electrolyte aqueous solutions were investigated with ultrafast multiple-dimensional vibrational spectroscopy. An analytical equation derived from the Fermi's Golden rule that correlates molecular structural parameters and vibrational energy transfer kinetics was found to be able to describe the intermolecular mode specific vibrational energy transfer. Under the assumption of the dipole-dipole approximation, the distance between anions in the aqueous solutions was obtained from the vibrational energy transfer measurements, confirmed with measurements on the corresponding crystalline samples. The result demonstrates that the mode-specific vibrational energy transfer method holds promise as an angstrom molecular ruler. PMID:21916443

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

    PubMed

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

    2015-02-25

    Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4'-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule. PMID:25282020

  13. Rates of intra- and intermolecular electron transfers in hydrogenase deduced from steady-state activity measurements.

    PubMed

    Dementin, Sébastien; Burlat, Bénédicte; Fourmond, Vincent; Leroux, Fanny; Liebgott, Pierre-Pol; Abou Hamdan, Abbas; Léger, Christophe; Rousset, Marc; Guigliarelli, Bruno; Bertrand, Patrick

    2011-07-01

    Electrons are transferred over long distances along chains of FeS clusters in hydrogenases, mitochondrial complexes, and many other respiratory enzymes. It is usually presumed that electron transfer is fast in these systems, despite the fact that there has been no direct measurement of rates of FeS-to-FeS electron transfer in any respiratory enzyme. In this context, we propose and apply to NiFe hydrogenase an original strategy that consists of quantitatively interpreting the variations of steady-state activity that result from changing the nature of the FeS clusters which connect the active site to the redox partner, and/or the nature of the redox partner. Rates of intra- and intermolecular electron transfer are deduced from such large data sets. The mutation-induced variations of electron transfer rates cannot be explained by changes in intercenter distances and reduction potentials. This establishes that FeS-to-FeS rate constants are extremely sensitive to the nature and coordination of the centers. PMID:21615141

  14. Effect of intermolecular orientation upon proton transfer within a polarizable medium.

    PubMed Central

    Scheiner, S; Duan, X

    1991-01-01

    Ab initio calculations are used to investigate the proton transfer process in bacteriorhodopsin. HN = CH2 serves as a small prototype of the Schiff base while HCOO- models its carboxylate-containing counterion and HO- the hydroxyl group of water of tyrosine, leading to the HCOO-..H+..NHCH2 and HO-..H+..NHCH2 complexes. In isolation, both complexes prefer a neutral pair configuration wherein the central proton is associated with the anion. However, the Schiff base may be protonated in the former complex, producing the HCOO-..+HNHCH2 ion pair, when there is a high degree of dielectric coupling with an external polarizable medium. Within a range of intermediate level coupling, the equilibrium position of the proton (on either the carboxylate or Schiff base) can be switched by suitable changes in the intermolecular angle. pK shift resulting from a 60 degrees reorientation are calculated to be some 5-12 pK U within the coupling range where proton transfers are possible. The energy barrier to proton transfer reinforces the ability of changes in angle and dielectric coupling to induce a proton transfer. PMID:1660318

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

    PubMed

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

    2015-07-15

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

  16. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid.

    PubMed

    Rury, Aaron S; Sorenson, Shayne; Dawlaty, Jahan M

    2016-03-14

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm(-1) oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology. PMID:26979698

  17. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

    NASA Astrophysics Data System (ADS)

    Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

    2016-03-01

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  18. Keto-enol tautomerization and intermolecular proton transfer in photoionized cyclopentanone dimer in the gas phase

    SciTech Connect

    Ghosh, Arup K.; Chatterjee, Piyali; Chakraborty, Tapas

    2014-07-28

    Time-of-flight mass spectra of cyclopentanone and its clusters cooled in a supersonic jet expansion have been measured following 4-, 3-, and 2-photon ionizations by the 2nd, 3rd, and 4th harmonic wavelengths, respectively, of a Q-switched Nd:YAG laser. The mass spectra reveal signatures of energetically favored keto to enol tautomerization of the molecular ion leading to intermolecular proton transfer, and this observation is found sharply dependent on the ionization wavelengths used. Electronic structure calculation predicts that in spite of the energetic preference, keto-enol conversion barrier of isolated molecular ion is high. However, the barrier is significantly reduced in a CH⋯O hydrogen-bonded dimer of the molecule. The transition states associated with tautomeric conversion of both cyclopentanone monomer and dimer cations have been identified by means of intrinsic reaction co-ordinate calculation. In a supersonic jet expansion, although a weakly bound dimer is readily generated, the corresponding cation and also the protonated counterpart are observed only for ionization by 532 nm. For other two ionization wavelengths, these species do not register in the mass spectra, where the competing reaction channels via α-cleavage of the ring become dominant. In contrast to the report of a recent study, we notice that the intact molecular ion largely survives fragmentations when ionized from the 2-photon resonant 3p Rydberg state as intermediate using nanosecond laser pulses, and the corresponding resonant 3-photon ionization spectrum has been recorded probing the intact molecular ion.

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

    PubMed

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

    2008-09-21

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

  20. Keto-enol tautomerization and intermolecular proton transfer in photoionized cyclopentanone dimer in the gas phase

    NASA Astrophysics Data System (ADS)

    Ghosh, Arup K.; Chatterjee, Piyali; Chakraborty, Tapas

    2014-07-01

    Time-of-flight mass spectra of cyclopentanone and its clusters cooled in a supersonic jet expansion have been measured following 4-, 3-, and 2-photon ionizations by the 2nd, 3rd, and 4th harmonic wavelengths, respectively, of a Q-switched Nd:YAG laser. The mass spectra reveal signatures of energetically favored keto to enol tautomerization of the molecular ion leading to intermolecular proton transfer, and this observation is found sharply dependent on the ionization wavelengths used. Electronic structure calculation predicts that in spite of the energetic preference, keto-enol conversion barrier of isolated molecular ion is high. However, the barrier is significantly reduced in a CH⋯O hydrogen-bonded dimer of the molecule. The transition states associated with tautomeric conversion of both cyclopentanone monomer and dimer cations have been identified by means of intrinsic reaction co-ordinate calculation. In a supersonic jet expansion, although a weakly bound dimer is readily generated, the corresponding cation and also the protonated counterpart are observed only for ionization by 532 nm. For other two ionization wavelengths, these species do not register in the mass spectra, where the competing reaction channels via α-cleavage of the ring become dominant. In contrast to the report of a recent study, we notice that the intact molecular ion largely survives fragmentations when ionized from the 2-photon resonant 3p Rydberg state as intermediate using nanosecond laser pulses, and the corresponding resonant 3-photon ionization spectrum has been recorded probing the intact molecular ion.

  1. Energy Decomposition Analysis with a Stable Charge-Transfer Term for Interpreting Intermolecular Interactions.

    PubMed

    Lao, Ka Un; Herbert, John M

    2016-06-14

    Many schemes for decomposing quantum-chemical calculations of intermolecular interaction energies into physically meaningful components can be found in the literature, but the definition of the charge-transfer (CT) contribution has proven particularly vexing to define in a satisfactory way and typically depends strongly on the choice of basis set. This is problematic, especially in cases of dative bonding and for open-shell complexes involving cation radicals, for which one might expect significant CT. Here, we analyze CT interactions predicted by several popular energy decomposition analyses and ultimately recommend the definition afforded by constrained density functional theory (cDFT), as it is scarcely dependent on basis set and provides results that are in accord with chemical intuition in simple cases, and in quantitative agreement with experimental estimates of the CT energy, where available. For open-shell complexes, the cDFT approach affords CT energies that are in line with trends expected based on ionization potentials and electron affinities whereas some other definitions afford unreasonably large CT energies in large-gap systems, which are sometimes artificially offset by underestimation of van der Waals interactions by density functional theory. Our recommended energy decomposition analysis is a composite approach, in which cDFT is used to define the CT component of the interaction energy and symmetry-adapted perturbation theory (SAPT) defines the electrostatic, polarization, Pauli repulsion, and van der Waals contributions. SAPT/cDFT provides a stable and physically motivated energy decomposition that, when combined with a new implementation of open-shell SAPT, can be applied to supramolecular complexes involving molecules, ions, and/or radicals. PMID:27049750

  2. Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2011-08-01

    A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA) 2] and [(o-TOL)(CA) 2] have been prepared. The 13C NMR, 1H NMR, 1H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H⋯N intermolecular hydrogen bond between 2NH 2 groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic.

  3. Determination of stepsize parameters for intermolecular vibrational energy transfer. Final report, May 1, 1987--December 31, 1991

    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.

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

    EPA Science Inventory

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

  5. Protein phosphorylation and intermolecular electron transfer: a joint experimental and computational study of a hormone biosynthesis pathway.

    PubMed

    Zöllner, Andy; Pasquinelli, Melissa A; Bernhardt, Rita; Beratan, David N

    2007-04-11

    Protein phosphorylation is a common regulator of enzyme activity. Chemical modification of a protein surface, including phosphorylation, could alter the function of biological electron-transfer reactions. However, the sensitivity of intermolecular electron-transfer kinetics to post-translational protein modifications has not been widely investigated. We have therefore combined experimental and computational studies to assess the potential role of phosphorylation in electron-transfer reactions. We investigated the steroid hydroxylating system from bovine adrenal glands, which consists of adrenodoxin (Adx), adrenodoxin reductase (AdR), and a cytochrome P450, CYP11A1. We focused on the phosphorylation of Adx at Thr-71, since this residue is located in the acidic interaction domain of Adx, and a recent study has demonstrated that this residue is phosphorylated by casein kinase 2 (CK2) in vitro.1 Optical biosensor experiments indicate that the presence of this phosphorylation slightly increases the binding affinity of oxidized Adx with CYP11A1ox but not AdRox. This tendency was confirmed by KA values extracted from Adx concentration-dependent stopped-flow experiments that characterize the interaction between AdRred and Adxox or between Adxred and CYP11A1ox. In addition, acceleration of the electron-transfer kinetics measured with stopped-flow is seen only for the phosphorylated Adx-CYP11A1 reaction. Biphasic reaction kinetics are observed only when Adx is phosphorylated at Thr-71, and the Brownian dynamics (BD) simulations suggest that this phosphorylation may enhance the formation of a secondary Adx-CYP11A1 binding complex that provides an additional electron-transfer pathway with enhanced coupling. PMID:17358057

  6. Mode-specific intermolecular vibrational energy transfer. I. Phenyl selenocyanate and deuterated chloroform mixture

    NASA Astrophysics Data System (ADS)

    Bian, Hongtao; Li, Jiebo; Wen, Xiewen; Zheng, Junrong

    2010-05-01

    Vibrational energy transfer from the first excited state (2252 cm-1) of the C-D stretch of deuterated chloroform (DCCl3) to the 0-1 transition (2155 cm-1) of the CN stretch of phenyl selenocyanate (C6H5SeCN) in their 1:1 liquid mixture was observed with a pump/probe two-color two dimensional infrared spectroscopic technique. The mode-specific energy transfer can occur mainly because of the long vibrational lifetime of the CN stretch first excited state (˜300 ps) and the relatively strong hydrogen-bond between the C-D and CN (calculated H-bond formation energy in gas phase ˜-5.4 kcal/mol). The mode-specific energy transfer is relatively low efficient (only ˜2%), which is mainly because of the relatively short vibrational lifetime (˜9 ps) of the C-D stretch first excited state and the big donor/acceptor energy mismatch (97 cm-1) and the slow transfer kinetics (1/kCD→CN=330 ps).

  7. Inner reorganization limiting electron transfer controlled hydrogen bonding: intra- vs. intermolecular effects.

    PubMed

    Martínez-González, Eduardo; Frontana, Carlos

    2014-05-01

    In this work, experimental evidence of the influence of the electron transfer kinetics during electron transfer controlled hydrogen bonding between anion radicals of metronidazole and ornidazole, derivatives of 5-nitro-imidazole, and 1,3-diethylurea as the hydrogen bond donor, is presented. Analysis of the variations of voltammetric EpIcvs. log KB[DH], where KB is the binding constant, allowed us to determine the values of the binding constant and also the electron transfer rate k, confirmed by experiments obtained at different scan rates. Electronic structure calculations at the BHandHLYP/6-311++G(2d,2p) level for metronidazole, including the solvent effect by the Cramer/Truhlar model, suggested that the minimum energy conformer is stabilized by intramolecular hydrogen bonding. In this structure, the inner reorganization energy, λi,j, contributes significantly (0.5 eV) to the total reorganization energy of electron transfer, thus leading to a diminishment of the experimental k. PMID:24653999

  8. Intermolecular electron transfer rate in diffusion limited region: Picosecond fluorescence studies

    NASA Astrophysics Data System (ADS)

    Venkataraman, B.; Periasamy, N.; Modi, S.; Dutt, G. Bhaskar; Doraiswamy, S.

    1992-12-01

    The temporal profiles of the quenched fluorescence decay of the free base meso-tetraphenyl porphyrin (H 2TPP) and its Zn derivative (ZnTPP) with quenchers such as quinones and m-dinitrobenzene have been analysed by methods developed for short time regimes which are known to be diffusion influenced [N. Periasamy et al., J. Chem. Phys.88, 1638 (1988); 89, 4799 (1988); Chem. Phys. Lett.160, 457 (1989); N. Periasamy, Biophys. J.. 54, 961 (1988); R. Das and N. Periasamy, Chem. Phys. 136, 361 (1989); G.C. Joshi et al., J. Phys. Chem.94, 2908 (1990)]. These quenchers are known to participate in an electron transfer reaction leading to a charge separation. The intrinsic rate constant ( ka) derived from the analysis is examined as a function of the change in free energy in the electron transfer reaction. Such a comparison indicates that ka can be related to the electron transfer rate, ket. The electron transfer rates measured in acetonitrile (solvent reorganization energy, λ s = 1.35) and toluene (λ s = 0.1) do not indicate the existence of an inverted region as predicted by Marcus. The trend agrees with the findings of Rehm and Weller [ Isr. J. Chem.8, 259 (1970)], except that the rate constants are at least one order of magnitude larger than the diffusion limited values.

  9. Combining intra- and intermolecular charge-transfer: a new strategy towards molecular ferromagnets and multiferroics

    PubMed Central

    Di Maiolo, Francesco; Sissa, Cristina; Painelli, Anna

    2016-01-01

    Organic ferroelectric materials are currently a hot research topic, with mixed stack charge transfer crystals playing a prominent role with their large, electronic-in-origin polarization and the possibility to tune the transition temperature down to the quantum limit and/or to drive the ferroelectric transition via an optical stimulus. By contrast, and in spite of an impressive research effort, organic ferromagnets are rare and characterized by very low transition temperatures. Coexisting magnetic and electric orders in multiferroics offer the possibility to control magnetic (electric) properties by an applied electric (magnetic) field with impressive technological potential. Only few examples of multiferroics are known today, based on inorganics materials. Here we demonstrate that, by decorating mixed stack charge transfer crystals with organic radicals, a new family of robust molecular ferromagnets can be designed, stable up to ambient temperature, and with a clear tendency towards multiferroic behaviour. PMID:26790963

  10. Combining intra- and intermolecular charge-transfer: a new strategy towards molecular ferromagnets and multiferroics

    NASA Astrophysics Data System (ADS)

    di Maiolo, Francesco; Sissa, Cristina; Painelli, Anna

    2016-01-01

    Organic ferroelectric materials are currently a hot research topic, with mixed stack charge transfer crystals playing a prominent role with their large, electronic-in-origin polarization and the possibility to tune the transition temperature down to the quantum limit and/or to drive the ferroelectric transition via an optical stimulus. By contrast, and in spite of an impressive research effort, organic ferromagnets are rare and characterized by very low transition temperatures. Coexisting magnetic and electric orders in multiferroics offer the possibility to control magnetic (electric) properties by an applied electric (magnetic) field with impressive technological potential. Only few examples of multiferroics are known today, based on inorganics materials. Here we demonstrate that, by decorating mixed stack charge transfer crystals with organic radicals, a new family of robust molecular ferromagnets can be designed, stable up to ambient temperature, and with a clear tendency towards multiferroic behaviour.

  11. Combining intra- and intermolecular charge-transfer: a new strategy towards molecular ferromagnets and multiferroics.

    PubMed

    Di Maiolo, Francesco; Sissa, Cristina; Painelli, Anna

    2016-01-01

    Organic ferroelectric materials are currently a hot research topic, with mixed stack charge transfer crystals playing a prominent role with their large, electronic-in-origin polarization and the possibility to tune the transition temperature down to the quantum limit and/or to drive the ferroelectric transition via an optical stimulus. By contrast, and in spite of an impressive research effort, organic ferromagnets are rare and characterized by very low transition temperatures. Coexisting magnetic and electric orders in multiferroics offer the possibility to control magnetic (electric) properties by an applied electric (magnetic) field with impressive technological potential. Only few examples of multiferroics are known today, based on inorganics materials. Here we demonstrate that, by decorating mixed stack charge transfer crystals with organic radicals, a new family of robust molecular ferromagnets can be designed, stable up to ambient temperature, and with a clear tendency towards multiferroic behaviour. PMID:26790963

  12. Dynamical aspects of intermolecular proton transfer in liquid water and low-density amorphous ices.

    PubMed

    Tahat, Amani; Martí, Jordi

    2014-05-01

    The microscopic dynamics of an excess proton in water and in low-density amorphous ices has been studied by means of a series of molecular dynamics simulations. Interaction of water with the proton species was modelled using a multistate empirical valence bond Hamiltonian model. The analysis of the effects of low temperatures on proton diffusion and transfer rates has been considered for a temperature range between 100 and 298 K at the constant density of 1 g cm(-3). We observed a marked slowdown of proton transfer rates at low temperatures, but some episodes are still seen at 100 K. In a similar fashion, mobility of the lone proton gets significantly reduced when temperature decreases below 273 K. The proton transfer in low-density amorphous ice is an activated process with energy barriers between 1-10 kJ/mol depending of the temperature range considered and eventually showing Arrhenius-like behavior. Spectroscopic data indicated the survival of both Zundel and Eigen structures along the whole temperature range, revealed by significant spectral frequency shifts. PMID:25353762

  13. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

    SciTech Connect

    Yao, Yi; Berkowitz, Max L. E-mail: ykanai@unc.edu; Kanai, Yosuke E-mail: ykanai@unc.edu

    2015-12-28

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na{sup +} and K{sup +} ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  14. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

    NASA Astrophysics Data System (ADS)

    Yao, Yi; Berkowitz, Max L.; Kanai, Yosuke

    2015-12-01

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na+ and K+ ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  15. 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.

  16. Intermolecular Energy Transfer Dynamics at a Hot-Spot Interface in RDX Crystals.

    PubMed

    Joshi, Kaushik; Losada, Martin; Chaudhuri, Santanu

    2016-02-01

    The phonon mediated vibrational up-pumping mechanisms assume an intact lattice and climbing of a vibrational ladder using strongly correlated multiphonon dynamics under equilibrium or near-equilibrium conditions. Important dynamic processes far from-equilibrium in regions of large temperature gradient after the onset of decomposition reactions in energetic solids are relatively unknown. In this work, we present a classical molecular dynamics (MD) simulation-based study of such processes using a nonreactive and a reactive potential to study a fully reacted and unreacted zone in RDX (1,3,5-trinitro-1,3,5-triazocyclohexane) crystal under nonequilibrium conditions. The energy transfer rate is evaluated as a function of temperature difference between the reacted and unreacted regions, and for different widths and cross-sectional area of unreacted RDX layers. Vibrational up-pumping processes probed using velocity autocorrelation functions indicate that the mechanisms at high-temperature interfaces are quite different from the standard phonon-based models proposed in current literature. In particular, the up-pumping of high-frequency vibrations are seen in the presence of small molecule collisions at the hot-spot interface with strong contributions from bending modes. It also explains some major difference in the order of decomposition of C-N and N-N bonds as seen in recent literature on initiation chemistry. PMID:26741283

  17. Intermolecular interactions and proton transfer in the hydrogen halide-superoxide anion complexes.

    PubMed

    Lee, Sebastian J R; Mullinax, J Wayne; Schaefer, Henry F

    2016-02-17

    The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the hydrogen halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 Å) hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier hydrogen halides with the resulting complexes characterized as long (>1.89 Å) hydrogen bonds between halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier hydrogen halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI. PMID:26852733

  18. Effect of laser intensity on the determination of intermolecular electron transfer rate constants—Observation of Marcus inverted region in photoinduced back electron transfer reactions

    NASA Astrophysics Data System (ADS)

    Weng, Yu-Xiang; Chan, Kwok-Chu; Tzeng, Biing-Chiau; Che, Chi-Ming

    1998-10-01

    The light intensity and concentration dependence of the photoproduct yield are investigated in a monophotonic process. The relationship of the photoproduct yield with the laser intensity and the complex concentration for a monophotonic process is derived under laser flash photolysis. The relationship is confirmed experimentally in a monophotonic process, i.e., triplet-triplet transition for a Cu(I) complex Cu6(DMNSN')6 (DMNSN'=4,6-dimethylpyrimidine-2-thiolate). At low light intensity, the relationship can be approximated by a linear inverse square root dependence on the light intensity. Based on this equation, a method is proposed to determine the intrinsic back electron transfer rate constant kETb in photoinduced intermolecular electron transfer reactions, precluding the effect from the diffusional encounter pairs. The Marcus "inverted region" is observed by using the method in photoinduced back electron transfer reactions of [Au2(dppm)2](ClO4)2 (dppm=bis(diphenylphosphino)methane) with a series of substituted pyridinium acceptors.

  19. Kinetics of intra- and intermolecular excited-state proton transfer of ω -(2-hydroxynaphthyl-1)-decanoic acid in homogeneous and micellar solutions

    NASA Astrophysics Data System (ADS)

    Solntsev, Kyril M.; Popov, Alexander V.; Solovyeva, Vera A.; Abou Al-Ainain, Sami; Il'ichev, Yuri V.; Hernandez, Rigoberto; Kuzmin, Michael G.

    2016-03-01

    The bifunctional photoacid ω-(2-hydroxynaphthyl-1)-decanoic acid (1S2N) takes part both in intramolecular excited-state proton transfer (ESPT) to the anion of a fatty acid and in intermolecular ESPT in the presence of a water solvent. Excited-state intra- and intermolecular proton transfer of 1S2N was investigated in homogeneous ethanol/water solution and in micellar solutions of various surfactants. The interfacial potential of micelles was changed by using cationic (CTAB), non-ionic (Brij-35) and anionic (SDS) surfactants. With the decrease of the interfacial potential, the protolytic photodissociation of naphthol and the diffusion-controlled intramolecular ESPT to carboxylic anion were suppressed.

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

    PubMed

    Yamane, Hiroyuki; Kosugi, Nobuhiro

    2013-08-23

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

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

    NASA Astrophysics Data System (ADS)

    Yamane, Hiroyuki; Kosugi, Nobuhiro

    2013-08-01

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

  2. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

    SciTech Connect

    Ye, ChuanXiang; Zhao, Yi E-mail: liangwz@xmu.edu.cn; Liang, WanZhen E-mail: liangwz@xmu.edu.cn

    2015-10-21

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT.

  3. Photophysical properties and photo-induced intermolecular electron transfer of a novel aryl benzyl ester dendritic axially substituted silicon (IV) phthalocyanine

    NASA Astrophysics Data System (ADS)

    Chen, Xiuqin; Ma, Dongdong; Wang, Xiongwei; Chen, Jianling; Ruan, Youhong; Qi, Yiling; Ye, Qiuhao; Peng, Yiru

    2014-11-01

    The photophysical properties of a novel dendritic phthalocyanine di-{3,5-di-(4-methoxycarbonyl group benzyloxy) benzyloxy) benzyloxy} axially substituted silicon (IV) phthalocyanine (DSiPc) were studied by UV/Vis, steady state and time-resolved spectroscopic methods. The effect of dendritic structure on the photophysical properties and photoinduced intermolecular electron transfer were investigated. The maximum absorption, fluorescence intensity, lifetime and fluorescence quantum yield of DSiPc were greatly sensitized by the dendritic structure on the axially position of silicon (IV) phthalocyanine. The photoinduced intermolecular electron transfer between this novel macromolecule and benzoquinone (BQ) was studied. The results showed that the fluorescence emission of this dendritic phthalocyanine could be quenched by BQ with KSV value of DSiPc is 52.84 dm3 mol-1. The cyclic voltammogram and square wave voltammogram of DSiPc in DMF further evidenced the electron was transfer from DSiPc to BQ from thermodynamics. Therefore, this novel dendritic phthalocyanine was an effective new electron donor and transmission complex could be used as a potential artificial photosynthesis system.

  4. Training Transfer: An Integrative Literature Review

    ERIC Educational Resources Information Center

    Burke, Lisa A.; Hutchins, Holly M.

    2007-01-01

    Given the proliferation of training transfer studies in various disciplines, we provide an integrative and analytical review of factors impacting transfer of training. Relevant empirical research for transfer across the management, human resource development (HRD), training, adult learning, performance improvement, and psychology literatures is…

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  6. Broadband visible light-harvesting naphthalenediimide (NDI) triad: study of the intra-/intermolecular energy/electron transfer and the triplet excited state.

    PubMed

    Wu, Shuang; Zhong, Fangfang; Zhao, Jianzhang; Guo, Song; Yang, Wenbo; Fyles, Tom

    2015-05-21

    A triad based on naphthalenediimides (NDI) was prepared to study the intersystem crossing (ISC), the fluorescence-resonance-energy-transfer (FRET), as well as the photoinduced electron transfer (PET) processes. In the triad, the 2-bromo-6-alkylaminoNDI moiety was used as singlet energy donor and the spin converter, whereas 2,6-dialkylaminoNDI was used as the singlet/triplet energy acceptor. This unique structural protocol and thus alignment of the energy levels ensures the competing ISC and FRET in the triad. The photophysical properties of the triad and the reference compounds were studied with steady-state UV-vis absorption spectra, fluorescence spectra, nanosecond transient absorption spectra, cyclic voltammetry, and DFT/TDDFT calculations. FRET was confirmed with steady-state UV-vis absorption and fluorescence spectroscopy. Intramolecular electron transfer was observed in polar solvents, demonstrated by the quenching of both the fluorescence and triplet state of the energy acceptor. Nanosecond transient absorption spectroscopy shows that the T1 state of the triad is exclusively localized on the 2,6-dialkylaminoNDI moiety in the triad upon selective photoexcitation into the energy donor, which indicates the intramolecular triplet state energy transfer. The intermolecular triplet state energy transfer between the two reference compounds was investigated with nanosecond transient absorption spectroscopy. The photophysical properties were rationalized by TDDFT calculations. PMID:25919420

  7. Theory and assignment of intermolecular charge transfer states in squaraines and their impact on efficiency in bulk heterojunction solar cells (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Collison, Christopher J.; Zheng, Chenyu; Hestand, Nicholas; Cona, Brandon; Penmetcha, Anirudh; Spencer, Susan; Cody, Jeremy; Spano, Frank

    2015-10-01

    Squaraines are targeted for organic photovoltaic devices because of their high extinction coefficients over a broad wavelength range from visible to near infra-red (NIR). Moreover, their side groups can be changed with profound effects upon their ability to crystallize, leading to improvements in charge mobility and exciton diffusion. The broadening in squaraine absorption is often qualitatively attributed to H- and J-aggregates based on the exciton model, proposed by Kasha. However, such assignment is misleading considering that spectral shifts can arise from sources other than excitonic coupling. Our group has shown that packing structure influences the rate of charge transfer; thus a complete and accurate reassessment of the excited states must be completed before the true charge transfer mechanism can be confirmed. In this work, we will show how squaraine H-aggregates can pack in complete vertical stacks or slipped vertical stacks depending upon sidegroups and processing conditions. Hence, we uncover the contribution of an intermolecular charge transfer (IMCT) state through essential states modeling validated by spectroscopic and X-Ray diffraction data. We further show external quantum efficiency data that describe the influence of the IMCT state on the efficiency of our devices. This comprehensive understanding of squaraine aggregates drives the development of more efficient organic photovoltaic devices, leading towards a prescription for derivatives that can be tailored for optimized exciton diffusion, charge transfer, higher mobilities and reduced recombination in small molecule OPV devices.

  8. Intramolecular vibrational energy redistribution and intermolecular energy transfer of benzene in supercritical CO 2: measurements from the gas phase up to liquid densities

    NASA Astrophysics Data System (ADS)

    von Benten, R.; Charvat, A.; Link, O.; Abel, B.; Schwarzer, D.

    2004-03-01

    Femtosecond pump probe spectroscopy was employed to measure intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) of benzene in the gas phase and in supercritical (sc) CO 2. We observe two IVR time scales the faster of which proceeds within τ IVR(1)<0.5 ps. The slower IVR component has a time constant of τ IVR(2)=(48±5) ps in the gas phase and in scCO 2 is accelerated by interactions with the solvent. At the highest CO 2 density it is reduced to τ IVR(2)=(6±1) ps. The corresponding IVR rate constants show a similar density dependence as the VET rate constants. Model calculations suggest that both quantities correlate with the local CO 2 density in the immediate surrounding of the benzene molecule.

  9. Effect of surface-plasmon polaritons on spontaneous emission and intermolecular energy-transfer rates in multilayered geometries

    SciTech Connect

    Marocico, C. A.; Knoester, J.

    2011-11-15

    We use a Green's tensor method to investigate the spontaneous emission rate of a molecule and the energy-transfer rate between molecules placed in two types of layered geometries: a slab geometry and a planar waveguide. We focus especially on the role played by surface-plasmon polaritons in modifying the spontaneous emission and energy-transfer rates as compared to free space. In the presence of more than one interface, the surface-plasmon polariton modes split into several branches, and each branch can contribute significantly to modifying the electromagnetic properties of atoms and molecules. Enhancements of several orders of magnitude both in the spontaneous emission rate of a molecule and the energy-transfer rate between molecules are obtained and, by tuning the parameters of the geometry, one has the ability to control the range and magnitude of these enhancements. For the energy-transfer rate interference effects between contributions of different plasmon-polariton branches are observed as oscillations in the distance dependence of this rate.

  10. Calculations of transfer integrals for tetracyanoquinodimethane salts

    NASA Astrophysics Data System (ADS)

    van Smaalen, Sander; Kommandeur, Jan

    1985-06-01

    Calculations of the transfer integral for the one-dimensional electron band of 7,7,8,8-tetracyanoquinodimethane (TCNQ) salts are presented. A critical discussion of the method is given, from which it follows that accurate estimates of these quantities are hard to obtain. However, relative values are expected to be more reliable. For the series of N-substituted morpholinium TCNQ salts a qualitative agreement between dc electrical conductivity and calculated transfer integral was found. For 1,2,6-trimethylpyridinium TCNQ, a counter-intuitive result is obtained, the ``crystallophic'' dimer and the ``electronic'' dimer being different.

  11. MHD Technology Transfer, Integration and Review Committee

    SciTech Connect

    Not Available

    1992-01-01

    This fifth semi-annual status report of the MHD Technology Transfer, Integration, and Review Committee (TTIRC) summarizes activities of the TTIRC during the period April 1990 through September 1990. It includes summaries and minutes of committee meetings, progress summaries of ongoing Proof-of-Concept (POC) contracts, discussions pertaining to technical integration issues in the POC program, and planned activities for the next six months.

  12. Intermolecular perturbation theory

    NASA Astrophysics Data System (ADS)

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

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

  13. Vehicle/engine integration. [orbit transfer vehicles

    NASA Technical Reports Server (NTRS)

    Cooper, L. P.; Vinopal, T. J.; Florence, D. E.; Michel, R. W.; Brown, J. R.; Bergeron, R. P.; Weldon, V. A.

    1984-01-01

    VEHICLE/ENGINE Integration Issues are explored for orbit transfer vehicles (OTV's). The impact of space basing and aeroassist on VEHICLE/ENGINE integration is discussed. The AOTV structure and thermal protection subsystem weights were scaled as the vehicle length and surface was changed. It is concluded that for increased allowable payload lengths in a ground-based system, lower length-to-diameter (L/D) is as important as higher mixture ration (MR) in the range of mid L/D ATOV's. Scenario validity, geometry constraints, throttle levels, reliability, and servicing are discussed in the context of engine design and engine/vehicle integration.

  14. DFT study of isocyanate chemisorption on Cu(100): Correlation between substrate-adsorbate charge transfer and intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Belelli, Patricia G.; Garda, Graciela R.; Ferullo, Ricardo M.

    2011-07-01

    The adsorption of isocyanate (- NCO) species on Cu(100) was studied using the density functional theory (DFT) and the periodic slab model. The calculations indicate that at low and intermediate coverages NCO adsorbs preferentially on bridge and hollow sites. Work function and dipole moment changes show a significant negative charge transfer from Cu to NCO. The resulting charged NCO species interact repulsively among themselves being these dipole-dipole interactions particularly intensive when they are adsorbed in adjacent sites. Consequently, isocyanates tend to be separated from each other generating the vacant sites required for the dissociation to N and CO. This condition for NCO dissociation has been suggested in the past from experimental observations. A comparison was also performed with the NCO adsorption on Pd(100). In particular, the calculated minimal energy barrier for NCO dissociation was found to be higher on Cu(100) than on Pd(100) in accord with the well known higher NCO stability on Cu(100).

  15. Mechanochromism of piroxicam accompanied by intermolecular proton transfer probed by spectroscopic methods and solid-phase changes.

    PubMed

    Sheth, Agam R; Lubach, Joseph W; Munson, Eric J; Muller, Francis X; Grant, David J W

    2005-05-11

    Structural and solid-state changes of piroxicam in its crystalline form under mechanical stress were investigated using cryogenic grinding, powder X-ray diffractometry, diffuse-reflectance solid-state ultraviolet-visible spectroscopy, variable-temperature solid-state (13)C nuclear magnetic resonance spectroscopy, and solid-state diffuse-reflectance infrared Fourier transform spectroscopy. Crystalline piroxicam anhydrate exists as colorless single crystals irrespective of the polymorphic form and contains neutral piroxicam molecules. Under mechanical stress, these crystals become yellow amorphous piroxicam, which has a strong propensity to recrystallize to a colorless crystalline phase. The yellow color of amorphous piroxicam is attributed to charged piroxicam molecules. Variable-temperature solid-state (13)C NMR spectroscopy indicates that most of the amorphous piroxicam consists of neutral piroxicam molecules; the charged species comprise only about 8% of the amorphous phase. This ability to quantify the fractions of charged and neutral molecules of piroxicam in the amorphous phase highlights the unique capability of solid-state NMR to quantify mixtures in the absence of standards. Other compounds of piroxicam, which are yellow, are known to contain zwitterionic piroxicam molecules. The present work describes a system in which proton transfer accompanies both solid-state disorder and a change in color induced by mechanical stress, a phenomenon which may be termed mechanochromism of piroxicam. PMID:15869285

  16. Valence anions in complexes of adenine and 9-methyladenine with formic acid: stabilization by intermolecular proton transfer.

    PubMed

    Mazurkiewicz, Kamil; Harańczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Radisic, Dunja; Eustis, Soren N; Wang, Di; Bowen, Kit H

    2007-02-01

    Photoelectron spectra of adenine-formic acid (AFA(-)) and 9-methyladenine-formic acid (MAFA(-)) anionic complexes have been recorded with 2.540 eV photons. These spectra reveal broad features with maxima at 1.5-1.4 eV that indicate formation of stable valence anions in the gas phase. The neutral and anionic complexes of adenine/9-methyladenine and formic acid were also studied computationally at the B3LYP, second-order Møller-Plesset, and coupled-cluster levels of theory with the 6-31++G** and aug-cc-pVDZ basis sets. The neutral complexes form cyclic hydrogen bonds, and the most stable dimers are bound by 17.7 and 16.0 kcal/mol for AFA and MAFA, respectively. The theoretical results indicate that the excess electron in both AFA(-) and MAFA(-) occupies a pi* orbital localized on adenine/9-methyladenine, and the adiabatic stability of the most stable anions amounts to 0.67 and 0.54 eV for AFA(-) and MAFA(-), respectively. The attachment of the excess electron to the complexes induces a barrier-free proton transfer (BFPT) from the carboxylic group of formic acid to a N atom of adenine or 9-methyladenine. As a result, the most stable structures of the anionic complexes can be characterized as neutral radicals of hydrogenated adenine (9-methyladenine) solvated by a deprotonated formic acid. The BFPT to the N atoms of adenine may be biologically relevant because some of these sites are not involved in the Watson-Crick pairing scheme and are easily accessible in the cellular environment. We suggest that valence anions of purines might be as important as those of pyrimidines in the process of DNA damage by low-energy electrons. PMID:17263404

  17. Integrated modeling, data transfers, and physical models

    NASA Astrophysics Data System (ADS)

    Brookshire, D. S.; Chermak, J. M.

    2003-04-01

    Difficulties in developing precise economic policy models for water reallocation and re-regulation in various regional and transboundary settings has been exacerbated not only by climate issues but also by institutional changes reflected in the promulgation of environmental laws, changing regional populations, and an increased focus on water quality standards. As complexity of the water issues have increased, model development at a micro-policy level is necessary to capture difficult institutional nuances and represent the differing national, regional and stakeholders' viewpoints. More often than not, adequate "local" or specific micro-data are not available in all settings for modeling and policy decisions. Economic policy analysis increasingly deals with this problem through data transfers (transferring results from one study area to another) and significant progress has been made in understanding the issue of the dimensionality of data transfers. This paper explores the conceptual and empirical dimensions of data transfers in the context of integrated modeling when the transfers are not only from the behavioral, but also from the hard sciences. We begin by exploring the domain of transfer issues associated with policy analyses that directly consider uncertainty in both the behavioral and physical science settings. We then, through a stylized, hybrid, economic-engineering model of water supply and demand in the Middle Rio Grand Valley of New Mexico (USA) analyze the impacts of; (1) the relative uncertainty of data transfers methods, (2) the uncertainty of climate data and, (3) the uncertainly of population growth. These efforts are motivated by the need to address the relative importance of more accurate data both from the physical sciences as well as from demography and economics for policy analyses. We evaluate the impacts by empirically addressing (within the Middle Rio Grand model): (1) How much does the surrounding uncertainty of the benefit transfer

  18. Integrating emissions transfers into policy-making

    NASA Astrophysics Data System (ADS)

    Springmann, Marco

    2014-03-01

    Net emissions transfers via international trade from developing to developed countries have increased fourfold in the past two decades--from 0.4 GtCO2 in 1990 to 1.6 GtCO2 in 2008. Consumption of goods and services in developed countries is one of the main driving forces of those emissions transfers. Therefore several proposals have been made to assign the responsibility for those emissions to the beneficiary, that is, to the consumer. Although consumption-based analyses have become popular, few proposals have been made for integrating emissions transfers into actual policy making. This study advances and critically evaluates three potential policy options that could be integrated in the climate-policy framework of developed countries. An energy-economic model with global coverage is used for the analysis. I find that connecting emissions transfers to international offset responsibilities is the most promising option from an environmental and economic perspective and may provide another rationale for international climate finance. The two alternative policy options of adjusting domestic emissions targets in developed countries and of implementing carbon-related tariffs and export subsidies are found to be environmentally ineffective in the latter case and economically detrimental, especially for developing countries, in both cases.

  19. MHD technology transfer, integration, and review committee

    NASA Astrophysics Data System (ADS)

    1990-05-01

    As part of Task 8 of the magnetohydrodynamic (MHD) Integrated Topping Cycle (ITC) project, TRW was given the responsibility to organize, charter and co-chair, with the Department of Energy (DOE), an MHD Technology Transfer, Integration and Review Committee (TTIRC). The TTIRC consists of an Executive Committee (EC) which acts as the governing body, and a General Committee (GC), also referred to as the main or full committee, consisting of representatives from the various POC contractors, participating universities and national laboratories, utilities, equipment suppliers, and other potential MHD users or investors. The purpose of the TTIRC is to: (1) review all Proof-of-Concept (POC) projects and schedules in the national MHD program; to assess their compatibility with each other and the first commercial MHD retrofit plant; (2) establish and implement technology transfer formats for users of this technology; (3) identify interfaces, issues, and funding structures directly impacting the success of the commercial retrofit; (4) investigate and identify the manner in which, and by whom, the above should be resolved; and (5) investigate and assess other participation (foreign and domestic) in the U.S. MHD Program. There are seven sections: introduction; Executive Committee and General Committee activity; Committee activities related to technology transfer; ongoing POC integration activities being performed under the auspices of the Executive Committee; recommendations passed on to the DOE by the Executive Committee; Planned activities for the next six months.

  20. Intermolecular energy-band dispersion in PTCDA multilayers

    NASA Astrophysics Data System (ADS)

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

    2003-07-01

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

  1. MHD Technology Transfer, Integration and Review Committee

    SciTech Connect

    Not Available

    1989-10-01

    As part of the MHD Integrated Topping Cycle (ITC) project, TRW was given the responsibility to organize, charter and co-chair, with the Department of Energy (DOE), an MHD Technology Transfer, Integration and Review Committee (TTIRC). The Charter of the TTIRC, which was approved by the DOE in June 1988 and distributed to the committee members, is included as part of this Summary. As stated in the Charter, the purpose of this committee is to: (1) review all Proof-of-Concept (POC) projects and schedules in the national MHD program; to assess their compatibility with each other and the first commercial MHD retrofit plant; (2) establish and implement technology transfer formats for users of this technology; (3) identify interfaces, issues, and funding structures directly impacting the success of the commercial retrofit; (4) investigate and identify the manner in which, and by whom, the above should be resolved; and (5) investigate and assess other participation (foreign and domestic) in the US MHD Program. The DOE fiscal year 1989 MHD Program Plan Schedule is included at the end of this Summary. The MHD Technology Transfer, Integration and Review Committee's activities to date have focused primarily on the technology transfer'' aspects of its charter. It has provided a forum for the dissemination of technical and programmatic information among workers in the field of MHD and to the potential end users, the utilities, by holding semi-annual meetings. The committee publishes this semi-annual report, which presents in Sections 2 through 11 capsule summaries of technical progress for all DOE Proof-of-Concept MHD contracts and major test facilities.

  2. Probing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy

    NASA Astrophysics Data System (ADS)

    Paarmann, A.; Hayashi, T.; Mukamel, S.; Miller, R. J. D.

    2008-05-01

    Two-dimensional infrared photon echo and pump probe studies of the OH stretch vibration provide a sensitive probe of the correlations and couplings in the hydrogen bond network of liquid water. The nonlinear response is simulated using numerical integration of the Schrödinger equation with a Hamiltonian constructed to explicitly treat intermolecular coupling and nonadiabatic effects in the highly disordered singly and doubly excited vibrational exciton manifolds. The simulated two-dimensional spectra are in close agreement with our recent experimental results. The high sensitivity of the OH stretch vibration to the bath dynamics is found to arise from intramolecular mixing between states in the two-dimensional anharmonic OH stretch potential. Surprisingly small intermolecular couplings reproduce the experimentally observed intermolecular energy transfer times.

  3. Motivation to Transfer Training: An Integrative Literature Review

    ERIC Educational Resources Information Center

    Gegenfurtner, Andreas; Veermans, Koen; Festner, Dagmar; Gruber, Hans

    2009-01-01

    Motivation to transfer is essential for the transfer of training. Without motivation, newly acquired knowledge and skills will not be applied at work. The purpose of this integrative literature review is to summarize, critique, and synthesize past transfer motivation research and to offer directions for future investigations. First, seven…

  4. Orbital transfer vehicle engine integration study

    NASA Technical Reports Server (NTRS)

    Ketchum, W. J.

    1984-01-01

    NASA-LeRC is sponsoring industry studies to establish the technology base for an advanced engine for orbital transfer vehicles for mid-1990s IOC. Engine contractors are being assisted by vehicle contractors to define the requirements, interface conditions, and operational design criteria for new LO2-LH2 propulsion systems applicable to future orbit transfer vehicles and to assess the impacts on space basing, man rating, and low-G transfer missions on propulsion system design requirements. The results of a study is presented. The primary study emphasis was to determine what the OTV engine thrust level should be, how many engines are required on the OTV, and how the OTV engine should be designed. This was accomplished by evaluating planned OTV missions and concepts to determine the requirements for the OTV propulsion system, conducting tradeoffs and comparisons to optimize OTV capability, and evaluating reliability and maintenance to determine the recommended OTV engine design for future development.

  5. The Role of Facebook in Fostering Transfer Student Integration

    ERIC Educational Resources Information Center

    Nehls, Kimberly

    2014-01-01

    Persistence of transfer students is greatly influenced by academic and social integration at receiving institutions. The purpose of this study was to examine how transfer students and student affairs professionals used Facebook during the initial transition to campus. Findings from 15 different institutional Facebook groups revealed that transfer…

  6. Orbital transfer vehicle engine integration study

    NASA Technical Reports Server (NTRS)

    Ketchum, W. J.

    1985-01-01

    Industry studies were undertaken to establish the technology base for an advanced engine for Orbital Transfer Vehicles for mid-1990s IOC. This paper presents the results of a study conducted by General Dynamics Convair Division, under contract to Aerojet TechSystems Company for NASA-LeRC, to define requirements, interface conditions, and operational design criteria for new LO2/LH2 propulsion systems applicable to future Orbit Transfer Vehicles, and to assess the impacts of space basing, man rating, and low-g transfer on propulsion system design requirements. The primary study emphasis was to determine what the OTV engine thrust level should be, how many engines are required on the OTV, and how the OTV engine should be designed. This was accomplished by evaluating planned OTV missions and concepts to determine the requirements for the OTV propulsion system, conducting tradeoffs and comparisons to optimize OTV capability, and evaluating reliability and maintenance to determine the recommended OTV engine design for future development.

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

    NASA Astrophysics Data System (ADS)

    Zander, M.

    1984-05-01

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

  8. Intermolecular electron transfer states of 1-methyl-3-(N-(1,8-naphthalimidyl)ethyl)imidazolium iodide obtained by constrained density functional theory.

    PubMed

    Otsuka, Takao; Sumita, Masato; Izawa, Hironori; Morihashi, Kenji

    2016-07-21

    Electron transfer (ET) states of 1-methyl-3-(N-(1,8-naphthalimidyl)ethyl)imidazolium iodide are responsible for its photophysics. Investigation of an ET state based on constrained density functional theory (CDFT) revealed that nonradiative decay from the ET excited state is mediated by the interaction of the iodine atom with the 1,8-naphthalimide or the imidazolium group. PMID:27222312

  9. Theoretical study of the transfer integral and density of states in spiro-linked triphenylamine derivatives.

    PubMed

    Kirkpatrick, James; Nelson, Jenny

    2005-08-22

    We present a method for calculating the parameters that control hopping transport in disordered molecular solids, i.e., the transfer integrals and the distribution of transport site energies. Average values of these parameters are obtained by performing quantum-chemical calculations on a large ensemble of bimolecular complexes in random relative orientations. The method is applied to triphenylamine (TPA) and three differently substituted spiro-linked phenylamine compounds, 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-MeOTAD), 2,2'7,7'-tetrakis-(N,N-diphenylhenylamino)-9,9'-spirobifluorene (spiro-TAD), and 2,2',7,7'-tetrakis-(N,N-di-m-methylphenylamino)-9,9'-spirobifluorene (spiro-m-TTB). In the case of TPA, the dependence of the root-mean-square hole transfer integral J on intermolecular separation r for the ensemble of relative orientations is compared with that obtained by performing the same calculations for a fixed, approximately cofacial, orientation of the two TPA molecules. The calculation for the disordered geometry predicts a larger localization radius r0, where J approximately exp(-r/r0), than the calculation for the fixed orientation and is in better agreement with experiment. In the case of the spiro-linked compounds, results from our method are compared with parameters extracted from time-of-flight mobility measurements analyzed with the Gaussian disorder model (GDM). We find that the highest occupied molecular-orbital (HOMO) energies of the bimolecular complexes are distributed on an asymmetric peak, whose width varies in qualitative agreement with the value of the energetic disorder sigma obtained from experimental data using the GDM. The mean-square hole transfer integral varies in accordance with the experimentally determined value of the mobility prefactor micro0. The differences between the differently substituted compounds are interpreted in terms of differences in the spatial extent of the wave function. Spiro

  10. Desensitization of metastable intermolecular composites

    DOEpatents

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

    2011-04-26

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

  11. A simple transfer function for nonlinear dendritic integration

    PubMed Central

    Singh, Matthew F.; Zald, David H.

    2015-01-01

    Relatively recent advances in patch clamp recordings and iontophoresis have enabled unprecedented study of neuronal post-synaptic integration (“dendritic integration”). Findings support a separate layer of integration in the dendritic branches before potentials reach the cell's soma. While integration between branches obeys previous linear assumptions, proximal inputs within a branch produce threshold nonlinearity, which some authors have likened to the sigmoid function. Here we show the implausibility of a sigmoidal relation and present a more realistic transfer function in both an elegant artificial form and a biophysically derived form that further considers input locations along the dendritic arbor. As the distance between input locations determines their ability to produce nonlinear interactions, models incorporating dendritic topology are essential to understanding the computational power afforded by these early stages of integration. We use the biophysical transfer function to emulate empirical data using biophysical parameters and describe the conditions under which the artificial and biophysically derived forms are equivalent. PMID:26321940

  12. Integrating proton coupled electron transfer (PCET) and excited states

    SciTech Connect

    Gagliardi, Christopher J.; Westlake, Brittany C.; Kent, Caleb A.; Paul, Jared J.; Papanikolas, John M.; Meyer, Thomas J.

    2010-11-01

    In many of the chemical steps in photosynthesis and artificial photosynthesis, proton coupled electron transfer (PCET) plays an essential role. An important issue is how excited state reactivity can be integrated with PCET to carry out solar fuel reactions such as water splitting into hydrogen and oxygen or water reduction of CO2 to methanol or hydrocarbons. The principles behind PCET and concerted electron–proton transfer (EPT) pathways are reasonably well understood. In Photosystem II antenna light absorption is followed by sensitization of chlorophyll P680 and electron transfer quenching to give P680+. The oxidized chlorophyll activates the oxygen evolving complex (OEC), a CaMn4 cluster, through an intervening tyrosine–histidine pair, YZ. EPT plays a major role in a series of four activation steps that ultimately result in loss of 4e-/4H+ from the OEC with oxygen evolution. The key elements in photosynthesis and artificial photosynthesis – light absorption, excited state energy and electron transfer, electron transfer activation of multiple-electron, multiple-proton catalysis – can also be assembled in dye sensitized photoelectrochemical synthesis cells (DS-PEC). In this approach, molecular or nanoscale assemblies are incorporated at separate electrodes for coupled, light driven oxidation and reduction. Separate excited state electron transfer followed by proton transfer can be combined in single semi-concerted steps (photo-EPT) by photolysis of organic charge transfer excited states with H-bonded bases or in metal-to-ligand charge transfer (MLCT) excited states in pre-associated assemblies with H-bonded electron transfer donors or acceptors. In these assemblies, photochemically induced electron and proton transfer occur in a single, semi-concerted event to give high-energy, redox active intermediates.

  13. Early Integration and Other Outcomes for Community College Transfer Students

    ERIC Educational Resources Information Center

    D'Amico, Mark M.; Dika, Sandra L.; Elling, Theodore W.; Algozzine, Bob; Ginn, Donna J.

    2014-01-01

    The purpose of this study was to explore academic and social integration and other outcomes for community college transfer students. The study used Tinto's ("Leaving college: Rethinking the causes and cures of student attrition," 1993) "Longitudinal Model of Institutional Departure" and Deil-Amen's ("J Higher…

  14. Double-shell tank waste transfer facilities integrity assessment plan

    SciTech Connect

    Hundal, T.S.

    1998-09-30

    This document presents the integrity assessment plan for the existing double-shell tank waste transfer facilities system in the 200 East and 200 West Areas of Hanford Site. This plan identifies and proposes the integrity assessment elements and techniques to be performed for each facility. The integrity assessments of existing tank systems that stores or treats dangerous waste is required to be performed to be in compliance with the Washington State Department of Ecology Dangerous Waste Regulations, Washington Administrative Code WAC-173-303-640 requirements.

  15. Prediction of local and integrated heat transfer in nozzles using an integral turbulent boundary layer method

    NASA Technical Reports Server (NTRS)

    Boldman, D. R.; Schmidt, J. F.; Ehlers, R. C.

    1972-01-01

    An empirical modification of an existing integral energy turbulent boundary layer method is proposed in order to improve the estimates of local heat transfer in converging-diverging nozzles and consequently, provide better assessments of the total or integrated heat transfer. The method involves the use of a modified momentum-heat analogy which includes an acceleration term comprising the nozzle geometry and free stream velocity. The original and modified theories are applied to heat transfer data from previous studies which used heated air in 30 deg - 15 deg, 45 deg - 15 deg, and 60 deg - 15 deg water-cooled nozzles.

  16. New Type of Dual Solid-State Thermochromism: Modulation of Intramolecular Charge Transfer by Intermolecular π-π Interactions, Kinetic Trapping of the Aci-Nitro Group, and Reversible Molecular Locking

    NASA Astrophysics Data System (ADS)

    Naumov, Panče; Lee, Sang Cheol; Ishizawa, Nobuo; Jeong, Young Gyu; Chung, Ihn Hee; Fukuzumi, Shunichi

    2009-09-01

    intramolecular proton transfer of one amino proton to the nitro group, whereupon an aci-nitro form is thermally populated. Contrary to the numerous examples of solid thermochromic molecules based on either pericyclic reactions or keto-enol tautomerism, this system appears to be the first organic thermochromic family where the thermochromic change appears as an effect of intermolecular π-π interactions and thermal intramolecular proton transfer to aromatic nitro group.

  17. New type of dual solid-state thermochromism: modulation of intramolecular charge transfer by intermolecular pi-pi interactions, kinetic trapping of the aci-nitro group, and reversible molecular locking.

    PubMed

    Naumov, Pance; Lee, Sang Cheol; Ishizawa, Nobuo; Jeong, Young Gyu; Chung, Ihn Hee; Fukuzumi, Shunichi

    2009-10-22

    by intramolecular proton transfer of one amino proton to the nitro group, whereupon an aci-nitro form is thermally populated. Contrary to the numerous examples of solid thermochromic molecules based on either pericyclic reactions or keto-enol tautomerism, this system appears to be the first organic thermochromic family where the thermochromic change appears as an effect of intermolecular pi-pi interactions and thermal intramolecular proton transfer to aromatic nitro group. PMID:19780605

  18. Intermolecular electrostatic energies using density fitting

    PubMed Central

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

    2009-01-01

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

  19. Maximizing Singlet Fission by Intermolecular Packing.

    PubMed

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

    2014-10-01

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

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

    PubMed Central

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

    2009-01-01

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

  1. Integration of Heat Transfer, Stress, and Particle Trajectory Simulation

    SciTech Connect

    Thuc Bui; Michael Read; Lawrence ives

    2012-05-17

    Calabazas Creek Research, Inc. developed and currently markets Beam Optics Analyzer (BOA) in the United States and abroad. BOA is a 3D, charged particle optics code that solves the electric and magnetic fields with and without the presence of particles. It includes automatic and adaptive meshing to resolve spatial scales ranging from a few millimeters to meters. It is fully integrated with CAD packages, such as SolidWorks, allowing seamless geometry updates. The code includes iterative procedures for optimization, including a fully functional, graphical user interface. Recently, time dependent, particle in cell capability was added, pushing particles synchronically under quasistatic electromagnetic fields to obtain particle bunching under RF conditions. A heat transfer solver was added during this Phase I program. Completed tasks include: (1) Added a 3D finite element heat transfer solver with adaptivity; (2) Determined the accuracy of the linear heat transfer field solver to provide the basis for development of higher order solvers in Phase II; (3) Provided more accurate and smoother power density fields; and (4) Defined the geometry using the same CAD model, while maintaining different meshes, and interfacing the power density field between the particle simulator and heat transfer solvers. These objectives were achieved using modern programming techniques and algorithms. All programming was in C++ and parallelization in OpenMP, utilizing state-of-the-art multi-core technology. Both x86 and x64 versions are supported. The GUI design and implementation used Microsoft Foundation Class.

  2. Integrated Charge Transfer in Organic Ferroelectrics for Flexible Multisensing Materials.

    PubMed

    Xu, Beibei; Ren, Shenqiang

    2016-09-01

    The ultimate or end point of functional materials development is the realization of strong coupling between all energy regimes (optical, electronic, magnetic, and elastic), enabling the same material to be utilized for multifunctionalities. However, the integration of multifunctionalities in soft materials with the existence of various coupling is still in its early stage. Here, the coupling between ferroelectricity and charge transfer by combining bis(ethylenedithio)tetrathiafulvalene-C60 charge-transfer crystals with ferroelectric polyvinylidene fluoride polymer matrix is reported, which enables external stimuli-controlled polarization, optoelectronic and magnetic field sensing properties. Such flexible composite films also display a superior strain-dependent capacitance and resistance change with a giant piezoresistance coefficient of 7.89 × 10(-6) Pa(-1) . This mutual coupled material with the realization of enhanced couplings across these energy domains opens up the potential for multisensing applications. PMID:27378088

  3. State-transfer simulation in integrated waveguide circuits

    NASA Astrophysics Data System (ADS)

    Latmiral, L.; Di Franco, C.; Mennea, P. L.; Kim, M. S.

    2015-08-01

    Spin-chain models have been widely studied in terms of quantum information processes, for instance for the faithful transmission of quantum states. Here, we investigate the limitations of mapping this process to an equivalent one through a bosonic chain. In particular, we keep in mind experimental implementations, which the progress in integrated waveguide circuits could make possible in the very near future. We consider the feasibility of exploiting the higher dimensionality of the Hilbert space of the chain elements for the transmission of a larger amount of information, and the effects of unwanted excitations during the process. Finally, we exploit the information-flux method to provide bounds to the transfer fidelity.

  4. Integrated controls and health monitoring for chemical transfer propulsion

    NASA Technical Reports Server (NTRS)

    Millis, Marc G.; Binder, Michael P.

    1990-01-01

    NASA is reviewing various propulsion technologies for exploring space. The requirements are examined for one enabling propulsion technology: Integrated Controls and Health Monitoring (ICHM) for Chemical Transfer Propulsion (CTP). Functional requirements for a CTP-ICHM system are proposed from tentative mission scenarios, vehicle configurations, CTP specifications, and technical feasibility. These CTP-ICHM requirements go beyond traditional reliable operation and emergency shutoff control to include: (1) enhanced mission flexibility; (2) continuously variable throttling; (3) tank-head start control; (4) automated prestart and post-shutoff engine check; (5) monitoring of space exposure degradation; and (6) product evolution flexibility. Technology development plans are also discussed.

  5. Transition-density-fragment interaction combined with transfer integral approach for excitation-energy transfer via charge-transfer states

    NASA Astrophysics Data System (ADS)

    Fujimoto, Kazuhiro J.

    2012-07-01

    A transition-density-fragment interaction (TDFI) combined with a transfer integral (TI) method is proposed. The TDFI method was previously developed for describing electronic Coulomb interaction, which was applied to excitation-energy transfer (EET) [K. J. Fujimoto and S. Hayashi, J. Am. Chem. Soc. 131, 14152 (2009)] and exciton-coupled circular dichroism spectra [K. J. Fujimoto, J. Chem. Phys. 133, 124101 (2010)]. In the present study, the TDFI method is extended to the exchange interaction, and hence it is combined with the TI method for applying to the EET via charge-transfer (CT) states. In this scheme, the overlap correction is also taken into account. To check the TDFI-TI accuracy, several test calculations are performed to an ethylene dimer. As a result, the TDFI-TI method gives a much improved description of the electronic coupling, compared with the previous TDFI method. Based on the successful description of the electronic coupling, the decomposition analysis is also performed with the TDFI-TI method. The present analysis clearly shows a large contribution from the Coulomb interaction in most of the cases, and a significant influence of the CT states at the small separation. In addition, the exchange interaction is found to be small in this system. The present approach is useful for analyzing and understanding the mechanism of EET.

  6. Design study of an integrated aerobraking orbital transfer vehicle

    NASA Technical Reports Server (NTRS)

    Scott, C. D.; Roberts, B. B.; Nagy, K.; Taylor, P.; Gamble, J. D.; Ceremeli, C. J.; Knoll, K. R.; Li, C. P.; Reid, R. C.

    1985-01-01

    An aerobraking orbital transfer vehicle (AOTV) concept, which has an aerobrake structure that is integrated with the propulsion stage, is discussed. The concept vehicle is to be assembled in space and is space-based. The advantages of aeroassist over an all propulsive vehicle are discussed and it is shown that the vehicle considered is very competitive with inflatable and deployable concepts from mass and performance aspects. The aerobrake geometry is an ellipsoidally blunted, raked-off, elliptical wide-angle cone with a toroidal skirt. Propellant tanks, engines, and subsystems are integrated into a closed, isogrid aerobrake structure which provides rigidity. The vehicle has two side-firing, gimbaled RL-10 type engines and carries 38,000 kg of useable propellant. The trajectory during aerobraking is determined from an adaptive guidance logic, and the heating is determined from engineering correlations as well as 3-D Navier-Stokes solutions. The AOTV is capable of placing 13,500 kg payload into geosynchronous Earth orbit (GEO) or carrying a LEO-GEO-LEO round-trip payload of 7100 kg. A two-stage version considered for lunar missions results in a lunar surface delivery capability of 18,000 kg or a round-trip capability of 6800 kg with 3860 kg delivery-only capability.

  7. Academic Transfer Shock and Social Integration: A Comparison of Outcomes for Traditional and Nontraditional Students Transferring from 2-Year to 4-Year Institutions

    ERIC Educational Resources Information Center

    Strahn-Koller, Brooke Lindsey

    2012-01-01

    The purpose of this study was to explore whether traditional and nontraditional students who transferred from 2-year to 4-year institutions experienced differences in transfer shock, academic integration, and social integration. A substantial body of knowledge comparing transfer students to native students on transfer shock exists, while only a…

  8. 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.

  9. Desensitization and recovery of metastable intermolecular composites

    DOEpatents

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

    2010-09-07

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

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

    SciTech Connect

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

    2002-05-01

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

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

    PubMed

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

    2002-05-01

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

  12. Determination of Multidimensional Intermolecular Potential Energy Surfaces

    NASA Astrophysics Data System (ADS)

    Cohen, Ronald Carl

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

  13. 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

  14. Advising Underprepared Transfer Students: Integrating English Assessment and Academic Advising.

    ERIC Educational Resources Information Center

    Cooper, Elizabeth J.; Franke, Johannah S.

    1992-01-01

    The City University of New York's Lehman College requires entering transfer students to demonstrate writing proficiency for appropriate placement. Academic advising is used to help students understand the need for this assessment. The relatively complex system has been found to save students' time, promote academic achievement, and improve…

  15. Teaching for Transfer through Integrated Online and Traditional Art Instruction

    ERIC Educational Resources Information Center

    Erickson, Mary

    2005-01-01

    This is an exploratory, design-based study of the development and implementation of an online art unit designed to teach for transfer. Secondary art teachers implemented a traditional and then a revised Web version of the unit. Four kinds of knowledge (content, procedural, strategic, and dispositional) provide the structure for reporting: a)…

  16. Lateral Transfer Students: The Role of Housing in Social Integration and Transition

    ERIC Educational Resources Information Center

    Utter, Mary; DeAngelo, Linda

    2015-01-01

    Social integration for lateral transfer students (four-to-four-year) is promoted by a living environment that encourages learning about campus, connecting to resources, and developing peer groups. Interviews with 27 lateral transfer students revealed that those who had previously lived on campus had expectations that residence halls would provide…

  17. Transfer of plasmid RP4 to Myxococcus xanthus and evidence for its integration into the chromosome.

    PubMed Central

    Breton, A M; Jaoua, S; Guespin-Michel, J

    1985-01-01

    The broad-host-range plasmid RP4 and its derivative R68.45 were transferred to Myxococcus xanthus DK101 and DZ1; RP4 was maintained integrated in the chromosome. Loss of plasmid markers occurred during the growth of the transconjugants, which could be prevented by selective pressure with oxytetracycline. The integrated plasmid was transferred back to Escherichia coli often as RP4-prime plasmids carrying various segments of the M. xanthus chromosome. It also mediated chromosomal transfer between M. xanthus strains. Images PMID:3918015

  18. Controlled electrical doping of organic semiconductors: a combined intra- and intermolecular perspective from first principles.

    PubMed

    Joo, Bora; Kim, Eung-Gun

    2016-07-21

    The process of introducing extra charge carriers into organic semiconductors, or simply molecular doping, takes place via intermolecular charge transfer from the donor to the acceptor molecule. Using density functional theory calculations on diverse donor-acceptor pairs, we show that there are two modes of charge transfer; in one, charge transfer is controlled by the sign and in the other, by the magnitude of the donor HOMO-acceptor LUMO level offset. Despite doping being an intermolecular process, the identification of the transfer modes requires a full account of intramolecular geometric changes during charge transfer. We further show that the degree of charge transfer can be represented entirely by the reorganization energy, a common measure of geometric changes, of either the donor or the acceptor. PMID:27314750

  19. Investigating Practices in Teacher Education That Promote and Inhibit Technology Integration Transfer in Early Career Teachers

    ERIC Educational Resources Information Center

    Brenner, Aimee M.; Brill, Jennifer M.

    2016-01-01

    The purpose of this study was to identify instructional technology integration strategies and practices in preservice teacher education that contribute to the transfer of technology integration knowledge and skills to the instructional practices of early career teachers. This study used a two-phase, sequential explanatory strategy. Data were…

  20. Computer integrated manufacturing and technology transfer for improving aerospace productivity

    NASA Astrophysics Data System (ADS)

    Farrington, P. A.; Sica, J.

    1992-03-01

    This paper reviews a cooperative effort, between the Alabama Industial Development Training Institute and the University of Alabama in Huntsville, to implement a prototype computer integrated manufacturing system. The primary use of this system will be to educate Alabama companies on the organizational and technological issues involved in the implementation of advanced manufacturing systems.

  1. A New Integrated Approach for the Transfer of Knowledge

    ERIC Educational Resources Information Center

    Lazanas, P.

    2006-01-01

    One of the purposes of knowledge generation at the higher education level is the creation of expertise. However, the mental structures that an expert uses to process information are not generally considered. Instead, information alone is presented to the learner and it is hoped that he or she will somehow integrate this information into knowledge…

  2. Fractional integration and radiative transfer in a multifractal atmosphere

    SciTech Connect

    Naud, C.; Schertzer, D.; Lovejoy, S.

    1996-04-01

    Recently, Cess et al. (1995) and Ramathan et al. (1995) cited observations which exhibit an anomalous absorption of cloudy skies in comparison with the value predicted by usual models and which thus introduce large uncertainties for climatic change assessments. These observation raise questions concerning the way general circulation models have been tuned for decades, relying on classical methods, of both radiative transfer and dynamical modeling. The observations also tend to demonstrate that homogeneous models are simply not relevant in relating the highly variable properties of clouds and radiation fields. However smoothed, the intensity of cloud`s multi-scattered radiation fields reflect this extreme variability.

  3. Activated-Carbon Sorbent With Integral Heat-Transfer Device

    NASA Technical Reports Server (NTRS)

    Jones, Jack A.; Yavrouian, Andre

    1996-01-01

    Prototype adsorption device used, for example, in adsorption heat pump, to store natural gas to power automobile, or to separate components of fluid mixtures. Device includes activated carbon held together by binder and molded into finned heat-transfer device providing rapid heating or cooling to enable rapid adsorption or desorption of fluids. Concepts of design and fabrication of device equally valid for such other highly thermally conductive devices as copper-finned tubes, and for such other high-surface-area sorbents as zeolites or silicates.

  4. Intermolecular Hydropyridylation of Unactivated Alkenes.

    PubMed

    Ma, Xiaoshen; Herzon, Seth B

    2016-07-20

    A general method for the hydropyridylation of unactivated alkenes is described. The transformation connects metal-mediated hydrogen atom transfer to alkenes and Minisci addition reactions. The reaction proceeds under mild conditions with high site-selectivities and allows for the construction of tertiary and quaternary centers from simple alkene starting materials. PMID:27384921

  5. Time delay and integration detectors using charge transfer devices

    NASA Technical Reports Server (NTRS)

    Mccann, D. H.; White, M. H.; Turly, A. P.

    1981-01-01

    An imaging system comprises a multi-channel matrix array of CCD devices wherein a number of sensor cells (pixels) in each channel are subdivided and operated in discrete intercoupled groups of subarrays with a readout CCD shift register terminating each end of the channels. Clock voltages, applied to the subarrays, selectively cause charge signal flow in each subarray in either direction independent of the other subarrays. By selective application of four phase clock voltages, either one, two or all three of the sections subarray sections cause charge signal flow in one direction, while the remainder cause charge signal flow in the opposite direction. This creates a form of selective electronic exposure control which provides an effective variable time delay and integration of three, six or nine sensor cells or integration stages. The device is constructed on a semiconductor sustrate with a buried channel and is adapted for front surface imaging through transparent doped tin oxide gates.

  6. Intermolecular electronic interactions in the primary charge separation in bacterial photosynthesis

    SciTech Connect

    Plato, M.; Moebius, K.; Michel-Beyerle, M.E.; Bixon, M.; Jortner, J. )

    1988-10-26

    In this paper the intermolecular overlap approximation is used to calculate the relative magnitudes of the electronic transfer integrals between the excited singlet state ({sup 1}P*) of the bacteriochlorophyll dimer (P) and the accessory bacteriochlorophyll (B) and between B{sup {minus}} and bacteriopheopytin (H), along the L and M subunits of the reaction center (RC) of Rps. viridis. The ratio of the electron-transfer integrals for B{sub L}{sup {minus}}H{sub L}{sup {minus}}B{sub L}H{sub L}{minus} and for B{sub M}{sup {minus}}H{sub M}{minus}B{sub M}H{sub M}{sup {minus}} was calculated to be 2.1 {plus minus} 0.5, which together with the value of 2.8 {plus minus} 0.7 for the ratio of the transfer integrals for {sup 1}P*B{sub L}-P{sup +}B{sub L}- and for {sup 1}P*B{sub M}-P{sup +}B{sub M}- results in the electronic contribution of 33 {plus minus} 16 to the ratio k{sub L}/k{sub m} of the rate constants k{sub L} and k{sub M} for the primary charge separation across the L and M branches of the RC, respectively. The asymmetry of the electronic coupling terms, which originates from the combination of the asymmetry in the charge distribution of {sup 1}P* and of structural asymmetry of the P-M and B-H arrangements across the L and M subunits, provides a major contribution to the unidirectionality of the charge separation in bacterial photosynthesis. A significant contribution to the transfer integrals between adjacent pigments originates from nearby methyl groups through hyperconjugation. The ratio 6 {plus minus} 2 of the transfer integrals for {sup 1}P*B{sub L}-P{sup +}B{sub L}- and for B{sub L}-H{sub L}-B{sub L}H{sub L}- was utilized to estimate the energetic parameters required to ensure the dominance of the superexchange mediated unistep electron transfer {sup 1}P*BH {yields} P{sup +}BH{sup {minus}} over the thermally activated {sup 1}P*B {yields} P{sup +}B{sup {minus}} process. 31 refs., 6 figs., 2 tabs.

  7. Conjugative transposons: an unusual and diverse set of integrated gene transfer elements.

    PubMed Central

    Salyers, A A; Shoemaker, N B; Stevens, A M; Li, L Y

    1995-01-01

    Conjugative transposons are integrated DNA elements that excise themselves to form a covalently closed circular intermediate. This circular intermediate can either reintegrate in the same cell (intracellular transposition) or transfer by conjugation to a recipient and integrate into the recipient's genome (intercellular transposition). Conjugative transposons were first found in gram-positive cocci but are now known to be present in a variety of gram-positive and gram-negative bacteria also. Conjugative transposons have a surprisingly broad host range, and they probably contribute as much as plasmids to the spread of antibiotic resistance genes in some genera of disease-causing bacteria. Resistance genes need not be carried on the conjugative transposon to be transferred. Many conjugative transposons can mobilize coresident plasmids, and the Bacteroides conjugative transposons can even excise and mobilize unlinked integrated elements. The Bacteroides conjugative transposons are also unusual in that their transfer activities are regulated by tetracycline via a complex regulatory network. PMID:8531886

  8. Integration of laser die transfer and magnetic self-assembly for ultra-thin chip placement

    NASA Astrophysics Data System (ADS)

    Eda Kuran, Emine; Berg, Yuval; Tichem, Marcel; Kotler, Zvi

    2015-04-01

    In this paper, we demonstrate the integration of a novel self-assembly method with laser die transfer for ultra-thin chip (UTC) placement. The laser die transfer technique provides high speed chip presentation into the assembly positions on the substrate, where the magnetic self-assembly traps and aligns the chips. Combination of these two technologies allows handling of UTCs without a direct mechanical contact throughout the assembly flow and provides high precision chip placement.

  9. Demonstration of strong near-field radiative heat transfer between integrated nanostructures.

    PubMed

    St-Gelais, Raphael; Guha, Biswajeet; Zhu, Linxiao; Fan, Shanhui; Lipson, Michal

    2014-12-10

    Near-field heat transfer recently attracted growing interest but was demonstrated experimentally only in macroscopic systems. However, several projected applications would be relevant mostly in integrated nanostructures. Here we demonstrate a platform for near-field heat transfer on-chip and show that it can be the dominant thermal transport mechanism between integrated nanostructures, overcoming background substrate conduction and the far-field limit (by factors 8 and 7, respectively). Our approach could enable the development of active thermal control devices such as thermal rectifiers and transistors. PMID:25420115

  10. Development of Innovative Integrated Simulator on Shipboard Crane Considering Ship Sway and Transfer Control

    NASA Astrophysics Data System (ADS)

    Ito, Ryuji; Terashima, Kazuhiko; Noda, Yoshiyuki; Iwasa, Takahiro

    In this paper, in order to systemize the state analysis of a shipboard crane, the integrated computer simulator tool of rotary crane with ship behavior in consideration of ship sway is newly built. The integrated simulator of shipboard crane considering ship sway was realized by corporating an external force interface routine of a component with Fluid analysis software. The transfer control system is conducted by HSA (Hybrid Shape Approach) using STT (Straight Transfer Transformation) method. The proposal method was confirmed to be effective in order to reduce both sway of a ship and a load by the simulation analysis.

  11. Shedding light on the photostability of two intermolecular charge-transfer complexes between highly fluorescent bis-1,8-naphthalimide dyes and some π-acceptors: A spectroscopic study in solution and solid states

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Ismail, Lamia A.; Adam, Abdel Majid A.

    2015-01-01

    Given the great importance of the various uses of 1,8-naphthalimides in the trends of biology, medicine and industry, the current study focused on extending the scope of these dyes by introducing some of their charge-transfer (CT) complexes. For this purpose, two highly fluorescent bis-1,8-naphthalimide dyes and their complexes with some π-acceptors have been synthesized and characterized spectroscopically. The π-acceptors include picric acid (PA), chloranilic acid (CLA), tetracyanoquinodimethane (TCNQ) and dichlorodicyanobenzoquinone (DDQ). The molecular structure, spectroscopic and fluorescence properties as well as the binding modes were deduced from IR, UV-vis and 1H NMR spectral studies. The binding ratio of complexation was determined to be 1:1 according to the elemental analyses and photometric titrations. It has been found that the order of acceptance ability for the different acceptors is TCNQ > DDQ > CLA > PA. The photostability of 1,8-naphthalimide dye as a donor and its charge-transfer complex doped in polymethyl methacrylate/PMMA were exposed to UV-Vis radiation and the change in the absorption spectra was achieved at different times during irradiation period.

  12. Shedding light on the photostability of two intermolecular charge-transfer complexes between highly fluorescent bis-1,8-naphthalimide dyes and some π-acceptors: a spectroscopic study in solution and solid states.

    PubMed

    Refat, Moamen S; Ismail, Lamia A; Adam, Abdel Majid A

    2015-01-01

    Given the great importance of the various uses of 1,8-naphthalimides in the trends of biology, medicine and industry, the current study focused on extending the scope of these dyes by introducing some of their charge-transfer (CT) complexes. For this purpose, two highly fluorescent bis-1,8-naphthalimide dyes and their complexes with some π-acceptors have been synthesized and characterized spectroscopically. The π-acceptors include picric acid (PA), chloranilic acid (CLA), tetracyanoquinodimethane (TCNQ) and dichlorodicyanobenzoquinone (DDQ). The molecular structure, spectroscopic and fluorescence properties as well as the binding modes were deduced from IR, UV-vis and (1)H NMR spectral studies. The binding ratio of complexation was determined to be 1:1 according to the elemental analyses and photometric titrations. It has been found that the order of acceptance ability for the different acceptors is TCNQ>DDQ>CLA>PA. The photostability of 1,8-naphthalimide dye as a donor and its charge-transfer complex doped in polymethyl methacrylate/PMMA were exposed to UV-Vis radiation and the change in the absorption spectra was achieved at different times during irradiation period. PMID:25022501

  13. 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

  14. Estimation of intermolecular interactions in polymer networks

    SciTech Connect

    Subrananian, P.R.; Galiatsatos, V.

    1993-12-31

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

  15. 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.

  16. Quantum-Classical Path Integral Simulation of Ferrocene-Ferrocenium Charge Transfer in Liquid Hexane.

    PubMed

    Walters, Peter L; Makri, Nancy

    2015-12-17

    We employ the quantum-classical path integral methodology to simulate the outer sphere charge-transfer process of the ferrocene-ferrocenium pair in liquid hexane with unprecedented accuracy. Comparison of the simulation results to those obtained by mapping the solvent on an effective harmonic bath demonstrates the accuracy of linear response theory in this system. PMID:26673195

  17. Integrating Key Skills in Higher Education: Employability, Transferable Skills and Learning for Life.

    ERIC Educational Resources Information Center

    Fallows, Stephen, Ed.; Steven, Christine, Ed.

    This book addresses issues related to the skills agenda in higher education, focusing on key skills, employability skills, transferable skills, and core skills. The chapters provide a practical guide to the ways skills can be effectively integrated into courses and institutions. The chapters are: (1) "The Skills Agenda" (Stephen Fallows and…

  18. Measurements of the Influence of Integral Length Scale on Stagnation Region Heat Transfer

    NASA Technical Reports Server (NTRS)

    Vanfossen, G. James; Ching, Chang Y.

    1994-01-01

    The purpose was twofold: first, to determine if a length scale existed that would cause the greatest augmentation in stagnation region heat transfer for a given turbulence intensity and second, to develop a prediction tool for stagnation heat transfer in the presence of free stream turbulence. Toward this end, a model with a circular leading edge was fabricated with heat transfer gages in the stagnation region. The model was qualified in a low turbulence wind tunnel by comparing measurements with Frossling's solution for stagnation region heat transfer in a laminar free stream. Five turbulence generating grids were fabricated; four were square mesh, biplane grids made from square bars. Each had identical mesh to bar width ratio but different bar widths. The fifth grid was an array of fine parallel wires that were perpendicular to the axis of the cylindrical leading edge. Turbulence intensity and integral length scale were measured as a function of distance from the grids. Stagnation region heat transfer was measured at various distances downstream of each grid. Data were taken at cylinder Reynolds numbers ranging from 42,000 to 193,000. Turbulence intensities were in the range 1.1 to 15.9 percent while the ratio of integral length scale to cylinder diameter ranged from 0.05 to 0.30. Stagnation region heat transfer augmentation increased with decreasing length scale. An optimum scale was not found. A correlation was developed that fit heat transfer data for the square bar grids to within +4 percent. The data from the array of wires were not predicted by the correlation; augmentation was higher for this case indicating that the degree of isotropy in the turbulent flow field has a large effect on stagnation heat transfer. The data of other researchers are also compared with the correlation.

  19. Computational modelling of placental amino acid transfer as an integrated system.

    PubMed

    Panitchob, N; Widdows, K L; Crocker, I P; Johnstone, E D; Please, C P; Sibley, C P; Glazier, J D; Lewis, R M; Sengers, B G

    2016-07-01

    Placental amino acid transfer is essential for fetal development and its impairment is associated with poor fetal growth. Amino acid transfer is mediated by a broad array of specific plasma membrane transporters with overlapping substrate specificity. However, it is not fully understood how these different transporters work together to mediate net flux across the placenta. Therefore the aim of this study was to develop a new computational model to describe how human placental amino acid transfer functions as an integrated system. Amino acid transfer from mother to fetus requires transport across the two plasma membranes of the placental syncytiotrophoblast, each of which contains a distinct complement of transporter proteins. A compartmental modelling approach was combined with a carrier based modelling framework to represent the kinetics of the individual accumulative, exchange and facilitative classes of transporters on each plasma membrane. The model successfully captured the principal features of transplacental transfer. Modelling results clearly demonstrate how modulating transporter activity and conditions such as phenylketonuria, can increase the transfer of certain groups of amino acids, but that this comes at the cost of decreasing the transfer of others, which has implications for developing clinical treatment options in the placenta and other transporting epithelia. PMID:27045077

  20. Clean graphene interfaces by selective dry transfer for large area silicon integration.

    PubMed

    Na, S R; Rahimi, S; Tao, L; Chou, H; Ameri, S K; Akinwande, D; Liechti, K M

    2016-03-31

    Here we present a very fast, selective mechanical approach for transferring graphene with low levels of copper contamination from seed wafers on which it was grown to target wafers for very large scale integration (VLSI) electronics. We found that graphene/copper or copper/silicon oxide delamination paths could be selected by slow and faster separation rates, respectively. Thus graphene can be transferred to a target wafer, either exposed or protected by the seed copper layer, which can later be removed by etching. Delamination paths were identified by SEM and Raman spectroscopy. The sheet resistance of the graphene produced by the two approaches was slightly higher than graphene transferred by a PMMA wet-transfer process, indicating reduced impurity doping, and the variation in the sheet resistance values was much lower. Copper contamination levels, quantitatively established by TOF-SIMS, were several orders of magnitude lower than the values for PMMA assisted transfer. In addition, we demonstrated that top-gated transistor devices from our mechanical, delamination transferred graphene exhibited superior transistor behavior to PMMA-assisted wet transfer graphene. The adhesion energy, strength and range of the interactions were quantitatively determined by nonlinear fracture analyses, and suggest that the roughness of the interface between graphene and copper plays an important role with implications for improvements in manufacturing processes. PMID:26902897

  1. Entropy-based analysis and bioinformatics-inspired integration of global economic information transfer.

    PubMed

    Kim, Jinkyu; Kim, Gunn; An, Sungbae; Kwon, Young-Kyun; Yoon, Sungroh

    2013-01-01

    The assessment of information transfer in the global economic network helps to understand the current environment and the outlook of an economy. Most approaches on global networks extract information transfer based mainly on a single variable. This paper establishes an entirely new bioinformatics-inspired approach to integrating information transfer derived from multiple variables and develops an international economic network accordingly. In the proposed methodology, we first construct the transfer entropies (TEs) between various intra- and inter-country pairs of economic time series variables, test their significances, and then use a weighted sum approach to aggregate information captured in each TE. Through a simulation study, the new method is shown to deliver better information integration compared to existing integration methods in that it can be applied even when intra-country variables are correlated. Empirical investigation with the real world data reveals that Western countries are more influential in the global economic network and that Japan has become less influential following the Asian currency crisis. PMID:23300959

  2. Entropy-Based Analysis and Bioinformatics-Inspired Integration of Global Economic Information Transfer

    PubMed Central

    An, Sungbae; Kwon, Young-Kyun; Yoon, Sungroh

    2013-01-01

    The assessment of information transfer in the global economic network helps to understand the current environment and the outlook of an economy. Most approaches on global networks extract information transfer based mainly on a single variable. This paper establishes an entirely new bioinformatics-inspired approach to integrating information transfer derived from multiple variables and develops an international economic network accordingly. In the proposed methodology, we first construct the transfer entropies (TEs) between various intra- and inter-country pairs of economic time series variables, test their significances, and then use a weighted sum approach to aggregate information captured in each TE. Through a simulation study, the new method is shown to deliver better information integration compared to existing integration methods in that it can be applied even when intra-country variables are correlated. Empirical investigation with the real world data reveals that Western countries are more influential in the global economic network and that Japan has become less influential following the Asian currency crisis. PMID:23300959

  3. Direct effects of ionizing radiation on integral membrane proteins. Noncovalent energy transfer requires specific interpeptide interactions

    SciTech Connect

    Jhun, E.; Jhun, B.H.; Jones, L.R.; Jung, C.Y. )

    1991-05-25

    The 12 transmembrane alpha helices (TMHs) of human erythrocyte glucose transporter were individually cut by pepsin digestion as membrane-bound 2.5-3.5-kDa peptide fragments. Radiation-induced chemical degradation of these fragments showed an average target size of 34 kDa. This is 10-12 x larger than the average size of an individual TMH, demonstrating that a significant energy transfer occurs among these TMHs in the absence of covalent linkage. Heating this TMH preparation at 100{degree}C for 15 min reduced the target size to 5 kDa or less, suggesting that the noncovalent energy transfer requires specific helix-helix interactions. Purified phospholamban, a small (6-kDa) integral membrane protein containing a single TMH, formed a pentameric assembly in sodium dodecyl sulfate. The chemical degradation target size of this phospholamban pentamer was 5-6 kDa, illustrating that not all integral membrane protein assemblies permit intersubunit energy transfer. These findings together with other published observations suggest strongly that significant noncovalent energy transfer can occur within the tertiary and quaternary structure of membrane proteins and that as yet undefined proper molecular interactions are required for such covalent energy transfer. Our results with pepsin-digested glucose transporter also illustrate the importance of the interhelical interaction as a predominating force in maintaining the tertiary structure of a transmembrane protein.

  4. Hydroeconomic optimization of integrated water management and transfers under stochastic surface water supply

    NASA Astrophysics Data System (ADS)

    Zhu, Tingju; Marques, Guilherme Fernandes; Lund, Jay R.

    2015-05-01

    Efficient reallocation and conjunctive operation of existing water supplies is gaining importance as demands grow, competitions among users intensify, and new supplies become more costly. This paper analyzes the roles and benefits of conjunctive use of surface water and groundwater and market-based water transfers in an integrated regional water system where agricultural and urban water users coordinate supply and demand management based on supply reliability and economic values of water. Agricultural users optimize land and water use for annual and perennial crops to maximize farm income, while urban users choose short-term and long-term water conservation actions to maintain reliability and minimize costs. The temporal order of these decisions is represented in a two-stage optimization that maximizes the net expected benefits of crop production, urban conservation and water management including conjunctive use and water transfers. Long-term decisions are in the first stage and short-term decisions are in a second stage based on probabilities of water availability events. Analytical and numerical analyses are made. Results show that conjunctive use and water transfers can substantially stabilize farmer's income and reduce system costs by reducing expensive urban water conservation or construction. Water transfers can equalize marginal values of water across users, while conjunctive use minimizes water marginal value differences in time. Model results are useful for exploring the integration of different water demands and supplies through water transfers, conjunctive use, and conservation, providing valuable insights for improving system management.

  5. Numerical Modeling of the Chilldown of Cryogenic Transfer Lines Using a Sinda/GFSSP Integrated Solver

    NASA Technical Reports Server (NTRS)

    LeClair, Andre

    2011-01-01

    An important first step in cryogenic propellant loading is the chilldown of transfer lines. During the chilldown of the transfer line, the flow is two-phase and unsteady, with solid to fluid heat transfer and therefore a coupled thermo-fluid analysis is necessary to model the system. This paper describes a numerical model of pipe chilldown that utilizes the Sinda/GFSSP Conjugate Integrator (SGCI). SGCI is a new analysis tool developed at NASA's Marshall Space Flight Center (MSFC). SGCI facilitates the solution of thermofluid problems in interconnected solid-fluid systems. The solid component of the system is modeled in MSC Patran and translated into an MSC Sinda thermal network model. The fluid component is modeled in GFSSP, the Generalized Fluid System Simulation Program. GFSSP is a general network flow solver developed at NASA/MSFC. GFSSP uses a finite-volume approach to model fluid systems that can include phase change, multiple species, fluid transients, and heat transfer to simple solid networks. SGCI combines the GFSSP Fortran code with the Sinda input file and compiles the integrated model. Sinda solves for the temperatures of the solid network, while GFSSP simultaneously solves the fluid network for pressure, temperature, and flow rate. The two networks are coupled by convection heat transfer from the solid wall to the cryogenic fluid. The model presented here is based on a series of experiments conducted in 1966 by the National Bureau of Standards (NBS). A vacuum-jacketed, 200 ft copper transfer line was chilled by liquid nitrogen and liquid hydrogen. The predictions of transient temperature profiles and chilldown time of the integrated Sinda/GFSSP model will be compared to the experimental measurements.

  6. Simulations of the THz spectrum of liquid water incorporating the effects of intermolecular charge fluxes through hydrogen bonds

    SciTech Connect

    Torii, Hajime

    2015-12-31

    The intensity of the band at ∼200 cm{sup −1} (∼6 THz) in the Terahertz spectrum of liquid water mainly arises from the modulations of the extent of intermolecular charge transfer through hydrogen bonds, called intermolecular charge fluxes, occurring upon molecular translations along the O…H hydrogen bonds. To obtain reasonable spectral profiles from simulations, it is necessary to effectively incorporate the effects of those intermolecular charge fluxes, but apparently it is not possible by simple classical molecular dynamics simulations with fixed atomic partial charges even if they are amended by molecular induced dipoles due to intermolecular electrostatic interactions. The present paper shows how we can do reasonably correct spectral simulations, without resorting to fully ab initio molecular dynamics.

  7. Efficient application of the spectrally integrated Voigt function to radiative transfer spectroscopy

    NASA Astrophysics Data System (ADS)

    Abrarov, Sanjar

    We present a new application of the spectrally integrated Voigt function (SIVF) to the radiative transfer spectroscopy that enables computation of the spectral radiance and radiance at reduced spectral resolution. Applying a technique based on the Fourier expansion of the exponential multiplier we obtain the series approximations providing high-accuracy and rapid SIVF computation. In contrast to traditional line-by-line (LBL) radiative transfer models, the proposed SIVF algorithm prevents underestimation in the absorption coefficients and, therefore, preserves the radiant energy. LBL sample computations utilizing SIVF algorithm show the advantages of the proposed methodology in terms of the accuracy and computational speed.

  8. Application of the spectrally integrated Voigt function to line-by-line radiative transfer modelling

    NASA Astrophysics Data System (ADS)

    Quine, B. M.; Abrarov, S. M.

    2013-09-01

    We show that a new approach based on the spectrally integrated Voigt function (SIVF) enables the computation of line-by-line (LBL) radiative transfer at reduced spectral resolution without loss of accuracy. The algorithm provides rapid and accurate computation of area under the Voigt function in a way that preserves spectral radiance and, consequently, radiant intensity. The error analysis we provide shows the high-accuracy of the proposed SIVF approximations. A comparison of the performance of the method with that of the traditional LBL approach is presented. Motivations for the use and advantage of the SIVF as a replacement for conventional line function computations in radiative transfer are discussed.

  9. The Use of Chromatin Insulators to Improve the Expression and Safety of Integrating Gene Transfer Vectors

    PubMed Central

    2011-01-01

    Abstract The therapeutic application of recombinant retroviruses and other integrating gene transfer vectors has been limited by problems of vector expression and vector-mediated genotoxicity. These problems arise in large part from the interactions between vector sequences and the genomic environment surrounding sites of integration. Strides have been made in overcoming both of these problems through the modification of deleterious vector sequences, the inclusion of better enhancers and promoters, and the use of alternative virus systems. However, these modifications often add other restrictions on vector design, which in turn can further limit therapeutic applications. As an alternative, several groups have been investigating a class of DNA regulatory elements known as chromatin insulators. These elements provide a means of blocking the interaction between an integrating vector and the target cell genome in a manner that is independent of the vector transgene, regulatory elements, or virus of origin. This review outlines the background, rationale, and evidence for using chromatin insulators to improve the expression and safety of gene transfer vectors. Also reviewed are topological factors that constrain the use of insulators in integrating gene transfer vectors, alternative sources of insulators, and the role of chromatin insulators as one of several components for optimal vector design. PMID:21247248

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    PubMed Central

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

    2014-01-01

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

  12. An isotopic mass effect on the intermolecular potential

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    PubMed

    Facelli, Julio C

    2006-03-01

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

  14. Interbasin water transfers and integrated water resources management: Where engineering, science and politics interlock

    NASA Astrophysics Data System (ADS)

    Gupta, J.; van der Zaag, P.

    As the pressure on water is increasing, the risk that the required amounts of water will not be available is also increasing in many semi-arid areas. Interbasin water transfers are designed to secure access by artificially conveying water to locations where people need it. These are typical supply oriented engineering measures to large societal challenges. The engineering works are frequently daunting, involving diversion works, tunnels and/or large pumping schemes and reservoirs, and the costs are correspondingly large. The scale of engineering works and funds required are indicative of the magnitude of the needs and interests to be served. Interbasin water transfers trigger pertinent questions from different interests groups and communities involved and affected. This paper assesses the phenomenon of interbasin water transfers from a multi-disciplinary perspective, and attempts to answer the question whether such transfers are compatible with the concept of integrated water resources management. The problems related to interbasin water transfers are first introduced by reviewing four selected interbasin transfers taking place in different parts of the world. Then the criteria for assessing such transfers as proposed by international commissions, policy communities and scientists are reviewed, from which a coherent set of evaluation criteria are distilled for interbasin transfer schemes. This set of criteria is subsequently applied to the River Linking project in India, in order to provide a preliminary assessment. This is followed by a discussion of the temporal, spatial and resource scale effects, and finally conclusions are drawn about the required institutional capacity to control water and to adapt to changing policy environments.

  15. Optimization on microlattice materials for sound absorption by an integrated transfer matrix method.

    PubMed

    Cai, Xiaobing; Yang, Jun; Hu, Gengkai

    2015-04-01

    Materials with well-defined microlattice structures are superlight, stable, and thus bear great potential in sound absorption. An integrated transfer matrix method (TMM) is proposed to evaluate the sound absorbing efficiency of these lattice materials, in which a massive number of micropores are densely placed. A comparison between integrated TMM and conventional TMM reveals that the proposed approach offers better predictions on sound absorption of microlattice. This approach is then employed to optimize the microlattice material to determine the best pore and porosity that lead to maximum absorbing efficiency capability and minimum required thickness to attain a target sound absorption. PMID:25920886

  16. Clean graphene interfaces by selective dry transfer for large area silicon integration

    NASA Astrophysics Data System (ADS)

    Na, S. R.; Rahimi, S.; Tao, L.; Chou, H.; Ameri, S. K.; Akinwande, D.; Liechti, K. M.

    2016-03-01

    Here we present a very fast, selective mechanical approach for transferring graphene with low levels of copper contamination from seed wafers on which it was grown to target wafers for very large scale integration (VLSI) electronics. We found that graphene/copper or copper/silicon oxide delamination paths could be selected by slow and faster separation rates, respectively. Thus graphene can be transferred to a target wafer, either exposed or protected by the seed copper layer, which can later be removed by etching. Delamination paths were identified by SEM and Raman spectroscopy. The sheet resistance of the graphene produced by the two approaches was slightly higher than graphene transferred by a PMMA wet-transfer process, indicating reduced impurity doping, and the variation in the sheet resistance values was much lower. Copper contamination levels, quantitatively established by TOF-SIMS, were several orders of magnitude lower than the values for PMMA assisted transfer. In addition, we demonstrated that top-gated transistor devices from our mechanical, delamination transferred graphene exhibited superior transistor behavior to PMMA-assisted wet transfer graphene. The adhesion energy, strength and range of the interactions were quantitatively determined by nonlinear fracture analyses, and suggest that the roughness of the interface between graphene and copper plays an important role with implications for improvements in manufacturing processes.Here we present a very fast, selective mechanical approach for transferring graphene with low levels of copper contamination from seed wafers on which it was grown to target wafers for very large scale integration (VLSI) electronics. We found that graphene/copper or copper/silicon oxide delamination paths could be selected by slow and faster separation rates, respectively. Thus graphene can be transferred to a target wafer, either exposed or protected by the seed copper layer, which can later be removed by etching

  17. Development of highly accurate approximate scheme for computing the charge transfer integral

    SciTech Connect

    Pershin, Anton; Szalay, Péter G.

    2015-08-21

    The charge transfer integral is a key parameter required by various theoretical models to describe charge transport properties, e.g., in organic semiconductors. The accuracy of this important property depends on several factors, which include the level of electronic structure theory and internal simplifications of the applied formalism. The goal of this paper is to identify the performance of various approximate approaches of the latter category, while using the high level equation-of-motion coupled cluster theory for the electronic structure. The calculations have been performed on the ethylene dimer as one of the simplest model systems. By studying different spatial perturbations, it was shown that while both energy split in dimer and fragment charge difference methods are equivalent with the exact formulation for symmetrical displacements, they are less efficient when describing transfer integral along the asymmetric alteration coordinate. Since the “exact” scheme was found computationally expensive, we examine the possibility to obtain the asymmetric fluctuation of the transfer integral by a Taylor expansion along the coordinate space. By exploring the efficiency of this novel approach, we show that the Taylor expansion scheme represents an attractive alternative to the “exact” calculations due to a substantial reduction of computational costs, when a considerably large region of the potential energy surface is of interest. Moreover, we show that the Taylor expansion scheme, irrespective of the dimer symmetry, is very accurate for the entire range of geometry fluctuations that cover the space the molecule accesses at room temperature.

  18. Development of highly accurate approximate scheme for computing the charge transfer integral.

    PubMed

    Pershin, Anton; Szalay, Péter G

    2015-08-21

    The charge transfer integral is a key parameter required by various theoretical models to describe charge transport properties, e.g., in organic semiconductors. The accuracy of this important property depends on several factors, which include the level of electronic structure theory and internal simplifications of the applied formalism. The goal of this paper is to identify the performance of various approximate approaches of the latter category, while using the high level equation-of-motion coupled cluster theory for the electronic structure. The calculations have been performed on the ethylene dimer as one of the simplest model systems. By studying different spatial perturbations, it was shown that while both energy split in dimer and fragment charge difference methods are equivalent with the exact formulation for symmetrical displacements, they are less efficient when describing transfer integral along the asymmetric alteration coordinate. Since the "exact" scheme was found computationally expensive, we examine the possibility to obtain the asymmetric fluctuation of the transfer integral by a Taylor expansion along the coordinate space. By exploring the efficiency of this novel approach, we show that the Taylor expansion scheme represents an attractive alternative to the "exact" calculations due to a substantial reduction of computational costs, when a considerably large region of the potential energy surface is of interest. Moreover, we show that the Taylor expansion scheme, irrespective of the dimer symmetry, is very accurate for the entire range of geometry fluctuations that cover the space the molecule accesses at room temperature. PMID:26298117

  19. An energy decomposition analysis for intermolecular interactions from an absolutely localized molecular orbital reference at the coupled-cluster singles and doubles level

    SciTech Connect

    Azar, R. Julian; Head-Gordon, Martin

    2012-01-14

    We propose a wave function-based method for the decomposition of intermolecular interaction energies into chemically-intuitive components, isolating both mean-field- and explicit correlation-level contributions. We begin by solving the locally-projected self-consistent field for molecular interactions equations for a molecular complex, obtaining an intramolecularly polarized reference of self-consistently optimized, absolutely-localized molecular orbitals (ALMOs), determined with the constraint that each fragment MO be composed only of atomic basis functions belonging to its own fragment. As explicit inter-electronic correlation is integral to an accurate description of weak forces underlying intermolecular interaction potentials, namely, coordinated fluctuations in weakly interacting electronic densities, we add dynamical correlation to the ALMO polarized reference at the coupled-cluster singles and doubles level, accounting for explicit dispersion and charge-transfer effects, which map naturally onto the cluster operator. We demonstrate the stability of energy components with basis set extension, follow the hydrogen bond-breaking coordinate in the C{sub s}-symmetry water dimer, decompose the interaction energies of dispersion-bound rare gas dimers and other van der Waals complexes, and examine charge transfer-dominated donor-acceptor interactions in borane adducts. We compare our results with high-level calculations and experiment when possible.

  20. Frontier orbital symmetry control of intermolecular electron transfer

    SciTech Connect

    Stevens, B.

    1991-09-01

    This report contains sections describing the selection of electron donor-acceptor systems, the synthesis and photophysical properties of linked electron-donor-acceptor systems, the estimation of photoinduced charge-separation rate constants from fluorescence quenching data, and radical ion-pair recombination by picosecond transient absorption spectroscopy. 9 refs., 1 fig., 7 tabs.

  1. MHD Technology Transfer, Integration and Review Committee. Second semiannual status report, July 1988--March 1989

    SciTech Connect

    Not Available

    1989-10-01

    As part of the MHD Integrated Topping Cycle (ITC) project, TRW was given the responsibility to organize, charter and co-chair, with the Department of Energy (DOE), an MHD Technology Transfer, Integration and Review Committee (TTIRC). The Charter of the TTIRC, which was approved by the DOE in June 1988 and distributed to the committee members, is included as part of this Summary. As stated in the Charter, the purpose of this committee is to: (1) review all Proof-of-Concept (POC) projects and schedules in the national MHD program; to assess their compatibility with each other and the first commercial MHD retrofit plant; (2) establish and implement technology transfer formats for users of this technology; (3) identify interfaces, issues, and funding structures directly impacting the success of the commercial retrofit; (4) investigate and identify the manner in which, and by whom, the above should be resolved; and (5) investigate and assess other participation (foreign and domestic) in the US MHD Program. The DOE fiscal year 1989 MHD Program Plan Schedule is included at the end of this Summary. The MHD Technology Transfer, Integration and Review Committee`s activities to date have focused primarily on the ``technology transfer`` aspects of its charter. It has provided a forum for the dissemination of technical and programmatic information among workers in the field of MHD and to the potential end users, the utilities, by holding semi-annual meetings. The committee publishes this semi-annual report, which presents in Sections 2 through 11 capsule summaries of technical progress for all DOE Proof-of-Concept MHD contracts and major test facilities.

  2. A STRUCTURAL INTEGRITY EVALUATION OF THE TANK FARM WASTE TRANSFER SYSTEM

    SciTech Connect

    Wiersma, B.

    2006-03-09

    Radioactive supernate, salt, and/or sludge wastes (i.e., high level wastes) are confined in 49 underground storage tanks at the Savannah River Site (SRS). The waste is transported between tanks within and between the F and H area tank farms and other facilities on site via underground and a limited number of aboveground transfer lines. The Department of Energy - Savannah River Operations Office (DOE-SR) performed a comprehensive assessment of the structural integrity program for the Tank Farm waste transfer system at the SRS. This document addresses the following issues raised during the DOE assessment: (1) Inspections of failed or replaced transfer lines indicated that the wall thickness of some core and jacket piping is less than nominal; (2) No corrosion allowance is utilized in the transfer line structural qualification calculations. No basis for neglecting corrosion was provided in the calculations; (3) Wall loss due to erosion is not addressed in the transfer line structural qualification calculations; and (4) No basis is provided for neglecting intergranular stress corrosion cracking in the transfer line structural qualification calculations. The common theme in most of these issues is the need to assess the potential for occurrence of material degradation of the transfer line piping. The approach used to resolve these issues involved: (1) Review the design and specifications utilized to construct and fabricate the piping system; (2) Review degradation mechanisms for stainless steel and carbon steel and determine their relevance to the transfer line piping; (3) Review the transfer piping inspection data; (4) Life estimation calculations for the transfer lines; and (5) A Fitness-For-Service evaluation for one of the transfer line jackets. The evaluation concluded that the transfer line system piping has performed well for over fifty years. Although there have been instances of failures of the stainless steel core pipe during off-normal service, no significant

  3. Cooperative Drought Adaptation: Integrating Infrastructure Development, Conservation, and Water Transfers into Adaptive Policy Pathways

    NASA Astrophysics Data System (ADS)

    Zeff, H. B.; Characklis, G. W.; Reed, P. M.; Herman, J. D.

    2015-12-01

    Water supply policies that integrate portfolios of short-term management decisions with long-term infrastructure development enable utilities to adapt to a range of future scenarios. An effective mix of short-term management actions can augment existing infrastructure, potentially forestalling new development. Likewise, coordinated expansion of infrastructure such as regional interconnections and shared treatment capacity can increase the effectiveness of some management actions like water transfers. Highly adaptable decision pathways that mix long-term infrastructure options and short-term management actions require decision triggers capable of incorporating the impact of these time-evolving decisions on growing water supply needs. Here, we adapt risk-based triggers to sequence a set of potential infrastructure options in combination with utility-specific conservation actions and inter-utility water transfers. Individual infrastructure pathways can be augmented with conservation or water transfers to reduce the cost of meeting utility objectives, but they can also include cooperatively developed, shared infrastructure that expands regional capacity to transfer water. This analysis explores the role of cooperation among four water utilities in the 'Research Triangle' region of North Carolina by formulating three distinct categories of adaptive policy pathways: independent action (utility-specific conservation and supply infrastructure only), weak cooperation (utility-specific conservation and infrastructure development with regional transfers), and strong cooperation (utility specific conservation and jointly developed of regional infrastructure that supports transfers). Results suggest that strong cooperation aids the utilities in meeting their individual objections at substantially lower costs and with fewer irreversible infrastructure options.

  4. Intermolecular electronic coupling in organic molecular thin films measured by temperature modulation spectroscopy

    SciTech Connect

    Yadav, Abhishek; Jin, Y; Chan, P. K. L.; Shtein, Max; Pipe, Kevin P.

    2010-01-01

    Temperature modulation spectroscopy is used to obtain the temperature dependences of oscillator strength, exciton transition energy, and line width for a copper phthalocyanine thin film. With increasing temperature, the oscillator strength exhibits a pronounced decrease for charge transfer (CT) excitons, making this technique suitable for differentiating exciton types. From the measured magnitude and temperature dependence of the CT oscillator strength, we obtain estimates for the intermolecular electronic coupling and its exponential decay coefficient.

  5. A STRUCTURAL INTEGRITY ASSESSMENT OF UNDERGROUND PIPING ASSOCIATED WITH THE TRANSFER OF RADIOACTIVE WASTE

    SciTech Connect

    Wiersma, B

    2006-04-25

    Radioactive wastes are confined in 49 underground storage tanks at the Savannah River Site. The waste is transported between tanks via underground transfer piping. An assessment of the structural integrity of the transfer piping was performed to ensure that the present condition of the piping was sound and to provide life expectancy estimates for the piping based on anticipated service. The assessment reviewed the original design of the piping, the potential and observed degradation mechanisms, the results from past inspections of the piping, and a Fitness-For-Service evaluation for a section of piping that experienced pitting in a locally thinned area. The assessment concluded that the piping was structurally sound. Assuming that service conditions remain the same, the piping will remain functional for its intended service life.

  6. 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

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

    PubMed

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

    2016-01-01

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

  8. The phase-integral method for radiative transfer problems with highly-peaked phase functions

    NASA Technical Reports Server (NTRS)

    Fricke, C. L.

    1978-01-01

    Complete solutions to the radiative transfer equation, including both azimuth and depth dependence, are provided by the discrete-ordinate method of Chandrasekhar, but these solutions are often limited because of large computer requirements. This paper presents a 'phase-integral' method which greatly reduces the number of discrete ordinates needed in the solution for highly peaked phase functions. A composite quadrature method is shown to be effective in further reducing the number of discrete ordinates required for highly anisotropic phase functions. Examples are given to indicate convergence requirements and expected accuracy in the complete solution for Henyey-Greenstein and cloud-type phase functions.

  9. Anisotropic light scattering in an inhomogeneous atmosphere. Invariance relations and integrals of radiative transfer equation

    SciTech Connect

    Yanovitskii, E.G.

    1981-01-01

    The general invariance principle (GIP) for arbitrary plane inhomogeneous atmospheres is formulated on the basis of ideas contained in (V. V. Ivanov, Sov. Astron. 19, 137 (1975)). All the known invariance relations follow as particular cases from the GIP. The problem of diffuse light reflection by a semi-infinite atmosphere and the Milne problem are analyzed in detail. The existence of a number of integrals, quadratic with respect to intensity, of the transfer equation is shown, the majority of which are invariant relative to optical depth.

  10. Computational attributes of the integral form of the equation of transfer

    NASA Technical Reports Server (NTRS)

    Frankel, J. I.

    1991-01-01

    Difficulties can arise in radiative and neutron transport calculations when a highly anisotropic scattering phase function is present. In the presence of anisotropy, currently used numerical solutions are based on the integro-differential form of the linearized Boltzmann transport equation. This paper, departs from classical thought and presents an alternative numerical approach based on application of the integral form of the transport equation. Use of the integral formalism facilitates the following steps: a reduction in dimensionality of the system prior to discretization, the use of symbolic manipulation to augment the computational procedure, and the direct determination of key physical quantities which are derivable through the various Legendre moments of the intensity. The approach is developed in the context of radiative heat transfer in a plane-parallel geometry, and results are presented and compared with existing benchmark solutions. Encouraging results are presented to illustrate the potential of the integral formalism for computation. The integral formalism appears to possess several computational attributes which are well-suited to radiative and neutron transport calculations.

  11. Heat Transfer Study of Heat-Integrated Distillation Column (HIDiC) Using Simulation Techniques

    NASA Astrophysics Data System (ADS)

    Pulido, Jeffrey León; Martínez, Edgar Leonardo; Wolf, Maria Regina; Filho, Rubens Maciel

    2011-08-01

    Separation processes is largely used in petroleum refining and alcohol industries. Distillation columns consume a huge amount of energy in industrial process. Therefore, the concept of Heat-Integrated Distillation Column (HIDiC) was studied using simulation techniques in order to overcome this drawback. In this configuration the column is composed for two concentric sections called rectifying and stripping. The heat transfer is conducted from the rectifying section (which works at higher pressure and temperature) to the stripping section (which works at lower pressure and temperature) using the heat present in the process and decreasing the energy charge required by the reboiler. The HIDiC column offers great potential to reduce energy consumption compared to conventional columns. However, the complexity of the internal configuration requires the development of rigorous works that enable a better understanding of the column operation. For this reason, techniques of simulation were used through of computational software. The current work presents a heat transfer study in a concentric stage of a HIDiC column. The results obtained by Aspen Plus and CFD simulation showed the internal heat transfer in a concentric tray as a promissory configuration in order to decrease energy consumption in distillation processes.

  12. Integration of Light Trapping Silver Nanostructures in Hydrogenated Microcrystalline Silicon Solar Cells by Transfer Printing.

    PubMed

    Mizuno, Hidenori; Sai, Hitoshi; Matsubara, Koji; Takato, Hidetaka; Kondo, Michio

    2015-01-01

    One of the potential applications of metal nanostructures is light trapping in solar cells, where unique optical properties of nanosized metals, commonly known as plasmonic effects, play an important role. Research in this field has, however, been impeded owing to the difficulty of fabricating devices containing the desired functional metal nanostructures. In order to provide a viable strategy to this issue, we herein show a transfer printing-based approach that allows the quick and low-cost integration of designed metal nanostructures with a variety of device architectures, including solar cells. Nanopillar poly(dimethylsiloxane) (PDMS) stamps were fabricated from a commercially available nanohole plastic film as a master mold. On this nanopatterned PDMS stamps, Ag films were deposited, which were then transfer-printed onto block copolymer (binding layer)-coated hydrogenated microcrystalline Si (µc-Si:H) surface to afford ordered Ag nanodisk structures. It was confirmed that the resulting Ag nanodisk-incorporated µc-Si:H solar cells show higher performances compared to a cell without the transfer-printed Ag nanodisks, thanks to plasmonic light trapping effect derived from the Ag nanodisks. Because of the simplicity and versatility, further device application would also be feasible thorough this approach. PMID:26575244

  13. Analysis of the depth of field in hexagonal array integral imaging systems based on modulation transfer function and Strehl ratio.

    PubMed

    Karimzadeh, Ayatollah

    2016-04-10

    Integral imaging is a technique for displaying three-dimensional images using microlens arrays. In this paper, a method for calculating root mean squared wavefront error and modulation transfer function (MTF) of a defocused integral imaging capture system with hexagonal aperture microlens arrays is introduced. Also, maximum allowable depth of field with Century MTF analyzing and Strehl criterion are obtained. PMID:27139873

  14. 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.

  15. Fresnel integrals and irreversible energy transfer in an oscillatory system with time-dependent parameters.

    PubMed

    Kovaleva, Agnessa; Manevitch, Leonid I; Kosevich, Yuriy A

    2011-02-01

    We demonstrate that in significant limiting cases the problem of irreversible energy transfer in an oscillatory system with time-dependent parameters can be efficiently solved in terms of the Fresnel integrals. For definiteness, we consider a system of two weakly coupled linear oscillators in which the first oscillator with constant parameters is excited by an initial impulse, whereas the coupled oscillator with a slowly varying frequency is initially at rest but then acts as an energy trap. We show that the evolution equations of the slow passage through resonance are identical to the equations of the Landau-Zener tunneling problem, and therefore, the suggested asymptotic solution of the classical problem provides a simple analytic description of the quantum Landau-Zener tunneling with arbitrary initial conditions over a finite time interval. A correctness of approximations is confirmed by numerical simulations. PMID:21405919

  16. Semiclassical Path Integral Dynamics: Photosynthetic Energy Transfer with Realistic Environment Interactions.

    PubMed

    Lee, Mi Kyung; Huo, Pengfei; Coker, David F

    2016-05-27

    This article reviews recent progress in the theoretical modeling of excitation energy transfer (EET) processes in natural light harvesting complexes. The iterative partial linearized density matrix path-integral propagation approach, which involves both forward and backward propagation of electronic degrees of freedom together with a linearized, short-time approximation for the nuclear degrees of freedom, provides an accurate and efficient way to model the nonadiabatic quantum dynamics at the heart of these EET processes. Combined with a recently developed chromophore-protein interaction model that incorporates both accurate ab initio descriptions of intracomplex vibrations and chromophore-protein interactions treated with atomistic detail, these simulation tools are beginning to unravel the detailed EET pathways and relaxation dynamics in light harvesting complexes. PMID:27090842

  17. Semiclassical Path Integral Dynamics: Photosynthetic Energy Transfer with Realistic Environment Interactions

    NASA Astrophysics Data System (ADS)

    Lee, Mi Kyung; Huo, Pengfei; Coker, David F.

    2016-05-01

    This article reviews recent progress in the theoretical modeling of excitation energy transfer (EET) processes in natural light harvesting complexes. The iterative partial linearized density matrix path-integral propagation approach, which involves both forward and backward propagation of electronic degrees of freedom together with a linearized, short-time approximation for the nuclear degrees of freedom, provides an accurate and efficient way to model the nonadiabatic quantum dynamics at the heart of these EET processes. Combined with a recently developed chromophore-protein interaction model that incorporates both accurate ab initio descriptions of intracomplex vibrations and chromophore-protein interactions treated with atomistic detail, these simulation tools are beginning to unravel the detailed EET pathways and relaxation dynamics in light harvesting complexes.

  18. Lightweight ECC based RFID authentication integrated with an ID verifier transfer protocol.

    PubMed

    He, Debiao; Kumar, Neeraj; Chilamkurti, Naveen; Lee, Jong-Hyouk

    2014-10-01

    The radio frequency identification (RFID) technology has been widely adopted and being deployed as a dominant identification technology in a health care domain such as medical information authentication, patient tracking, blood transfusion medicine, etc. With more and more stringent security and privacy requirements to RFID based authentication schemes, elliptic curve cryptography (ECC) based RFID authentication schemes have been proposed to meet the requirements. However, many recently published ECC based RFID authentication schemes have serious security weaknesses. In this paper, we propose a new ECC based RFID authentication integrated with an ID verifier transfer protocol that overcomes the weaknesses of the existing schemes. A comprehensive security analysis has been conducted to show strong security properties that are provided from the proposed authentication scheme. Moreover, the performance of the proposed authentication scheme is analyzed in terms of computational cost, communicational cost, and storage requirement. PMID:25096968

  19. Orbit transfer rocket engine integrated control and health monitoring system technology readiness assessment

    NASA Technical Reports Server (NTRS)

    Bickford, R. L.; Collamore, F. N.; Gage, M. L.; Morgan, D. B.; Thomas, E. R.

    1992-01-01

    The objectives of this task were to: (1) estimate the technology readiness of an integrated control and health monitoring (ICHM) system for the Aerojet 7500 lbF Orbit Transfer Vehicle engine preliminary design assuming space based operations; and (2) estimate the remaining cost to advance this technology to a NASA defined 'readiness level 6' by 1996 wherein the technology has been demonstrated with a system validation model in a simulated environment. The work was accomplished through the conduct of four subtasks. In subtask 1 the minimally required functions for the control and monitoring system was specified. The elements required to perform these functions were specified in Subtask 2. In Subtask 3, the technology readiness level of each element was assessed. Finally, in Subtask 4, the development cost and schedule requirements were estimated for bringing each element to 'readiness level 6'.

  20. Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics

    SciTech Connect

    Huo, Pengfei; Miller, Thomas F. III; Coker, David F.

    2013-10-21

    A partial linearized path integral approach is used to calculate the condensed phase electron transfer (ET) rate by directly evaluating the flux-flux/flux-side quantum time correlation functions. We demonstrate for a simple ET model that this approach can reliably capture the transition between non-adiabatic and adiabatic regimes as the electronic coupling is varied, while other commonly used semi-classical methods are less accurate over the broad range of electronic couplings considered. Further, we show that the approach reliably recovers the Marcus turnover as a function of thermodynamic driving force, giving highly accurate rates over four orders of magnitude from the normal to the inverted regimes. We also demonstrate that the approach yields accurate rate estimates over five orders of magnitude of inverse temperature. Finally, the approach outlined here accurately captures the electronic coherence in the flux-flux correlation function that is responsible for the decreased rate in the inverted regime.

  1. a Conceptual Model of Integrating Sensor Network and Radiative Heat Transfer Equation for Ethylene Furnace

    NASA Astrophysics Data System (ADS)

    Abas, Z. Abal; Salleh, S.; Basari, A. S. Hassan; Ibrahim, Nuzulha Khilwani

    2010-11-01

    A conceptual model of integrating the sensor network and the radiative heat transfer equation is developed and presented in this paper. The idea is to present possible deployment of sensor networks in the Ethylene furnace so that valuable input in the form of boundary value can be generated in order to produce intensity distribution and heat flux distribution. Once the location of sensor deployment has been recommended, the mesh at the physical space between the furnace wall and the reactor tube is constructed. The paper concentrates only at 2D model with only 1 U-bend reactor tube in the ethylene furnace as an initial phase of constructing a complete simulation in real furnace design.

  2. Study of Thermodynamic Vent and Screen Baffle Integration for Orbital Storage and Transfer of Liquid Hydrogen

    NASA Technical Reports Server (NTRS)

    Cady, E. C.

    1973-01-01

    A comprehensive analytical and experimental program was performed to determine the feasibility of integrating an internal thermodynamic vent system and a full wall-screen liner for the orbital storage and transfer of liquid hydrogen (LH2). Ten screens were selected from a comprehensive screen survey. The experimental study determined the screen bubble point, flow-through pressure loss, and pressure loss along rectangular channels lined with screen on one side, for the 10 screens using LH2 saturated at 34.5 N/cm2 (50 psia). The correlated experimental data were used in an analysis to determine the optimum system characteristics in terms of minimum weight for 6 tanks ranging from 141.6 m3 (5,000 ft3) to 1.416 m3 (50 ft3) for orbital storage times of 30 and 300 days.

  3. Protein Homeostasis Imposes a Barrier on Functional Integration of Horizontally Transferred Genes in Bacteria

    PubMed Central

    Bhattacharyya, Sanchari; Manhart, Michael; Choi, Jeong-Mo; Mu, Wanmeng; Zhou, Jingwen; Shakhnovich, Eugene I.

    2015-01-01

    Horizontal gene transfer (HGT) plays a central role in bacterial evolution, yet the molecular and cellular constraints on functional integration of the foreign genes are poorly understood. Here we performed inter-species replacement of the chromosomal folA gene, encoding an essential metabolic enzyme dihydrofolate reductase (DHFR), with orthologs from 35 other mesophilic bacteria. The orthologous inter-species replacements caused a marked drop (in the range 10–90%) in bacterial growth rate despite the fact that most orthologous DHFRs are as stable as E.coli DHFR at 37°C and are more catalytically active than E. coli DHFR. Although phylogenetic distance between E. coli and orthologous DHFRs as well as their individual molecular properties correlate poorly with growth rates, the product of the intracellular DHFR abundance and catalytic activity (k cat/KM), correlates strongly with growth rates, indicating that the drop in DHFR abundance constitutes the major fitness barrier to HGT. Serial propagation of the orthologous strains for ~600 generations dramatically improved growth rates by largely alleviating the fitness barriers. Whole genome sequencing and global proteome quantification revealed that the evolved strains with the largest fitness improvements have accumulated mutations that inactivated the ATP-dependent Lon protease, causing an increase in the intracellular DHFR abundance. In one case DHFR abundance increased further due to mutations accumulated in folA promoter, but only after the lon inactivating mutations were fixed in the population. Thus, by apparently distinguishing between self and non-self proteins, protein homeostasis imposes an immediate and global barrier to the functional integration of foreign genes by decreasing the intracellular abundance of their products. Once this barrier is alleviated, more fine-tuned evolution occurs to adjust the function/expression of the transferred proteins to the constraints imposed by the intracellular

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

    SciTech Connect

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

    2002-01-01

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

  5. Integration of an insertion-type transferred DNA vector from Agrobacterium tumefaciens into the Saccharomyces cerevisiae genome by gap repair.

    PubMed Central

    Risseeuw, E; Franke-van Dijk, M E; Hooykaas, P J

    1996-01-01

    Recently, it was shown that Agrobacterium tumefaciens can transfer transferred DNA (T-DNA) to Saccharomyces cerevisiae and that this T-DNA, when used as a replacement vector, is integrated via homologous recombination into the yeast genome. To test whether T-DNA can be a suitable substrate for integration via the gap repair mechanism as well, a model system developed for detection of homologous recombination events in plants was transferred to S. cerevisiae. Analysis of the yeast transformants revealed that an insertion type T-DNA vector can indeed be integrated via gap repair. Interestingly, the transformation frequency and the type of recombination events turned out to depend strongly on the orientation of the insert between the borders in such an insertion type T-DNA vector. PMID:8816506

  6. Integrative gene transfer in the truffle Tuber borchii by Agrobacterium tumefaciens-mediated transformation

    PubMed Central

    2014-01-01

    Agrobacterium tumefaciens-mediated transformation is a powerful tool for reverse genetics and functional genomic analysis in a wide variety of plants and fungi. Tuber spp. are ecologically important and gastronomically prized fungi (“truffles”) with a cryptic life cycle, a subterranean habitat and a symbiotic, but also facultative saprophytic lifestyle. The genome of a representative member of this group of fungi has recently been sequenced. However, because of their poor genetic tractability, including transformation, truffles have so far eluded in-depth functional genomic investigations. Here we report that A. tumefaciens can infect Tuber borchii mycelia, thereby conveying its transfer DNA with the production of stably integrated transformants. We constructed two new binary plasmids (pABr1 and pABr3) and tested them as improved transformation vectors using the green fluorescent protein as reporter gene and hygromycin phosphotransferase as selection marker. Transformants were stable for at least 12 months of in vitro culture propagation and, as revealed by TAIL- PCR analysis, integration sites appear to be heterogeneous, with a preference for repeat element-containing genome sites. PMID:24949275

  7. MAR-mediated integration of plasmid vectors for in vivo gene transfer and regulation

    PubMed Central

    2013-01-01

    Background The in vivo transfer of naked plasmid DNA into organs such as muscles is commonly used to assess the expression of prophylactic or therapeutic genes in animal disease models. Results In this study, we devised vectors allowing a tight regulation of transgene expression in mice from such non-viral vectors using a doxycycline-controlled network of activator and repressor proteins. Using these vectors, we demonstrate proper physiological response as consequence of the induced expression of two therapeutically relevant proteins, namely erythropoietin and utrophin. Kinetic studies showed that the induction of transgene expression was only transient, unless epigenetic regulatory elements termed Matrix Attachment Regions, or MAR, were inserted upstream of the regulated promoters. Using episomal plasmid rescue and quantitative PCR assays, we observed that similar amounts of plasmids remained in muscles after electrotransfer with or without MAR elements, but that a significant portion had integrated into the muscle fiber chromosomes. Interestingly, the MAR elements were found to promote plasmid genomic integration but to oppose silencing effects in vivo, thereby mediating long-term expression. Conclusions This study thus elucidates some of the determinants of transient or sustained expression from the use of non-viral regulated vectors in vivo. PMID:24295286

  8. Transfer of care and offload delay: continued resistance or integrative thinking?

    PubMed

    Schwartz, Brian

    2015-11-01

    The disciplines of paramedicine and emergency medicine have evolved synchronously over the past four decades, linked by emergency physicians with expertise in prehospital care. Ambulance offload delay (OD) is an inevitable consequence of emergency department overcrowding (EDOC) and compromises the care of the patient on the ambulance stretcher in the emergency department (ED), as well as paramedic emergency medical service response in the community. Efforts to define transfer of care from paramedics to ED staff with a view to reducing offload time have met with resistance from both sides with different agendas. These include the need to return paramedics to serve the community versus the lack of ED capacity to manage the patient. Innovative solutions to other system issues, such as rapid access to trauma teams, reducing door-to-needle time, and improving throughput in the ED to reduce EDOC, have been achieved by involving all stakeholders in an integrative thinking process. Only by addressing this issue in a similar integrative process will solutions to OD be realized. PMID:26012478

  9. Integrative gene transfer in the truffle Tuber borchii by Agrobacterium tumefaciens-mediated transformation.

    PubMed

    Brenna, Andrea; Montanini, Barbara; Muggiano, Eleonora; Proietto, Marco; Filetici, Patrizia; Ottonello, Simone; Ballario, Paola

    2014-01-01

    Agrobacterium tumefaciens-mediated transformation is a powerful tool for reverse genetics and functional genomic analysis in a wide variety of plants and fungi. Tuber spp. are ecologically important and gastronomically prized fungi ("truffles") with a cryptic life cycle, a subterranean habitat and a symbiotic, but also facultative saprophytic lifestyle. The genome of a representative member of this group of fungi has recently been sequenced. However, because of their poor genetic tractability, including transformation, truffles have so far eluded in-depth functional genomic investigations. Here we report that A. tumefaciens can infect Tuber borchii mycelia, thereby conveying its transfer DNA with the production of stably integrated transformants. We constructed two new binary plasmids (pABr1 and pABr3) and tested them as improved transformation vectors using the green fluorescent protein as reporter gene and hygromycin phosphotransferase as selection marker. Transformants were stable for at least 12 months of in vitro culture propagation and, as revealed by TAIL- PCR analysis, integration sites appear to be heterogeneous, with a preference for repeat element-containing genome sites. PMID:24949275

  10. FAD oxidizes the ERO1-PDI electron transfer chain: The role of membrane integrity

    SciTech Connect

    Papp, Eszter; Nardai, Gabor; Mandl, Jozsef; Banhegyi, Gabor; Csermely, Peter . E-mail: csermely@puskin.sote.hu

    2005-12-16

    The molecular steps of the electron transfer in the endoplasmic reticulum from the secreted proteins during their oxidation are relatively unknown. We present here that flavine adenine dinucleotide (FAD) is a powerful oxidizer of the oxidoreductase system, Ero1 and PDI, besides the proteins of rat liver microsomes and HepG2 hepatoma cells. Inhibition of FAD transport hindered the action of FAD. Microsomal membrane integrity was mandatory for all FAD-related oxidation steps downstream of Ero1. The PDI inhibitor bacitracin could inhibit FAD-mediated oxidation of microsomal proteins and PDI, but did not hinder the FAD-driven oxidation of Ero1. Our data demonstrated that Ero1 can utilize FAD as an electron acceptor and that FAD-driven protein oxidation goes through the Ero1-PDI pathway and requires the integrity of the endoplasmic reticulum membrane. Our findings prompt further studies to elucidate the membrane-dependent steps of PDI oxidation and the role of FAD in redox folding.

  11. Integration of solid-state nanopores in microfluidic networks via transfer printing of suspended membranes.

    PubMed

    Jain, Tarun; Guerrero, Ricardo Jose S; Aguilar, Carlos A; Karnik, Rohit

    2013-04-16

    Solid-state nanopores have emerged as versatile single-molecule sensors for applications including DNA sequencing, protein unfolding, micro-RNA detection, label-free detection of single nucleotide polymorphisms, and mapping of DNA-binding proteins involved in homologous recombination. While machining nanopores in dielectric membranes provides nanometer-scale precision, the rigid silicon support for the membrane contributes capacitive noise and limits integration with microfluidic networks for sample preprocessing. Herein, we demonstrate a technique to directly transfer solid-state nanopores machined in dielectric membranes from a silicon support into a microfluidic network. The resulting microfluidic-addressable nanopores can sense single DNA molecules at high bandwidths and with low noise, owing to significant reductions in membrane capacitance. This strategy will enable large-scale integration of solid-state nanopores with microfluidic upstream and downstream processing and permit new functions with nanopores such as complex manipulations for multidimensional analysis and parallel sensing in two and three-dimensional architectures. PMID:23347165

  12. Integration of Solid-State Nanopores in Microfluidic Networks via Transfer Printing of Suspended Membranes

    PubMed Central

    Jain, Tarun; Guerrero, Ricardo Jose S.; Aguilar, Carlos A.; Karnik, Rohit

    2013-01-01

    Solid-state nanopores have emerged as versatile single-molecule sensors for applications including DNA sequencing, protein unfolding, micro-RNA detection, label-free detection of single nucleotide polymorphisms, and mapping of DNA-binding proteins involved in homologous recombination. While machining nanopores in dielectric membranes provides nanometer-scale precision, the rigid silicon support for the membrane contributes capacitive noise and limits integration with microfluidic networks for sample pre-processing. Herein, we demonstrate a technique to directly transfer solid-state nanopores machined in dielectric membranes from a silicon support into a microfluidic network. The resulting microfluidic-addressable nanopores can sense single DNA molecules at high bandwidths and with low noise, owing to significant reductions in membrane capacitance. This strategy will enable large-scale integration of solid-state nanopores with microfluidic upstream and downstream processing and permit new functions with nanopores such as complex manipulations for multidimensional analysis and parallel sensing in two and three-dimensional architectures. PMID:23347165

  13. 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

  14. MHD Technology Transfer, Integration and Review Committee. Fifth semi-annual status report, April 1990--September 1990

    SciTech Connect

    Not Available

    1992-01-01

    This fifth semi-annual status report of the MHD Technology Transfer, Integration, and Review Committee (TTIRC) summarizes activities of the TTIRC during the period April 1990 through September 1990. It includes summaries and minutes of committee meetings, progress summaries of ongoing Proof-of-Concept (POC) contracts, discussions pertaining to technical integration issues in the POC program, and planned activities for the next six months.

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

    SciTech Connect

    Averbukh, V.; Cederbaum, L. S.

    2007-11-29

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

  16. Structural integrity of the corpus callosum predicts long-term transfer of fluid intelligence-related training gains in normal aging.

    PubMed

    Wolf, Dominik; Fischer, Florian Udo; Fesenbeckh, Johanna; Yakushev, Igor; Lelieveld, Irene Maria; Scheurich, Armin; Schermuly, Ingrid; Zschutschke, Lisa; Fellgiebel, Andreas

    2014-01-01

    Although cognitive training usually improves cognitive test performance, the capability to transfer these training gains into respective or functionally related cognitive domains varies significantly. Since most studies demonstrate rather limited transfer effects in older adults, aging might be an important factor in transfer capability differences. This study investigated the transfer capability of logical reasoning training gains to a measure of Fluid Intelligence (Gf) in relation to age, general intelligence, and brain structural integrity as measured by diffusion tensor imaging. In a group of 41 highly educated healthy elderly, 71% demonstrated successful transfer immediately after a 4-week training session (i.e. short-term transfer). In a subgroup of 22% of subjects transfer maintained over a 3-month follow-up period (i.e. long-term transfer). While short-term transfer was not related to structural integrity, long-term transfer was associated with increased structural integrity in corpus and genu of the corpus callosum. Since callosal structural integrity was also related to age (in the present and foregoing studies), previously observed associations between age and transfer might be moderated by the structural integrity. Surprisingly, age was not directly associated with transfer in this study which could be explained by the multi-dependency of the structural integrity (modulating factors beside age, e.g. genetics). In this highly educated sample, general intelligence was not related to transfer suggesting that high intelligence is not sufficient for transfer in normal aging. Further studies are needed to reveal the interaction of transfer, age, and structural integrity and delineate mechanisms of age-dependent transfer capabilities. PMID:22965837

  17. Density functional theory based calculations of the transfer integral in a redox-active single-molecule junction

    NASA Astrophysics Data System (ADS)

    Kastlunger, Georg; Stadler, Robert

    2014-03-01

    There are various quantum chemical approaches for an ab initio description of transfer integrals within the framework of Marcus theory in the context of electron transfer reactions. In our paper, we aim to calculate transfer integrals in redox-active single molecule junctions, where we focus on the coherent tunneling limit with the metal leads taking the position of donor and acceptor and the molecule acting as a transport mediating bridge. This setup allows us to derive a conductance, which can be directly compared with recent results from a nonequilibrium Green's function approach. Compared with purely molecular systems we face additional challenges due to the metallic nature of the leads, which rules out some of the common techniques, and due to their periodicity, which requires k-space integration. We present three different methods, all based on density functional theory, for calculating the transfer integral under these constraints, which we benchmark on molecular test systems from the relevant literature. We also discuss many-body effects and apply all three techniques to a junction with a Ruthenium complex in different oxidation states.

  18. An Integrative Model of Organizational Learning and Social Capital on Effective Knowledge Transfer and Perceived Organizational Performance

    ERIC Educational Resources Information Center

    Rhodes, Jo; Lok, Peter; Hung, Richard Yu-Yuan; Fang, Shih-Chieh

    2008-01-01

    Purpose: The purpose of this paper is to set out to examine the relationships of organizational learning, social capital and the effectiveness of knowledge transfer and perceived organisational performance. Integrating organizational learning capability with social capital networks to shape a holistic knowledge sharing and management enterprise…

  19. MHD Technology Transfer, Integration and Review Committee. Seventh semi-annual status report, April 1991--September 1991

    SciTech Connect

    Not Available

    1993-02-01

    This seventh semi-annual status report of the MHD Technology Transfer, Integration and Review Committee (TTIRC) summarizes activities of the TTIRC during the period April 1991 through September 1991. It includes a summary and minutes of the General Committee meeting, progress summaries of ongoing POC contracts, discussions pertaining to technical integration issues in the POC program, and planned activities for the next six months. The meeting included test plan with Western coal, seed regeneration economics, power management for the integrated topping cycle and status of the Clean Coal Technology Proposal activities. Appendices cover CDIF operations HRSR development, CFFF operations etc.

  20. Effect of intermolecular potential on compressible Couette flow in slip and transitional regimes

    NASA Astrophysics Data System (ADS)

    Weaver, Andrew B.; Venkattraman, A.; Alexeenko, Alina A.

    2014-10-01

    The effect of intermolecular potentials on compressible, planar flow in slip and transitional regimes is investigated using the direct simulation Monte Carlo method. Two intermolecular interaction models, the variable hard sphere (VHS) and the Lennard-Jones (LJ) models, are first compared for subsonic and supersonic Couette flows of argon at temperatures of 40, 273, and 1,000 K, and then for Couette flows in the transitional regime ranging from Knudsen numbers (Kn) of 0.0051 to 1. The binary scattering model for elastic scattering using the Lennard-Jones (LJ) intermolecular potential proposed recently [A. Venkattraman and A. Alexeenko, "Binary scattering model for Lennard-Jones potential: Transport coefficients and collision integrals for non-equilibrium gas flow simulations," Phys. Fluids 24, 027101 (2012)] is shown to accurately reproduce both the theoretical collision frequency in an equilibrium gas as well as the theoretical viscosity variation with temperature. The use of a repulsive-attractive instead of a purely repulsive potential is found to be most important in the continuum and slip regimes as well as in flows with large temperature variations. Differences in shear stress of up to 28% between the VHS and LJ models is observed at Kn=0.0051 and is attributed to differences in collision frequencies, ultimately affecting velocity gradients at the wall. For Kn=1 where the Knudsen layer expands the entire domain, the effect of the larger collision frequency in the LJ model relative to VHS diminishes, and a 7% difference in shear stress is observed.

  1. Integrated control and health management. Orbit transfer rocket engine technology program

    NASA Technical Reports Server (NTRS)

    Holzmann, Wilfried A.; Hayden, Warren R.

    1988-01-01

    To insure controllability of the baseline design for a 7500 pound thrust, 10:1 throttleable, dual expanded cycle, Hydrogen-Oxygen, orbit transfer rocket engine, an Integrated Controls and Health Monitoring concept was developed. This included: (1) Dynamic engine simulations using a TUTSIM derived computer code; (2) analysis of various control methods; (3) Failure Modes Analysis to identify critical sensors; (4) Survey of applicable sensors technology; and, (5) Study of Health Monitoring philosophies. The engine design was found to be controllable over the full throttling range by using 13 valves, including an oxygen turbine bypass valve to control mixture ratio, and a hydrogen turbine bypass valve, used in conjunction with the oxygen bypass to control thrust. Classic feedback control methods are proposed along with specific requirements for valves, sensors, and the controller. Expanding on the control system, a Health Monitoring system is proposed including suggested computing methods and the following recommended sensors: (1) Fiber optic and silicon bearing deflectometers; (2) Capacitive shaft displacement sensors; and (3) Hot spot thermocouple arrays. Further work is needed to refine and verify the dynamic simulations and control algorithms, to advance sensor capabilities, and to develop the Health Monitoring computational methods.

  2. Obtaining the Bidirectional Transfer Distribution Function ofIsotropically Scattering Materials Using an Integrating Sphere

    SciTech Connect

    Jonsson, Jacob C.; Branden, Henrik

    2006-10-19

    This paper demonstrates a method to determine thebidirectional transfer distribution function (BTDF) using an integratingsphere. Information about the sample's angle dependent scattering isobtained by making transmittance measurements with the sample atdifferent distances from the integrating sphere. Knowledge about theilluminated area of the sample and the geometry of the sphere port incombination with the measured data combines to an system of equationsthat includes the angle dependent transmittance. The resulting system ofequations is an ill-posed problem which rarely gives a physical solution.A solvable system is obtained by using Tikhonov regularization on theill-posed problem. The solution to this system can then be used to obtainthe BTDF. Four bulk-scattering samples were characterised using both twogoniophotometers and the described method to verify the validity of thenew method. The agreement shown is great for the more diffuse samples.The solution to the low-scattering samples contains unphysicaloscillations, butstill gives the correct shape of the solution. Theorigin of the oscillations and why they are more prominent inlow-scattering samples are discussed.

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

    PubMed

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

    2016-03-31

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  5. Integration of Aquifer Storage Transfer and Recovery and HACCP for Ensuring Drinking Water Quality

    NASA Astrophysics Data System (ADS)

    Lee, S. I.; Ji, H. W.

    2015-12-01

    The integration of ASTR (Aquifer Storage Transfer and Recovery) and HACCP (Hazard Analysis and Critical Control Point) is being attempted to ensure drinking water quality in a delta area. ASTR is a water supply system in which surface water is injected into a well for storage and recovered from a different well. During the process natural water treatment is achieved in the aquifer. ASTR has advantages over surface reservoirs in that the water is protected from external contaminants and free from water loss by evaporation. HACCP, originated from the food industry, can efficiently manage hazards and reduce risks when it is introduced to the drinking water production. The study area is the located in the Nakdong River Delta, South Korea. Water quality of this region has been deteriorated due to the increased pollution loads from the upstream cities and industrial complexes. ASTR equipped with HACCP system is suggested as a means to heighten the public trust in drinking water. After the drinking water supply system using ASTR was decomposed into ten processes, principles of HACCP were applied. Hazardous event analysis was conducted for 114 hazardous events and nine major hazardous events were identified based on the likelihood and the severity assessment. Potential risk of chemical hazards, as a function of amounts, travel distance and toxicity, was evaluated and the result shows the relative threat a city poses to the drinking water supply facility. Next, critical control points were determined using decision tree analysis. Critical limits, maximum and/or minimum values to which biological, chemical or physical parameters must be controlled, were established. Other procedures such as monitoring, corrective actions and will be presented.

  6. Intermolecular exciton-exciton annihilation in phospholipid vesicles doped with [Ru(bpy)2dppz]2+

    NASA Astrophysics Data System (ADS)

    De la Cadena, Alejandro; Pascher, Torbjörn; Davydova, Dar'ya; Akimov, Denis; Herrmann, Felix; Presselt, Martin; Wächtler, Maria; Dietzek, Benjamin

    2016-01-01

    The ultrafast photophysics of [Ru(bpy)2dppz]2+ (dppz = dipyrido[3,2-a:2‧,3‧-c]-phenazine) embedded into the walls of phospholipid vesicles has been studied by femtosecond time-resolved pump-probe spectroscopy. While [Ru(bpy)2dppz]2+ has been studied intensively with respect to its intramolecular charge transfer processes, which are associated with the well known light-switch effect, this study focuses on intermolecular energy transfer processes taking place upon dense packing of the complexes into a phospholipid membrane composed of dipalmitoyl-L-α-phosphatidylglycerol, which can be thought of as a simplistic model of a cellular membrane. The data indicate additional quenching of excited [Ru(bpy)2dppz]2+ upon increasing the pump-pulse intensity. Hence, the observed photophysics, which is assigned to the presence of intermolecular exciton-exciton annihilation at high pump-intensities, might be related to the ultrafast photophysics of [Ru(bpy)2dppz]2+ when used as a chromophore to stain cells, an effect that may be taken into account during the employment of novel cellular markers based on Ru polypyridine complexes.

  7. Intermolecular artifacts in probe microscope images of C60 assemblies

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    PubMed

    Haslmayr, Johannes; Renger, Thomas

    2013-07-28

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

  9. Highly variable individual donor cell fates characterize robust horizontal gene transfer of an integrative and conjugative element

    PubMed Central

    Delavat, François; Mitri, Sara; Pelet, Serge; van der Meer, Jan Roelof

    2016-01-01

    Horizontal gene transfer is an important evolutionary mechanism for bacterial adaptation. However, given the typical low transfer frequencies in a bacterial population, little is known about the fate and interplay of donor cells and the mobilized DNA during transfer. Here we study transfer of an integrative and conjugative element (ICE) among individual live bacterial cells. ICEs are widely distributed mobile DNA elements that are different than plasmids because they reside silent in the host chromosome and are maintained through vertical descent. Occasionally, ICEs become active, excise, and transmit their DNA to a new recipient, where it is reintegrated. We develop a fluorescent tool to differentiate excision, transfer, and reintegration of a model ICE named ICEclc (for carrying the clc genes for chlorocatechol metabolism) among single Pseudomonas cells by using time-lapse microscopy. We find that ICEclc activation is initiated in stationary phase cells, but excision and transfer predominantly occur only when such cells have been presented with new nutrients. Donors with activated ICE develop a number of different states, characterized by reduced cell division rates or growth arrest, persistence, or lysis, concomitant with ICE excision, and likely, ICE loss or replication. The donor cell state transitions can be described by using a stochastic model, which predicts that ICE fitness is optimal at low initiation rates in stationary phase. Despite highly variable donor cell fates, ICE transfer is remarkably robust overall, with 75% success after excision. Our results help to better understand ICE behavior and shed a new light on bacterial cellular differentiation during horizontal gene transfer. PMID:27247406

  10. Highly variable individual donor cell fates characterize robust horizontal gene transfer of an integrative and conjugative element.

    PubMed

    Delavat, François; Mitri, Sara; Pelet, Serge; van der Meer, Jan Roelof

    2016-06-14

    Horizontal gene transfer is an important evolutionary mechanism for bacterial adaptation. However, given the typical low transfer frequencies in a bacterial population, little is known about the fate and interplay of donor cells and the mobilized DNA during transfer. Here we study transfer of an integrative and conjugative element (ICE) among individual live bacterial cells. ICEs are widely distributed mobile DNA elements that are different than plasmids because they reside silent in the host chromosome and are maintained through vertical descent. Occasionally, ICEs become active, excise, and transmit their DNA to a new recipient, where it is reintegrated. We develop a fluorescent tool to differentiate excision, transfer, and reintegration of a model ICE named ICEclc (for carrying the clc genes for chlorocatechol metabolism) among single Pseudomonas cells by using time-lapse microscopy. We find that ICEclc activation is initiated in stationary phase cells, but excision and transfer predominantly occur only when such cells have been presented with new nutrients. Donors with activated ICE develop a number of different states, characterized by reduced cell division rates or growth arrest, persistence, or lysis, concomitant with ICE excision, and likely, ICE loss or replication. The donor cell state transitions can be described by using a stochastic model, which predicts that ICE fitness is optimal at low initiation rates in stationary phase. Despite highly variable donor cell fates, ICE transfer is remarkably robust overall, with 75% success after excision. Our results help to better understand ICE behavior and shed a new light on bacterial cellular differentiation during horizontal gene transfer. PMID:27247406

  11. Transfer-printing-based integration of single-mode waveguide-coupled III-V-on-silicon broadband light emitters.

    PubMed

    De Groote, Andreas; Cardile, Paolo; Subramanian, Ananth Z; Fecioru, Alin M; Bower, Christopher; Delbeke, Danae; Baets, Roel; Roelkens, Günther

    2016-06-27

    We present the first III-V opto-electronic components transfer printed on and coupled to a silicon photonic integrated circuit. Thin InP-based membranes are transferred to an SOI waveguide circuit, after which a single-spatial-mode broadband light source is fabricated. The process flow to create transfer print-ready coupons is discussed. Aqueous FeCl3 at 5°C was found to be the best release agent in combination with the photoresist anchoring structures that were used. A thin DVS-BCB layer provides a strong bond, accommodating the post-processing of the membranes. The resulting optically pumped LED has a 3 dB bandwidth of 130 nm, comparable to devices realized using a traditional die-to-wafer bonding method. PMID:27410539

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

    PubMed

    Renaud, Nicolas; Grozema, Ferdinand C

    2015-02-01

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

  13. "It Takes an Integrated, College-Wide Effort" and Other Lessons from Seven High Transfer Colleges

    ERIC Educational Resources Information Center

    Mery, Pamela; Schiorring, Eva

    2011-01-01

    The Successful Transfer Approach Research (STAR) Project investigated seven California Community Colleges with consistently high transfer rates. Teams of experienced researchers spent two days at each college, interviewing 16-18 administrators, faculty, researchers, and student support service professionals. Focus groups and interviews were also…

  14. 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

  15. Preoperational test report, cross-site transfer system integrated test (POTR-007)

    SciTech Connect

    Pacquet, E.A.

    1998-04-02

    This report documents the results obtained during the performance of Preoperational Test POTP-007, from December 12, 1997 to March 27, 1998. The main objectives were to demonstrate the operation of the following Cross-Site Transfer System components: Booster pumps P-3125A and P-3125B interlocks and controls, both local and remote; Booster pump P-3125A and P-3125B and associated variable speed drives VSD-1 and VSD-2 performance in both manual and automatic modes; and Water filling, circulation, venting and draining of the transfer headers (supernate and slurry line). As described in reference 1, the following components of the Cross-Site Transfer System that would normally be used during an actual waste transfer, are not used in this specific test: Water Flush System; Valving and instrumentation associated with the 241-SY-A valve pit jumpers; and Valving and instrumentation associated with the 244-A lift station.

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

    DOE PAGESBeta

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

    2015-02-19

    Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this study, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field,more » the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (H2O)2 cluster. Below the critical electric field, it is observed that with increasing field strength, H-bonding orbitals display gradual evolutions in the orbital energy, orbital ordering, and orbital nature (i.e., from typical -style orbital to unusual -style double H-bonding orbital). We also show that beyond the critical electric field, a single water whisker may disintegrate to form a loosely bound zwitterionic chain due to a relay-style proton transfer, whereas two water whiskers may undergo intermolecular cross-linking to form a quasi-two-dimensional water network. In conclusion, these results help shed new insight on the effects of electric fields on water whisker formation.« less

  17. 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.

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

    PubMed

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

    2013-11-14

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

  19. 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…

  20. Direct observation of intermolecular interactions mediated by hydrogen bonding

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  1. 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.

  2. 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.

  3. 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.

  4. 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…

  5. 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…

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

    PubMed

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

    2015-06-22

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

  7. An Integrated Approach to Modeling Solar Electric Propulsion Vehicles During Long Duration, Near-Earth Orbit Transfers

    NASA Technical Reports Server (NTRS)

    Smith, David A.; Hojnicki, Jeffrey S.; Sjauw, Waldy K.

    2014-01-01

    Recent NASA interest in utilizing solar electronic propulsion (SEP) technology to transfer payloads, e.g. from low-Earth orbit (LEO) to higher energy geostationary-Earth orbit (GEO) or to Earth escape, has necessitated the development of high fidelity SEP vehicle models and simulations. These models and simulations need to be capable of capturing vehicle dynamics and sub-system interactions experienced during the transfer trajectories which are typically accomplished with continuous-burn (potentially interrupted by solar eclipse), long duration "spiral out" maneuvers taking several months or more to complete. This paper presents details of an integrated simulation approach achieved by combining a high fidelity vehicle simulation code with a detailed solar array model. The combined simulation tool gives researchers the functionality to study the integrated effects of various vehicle sub-systems (e.g. vehicle guidance, navigation and control (GN&C), electric propulsion system (EP)) with time varying power production. Results from a simulation model of a vehicle with a 50 kW class SEP system using the integrated tool are presented and compared to the results from another simulation model employing a 50 kW end-of-life (EOL) fixed power level assumption. These models simulate a vehicle under three degree of freedom dynamics (i.e. translational dynamics only) and include the effects of a targeting guidance algorithm (providing a "near optimal" transfer) during a LEO to near Earth escape (C (sub 3) = -2.0 km (sup 2) / sec (sup -2) spiral trajectory. The presented results include the impact of the fully integrated, time-varying solar array model (e.g. cumulative array degradation from traversing the Van Allen belts, impact of solar eclipses on the vehicle and the related temperature responses in the solar arrays due to operating in the Earth's thermal environment, high fidelity array power module, etc.); these are used to assess the impact on vehicle performance (i

  8. One-step transfer and integration of multifunctionality in CVD graphene by TiO₂/graphene oxide hybrid layer.

    PubMed

    Jeong, Hee Jin; Kim, Ho Young; Jeong, Hyun; Han, Joong Tark; Jeong, Seung Yol; Baeg, Kang-Jun; Jeong, Mun Seok; Lee, Geon-Woong

    2014-05-28

    We present a straightforward method for simultaneously enhancing the electrical conductivity, environmental stability, and photocatalytic properties of graphene films through one-step transfer of CVD graphene and integration by introducing TiO2/graphene oxide layer. A highly durable and flexible TiO2 layer is successfully used as a supporting layer for graphene transfer instead of the commonly used PMMA. Transferred graphene/TiO2 film is directly used for measuring the carrier transport and optoelectronic properties without an extra TiO2 removal and following deposition steps for multifunctional integration into devices because the thin TiO2 layer is optically transparent and electrically semiconducting. Moreover, the TiO2 layer induces charge screening by electrostatically interacting with the residual oxygen moieties on graphene, which are charge scattering centers, resulting in a reduced current hysteresis. Adsorption of water and other chemical molecules onto the graphene surface is also prevented by the passivating TiO2 layer, resulting in the long term environmental stability of the graphene under high temperature and humidity. In addition, the graphene/TiO2 film shows effectively enhanced photocatalytic properties because of the increase in the transport efficiency of the photogenerated electrons due to the decrease in the injection barrier formed at the interface between the F-doped tin oxide and TiO2 layers. PMID:24578338

  9. Integrated Compartment Method appication to the transient heat transfer in gas-cooled reactor

    SciTech Connect

    Chen, N.C.J.; Yeh, G.T.

    1983-01-01

    Integrated Compartment Method (ICM), an effective numerical integration algorithm, was developed to solve the transient heat conduction coupled with convection. Application of the ICM to the mathematical model simulating a graphite test structure heated in an annular flow stream of hot helium has been successfully demonstrated. However, the model validation can not be performed until experimental data become available.

  10. Arts Integration Professional Development: Teacher Perspective and Transfer to Instructional Practice

    ERIC Educational Resources Information Center

    Garrett, Jo Ann

    2010-01-01

    Limited data connect teacher training in arts integration (AI) to evidence that students benefit from arts integrated instruction. As teachers are challenged to facilitate instruction for a wide continuum of learning needs, and students are challenged to demonstrate learning through high-stakes testing, more data are needed on how teachers learn…

  11. 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.

  12. Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation

    SciTech Connect

    Moix, Jeremy M.; Ma, Jian; Cao, Jianshu

    2015-03-07

    A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters.

  13. Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation.

    PubMed

    Moix, Jeremy M; Ma, Jian; Cao, Jianshu

    2015-03-01

    A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters. PMID:25747062

  14. High performance organic integrated device with ultraviolet photodetective and electroluminescent properties consisting of a charge-transfer-featured naphthalimide derivative

    NASA Astrophysics Data System (ADS)

    Wang, Hanyu; Zhou, Jie; Wang, Xu; Lu, Zhiyun; Yu, Junsheng

    2014-08-01

    A high performance organic integrated device (OID) with ultraviolet photodetective and electroluminescent (EL) properties was fabricated by using a charge-transfer-featured naphthalimide derivative of 6-{3,5-bis-[9-(4-t-butylphenyl)-9H-carbazol-3-yl]-phenoxy}-2-(4-t-butylphenyl)-benzo[de]isoquinoline-1,3-dione (CzPhONI) as the active layer. The results showed that the OID had a high detectivity of 1.5 × 1011 Jones at -3 V under the UV-350 nm illumination with an intensity of 0.6 mW/cm2, and yielded an exciplex EL light emission with a maximum brightness of 1437 cd/m2. Based on the energy band diagram, both the charge transfer feature of CzPhONI and matched energy level alignment were responsible for the dual ultraviolet photodetective and EL functions of OID.

  15. Differential, integral, and momentum-transfer cross sections for elastic electron scattering by neon - 5 to 100 eV

    NASA Technical Reports Server (NTRS)

    Register, D. F.; Trajmar, S.

    1984-01-01

    Relative elastic-scattering differential cross sections were measured in the 5-100-eV impact energy and 10-145 deg angular ranges. Normalization of these cross sections was achieved by utilizing accurate total electron-scattering cross sections. A phase-shift analysis of the angular distributions in terms of real phase shifts has been carried out. From the differential cross sections, momentum-transfer cross sections were obtained and the values of the critical energy and angle were established (associated with the lowest value of the differential cross section) as 62.5 + or - 2.5 eV and 101.7 deg + or - 1.5 deg, respectively. The present phase shifts, the critical parameters, and differential, integral, and momentum-transfer cross sections are compared to previous experimental and theoretical results. The error associated with the present data is about 10 percent.

  16. Promoting Transfer and an Integrated Understanding for Pre-Service Teachers of Technology Education

    ERIC Educational Resources Information Center

    Morrison-Love, David

    2014-01-01

    The ability of pre-service teachers (PSTs) to transfer learning between subjects and contexts when problem solving is critical for developing their capability as technologists and teachers of technology. However, a growing body of literature suggests this ability is often assumed or over-estimated, and rarely developed explicitly within courses or…

  17. Integrating dynamic stopping, transfer learning and language models in an adaptive zero-training ERP speller

    NASA Astrophysics Data System (ADS)

    Kindermans, Pieter-Jan; Tangermann, Michael; Müller, Klaus-Robert; Schrauwen, Benjamin

    2014-06-01

    Objective. Most BCIs have to undergo a calibration session in which data is recorded to train decoders with machine learning. Only recently zero-training methods have become a subject of study. This work proposes a probabilistic framework for BCI applications which exploit event-related potentials (ERPs). For the example of a visual P300 speller we show how the framework harvests the structure suitable to solve the decoding task by (a) transfer learning, (b) unsupervised adaptation, (c) language model and (d) dynamic stopping. Approach. A simulation study compares the proposed probabilistic zero framework (using transfer learning and task structure) to a state-of-the-art supervised model on n = 22 subjects. The individual influence of the involved components (a)-(d) are investigated. Main results. Without any need for a calibration session, the probabilistic zero-training framework with inter-subject transfer learning shows excellent performance—competitive to a state-of-the-art supervised method using calibration. Its decoding quality is carried mainly by the effect of transfer learning in combination with continuous unsupervised adaptation. Significance. A high-performing zero-training BCI is within reach for one of the most popular BCI paradigms: ERP spelling. Recording calibration data for a supervised BCI would require valuable time which is lost for spelling. The time spent on calibration would allow a novel user to spell 29 symbols with our unsupervised approach. It could be of use for various clinical and non-clinical ERP-applications of BCI.

  18. Integration Of Heat Transfer Coefficient In Glass Forming Modeling With Special Interface Element

    SciTech Connect

    Moreau, P.; Gregoire, S.; Lochegnies, D.; Cesar de Sa, J.

    2007-05-17

    Numerical modeling of the glass forming processes requires the accurate knowledge of the heat exchange between the glass and the forming tools. A laboratory testing is developed to determine the evolution of the heat transfer coefficient in different glass/mould contact conditions (contact pressure, temperature, lubrication...). In this paper, trials are performed to determine heat transfer coefficient evolutions in experimental conditions close to the industrial blow-and-blow process conditions. In parallel of this work, a special interface element is implemented in a commercial Finite Element code in order to deal with heat transfer between glass and mould for non-meshing meshes and evolutive contact. This special interface element, implemented by using user subroutines, permits to introduce the previous heat transfer coefficient evolutions in the numerical modelings at the glass/mould interface in function of the local temperatures, contact pressures, contact time and kind of lubrication. The blow-and-blow forming simulation of a perfume bottle is finally performed to assess the special interface element performance.

  19. Integration Of Heat Transfer Coefficient In Glass Forming Modeling With Special Interface Element

    NASA Astrophysics Data System (ADS)

    Moreau, P.; César de Sá, J.; Grégoire, S.; Lochegnies, D.

    2007-05-01

    Numerical modeling of the glass forming processes requires the accurate knowledge of the heat exchange between the glass and the forming tools. A laboratory testing is developed to determine the evolution of the heat transfer coefficient in different glass/mould contact conditions (contact pressure, temperature, lubrication…). In this paper, trials are performed to determine heat transfer coefficient evolutions in experimental conditions close to the industrial blow-and-blow process conditions. In parallel of this work, a special interface element is implemented in a commercial Finite Element code in order to deal with heat transfer between glass and mould for non-meshing meshes and evolutive contact. This special interface element, implemented by using user subroutines, permits to introduce the previous heat transfer coefficient evolutions in the numerical modelings at the glass/mould interface in function of the local temperatures, contact pressures, contact time and kind of lubrication. The blow-and-blow forming simulation of a perfume bottle is finally performed to assess the special interface element performance.

  20. Transfer Advisement at One Community College: Integrating Technology, Initiatives and Programs for Increased Student Learning.

    ERIC Educational Resources Information Center

    DeWitt, Kristine; And Others

    In spring 1996, Maryland's Carroll Community College (CCC) began efforts to shift institutional focus and mission from that of a teaching institution to a learning-centered institution. The college's Counseling and Advising Services unit, responsible for advising and transfer, has adapted this educational shift to its unique position in the…

  1. CO-INJECTION RESIN TRANSFER MOLDING FOR OPTIMIZATION OF INTEGRAL ARMOR

    EPA Science Inventory

    To address the cost and performance barriers which hinder the introduction of composite materials for combat ground vehicle applications, Co-Injection Resin Transfer Molding (CIRTM) and Diffusion Enhanced Adhesion (DEA) have been recently invented and developed at the Army Resear...

  2. H-NS Facilitates Sequence Diversification of Horizontally Transferred DNAs during Their Integration in Host Chromosomes.

    PubMed

    Higashi, Koichi; Tobe, Toru; Kanai, Akinori; Uyar, Ebru; Ishikawa, Shu; Suzuki, Yutaka; Ogasawara, Naotake; Kurokawa, Ken; Oshima, Taku

    2016-01-01

    Bacteria can acquire new traits through horizontal gene transfer. Inappropriate expression of transferred genes, however, can disrupt the physiology of the host bacteria. To reduce this risk, Escherichia coli expresses the nucleoid-associated protein, H-NS, which preferentially binds to horizontally transferred genes to control their expression. Once expression is optimized, the horizontally transferred genes may actually contribute to E. coli survival in new habitats. Therefore, we investigated whether and how H-NS contributes to this optimization process. A comparison of H-NS binding profiles on common chromosomal segments of three E. coli strains belonging to different phylogenetic groups indicated that the positions of H-NS-bound regions have been conserved in E. coli strains. The sequences of the H-NS-bound regions appear to have diverged more so than H-NS-unbound regions only when H-NS-bound regions are located upstream or in coding regions of genes. Because these regions generally contain regulatory elements for gene expression, sequence divergence in these regions may be associated with alteration of gene expression. Indeed, nucleotide substitutions in H-NS-bound regions of the ybdO promoter and coding regions have diversified the potential for H-NS-independent negative regulation among E. coli strains. The ybdO expression in these strains was still negatively regulated by H-NS, which reduced the effect of H-NS-independent regulation under normal growth conditions. Hence, we propose that, during E. coli evolution, the conservation of H-NS binding sites resulted in the diversification of the regulation of horizontally transferred genes, which may have facilitated E. coli adaptation to new ecological niches. PMID:26789284

  3. Influence of bias voltage and temperature on charge transfer states in organic photovoltaic and electroluminescent integrated device

    SciTech Connect

    Huang, Jiang; Wang, Hanyu; Qi, Yige; Yu, Junsheng

    2014-05-19

    Based on the organic photovoltaic (PV) and electroluminescent (EL) integrated device with a structure of SubPc/C{sub 60} heterojunction, both PV and EL properties of charge transfer states (CTSs) were simultaneously investigated. By means of infrared and visible isolating method, the EL characteristics of CTSs and singlet-triplet excitons were separated, and their properties dependence on bias voltage and temperature was analyzed by introducing modified diode models. From the simulation on the emissive photons from CTSs, the temperature independent parameters of CTSs were extracted, which have close relationship with thermal activation energy and effective emissive state number of CTSs at the SubPc/C{sub 60} interface.

  4. Thermodynamic Integration Networks and Their Application to Charge Transfer Reactions within the AauDyPI Fungal Peroxidase.

    PubMed

    Bauß, Anna; Langenmaier, Michael; Strittmatter, Eric; Plattner, Dietmar A; Koslowski, Thorsten

    2016-06-01

    We present a computer simulation study of the thermodynamics and kinetics of charge transfer reactions within the fungal peroxidase AauDyPI from Auricularia auriculae-judae. Driving forces and reorganization energies are obtained from a thermodynamic integration scheme based upon molecular dynamics simulations. To enhance the numerical accuracy, the free energies are analyzed within a least-squares scheme of a closely knit thermodynamic network. We identify Tyr147, Tyr229, and Trp105 as oxidative agents, and find Trp377 to be a long-lived reaction intermediate. The results are compared to recent experimental findings. PMID:27182684

  5. Proton Transfer Studied Using a Combined Ab Initio Reactive Potential Energy Surface with Quantum Path Integral Methodology

    PubMed Central

    Wong, Kim F.; Sonnenberg, Jason L.; Paesani, Francesco; Yamamoto, Takeshi; Vaníček, Jiří; Zhang, Wei; Schlegel, H. Bernhard; Case, David A.; Cheatham, Thomas E.; Miller, William H.; Voth, Gregory A.

    2010-01-01

    The rates of intramolecular proton transfer are calculated on a full-dimensional reactive electronic potential energy surface that incorporates high level ab initio calculations along the reaction path and by using classical Transition State theory, Path-Integral Quantum Transition State Theory, and the Quantum Instanton approach. The specific example problem studied is malonaldehyde. Estimates of the kinetic isotope effect using the latter two methods are found to be in reasonable agreement with each other. Improvements and extensions of this practical, yet chemically accurate framework for the calculations of quantized, reactive dynamics are also discussed. PMID:21116485

  6. T-DNA transfer and T-DNA integration efficiencies upon Arabidopsis thaliana root explant cocultivation and floral dip transformation.

    PubMed

    Ghedira, Rim; De Buck, Sylvie; Van Ex, Frédéric; Angenon, Geert; Depicker, Ann

    2013-12-01

    T-DNA transfer and integration frequencies during Agrobacterium-mediated root explant cocultivation and floral dip transformations of Arabidopsis thaliana were analyzed with and without selection for transformation-competent cells. Based on the presence or absence of CRE recombinase activity without or with the CRE T-DNA being integrated, transient expression versus stable transformation was differentiated. During root explant cocultivation, continuous light enhanced the number of plant cells competent for interaction with Agrobacterium and thus the number of transient gene expression events. However, in transformation competent plant cells, continuous light did not further enhance cotransfer or cointegration frequencies. Upon selection for root transformants expressing a first T-DNA, 43-69 % of these transformants showed cotransfer of another non-selected T-DNA in two different light regimes. However, integration of the non-selected cotransferred T-DNA occurred only in 19-46 % of these transformants, indicating that T-DNA integration in regenerating root cells limits the transformation frequencies. After floral dip transformation, transient T-DNA expression without integration could not be detected, while stable T-DNA transformation occurred in 0.5-1.3 % of the T1 seedlings. Upon selection for floral dip transformants with a first T-DNA, 8-34 % of the transformants showed cotransfer of the other non-selected T-DNA and in 93-100 % of them, the T-DNA was also integrated. Therefore, a productive interaction between the agrobacteria and the female gametophyte, rather than the T-DNA integration process, restricts the floral dip transformation frequencies. PMID:23975012

  7. Process for producing an activated carbon adsorbent with integral heat transfer apparatus

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor); Yavrouian, Andre H. (Inventor)

    1996-01-01

    A process for producing an integral adsorbent-heat exchanger apparatus useful in ammonia refrigerant heat pump systems. In one embodiment, the process wets an activated carbon particles-solvent mixture with a binder-solvent mixture, presses the binder wetted activated carbon mixture on a metal tube surface and thereafter pyrolyzes the mixture to form a bonded activated carbon matrix adjoined to the tube surface. The integral apparatus can be easily and inexpensively produced by the process in large quantities.

  8. Controlling electronic effects and intermolecular packing in contorted polyaromatic hydrocarbons (c-PAHs): towards high mobility field effect transistors.

    PubMed

    Bhattacharyya, Kalishankar; Mukhopadhyay, Titas Kumar; Datta, Ayan

    2016-06-01

    We have investigated the electronic and charge transport properties of two regioisomeric contorted polyaromatic hydrocarbons at the molecular level as well as in the crystalline state. Electron and hole transport is studied on the basis of an incoherent charge hopping model through DFT calculations. For trifluro-dibenzoperylene (CF3-DBP, ), which crystallizes as a herringbone network, the computed drift hole and electron mobilities are 0.234 and 0.008 cm(2) V(-1) S(-1), respectively. The greater hole mobility in the DBP crystal (μh/μe = 29) can be rationalized by its lower hole reorganization energy and higher hole transfer integral simultaneously. These calculations for the pristine DBP crystal differ from recent experiments indicating its preferential electron conductivity. This might be attributed to the interaction of the molecules with the gold source/drain electrodes. Its second regioisomer, , having a HOMO-LUMO gap of 3.2 eV and thus expectedly inefficient, can be converted into an effective OFET material by replacing the Ph-CF3 groups by oxo groups (>C[double bond, length as m-dash]O) in the 9 and 10 positions (9,10-dioxotribenzopyrene, ). has a suitable HOMO-LUMO gap of 2.18 eV. This bowl-shaped molecule is predicted to pack in a stacked orientation with preferential concaveconcave pairs having a short intermolecular distance of 4.15 Å and identical inter-chromophoric electron/hole coupling (th ∼ te). This creates an ambipolar charge transport behavior in . Clearly, fine tuning the structure-property relationship opens up the possibility of implanting tailored OFET properties in the existing library of molecules. PMID:27189183

  9. Magnetic Field Mapping and Integral Transfer Function Matching of the Prototype Dipoles for the NSLS-II at BNL

    SciTech Connect

    He, P.; Jain, A., Gupta, R., Skaritka, J., Spataro, C., Joshi, P., Ganetis, G., Anerella, M., Wanderer, P.

    2011-03-28

    The National Synchrotron Light Source-II (NSLS-II) storage ring at Brookhaven National Laboratory (BNL) will be equipped with 54 dipole magnets having a gap of 35 mm, and 6 dipoles having a gap of 90 mm. Each dipole has a field of 0.4 T and provides 6 degrees of bending for a 3 GeV electron beam. The large aperture magnets are necessary to allow the extraction of long-wavelength light from the dipole magnet to serve a growing number of users of low energy radiation. The dipoles must not only have good field homogeneity (0.015% over a 40 mm x 20 mm region), but the integral transfer functions and integral end harmonics of the two types of magnets must also be matched. The 35 mm aperture dipole has a novel design where the yoke ends are extended up to the outside dimension of the coil using magnetic steel nose pieces. This design increases the effective length of the dipole without increasing the physical length. These nose pieces can be tailored to adjust the integral transfer function as well as the homogeneity of the integrated field. One prototype of each dipole type has been fabricated to validate the designs and to study matching of the two dipoles. A Hall probe mapping system has been built with three Group 3 Hall probes mounted on a 2-D translation stage. The probes are arranged with one probe in the midplane of the magnet and the others vertically offset by {+-}10 mm. The field is mapped around a nominal 25 m radius beam trajectory. The results of measurements in the as-received magnets, and with modifications made to the nose pieces are presented.

  10. 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.

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

    PubMed

    Schöps, Philipp; Plackmeyer, Jörn; Marko, Andriy

    2016-08-01

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

  12. 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.

  13. 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

  14. Calculations of helical twisting powers from intermolecular torques.

    PubMed

    Earl, David J; Wilson, Mark R

    2004-05-22

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

  15. Reexamining surface-integral formulations for one-nucleon transfers to bound and resonance states

    NASA Astrophysics Data System (ADS)

    Escher, J. E.; Thompson, I. J.; Arbanas, G.; Elster, Ch.; Eremenko, V.; Hlophe, L.; Nunes, F. M.; Torus Collaboration

    2014-05-01

    One-nucleon transfer reactions, in particular (d ,p) reactions, have played a central role in nuclear structure studies for many decades. Present theoretical descriptions of the underlying reaction mechanisms are insufficient for addressing the challenges and opportunities that are opening up with new radioactive beam facilities. We investigate a theoretical approach that was proposed recently to address shortcomings in the description of transfers to resonance states. The method builds on ideas from the very successful R-matrix theory; in particular, it uses a similar separation of the coordinate space into interior and exterior regions and introduces a parametrization that can be related to physical observables, which, in principle, makes it possible to extract meaningful spectroscopic information from experiments. We carry out calculations, for a selection of isotopes and energies, to test the usefulness of the new approach.

  16. IR spectroscopy of monohydrated tryptamine cation: Rearrangement of the intermolecular hydrogen bond induced by photoionization

    NASA Astrophysics Data System (ADS)

    Sakota, Kenji; Kouno, Yuuki; Harada, Satoshi; Miyazaki, Mitsuhiko; Fujii, Masaaki; Sekiya, Hiroshi

    2012-12-01

    Rearrangement of intermolecular hydrogen bond in a monohydrated tryptamine cation, [TRA(H2O)1]+, has been investigated in the gas phase by IR spectroscopy and quantum chemical calculations. In the S0 state of TRA(H2O)1, a water molecule is hydrogen-bonded to the N atom of the amino group of a flexible ethylamine side chain [T. S. Zwier, J. Phys. Chem. A 105, 8827 (2001), 10.1021/jp011659+]. A remarkable change in the hydrogen-bonding motif of [TRA(H2O)]+ occurs upon photoionization. In the D0 state of [TRA(H2O)1]+, the water molecule is hydrogen-bonded to the NH group of the indole ring of TRA+, indicating that the water molecule transfers from the amino group to NH group. Quantum chemical calculations are performed to investigate the pathway of the water transfer. Two potential energy barriers emerge in [TRA(H2O)1]+ along the intrinsic reaction coordinate of the water transfer. The water transfer event observed in [TRA(H2O)1]+ is not an elementary but a complex process.

  17. 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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

    Nagy, Peter I

    2014-01-01

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

  20. Intramolecular and intermolecular vibrational energy relaxation of CH 2I 2 dissolved in supercritical fluid

    NASA Astrophysics Data System (ADS)

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

    2002-04-01

    A pump-probe experiment was performed to examine vibrational population relaxation of diiodomethane (CH 2I 2) molecule dissolved in supercritical CO 2. Using an apparatus with femtosecond time resolution, we observed the contributions of intramolecular vibrational energy redistribution (IVR) and intermolecular vibrational energy transfer (VET) separately. IVR and VET rates were measured with varying solvent densities at a constant temperature. It is shown that the IVR rate is not density dependent while the VET rate increases with increasing density from 0.4 to 0.8 g cm-3. This observation suggests that the rate of the VET process is determined by solute-solvent collisions whereas the IVR rate is not much affected by solute-solvent interaction.

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

    NASA Astrophysics Data System (ADS)

    Krummel, Amber

    2014-03-01

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

  2. Polar solvation and electron transfer

    SciTech Connect

    Not Available

    1993-04-13

    The report is divided into the following sections: completion of previous studies on solvation dynamics, dipole lattice studies, inertial components of solvation response, simple models of solvation dynamics, rotational dynamics and dielectric friction, intramolecular electron transfer reactions, and intermolecular donor-acceptor complexes.

  3. 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.

  4. Integrated titer plate-injector head for microdrop array preparation, storage and transfer

    DOEpatents

    Swierkowski, Stefan P.

    2000-01-01

    An integrated titer plate-injector head for preparing and storing two-dimensional (2-D) arrays of microdrops and for ejecting part or all of the microdrops and inserting same precisely into 2-D arrays of deposition sites with micrometer precision. The titer plate-injector head includes integrated precision formed nozzles with appropriate hydrophobic surface features and evaporative constraints. A reusable pressure head with a pressure equalizing feature is added to the titer plate to perform simultaneous precision sample ejection. The titer plate-injector head may be utilized in various applications including capillary electrophoresis, chemical flow injection analysis, microsample array preparation, etc.

  5. Full surface local heat transfer coefficient measurements in a model of an integrally cast impingement cooling geometry

    SciTech Connect

    Gillespie, D.R.H.; Wang, Z.; Ireland, P.T.; Kohler, S.T.

    1998-01-01

    Cast impingement cooling geometries offer the gas turbine designer higher structural integrity and improved convective cooling when compared to traditional impingement cooling systems, which rely on plate inserts. In this paper, it is shown that the surface that forms the jets contributes significantly to the total cooling. Local heat transfer coefficient distributions have been measured in a model of an engine wall cooling geometry using the transient heat transfer technique. The method employs temperature-sensitive liquid crystals to measure the surface temperature of large-scale perspex models during transient experiments. Full distributions of local Nusselt number on both surfaces of the impingement plate, and on the impingement target plate, are presented at engine representative Reynolds numbers. The relative effects of the impingement plate thermal boundary condition and the coolant supply temperature on the target plate heat transfer have been determined by maintaining an isothermal boundary condition at the impingement plate during the transient tests. The results are discussed in terms of the interpreted flow field.

  6. Integral Method for the Assessment of U-RANS Effectiveness in Non-Equilibrium Flows and Heat Transfer

    NASA Astrophysics Data System (ADS)

    Pond, Ian; Edabi, Alireza; Dubief, Yves; White, Christopher

    2015-11-01

    Reynolds Average Navier Stokes (RANS) modeling has established itself as a critical design tool in many engineering applications, thanks to its superior computational efficiency. The drawbacks of RANS models are well known, but not necessarily well understood: poor prediction of transition, non equilibrium flows, mixing and heat transfer, to name the ones relevant to our study. In the present study, we use a DNS of a reciprocating channel flow driven by an oscillating pressure gradient to test several low- and high-Reynolds RANS models. Temperature is introduced as a passive scalar to study heat transfer modeling. Low-Reynolds models manage to capture the overall physics of wall shear and heat flux well, yet with some phase discrepancies, whereas high Reynolds models fail. Under the microscope of the integral method for wall shear and wall heat flux, the qualitative agreement appears more serendipitous than driven by the ability of the models to capture the correct physics. The integral method is shown to be more insightful in the benchmarking of RANS models than the typical comparisons of statistical quantities. The authors acknowledges the support of NSF and DOE under grant NSF/DOE 1258697 (VT) and 1258702 (NH).

  7. An Investigation into the Process of Transference, through the Integration of Art with Science and Math Curricula, in a California Community College: A Case Study

    ERIC Educational Resources Information Center

    Rachford, Maryann Kvietkauskas

    2011-01-01

    The transference of learning from one discipline to another creates new knowledge between subjects. Students can connect and apply what they learn in one subject to previously existing knowledge. Art expression is an integral part of human nature and has been a means of communication throughout history. Through the integration of art with science…

  8. Active rc networks of low sensitivity for integrated circuit transfer function

    NASA Technical Reports Server (NTRS)

    Huelsman, L. P.; Kerwin, W. J.; Newcomb, R. W.

    1968-01-01

    Active RC network is capable of extremely high Q performance with exceptional stability and has independently adjustable zeros and poles. The circuit consists of two integrators and two summers that are interconnected to produce a complete second-order numerator and a second-order denominator.

  9. Clues to Coral Reef Health: Integrating Radiative Transfer Modeling and Hyperspectral Data

    NASA Astrophysics Data System (ADS)

    Guild, L.; Ganapol, B.; Kramer, P.; Armstrong, R.; Gleason, A.; Torres, J.; Johnson, L.; Garfield, N.

    2002-12-01

    An important contribution to coral reef research is to improve spectral distinction between various health states of coral species in areas subject to harmful anthropogenic activity and climate change. New insights into radiative transfer properties of corals under healthy and stressed conditions can advance understandings of ecological processes on reefs and allow better assessments of the impacts of large-scale bleaching and disease events. Our objective is to examine the spectral and spatial properties of hyperspectral sensors that may be used to remotely sense changes in reef community health. We compare in situ reef environment spectra (healthy coral, stressed coral, dead coral, algae, and sand) with airborne hyperspectral data to identify important spectral characteristics and indices. Additionally, spectral measurements over a range of water depths, relief, and bottom types are compared to help quantify bottom-water column influences. In situ spectra was collected in July and August 2002 at the Long Rock site in the Andros Island, Bahamas coastal zone coral reef. Our primary emphasis is on Acropora palmata (or elkhorn coral), a major reef building coral, which is prevalent in the study area, but is suffering from white band disease. A. palmata is currently being proposed as an endangered species because its populations have severely declined in many areas of the Caribbean. In addition to the A. palmata biotope, we have collected spectra of at least seven other coral biotopes that exist within the study area, each with different coral community composition, density of corals, relief, and size of corals. Coral spectral reflectance is input into a radiative transfer model, CORALMOD (CM1), which is based on a leaf radiative transfer model. In CM1, input coral reflectance measurements produce modeled reflectance through an inversion at each visible wavelength to provide the absorption spectrum. Initially, we have imposed a scattering baseline that is the same

  10. Clues to Coral Reef Health: Integrating Radiative Transfer Modeling and Hyperspectral Data

    NASA Technical Reports Server (NTRS)

    Guild, Liane; Ganapol, Barry; Kramer, Philip; Armstrong, Roy; Gleason, Art; Torres, Juan; Johnson, Lee; Garfield, Toby; Peterson, David L. (Technical Monitor)

    2002-01-01

    An important contribution to coral reef research is to improve spectral distinction between various health states of coral species in areas subject to harmful anthropogenic activity and climate change. New insights into radiative transfer properties of corals under healthy and stressed conditions can advance understandings of ecological processes on reefs and allow better assessments of the impacts of large-scale bleaching and disease events, Our objective was to examine the spectral and spatial properties of hyperspectral sensors that may be used to remotely sense changes in reef community health. We compare in situ reef environment spectra (healthy coral, stressed coral, dead coral, algae, and sand) with airborne hyperspectral data to identify important spectral characteristics and indices. Additionally, spectral measurements over a range of water depths, relief, and bottom types are compared to help quantify bottom-water column influences. In situ spectra were collected in July and August 2002 at the Long Rock site in the Andros Island, Bahamas coastal zone coral reef. Our primary emphasis was on Acropora palmata (or elkhorn coral), a major reef building coral, which is prevalent in the study area, but is suffering from white band disease. A. palmata is currently being, proposed as an endangered species because its populations have severely declined in many areas of the Caribbean. In addition to the A. palmata biotope, we have collected spectra of at least seven other coral biotopes that exist within the study area, each with different coral community composition, density of corals, relief, and size of corals. Coral spectral reflectance was then input into a radiative transfer model, CORALMOD (CM1), which is based on a leaf radiative transfer model. In CM1, input coral reflectance measurements produce modeled reflectance through an inversion at each visible wavelength to provide the absorption spectrum. Initially, we imposed a scattering baseline that is the