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Sample records for intermolecular transfer integral

  1. 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)

  2. 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.

  3. Fluorescence photoactivation by intermolecular proton transfer.

    PubMed

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

    2012-10-11

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

  4. Intermolecular-charge-transfer-induced fluorescence quenching in protic solvent

    NASA Astrophysics Data System (ADS)

    Lin, Tao; Liu, Xiaojun; Lou, Zhidong; Hou, Yanbing; Teng, Feng

    2016-11-01

    The fluorescence quenching of fluorenone in protic solvent has been extensively investigated, and the intermolecular hydrogen bond was found to play a crucial role. Unfortunately, the mechanism at atomic level is still not clear. In the present work, we theoretically put forward the charge transfer along the hydrogen bond in the excited states. The vertical excitation energies of the fluorenone-methanol complex as well as the potential energy profiles and surfaces of the vertical excited states and charge transfer states were calculated by using the ab initio electronic-structure methods. The photochemical reactions occurring in the diverse charge transfer states were compared and their decisiveness to the fluorescence quenching was discussed in the paper.

  5. 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.

  6. 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.

  7. Effect of intermolecular hydrogen bonding and proton transfer on fluorescence of salicylic acid

    NASA Astrophysics Data System (ADS)

    Denisov, G. S.; Golubev, N. S.; Schreiber, V. M.; Shajakhmedov, Sh. S.; Shurukhina, A. V.

    1997-12-01

    Effects of intermolecular interactions, in particular the influence of intermolecular hydrogen bonds formed by salicylic acid (SA) as a proton donor with proton acceptors of different strength, on fluorescence spectra of SA in non-aqueous solutions have been investigated. Infrared spectra of studied systems have been analyzed in order to elucidate the ground state structure of the complexes formed. It has been found that at the room temperature in dilute solutions in non-polar or slightly polar aprotic solvents, where the SA molecule is not involved in intermolecular hydrogen bonding, the position of the main (blue) fluorescence component is determined by the excited state intramolecular proton transfer (ESIPT) in the lowest singlet excited state S 1. With increasing proton acceptor ability of the environment, when formation of weak or middle strength intermolecular H-bonds is possible, the emission band shifts gradually to lower frequency, the quantum yield falls and poorly resolved doublet structure becomes more pronounced, especially in the solvents containing heavy bromine atoms. As a possible reason for these effects, coupling between the S 1 and closely lying triplet term is considered. With the strongest proton acceptors like aliphatic amines, intermolecular proton transfer with ionic pair formation in the ground state and double (intra- and intermolecular) proton transfer in the excited state take place, resulting in a blue shift of the emission band. Similar emission is typical for the SA anion in aqueous solutions. The p Ka value of SA in S 1 state has been found to be 3.1. Such a small value can be explained taking into account the ESIPT reaction following the excitation. The SA complex with pyridine exhibits emission spectrum containing both molecular-like and anion-like bands with relative intensities strongly dependent on the temperature and solvent properties. The most probable origin of this dual emission is the molecular-ionic tautomerism caused by

  8. Long range intermolecular forces in change-of-phase heat transfer

    SciTech Connect

    Wayner, P.C. Jr.

    1999-07-01

    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, temperature and concentration on the heat transfer characteristics and stability of thin films and larger systems are reviewed. A judicious selection of literature gives a consistent set of models of particular use in heat transfer. Examples of experimental verification in this rapidly developing field are also presented.

  9. 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.

  10. Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N2 Collisions.

    PubMed

    Kim, Hyunsik; Paul, Amit K; Pratihar, Subha; Hase, William L

    2016-07-14

    Chemical dynamics simulations were performed to investigate collisional energy transfer from highly vibrationally excited azulene (Az*) in a N2 bath. The intermolecular potential between Az and N2, used for the simulations, was determined from MP2/6-31+G* ab initio calculations. Az* is prepared with an 87.5 kcal/mol excitation energy by using quantum microcanonical sampling, including its 95.7 kcal/mol zero-point energy. The average energy of Az* versus time, obtained from the simulations, shows different rates of Az* deactivation depending on the N2 bath density. Using the N2 bath density and Lennard-Jones collision number, the average energy transfer per collision ⟨ΔEc⟩ was obtained for Az* as it is collisionally relaxed. By comparing ⟨ΔEc⟩ versus the bath density, the single collision limiting density was found for energy transfer. The resulting ⟨ΔEc⟩, for an 87.5 kcal/mol excitation energy, is 0.30 ± 0.01 and 0.32 ± 0.01 kcal/mol for harmonic and anharmonic Az potentials, respectively. For comparison, the experimental value is 0.57 ± 0.11 kcal/mol. During Az* relaxation there is no appreciable energy transfer to Az translation and rotation, and the energy transfer is to the N2 bath. PMID:27182630

  11. Exploring the extent of magnetic field effect on intermolecular photoinduced electron transfer in different organized assemblies.

    PubMed

    Choudhury, Sharmistha Dutta; Basu, Samita

    2005-09-15

    Magnetic field effect (MFE) on the photoinduced electron transfer (PET) between phenazine (PZ) and the amines, N,N-dimethylaniline , N,N-diethylaniline, 4,4'-bis(dimethylamino)diphenylmethane (DMDPM), and triethylamine, has been studied in micelles, reverse micelles, and small unilamellar vesicles (SUVs) with a view to understand the effect of spatial location of the donor and acceptor moieties on the magnetic field behavior. The structure of the assembly is found to influence greatly the PET dynamics and hence the MFE of all the systems studied. The magnetic field behavior in micelles is consistent with the hyperfine mechanism, but high B(1/2) values have been obtained which have been ascribed to hopping and lifetime broadening. The variation of MFE with W(0), in reverse micelles, proves yet again that the MFE maximizes at an optimum separation distance between the acceptor and donor. This is the first example of such behavior for intermolecular PET in heterogeneous medium. We have also reported for the first time MFE on intermolecular PET in SUVs. In this case, the PZ-DMDPM system responds most appreciably to an external field compared to the other acceptor-donor systems because it is appropriately positioned in the bilayer. The differential behavior of the amines has been discussed in terms of their confinement in different zones of the organized assemblies depending on their bulk, hydrophobic, and electrostatic effects.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. A unified model for simulating liquid and gas phase, intermolecular energy transfer: N₂ + C₆F₆ collisions.

    PubMed

    Paul, Amit K; Kohale, Swapnil C; Pratihar, Subha; Sun, Rui; North, Simon W; Hase, William L

    2014-05-21

    Molecular dynamics simulations were used to study relaxation of a vibrationally excited C6F6* molecule in a N2 bath. Ab initio calculations were performed to develop N2-N2 and N2-C6F6 intermolecular potentials for the simulations. Energy transfer from "hot" C6F6 is studied versus the bath density (pressure) and number of bath molecules. For the large bath limit, there is no heating of the bath. As C6F6* is relaxed, the average energy of C6F6* is determined versus time, i.e., ⟨E(t)⟩, and for each bath density ⟨E(t)⟩ is energy dependent and cannot be fit by a single exponential. In the long-time limit C6F6 is fully equilibrated with the bath. For a large bath and low pressures, the simulations are in the fixed temperature, independent collision regime and the simulation results may be compared with gas phase experiments of collisional energy transfer. The derivative d[⟨E(t)⟩]/dt divided by the collision frequency ω of the N2 bath gives the average energy transferred from C6F6* per collision ⟨ΔE(c)⟩, which is in excellent agreement with experiment. For the ~100-300 ps simulations reported here, energy transfer from C6F6* is to N2 rotation and translation in accord with the equipartition model, with no energy transfer to N2 vibration. The energy transfer dynamics from C6F6* is not statistically sensitive to fine details of the N2-C6F6 intermolecular potential. Tests, with simulation ensembles of different sizes, show that a relatively modest ensemble of only 24 trajectories gives statistically meaningful results.

  17. Intermolecular electron transfer promoted by directional donor-acceptor attractions in self-assembled diketopyrrolopyrrole-thiophene films.

    PubMed

    Liu, Huiying; Jia, Hui; Wang, Lanfen; Wu, Yishi; Zhan, Chuanlang; Fu, Hongbing; Yao, Jiannian

    2012-11-01

    The photophysics of a symmetric triad consisting of two bithiophene (BT) units covalently linked to a central diketopyrrolopyrrole unit (DPP) has been investigated both in dichloromethane and in the thin film. The DPP-BT film exhibits a red-shifted low-energy absorption band compared to its solution, which is indicative of efficient π-π interactions in the solid-state phase. The steady-state and time-resolved fluorescence results revealed that the photoluminescence was subjected to severe emission quenching when DPP-BT changes from its solution phase to its film form. Further femtosecond transient absorption studies clarified that rapid intermolecular electron transfer accounts for the considerable fluorescence quenching event. The structural characterization of DPP-BT nanobelts, based on GIXRD and SAED patterns, suggested that the composite may be self-assembled into a slipped face-to-face configuration in the film, providing compact interlayer D-A interactions. As a result, intermolecular electron transfer is promoted by the favorable donor-acceptor attractions between the adjacent molecules. Moreover, this packing configuration provides a moderate channel for charge transportation. The hole mobility, which was measured based on a single-belt field-effect transistor, was found to be around 0.07 cm(2) V(-1) s(-1). Our observation reveals the role of spatial orientation in photophysical processes and the consequential semiconductor performance, providing guidance for the development and self-assembly of new opto-electronic molecules. PMID:22951990

  18. Intermolecular Atom Transfer Radical Addition to Olefins Mediated by Oxidative Quenching of Photoredox Catalysts

    PubMed Central

    Nguyen, John D.; Tucker, Joseph W.; Konieczynska, Marlena D.; Stephenson, Corey R. J.

    2011-01-01

    Atom transfer radical addition of haloalkanes and α-halocarbonyls to olefins is efficiently performed with the photocatalyst Ir[(dF(CF3)ppy)2(dtbbpy)]PF6. This protocol is characterized by excellent yields, mild conditions, low catalyst loading, and broad scope. In addition, the atom transfer protocol can be used to quickly and efficiently introduce vinyl trifluoromethyl groups to olefins and access 1,1-cyclopropane diesters. PMID:21381734

  19. On the reaction mechanism of the complete intermolecular O2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands.

    PubMed

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J; Liakos, Dimitrios G; Neese, Frank

    2014-10-01

    The recently described intermolecular O2 transfer between the side-on Ni-O2 complex [(12-TMC)Ni-O2](+) and the manganese complex [(14-TMC)Mn](2+), where 12-TMC and 14-TMC are 12- and 14-membered macrocyclic ligands, 12-TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane and 14-TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long-range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two-step reaction, with a first rate-determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ-η(1):η(1)-O2 coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.

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

    PubMed

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

    2009-01-01

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

  1. 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

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

    PubMed

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

    2016-01-21

    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.

  3. 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

  4. 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.

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

    PubMed

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

    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(+) and K(+) ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  6. 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.

  7. Structural tuning intra- versus inter-molecular proton transfer reaction in the excited state.

    PubMed

    Chung, Min-Wen; Liao, Jia-Ling; Tang, Kuo-Chun; Hsieh, Cheng-Chih; Lin, Tsung-Yi; Liu, Chun; Lee, Gene-Hsiang; Chi, Yun; Chou, Pi-Tai

    2012-07-01

    A series of 2-pyridyl-pyrazole derivatives 1-4 possessing five-membered ring hydrogen bonding configuration are synthesized, the structural flexibility of which is strategically tuned to be in the order of 1 > 2 > 3 > 4. This system then serves as an ideal chemical model to investigate the correlation between excited-state intramolecular proton transfer (ESIPT) reaction and molecular skeleton motion associated with hydrogen bonds. The resulting luminescence data reveal that the rate of ESIPT decreases upon increasing the structural constraint. At sufficiently low concentration where negligible dimerization is observed, ESIPT takes place in 1 and 2 but is prohibited in 3 and 4, for which high geometry constraint is imposed. The results imply that certain structural bending motions associated with hydrogen bonding angle/distance play a key role in ESIPT. This trend is also well supported by the DFT computational approach, in which the barrier associated with ESIPT is in the order of 1 < 2 < 3 < 4. Upon increasing the concentration in cyclohexane, except for 2, the rest of the title compounds undergo ground-state dimerization, from which the double proton transfer takes place in the excited state, resulting in a relatively blue shifted dimeric tautomer emission (cf. the monomer tautomer emission). The lack of dimerization in 2 is rationalized by substantial energy required to adjust the angle of hydrogen bond via twisting the propylene bridge prior to dimerization. PMID:22618273

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

    SciTech Connect

    Mercatelli, Raffaella; Quercioli, Franco; Barsanti, Laura; Evangelista, Valter; Coltelli, Primo; Passarelli, Vincenzo; Frassanito, Anna Maria; Gualtieri, Paolo

    2009-07-24

    In this paper we report the results of measurements performed by FLIM on the photoreceptor of Euglenagracilis. This organelle consists of optically bistable proteins, characterized by two thermally stable isomeric forms: A{sub 498,} non fluorescent and B{sub 462}, fluorescent. Our data indicate that the primary photoevent of Euglena photoreception upon photon absorption consists of two contemporaneous different phenomena: an intramolecular photo-switch (i.e., A{sub 498} becomes B{sub 462}), and a intermolecular and unidirectional Forster-type energy transfer. During the FRET process, the fluorescent B{sub 462} form acts as donor for the non-fluorescent A{sub 498} form of the protein nearby, which acts as acceptor. We hypothesize that in nature these phenomena follow each other with a domino progression along the orderly organized and closely packed proteins in the photoreceptor layer(s), modulating the isomeric composition of the photoreceptive protein pool. This mechanism guarantees that few photons are sufficient to produce a signal detectable by the cell.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. Intermolecular proton transfer in solid phase: a rare example of crystal-to-crystal transformation from hydroxo- to oxo-bridged iron(III) molecule-based magnet.

    PubMed

    Armentano, Donatella; De Munno, Giovanni; Mastropietro, Teresa F; Julve, Miguel; Lloret, Francesc

    2005-08-10

    Intermolecular proton transfer in solid phase from the hydroxo bridge to a water molecule occurs in a new mu-hydroxo iron(III) compound of formula {EtNH3[Fe2(ox)2Cl2(mu-OH)].2H2O}n leading to a still crystalline compound in which the mu-oxo bridge replaces the mu-hydroxo one. Both three-dimensional compounds exhibit magnetic ordering at Tc ca. 70 K due to a spin canting.

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

    PubMed Central

    2013-01-01

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

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Cappelletti, David; Falcinelli, Stefano; Pirani, Fernando

    2016-10-01

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

  17. Mode-specific vibrational energy relaxation of amide I' and II' modes in N-methylacetamide/water clusters: intra- and intermolecular energy transfer mechanisms.

    PubMed

    Zhang, Yong; Fujisaki, Hiroshi; Straub, John E

    2009-04-01

    The mode-specific vibrational energy relaxation of the amide I' and amide II' modes in NMA-d(1)/(D(2)O)(n) (n = 0-3) clusters were studied using the time-dependent perturbation theory at the B3LYP/aug-cc-pvdz level. The amide modes were identified for each cluster based on the potential energy distribution of each mode. The vibrational population relaxation time constants were derived for the amide I' and II' modes. Results for the amide I' mode relaxation of NMA-d(1)/(D(2)O)(3) agree well with previous experimental results. The energy relaxation pathways were identified, and both intra- and intermolecular mechanisms were found to be important. The amide II' mode was identified in the energy transfer pathways from the excited amide I' mode of NMA-d(1)/(D(2)O)(n) (n = 1-3) clusters. The modes associated with methyl group deformation were found to play a role in the mechanism of energy transfer from both excited amide I' and II' modes. The kinetics of energy flow in the cluster were examined by solving a master equation describing the vibrational energy relaxation process from excited system mode as a multistep reaction with the third order Fermi resonance parameters as the reaction rate constants. The intramolecular energy transfer mechanism was found to dominate the short time energy flow dynamics, whereas the intermolecular mechanism was found to be dominant at longer times.

  18. 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…

  19. 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

  20. 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

  1. 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.

  2. Interplay of Halogen and π-π Charge-Transfer Bondings in Intermolecular Associates of Bromo- or Iododinitrobenzene with Tetramethyl-p-phenylenediamine.

    PubMed

    Rosokha, Sergiy V; Loboda, Eric A

    2015-04-23

    Two modes of intermolecular interactions (halogen and π-π charge-transfer bonding) between bromo- or iododinitrobenzene (XDNB) and tetramethyl-p-phenylenediamine (TMPD) are compared. X-ray crystallography revealed that TMPD·XDNB cocrystals comprise alternating donors/acceptors stacks formed by π-bonded (cofacial) TMPD and XDNB molecules. These structures also show two-point (C-X···O-N) halogen bonding between XDNB molecules resulting in formation of (XDNB)2 dimers. In solutions, XDNB and TMPD molecules formed 1:1 complexes showing strong absorption bands near 550 nm which followed the same Mulliken correlation as the associates of TMPD with the (halogen-free) nitro- and cyanobenzenes. In accord with the experimental data, density functional theory calculations with the M062X functional showed that TMPD·XDNB associates formed via π-π charge-transfer bonding are more stable (by 6-12 kcal/mol) than their halogen-bonded analogues. If XDNB is replaced with iodo- or bromoperfluorinated benzenes, or TMPD is replaced with pyridine, the energy gap between the π-π and halogen-bonded associates decreased. The analysis of the molecular-orbital interactions and surface electrostatic potentials of the interacting species indicated that charge-transfer contributions represent a critical component which determines variations of the strength of halogen bonding in these systems.

  3. 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.

  4. 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.

  5. 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.

  6. Barrier-Free Intermolecular Proton Transfer Induced by Excess Electron Attachment to the Complex of Alanine with Uracil

    SciTech Connect

    Dabkowska, Iwona; Rak, Janusz; Gutowski, Maciej S.; Nilles, J.M.; Stokes, Sarah; Bowen, Kit H.

    2004-04-01

    The photoelectron spectrum of the uracil-alanine anionic complex (UA)- has been recorded with 2.540 eV photons. This spectrum reveals a broad feature with a maximum between 1.6-2.1 eV. The vertical electron detachment energy is too large to be attributed to an (UA)- anionic complex in which an intact uracil anion is solvated by alanine, or vice versa. The neutral and anionic complexes of uracil and alanine were studied at the B3LYP and second order Moeller-Plesset level of theory with 6-31++G** basis sets. The neutral complexes form cyclic hydrogen bonds and the three most stable neutral complexes are bound by 0.72, 0.61 and 0.57 eV. The electron hole in complexes of uracil with alaninie is localized on uracil, but the formation of a complex with alanine strongly modulates the vertical ionization energy of uracil. The theoretical results indicate that the excess electron in (UA)- occupies a p* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of alanine to the O8 atom of uracil. As a result, the four most stable structures of the uracil-alanine anionic complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated alanine. Our current results for the anionic complex of uracil with alanine are similar to our previous results for the anion of uracil with glycine [Eur. Phys. J. D 20, 431 (2002)], and together they indicate that the BFPT process is not very sensitive to the nature of the amino acid's hydrophobic residual group. The BFPT to the O8 atom of uracil may be relevant to the damage suffered by nucleic acid bases due to exposure to low energy electrons.

  7. 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.

  8. 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.

  9. 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.

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

    PubMed

    Delchev, Vassil B; Shterev, Ivan G

    2009-04-01

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

  11. 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…

  12. 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…

  13. Photoassociation and photoinduced charge transfer in bridged diaryl compounds. 6. Intramolecular triplet excimers of dicarbazolylalkanes and their comparison to an intermolecular triplet excimer of carbazole

    SciTech Connect

    Cai, J.; Lim, E.C. )

    1994-03-10

    A time-resolved emission study of intramolecular triplet excimer formation has been carried out for dicarbazolylmethane (DCM) and dicarbazolylpropane (DCP) in fluid solution at room temperature. The triplet excimer formation was deduced from the comparison of the phosphorescence with the corresponding emission from the intermolecular triplet excimer of carbazole. It has been found that whereas the triplet excimer formation in DCP is evident in both polar and nonpolar solvents, the excimer formation in DCM is observed only in polar solvents at longer delay times. The result indicates that the conformation favored by the triplet excimer is more readily attainable in DCP than in DCM. The enhancement of the triplet excimer formation by polar solvent, which is also observed for carbazole, suggests that the triplet excimers are stabilized (at least in part) by charge resonance interactions. Comparison of the temporal characteristics of the normal delayed fluorescence of DCP with those of the corresponding excimer phosphorescence suggests that the delayed fluorescence at long delay times is produced by bimolecular annihilation of the intramolecular triplet excimers. This in turn implies that the excited singlet-state species produced by bimolecular annihilation of the triplet excimers is unstable and rearranges into monomeric (i.e., non-interacting) conformation prior to its decay by emission of radiation. 16 refs., 7 figs.

  14. A simple transfer function for nonlinear dendritic integration.

    PubMed

    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.

  15. 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

  16. Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

    NASA Astrophysics Data System (ADS)

    Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

    2006-05-01

    The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

  17. 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.

  18. 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.

  19. 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.

  20. Density functional study of the proton transfer effect on vibrations of strong (short) intermolecular O-H...N/O-...H-N+ hydrogen bonds in aprotic solvents.

    PubMed

    Kong, Shushu; Shenderovich, Ilja G; Vener, Mikhail V

    2010-02-18

    The structure and spectroscopic properties of the 1:1 complexes of substituted pyridines with benzoic acid and phenol derivatives in aprotic solvents are studied using B3LYP functional combined with the polarizable continuum model approximation. Two extreme structures are investigated: the state without (HB) and with proton transfer (PT). In the presence of an external electric field the O...N distance is contracted and the PT state does appear. The PT state of both the pyridine-benzoic and the pyridine-phenol complexes displays the only IR-active band in the 2800-1800 frequency region, which is located around 2000 cm(-1). However, the nature of the band is different for these two complexes. In the pyridine-benzoic acid complex it is practically a pure stretching vibration of the HN(+) group, while in the pyridine-phenol complex it is the mixed vibration of the bridging proton. A specific feature of the PT state in the pyridine-phenol complex is an IR-intensive band near 600 cm(-1), associated with the asymmetric stretching vibrations of the O(-)...HN(+) fragment. Its intensity is reciprocally proportional to the O...N distance. The appearance of this band provides an efficient criterion to differentiate between the HB and PT states of the 1:1 complexes of phenols with pyridines in aprotic solvents. PMID:20104882

  1. Integrating network and transfer metrics to optimize transfer efficiency and experiment workflows

    NASA Astrophysics Data System (ADS)

    McKee, S.; Babik, M.; Campana, S.; Di Girolamo, A.; Wildish, T.; Closier, J.; Roiser, S.; Grigoras, C.; Vukotic, I.; Salichos, M.; De, Kaushik; Garonne, V.; Cruz, J. A. D.; Forti, A.; Walker, C. J.; Rand, D.; de Salvo, A.; Mazzoni, E.; Gable, I.; Chollet, F.; Caillat, L.; Schaer, F.; Chen, Hsin-Yen; Tigerstedt, U.; Duckeck, G.; Hoeft, B.; Petzold, A.; Lopez, F.; Flix, J.; Stancu, S.; Shade, J.; O'Connor, M.; Kotlyar, V.; Zurawski, J.

    2015-12-01

    The Worldwide LHC Computing Grid relies on the network as a critical part of its infrastructure and therefore needs to guarantee effective network usage and prompt detection and resolution of any network issues, including connection failures, congestion, traffic routing, etc. The WLCG Network and Transfer Metrics project aims to integrate and combine all network-related monitoring data collected by the WLCG infrastructure. This includes FTS monitoring information, monitoring data from the XRootD federation, as well as results of the perfSONAR tests. The main challenge consists of further integrating and analyzing this information in order to allow the optimizing of data transfers and workload management systems of the LHC experiments. In this contribution, we present our activity in commissioning WLCG perfSONAR network and integrating network and transfer metrics: We motivate the need for the network performance monitoring, describe the main use cases of the LHC experiments as well as status and evolution in the areas of configuration and capacity management, datastore and analytics, including integration of transfer and network metrics and operations and support.

  2. 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.

  3. Intermolecular electrostatic energies using density fitting.

    PubMed

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

    2005-07-22

    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.

  4. 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.

  5. 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

  6. Assembly and transfer of tripartite integrative and conjugative genetic elements

    PubMed Central

    Haskett, Timothy L.; Terpolilli, Jason J.; Bekuma, Amanuel; O’Hara, Graham W.; Sullivan, John T.; Wang, Penghao; Ronson, Clive W.

    2016-01-01

    Integrative and conjugative elements (ICEs) are ubiquitous mobile genetic elements present as “genomic islands” within bacterial chromosomes. Symbiosis islands are ICEs that convert nonsymbiotic mesorhizobia into symbionts of legumes. Here we report the discovery of symbiosis ICEs that exist as three separate chromosomal regions when integrated in their hosts, but through recombination assemble as a single circular ICE for conjugative transfer. Whole-genome comparisons revealed exconjugants derived from nonsymbiotic mesorhizobia received three separate chromosomal regions from the donor Mesorhizobium ciceri WSM1271. The three regions were each bordered by two nonhomologous integrase attachment (att) sites, which together comprised three homologous pairs of attL and attR sites. Sequential recombination between each attL and attR pair produced corresponding attP and attB sites and joined the three fragments to produce a single circular ICE, ICEMcSym1271. A plasmid carrying the three attP sites was used to recreate the process of tripartite ICE integration and to confirm the role of integrase genes intS, intM, and intG in this process. Nine additional tripartite ICEs were identified in diverse mesorhizobia and transfer was demonstrated for three of them. The transfer of tripartite ICEs to nonsymbiotic mesorhizobia explains the evolution of competitive but suboptimal N2-fixing strains found in Western Australian soils. The unheralded existence of tripartite ICEs raises the possibility that multipartite elements reside in other organisms, but have been overlooked because of their unusual biology. These discoveries reveal mechanisms by which integrases dramatically manipulate bacterial genomes to allow cotransfer of disparate chromosomal regions. PMID:27733511

  7. 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.

  8. Perturbation analyses of intermolecular interactions.

    PubMed

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

    2011-08-01

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

  9. Perturbation analyses of intermolecular interactions

    NASA Astrophysics Data System (ADS)

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

    2011-08-01

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

  10. Computational studies on intermolecular interactions in solvation

    NASA Astrophysics Data System (ADS)

    Song, Weiping

    was found that the geometric combining rule fails to predict the "weaker-than-expected" alkane-perfluoroalkane interactions, as illustrated by the systematic disagreements with experiment in the case of cross second pressure viral coefficients, gas solubilities, and liquid-liquid mixing properties. In Chapter 6, this study was extended to the investigation on combining rules and potential functions by looking extensively at the limit of accuracy of using some 2-parameter potential functions with some combining rules to represent a wide range of nonpolar interactions by fitting to experimental 2nd pressure virial coefficients. Overall, no pairing of potential function and any combining rules were found to represent simultaneously the intermolecular interactions within the provided experimental uncertainties for the range of molecules involved in the study. The limit of accuracy of representing the interactions using transferable parameters was found to be approximately 10--15%.

  11. 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.

  12. 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…

  13. ATOMIC AND MOLECULAR PHYSICS: Integral Reduction Arising in Double Transfer and Excitation Amplitude

    NASA Astrophysics Data System (ADS)

    Zerarka, A.; Soukeur, A.; Bensalah, N.

    2010-03-01

    The purpose of this article is to develop an integral derived from the double transfer and excitation theory. The reduced form of this integral, so obtained, can serve in the computation of the transition amplitude which is from numerical point of view difficult to implement. This amplitude is of great interest in the resonant and non resonant transfer and excitation (RTE and NTE) processes.

  14. 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.

  15. Desensitization and recovery of metastable intermolecular composites

    DOEpatents

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

    2010-09-07

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

  16. Effects of competition for charge capture from the matrix on intermolecular electron-tunneling reactions

    SciTech Connect

    Huddleston, R.K.; Miller, J.R.

    1982-04-15

    A general method is presented for correcting for the direct capture of matrix charges by the acceptor in an intermolecular electron-transfer reaction in a rigid medium. The method is based on a two-step electron-tunneling model that takes into account the correlation between matrix charge capture and intermolecular electron transfer. As an experimental test of the method, electron transfer from the anion of cinnamaldehyde to neutral pryomellitic dianhydride was studied in 2-methyltetrahydrofuran glass at 77/sup 0/K. Good agreement between the model and the experimental kinetic results was obtained.

  17. Proton Transfer Dynamics in Crystalline Maleic Acid from Molecular Dynamics Calculations.

    PubMed

    Dopieralski, Przemyslaw D; Latajka, Zdzislaw; Olovsson, Ivar

    2010-05-11

    The crystal structure of maleic acid, the cis conformer of HOOC-CH═CH-COOH has been investigated by Car-Parrinello molecular dynamics (CPMD) and path integral molecular dynamics (PIMD) simulations. The interesting feature of this compound, compared to the trans conformer, fumaric acid, is that both intra- and intermolecular hydrogen bonds are present. CPMD simulations at 100 K indicate that the energy barrier height for proton transfer is too high for thermal jumps over the barrier in both the intra- and intermolecular hydrogen bonds. Dynamics at 295 K reveal that the occupancy ratio of the proton distribution in both the intra- and intermolecular hydrogen bonds is 0.96/0.04. The time lag between the proton transfers in the intra- and intermolecular hydrogen bonds is in the range of 2-9 fs. This is slightly shorter than the time lag obtained previously for fumaric acid, where only intermolecular hydrogen bonds are present. It is also interesting to notice that in most cases the proton transfer process starts in the intramolecular hydrogen bond and subsequently follows in the intermolecular hydrogen bond. Vibrational spectra of the investigated system and its deuterated analogs HOOC-CH═CH-COOD and DOOC-CH═CH-COOD have been calculated and compared with experimental data. PMID:26615682

  18. 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.

  19. 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

  20. A Comprehensive and Integrated Automated Transfer Evaluation System.

    ERIC Educational Resources Information Center

    Kramer, Gary L.; And Others

    1992-01-01

    Brigham Young University (Utah) has an automated system for evaluating student transfer information, using an established database containing a historical record of courses taken at other schools. A unique feature of the system is that course evaluation and degree audit are completed the day the student is admitted. (Author/MSE)

  1. An Integrated Behavioral Approach to Transfer of Interpersonal Leadership Skills.

    ERIC Educational Resources Information Center

    Fleming, Richard K.

    1992-01-01

    Academic institutions need to prepare management students by teaching interpersonal leadership skills. This article reviews current experimental methods in management education, presents an operant conceptualization of transfer, illustrates applications of behavior instruction to management and other fields, and proposes a field-based behavioral…

  2. 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…

  3. 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

  4. 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…

  5. 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.

  6. 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…

  7. 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.

  8. 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.

  9. 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.

  10. Intramolecular screening of intermolecular forces

    NASA Astrophysics Data System (ADS)

    Liang, Ying Q.; Hunt, K. L. C.

    1993-03-01

    By use of nonlocal polarizability densities, we analyze the intramolecular screening of intermolecular fields. For two interacting molecules A and B with weak or negligible charge overlap, we show that the reaction field and the field due to the unperturbed charge distribution of the neighboring molecule are screened identically via the Sternheimer shielding tensor and its generalizations to nonuniform fields and nonlinear response. The induction force on nucleus I in molecule A, derived from perturbation theory, results from linear screening of the reaction field due to B and nonlinear screening of the field from the permanent charge distribution of B. In general, at first or second order in the molecular interaction, the screening-tensor expressions for the force on nucleus I involve susceptibilities of one order higher than the expressions derived from perturbation theory. The first-order force from perturbation theory involves permanent charge moments, while the first-order screened force involves linear response tensors; and the second-order screened force depends on hyperpolarizabilities, while second-order induction effects are specified in terms of static, lowest-order susceptibilities. The equivalence of the two formulations for these forces, order by order, is a new illustration of the interrelations we have found among permanent moments, linear-response tensors, and nonlinear response. This work also provides new insight into the dispersion forces on an individual nucleus I in molecule A by separating the forces into two distinct terms—the first term results from changes in the reaction of A to the fluctuating charge distribution of the neighboring molecule B, when nucleus I shifts infinitesimally, and the second term stems from changes in correlations of the fluctuating charge distribution of A itself. Changes in the fluctuation correlations are determined by changes in the classical Coulomb field of nucleus I and by the imaginary part of the

  11. 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

  12. 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

  13. 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.

  14. Intra- and Interdimer Transfer Integrals Effectively Modified by Pulsed and Continuous-Wave Lasers for Controlling Charge Transfers in Molecular Crystals

    NASA Astrophysics Data System (ADS)

    Nishioka, Keita; Yonemitsu, Kenji

    2014-02-01

    We theoretically study the field-intensity dependence of charge transfers driven by continuous-wave and pulsed lasers in a two-dimensional crystal consisting of molecular dimers by numerically solving the time-dependent Schrödinger equation for an extended Hubbard model. Generally, electronic transfer integrals are regarded as renormalized when an oscillating external field is applied, as far as the electronic dynamics averaged over the oscillation period is concerned. The cases where effective transfer integrals vanish are known as dynamic localization. Interdimer charge transfers driven by continuous-wave lasers are thus governed by effective interdimer transfer integrals. After the field is switched off, the dynamic localization is no longer relevant. Then, we show that interdimer charge transfers driven by pulsed lasers of energy resonant with an intradimer transition are governed by an effective intradimer transfer integral. The total-energy increment depends on how the intradimer transfer integral is renormalized. The same holds for interdimer charge transfers. This interdimer dynamics governed by effective intradimer parameters is evident even for one- and two-cycle pulses, suggesting possible control of photoinduced charge-order melting.

  15. 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.

  16. Studies on the selectivity between nickel-catalyzed 1,2-cis-2-amino glycosylation of hydroxyl groups of thioglycoside acceptors with C2-substituted benzylidene N-phenyl trifluoroacetimidates and intermolecular aglycon transfer of the sulfide group.

    PubMed

    Yu, Fei; Nguyen, Hien M

    2012-09-01

    The stereoselective synthesis of saccharide thioglycosides containing 1,2-cis-2-amino glycosidic linkages is challenging. In addition to the difficulties associated with achieving high α-selectivity in the formation of 1,2-cis-2-amino glycosidic bonds, the glycosylation reaction is hampered by undesired transfer of the anomeric sulfide group from the glycosyl acceptor to the glycosyl donor. Overcoming these obstacles will pave the way for the preparation of oligosaccharides and glycoconjugates bearing the 1,2-cis-2-amino glycosidic linkages because the saccharide thioglycosides obtained can serve as donors for another coupling iteration. This approach streamlines selective deprotection and anomeric derivatization steps prior to the subsequent coupling event. We have developed an efficient approach for the synthesis of highly yielding and α-selective saccharide thioglycosides containing 1,2-cis-2-amino glycosidic bonds, via cationic nickel-catalyzed glycosylation of thioglycoside acceptors bearing the 2-trifluoromethylphenyl aglycon with N-phenyl trifluoroacetimidate donors. The 2-trifluoromethylphenyl group effectively blocks transfer of the anomeric sulfide group from the glycosyl acceptor to the C(2)-benzylidene donor and can be easily installed and activated. The current method also highlights the efficacy of the nickel catalyst selectively activating the C(2)-benzylidene imidate group in the presence of the anomeric sulfide group on the glycosyl acceptors. PMID:22838405

  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. 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.

  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

    2016-04-14

    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.

  1. 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

    2016-04-14

    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

  2. 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.

  3. 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.

  4. An integrated orthognathic surgery system for virtual planning and image-guided transfer without intermediate splint.

    PubMed

    Kim, Dae-Seung; Woo, Sang-Yoon; Yang, Hoon Joo; Huh, Kyung-Hoe; Lee, Sam-Sun; Heo, Min-Suk; Choi, Soon-Chul; Hwang, Soon Jung; Yi, Won-Jin

    2014-12-01

    Accurate surgical planning and transfer of the planning in orthognathic surgery are very important in achieving a successful surgical outcome with appropriate improvement. Conventionally, the paper surgery is performed based on a 2D cephalometric radiograph, and the results are expressed using cast models and an articulator. We developed an integrated orthognathic surgery system with 3D virtual planning and image-guided transfer. The maxillary surgery of orthognathic patients was planned virtually, and the planning results were transferred to the cast model by image guidance. During virtual planning, the displacement of the reference points was confirmed by the displacement from conventional paper surgery at each procedure. The results of virtual surgery were transferred to the physical cast models directly through image guidance. The root mean square (RMS) difference between virtual surgery and conventional model surgery was 0.75 ± 0.51 mm for 12 patients. The RMS difference between virtual surgery and image-guidance results was 0.78 ± 0.52 mm, which showed no significant difference from the difference of conventional model surgery. The image-guided orthognathic surgery system integrated with virtual planning will replace physical model surgical planning and enable transfer of the virtual planning directly without the need for an intermediate splint.

  5. 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.

  6. 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.

  7. The use of chromatin insulators to improve the expression and safety of integrating gene transfer vectors.

    PubMed

    Emery, David W

    2011-06-01

    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.

  8. Conjugative Transfer of the Integrative Conjugative Elements ICESt1 and ICESt3 from Streptococcus thermophilus▿ †

    PubMed Central

    Bellanger, Xavier; Roberts, Adam P.; Morel, Catherine; Choulet, Frédéric; Pavlovic, Guillaume; Mullany, Peter; Decaris, Bernard; Guédon, Gérard

    2009-01-01

    Integrative and conjugative elements (ICEs), also called conjugative transposons, are genomic islands that excise, self-transfer by conjugation, and integrate in the genome of the recipient bacterium. The current investigation shows the intraspecies conjugative transfer of the first described ICEs in Streptococcus thermophilus, ICESt1 and ICESt3. Mitomycin C, a DNA-damaging agent, derepresses ICESt3 conjugative transfer almost 25-fold. The ICESt3 host range was determined using various members of the Firmicutes as recipients. Whereas numerous ICESt3 transconjugants of Streptococcus pyogenes and Enterococcus faecalis were recovered, only one transconjugant of Lactococcus lactis was obtained. The newly incoming ICEs, except the one from L. lactis, are site-specifically integrated into the 3′ end of the fda gene and are still able to excise in these transconjugants. Furthermore, ICESt3 was retransferred from E. faecalis to S. thermophilus. Recombinant plasmids carrying different parts of the ICESt1 recombination module were used to show that the integrase gene is required for the site-specific integration and excision of the ICEs, whereas the excisionase gene is required for the site-specific excision only. PMID:19181800

  9. 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.

  10. StorNet: Integrated Dynamic Storage and Network Resource Provisioning and Management for Automated Data Transfers

    NASA Astrophysics Data System (ADS)

    Gu, Junmin; Katramatos, Dimitrios; Liu, Xin; Natarajan, Vijaya; Shoshani, Arie; Sim, Alex; Yu, Dantong; Bradley, Scott; McKee, Shawn

    2011-12-01

    StorNet is a joint project of Brookhaven National Laboratory (BNL) and Lawrence Berkeley National Laboratory (LBNL) to research, design, and develop an integrated end-to-end resource provisioning and management framework for high-performance data transfers. The StorNet framework leverages heterogeneous network protocols and storage types in a federated computing environment to provide the capability of predictable, efficient delivery of high-bandwidth data transfers for data intensive applications. The framework incorporates functional modules to perform such data transfers through storage and network bandwidth co-scheduling, storage and network resource provisioning, and performance monitoring, and is based on LBNL's BeStMan/SRM, BNL's TeraPaths, and ESNet's OSCARS systems.

  11. 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

  12. 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.

  13. 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

  14. Electron impact excitation of SO2 - Differential, integral, and momentum transfer cross sections

    NASA Technical Reports Server (NTRS)

    Vuskovic, L.; Trajmar, S.

    1982-01-01

    Electron impact excitation of the electronic states of SO2 was investigated. Differential, integral, and inelastic momentum transfer cross sections were obtained by normalizing the relative measurements to the elastic cross sections. The cross sections are given for seven spectral ranges of the energy-loss spectra extending from the lowest electronic state to near the first ionization limit. Most of the regions represent the overlap of several electronic transitions. No measurements for these cross sections have been reported previously.

  15. 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

  16. 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

  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. Intermolecular dimerization with pillared layered clay templates.

    SciTech Connect

    Wiederrecht, G. P.; Sandi, G.; Carrado, K. A.; Seifert, S.; Chemistry

    2001-11-19

    Solutions of pyrene in the presence of a pillared, layered montmorillonite clay produce hybrid organic-inorganic materials with substantial molecular loading in the gallery regions between the clay layers. The results are in sharp contrast to other aromatics, such as benzene, naphthalene, or perylene, which show minimal incorporation of the molecules into the gallery regions of the clay. We present evidence that the unusual affinity for pyrene to form intermolecular dimers is the reason for the high loading. Pyrene monomers are easily introduced to the layers. Through steric hindrance, subsequent intermolecular dimer formation is allowed, and they are captured by the pillared, layered structure. CW and time-resolved emission spectra strongly indicate the presence of face-to-face intermolecular dimers (excimers) within the clay galleries. The combination of the ease of high molecular loading into an inorganic, high aspect ratio template and the collective optical properties of the organic layer may be useful as a new means to create hybrid structures.

  19. An isotopic mass effect on the intermolecular potential

    SciTech Connect

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

    2015-09-28

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

  20. 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.

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

    PubMed

    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(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.

  2. 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.

  3. 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.

  4. 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

  5. Site-specific integration and tailoring of cassette design for sustainable gene transfer.

    PubMed

    Lombardo, Angelo; Cesana, Daniela; Genovese, Pietro; Di Stefano, Bruno; Provasi, Elena; Colombo, Daniele F; Neri, Margherita; Magnani, Zulma; Cantore, Alessio; Lo Riso, Pietro; Damo, Martina; Pello, Oscar M; Holmes, Michael C; Gregory, Philip D; Gritti, Angela; Broccoli, Vania; Bonini, Chiara; Naldini, Luigi

    2011-08-21

    Integrative gene transfer methods are limited by variable transgene expression and by the consequences of random insertional mutagenesis that confound interpretation in gene-function studies and may cause adverse events in gene therapy. Site-specific integration may overcome these hurdles. Toward this goal, we studied the transcriptional and epigenetic impact of different transgene expression cassettes, targeted by engineered zinc-finger nucleases to the CCR5 and AAVS1 genomic loci of human cells. Analyses performed before and after integration defined features of the locus and cassette design that together allow robust transgene expression without detectable transcriptional perturbation of the targeted locus and its flanking genes in many cell types, including primary human lymphocytes. We thus provide a framework for sustainable gene transfer in AAVS1 that can be used for dependable genetic manipulation, neutral marking of the cell and improved safety of therapeutic applications, and demonstrate its feasibility by rapidly generating human lymphocytes and stem cells carrying targeted and benign transgene insertions.

  6. 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.

  7. Total Synthesis and Structural Reassignment of Lyngbyaloside C Highlighted by Intermolecular Ketene Esterification.

    PubMed

    Chang, Chia-Fu; Stefan, Eric; Taylor, Richard E

    2015-07-20

    Lyngbyaloside C, a classic macrolide, isolated from Lyngbya bouilloni, has shown moderate anticancer activity against several cancer cell lines. Here, we report the first total synthesis and stereochemical configuration reassignment of lyngbyaloside C. The synthesis highlights a one-pot intermolecular ketene esterification reaction to form the crucial tertiary ester and tetrahydropyran. In addition, a novel and concise synthetic pathway towards the 1,3-syn secondary, tertiary diol fragment is described using a regio- and stereospecific electrophilic ether transfer reaction.

  8. 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.

  9. 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.

  10. The diversity of physical forces and mechanisms in intermolecular interactions.

    PubMed

    Berezovsky, Igor N

    2011-06-01

    Intermolecular interactions became an inherent part of the structure-function paradigm. Therefore, the generalized concept of protein stability and interactions should consider the balance of stabilizing forces working in different types of intermolecular interactions. We consider here two 'extremes' of protein interactions, viral protein with high intrinsic disorder and hyperthermostable protein complexes. Intermolecular interactions provide folding upon binding as a part of function in the viral case, while they secure and stabilize specific native interfaces as a prerequisite for function in hyperthermostable complexes. We propose a generalized concept of protein stability and interactions, which includes intermolecular interactions comprising distinct combinations of stabilizing forces depending on the types of interacting partners.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. Some mathematical models of intermolecular autophosphorylation.

    PubMed

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

    2015-04-01

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

  18. An isotopic mass effect on the intermolecular potential

    DOE PAGES

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

    2015-09-28

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

  19. Theoretical study on intermolecular interactions in BrF/H nX adducts

    NASA Astrophysics Data System (ADS)

    Wu, Junyong; Zhang, Jingchang; Wang, Zhaoxu; Cao, Weiliang

    2007-09-01

    Equilibrium geometries, interaction energies, and charge transfer for the intermolecular interactions between BrF and H nX (HF, H 2O, and NH 3) were studied at the MP2/6-311++G(3d,3p) level. The halogen-bonded geometry and hydrogen-bonded geometry are observed in these interactions. The calculated interaction energies show that the halogen-bonded structures are more stable than the corresponding hydrogen-bonded structures. To study the nature of the intermolecular interactions, symmetry-adapted perturbation theory (SAPT) calculations were carried out and the results indicate that the halogen bonding interactions are dominantly inductive energy in nature, while electrostatic energy governs the hydrogen bonding interactions.

  20. 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.

  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. 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.

  3. Proton transfer dynamics in the propionic acid dimer from path integral molecular dynamics calculations.

    PubMed

    Durlak, Piotr; Latajka, Zdzisław

    2011-09-01

    The double proton transfer process in the cyclic dimer of propionic acid in the gas phase was studied using a path integral molecular dynamics method. Structures, energies and proton trajectories were determined. Very large amplitude motions of the skeleton of a propionic acid molecule were observed during the simulations, and almost free rotation of the C(2)H(5) group around the C(α)-C bond. A double-well symmetric potential with a very small energy barrier was determined from the free energy profile for the proton motions. Infrared spectra for different isotopomers were calculated, and comparative vibrational analysis was performed. The vibrational results from CPMD appear to be in qualitative agreement with the experimental ones. PMID:21213001

  4. 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.

  5. 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.

  6. 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'.

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

    PubMed

    Bershtein, Shimon; Serohijos, Adrian W R; Bhattacharyya, Sanchari; Manhart, Michael; Choi, Jeong-Mo; Mu, Wanmeng; Zhou, Jingwen; Shakhnovich, Eugene I

    2015-10-01

    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 (kcat/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

  8. 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

  9. NitroScape: a model to integrate nitrogen transfers and transformations in rural landscapes.

    PubMed

    Duretz, S; Drouet, J L; Durand, P; Hutchings, N J; Theobald, M R; Salmon-Monviola, J; Dragosits, U; Maury, O; Sutton, M A; Cellier, P

    2011-11-01

    Modelling nitrogen transfer and transformation at the landscape scale is relevant to estimate the mobility of the reactive forms of nitrogen (N(r)) and the associated threats to the environment. Here we describe the development of a spatially and temporally explicit model to integrate N(r) transfer and transformation at the landscape scale. The model couples four existing models, to simulate atmospheric, farm, agro-ecosystem and hydrological N(r) fluxes and transformations within a landscape. Simulations were carried out on a theoretical landscape consisting of pig-crop farms interspersed with unmanaged ecosystems. Simulation results illustrated the effect of spatial interactions between landscape elements on N(r) fluxes and losses to the environment. More than 10% of the total N(2)O emissions were due to indirect emissions. The nitrogen budgets and transformations of the unmanaged ecosystems varied considerably, depending on their location within the landscape. The model represents a new tool for assessing the effect of changes in landscape structure on N(r) fluxes.

  10. 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.

  11. Exact triple integrals of beam functions. [in application of Galerkin method to heat and mass transfer problems

    NASA Technical Reports Server (NTRS)

    Jhaveri, B. S.; Rosenberger, F.

    1982-01-01

    Definite triple integrals encountered in applying the Galerkin method to the problem of heat and mass transfer across rectangular enclosures are discussed. Rather than evaluating them numerically, the technique described by Reid and Harris (1958) was extended to obtain the exact solution of the integrals. In the process, four linear simultaneous equations with triple integrals as unknowns were obtained. These equations were then solved exactly to obtain the closed form solution. Since closed form representations of this type have been shown to be useful in solving nonlinear hydrodynamic problems by series expansion, the integrals are presented here in general form.

  12. Resonant Auger decay driving intermolecular Coulombic decay in molecular dimers

    NASA Astrophysics Data System (ADS)

    Trinter, F.; Schöffler, M. S.; Kim, H.-K.; Sturm, F. P.; Cole, K.; Neumann, N.; Vredenborg, A.; Williams, J.; Bocharova, I.; Guillemin, R.; Simon, M.; Belkacem, A.; Landers, A. L.; Weber, Th.; Schmidt-Böcking, H.; Dörner, R.; Jahnke, T.

    2014-01-01

    In 1997, it was predicted that an electronically excited atom or molecule placed in a loosely bound chemical system (such as a hydrogen-bonded or van-der-Waals-bonded cluster) could efficiently decay by transferring its excess energy to a neighbouring species that would then emit a low-energy electron. This intermolecular Coulombic decay (ICD) process has since been shown to be a common phenomenon, raising questions about its role in DNA damage induced by ionizing radiation, in which low-energy electrons are known to play an important part. It was recently suggested that ICD can be triggered efficiently and site-selectively by resonantly core-exciting a target atom, which then transforms through Auger decay into an ionic species with sufficiently high excitation energy to permit ICD to occur. Here we show experimentally that resonant Auger decay can indeed trigger ICD in dimers of both molecular nitrogen and carbon monoxide. By using ion and electron momentum spectroscopy to measure simultaneously the charged species created in the resonant-Auger-driven ICD cascade, we find that ICD occurs in less time than the 20femtoseconds it would take for individual molecules to undergo dissociation. Our experimental confirmation of this process and its efficiency may trigger renewed efforts to develop resonant X-ray excitation schemes for more localized and targeted cancer radiation therapy.

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. Non-specific lipid transfer proteins in plants: presenting new advances and an integrated functional analysis.

    PubMed

    Liu, Fang; Zhang, Xiaobo; Lu, Changming; Zeng, Xinhua; Li, Yunjing; Fu, Donghui; Wu, Gang

    2015-09-01

    Plant non-specific lipid-transfer proteins (nsLTPs) are small, basic proteins present in abundance in higher plants. They are involved in key processes of plant cytology, such as the stablization of membranes, cell wall organization, and signal transduction. nsLTPs are also known to play important roles in resistance to biotic and abiotic stress, and in plant growth and development, such as sexual reproduction, seed development and germination. The structures of plant nsLTPs contain an eight-cysteine residue conserved motif, linked by four disulfide bonds, and an internal hydrophobic cavity, which comprises the lipid-binding site. This structure endows stability and increases the ability to bind and/or carry hydrophobic molecules. There is growing interest in nsLTPs, due to their critical roles, resulting in the need for a comprehensive review of their form and function. Relevant topics include: nsLTP structure and biochemical features, their classification, identification, and characterization across species, sub-cellular localization, lipid binding and transfer ability, expression profiling, functionality, and evolution. We present advances, as well as limitations and trends, relating to the different topics of the nsLTP gene family. This review collates a large body of research pertaining to the role of nsLTPs across the plant kingdom, which has been integrated as an in depth functional analysis of this group of proteins as a whole, and their activities across multiple biochemical pathways, based on a large number of reports. This review will enhance our understanding of nsLTP activity in planta, prompting further work and insights into the roles of this multifaceted protein family in plants.

  2. 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

  3. Charge-transfer in some physical processes

    NASA Astrophysics Data System (ADS)

    Nešpůrek, S.; Nožár, J.; Rais, D.; Pochekaylov, S.; Šebera, J.; Kochalska, A.

    2010-11-01

    The background of the intra- and inter-molecular electron transfer and some properties of charge transfer states (excitons) are mentioned. On the example of gas sensors the importance of the charge transfer in the dark is discussed. The utilization of the photoinduced charge transfer in electronic processes is demonstrated on the examples of photoconductivity, polymer photodegradation and molecular orientation.

  4. 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…

  5. Bioelectronome. Integrated approach to receptor chemistry, radicals, electrochemistry, cell signaling, and physiological effects based on electron transfer.

    PubMed

    Kovacic, Peter; Pozos, Robert S

    2007-01-01

    Bioelectronome refers to the host of electron transfer (ET) reactions that occur in living systems. This review presents an integrated approach to receptor chemistry based on electron transfer, radicals, electrochemistry, cell signaling, and end result. First, receptor activity is addressed from the unifying standpoint of redox transformations in which various receptors are discussed. After a listing of receptor-binding modes, receptor chemistry is treated with focus on generation of reactive oxygen species (ROS), activation by ROS, and subsequent cell signaling involving ROS. A general electrostatic mechanism is proposed for receptor-ligand action with supporting evidence. Cell-signaling processes appear to entail electron transfer, ROS, redox chains, and relays. The widespread involvement of phosphate from phosphorylation may be rationalized electrostatically by analogy with DNA phosphate. Extensive evidence supports important participation of ET functionalities in the mechanism of drugs and toxins. The integrated approach is applied to the main ET classes, namely, quinones, metal complexes, iminium species, and aromatic nitro compounds.

  6. Wolbachia genome integrated in an insect chromosome: Evolution and fate of laterally transferred endosymbiont genes

    PubMed Central

    Nikoh, Naruo; Tanaka, Kohjiro; Shibata, Fukashi; Kondo, Natsuko; Hizume, Masahiro; Shimada, Masakazu; Fukatsu, Takema

    2008-01-01

    Recent accumulation of microbial genome data has demonstrated that lateral gene transfers constitute an important and universal evolutionary process in prokaryotes, while those in multicellular eukaryotes are still regarded as unusual, except for endosymbiotic gene transfers from mitochondria and plastids. Here we thoroughly investigated the bacterial genes derived from a Wolbachia endosymbiont on the nuclear genome of the beetle Callosobruchus chinensis. Exhaustive PCR detection and Southern blot analysis suggested that ∼30% of Wolbachia genes, in terms of the gene repertoire of wMel, are present on the insect nuclear genome. Fluorescent in situ hybridization located the transferred genes on the proximal region of the basal short arm of the X chromosome. Molecular evolutionary and other lines of evidence indicated that the transferred genes are probably derived from a single lateral transfer event. The transferred genes were, for the length examined, structurally disrupted, freed from functional constraints, and transcriptionally inactive. Hence, most, if not all, of the transferred genes have been pseudogenized. Notwithstanding this, the transferred genes were ubiquitously detected from Japanese and Taiwanese populations of C. chinensis, while the number of the transferred genes detected differed between the populations. The transferred genes were not detected from congenic beetle species, indicating that the transfer event occurred after speciation of C. chinensis, which was estimated to be one or several million years ago. These features of the laterally transferred endosymbiont genes are compared with the evolutionary patterns of mitochondrial and plastid genome fragments acquired by nuclear genomes through recent endosymbiotic gene transfers. PMID:18073380

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. The influence of the vinyl terminal group on the poly(para-phenylenevinylene) charge transfer integrals.

    PubMed

    Ottonelli, Massimo; Duce, Daniele; Thea, Sergio; Dellepiane, Giovanna

    2013-07-01

    The charge transport properties of organic semiconductors are one of the foremost limiting factors in technological applications of these materials, which are becoming important competitors with respect to the inorganic semiconductors. In fact, conjugated organic molecules are used at present as active materials in different types of devices. For this reason, the theoretical study of the electron and hole mobility, carried out in order to give hints for the design of new molecules or for the optimization of their supramolecular organization, is a task of great interest. Here, we present the results of a quantum chemical study, in the framework of the Marcus and density functional theories, on the effects of terminal groups (when they directly interact with the pi-conjugated system of the organic semiconductors) on the charge carriers mobility of organic semiconductors. In particular, using a representative oligomer of poly(para-phenylenevinylene) as a model system, we have found that strong effects on the predicted values of the intramolecular transfer integrals as well as on their dependence on the supramolecular organizations occur, when the vinyl moiety (as ending group) is taken into account.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. 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

  19. "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…

  20. Integration of complete transferred DNA units is dependent on the activity of virulence E2 protein of Agrobacterium tumefaciens.

    PubMed

    Rossi, L; Hohn, B; Tinland, B

    1996-01-01

    Agrobacterium tumefaciens transfers transferred DNA (T-DNA), a single-stranded segment of its tumor-inducing (Ti) plasmid, to the plant cell nucleus. The Ti-plasmid-encoded virulence E2 (VirE2) protein expressed in the bacterium has single-stranded DNA (ssDNA)-binding properties and has been reported to act in the plant cell. This protein is thought to exert its influence on transfer efficiency by coating and accompanying the single-stranded T-DNA (ss-T-DNA) to the plant cell genome. Here, we analyze different putative roles of the VirE2 protein in the plant cell. In the absence of VirE2 protein, mainly truncated versions of the T-DNA are integrated. We infer that VirE2 protects the ss-T-DNA against nucleolytic attack during the transfer process and that it is interacting with the ss-T-DNA on its way to the plant cell nucleus. Furthermore, the VirE2 protein was found not to be involved in directing the ss-T-DNA to the plant cell nucleus in a manner dependent on a nuclear localization signal, a function which is carried by the NLS of VirD2. In addition, the efficiency of T-DNA integration into the plant genome was found to be VirE2 independent. We conclude that the VirE2 protein of A. tumefaciens is required to preserve the integrity of the T-DNA but does not contribute to the efficiency of the integration step per se. PMID:8552588

  1. Transfer of pRD1 to Pseudomonas syringae and evidence for its integration into the chromosome.

    PubMed Central

    Vincent, J R; Fulbright, D W

    1983-01-01

    Plasmid pRD1 was conjugatively transferred from Escherichia coli to Pseudomonas syringae. Subculturing the transconjugate on a medium that selected for pRD1-determined His+ Kmr resulted in the loss of pRD1 as an extrachromosomal element as detected by agarose gel electrophoresis. DNA hybridization provided evidence for the integration of pRD1 into the P. syringae chromosome. Images PMID:6358197

  2. Electronic Structure Theory for Radicaloid Systems and Intermolecular Interactions

    NASA Astrophysics Data System (ADS)

    Kurlancheek, Westin

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

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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.

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

    DOE PAGES

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

  10. 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…

  11. Learning about Intermolecular Interactions from the Cambridge Structural Database

    ERIC Educational Resources Information Center

    Battle, Gary M.; Allen, Frank H.

    2012-01-01

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

  12. Ionic strength and intermolecular contacts in protein crystals

    NASA Astrophysics Data System (ADS)

    Iyer, Ganesh H.; Dasgupta, Swagata; Bell, Jeffrey A.

    2000-08-01

    The ionic strengths of crystallization solutions for 206 proteins were observed to form a bimodal distribution. The data was divided into two sets at an ionic strength of 4.4 M, and knowledge-based potentials were calculated to determine contact preferences at intermolecular crystal interfaces. Consistent with previous observations over all ionic strengths, intermolecular crystal contacts tend to exclude nonpolar amino acids; lysine is the least favored polar amino acid at crystal contacts; and arginine and glutamine are the two most favored amino acid at crystal contacts. However, some aspects of intermolecular contact preferences within protein crystals are significantly dependent on ionic strength. Arginine is the most favored residue at low ionic strength, but it takes second place to glutamine at high ionic strength. Other major ionic strength-dependent differences in protein crystal contacts can be explained by the binding of cations or anions. While others have shown the importance of ion binding experimentally in selected protein crystals, these statistical results indicate that intermolecular interface formation must involve ion-mediated contacts in a large number of protein crystals.

  13. 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.

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

    PubMed

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

    2015-03-01

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

  15. 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…

  16. 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.

  17. 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.

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

  19. Intermolecular G-quadruplex-based universal quencher free molecular beacon.

    PubMed

    Zhou, Hui; Xie, Su-Jin; Li, Ji-Shan; Wu, Zai-Sheng; Shen, Guo-Li

    2012-11-11

    A simple and universal quencher-free molecular beacon (MB) with low background fluorescence is developed based on an intermolecular G-quadruplex signaling probe. Unlike previous fluorescent MB strategies, it can function without any fluorophore and quencher modifications on its hairpin sequence.

  20. 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

  1. 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.

  2. 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…

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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…

  9. Design of a Holographic Read-Only for Parallel Data Transfer to Integrated CMOS Circuits.

    NASA Astrophysics Data System (ADS)

    Gallo, John Thomas

    A procedure for optimizing the design of page -oriented, holographic memories (POHMs) for transferring large blocks of memory in parallel to CMOS detector arrays is presented. The investigation focuses on identifying the inter-relationships between the large number of parameters associated with systems for transferring data from optical read-only-memories (ROMs) to electronic random-access-memories (RAMs) and using those relationships to determine the values of the parameters required to maximize the storage capacities and data transfer rates of those systems. The procedure is designed for a specific POHM system, although it may also be used for general POHM designs. Limitations on the storage capacity of the POHM based upon the performance requirements of the data transfer system and the restrictions imposed by the optical components of the POHM read system are stated. The inter-relationships between the system parameters that appear in the equations that limit the capacity are determined. The relationship between the sub-hologram size and the storage capacity is one of the major considerations investigated. Also, the effect of shrinkage of the holographic material after recording on the reconstructed images is presented. The procedure presented uses information gathered from these relationships to optimize several of the key parameters of the system. The optimization procedure has been applied to produce a set of system parameters, based upon currently available optical components, that results in a storage capacity of 1.62 times 10 ^9 bits with a data transfer rate of 2 times 10^{10} when the read laser is used most efficiently. An optical system was designed to read out the spatially- and angularly -multiplexed pages of the optimized POHM onto a CMOS detector array. Critical features of this design have been demonstrated using a prototype system with a maximum capacity of 4096 bits. This research supports the development of a massively parallel, optical

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

    PubMed Central

    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

  11. Intermolecular cope-type hydroamination of alkenes and alkynes using hydroxylamines.

    PubMed

    Moran, Joseph; Gorelsky, Serge I; Dimitrijevic, Elena; Lebrun, Marie-Eve; Bédard, Anne-Catherine; Séguin, Catherine; Beauchemin, André M

    2008-12-31

    The development of the Cope-type hydroamination as a method for the metal- and acid-free intermolecular hydroamination of hydroxylamines with alkenes and alkynes is described. Aqueous hydroxylamine reacts efficiently with alkynes in a Markovnikov fashion to give oximes and with strained alkenes to give N-alkylhydroxylamines, while unstrained alkenes are more challenging. N-Alkylhydroxylamines also display similar reactivity with strained alkenes and give modest to good yields with vinylarenes. Electron-rich vinylarenes lead to branched products while electron-deficient vinylarenes give linear products. A beneficial additive effect is observed with sodium cyanoborohydride, the extent of which is dependent on the structure of the hydroxylamine. The reaction conditions are found to be compatible with common protecting groups, free OH and NH bonds, as well as bromoarenes. Both experimental and theoretical results suggest the proton transfer step of the N-oxide intermediate is of vital importance in the intermolecular reactions of alkenes. Details are disclosed concerning optimization, reaction scope, limitations, and theoretical analysis by DFT, which includes a detailed molecular orbital description for the concerted hydroamination process and an exhaustive set of calculated potential energy surfaces for the reactions of various alkenes, alkynes, and hydroxylamines.

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

    SciTech Connect

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

    1985-05-01

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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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).

  18. Streptococcal group B integrative and mobilizable element IMESag-rpsI encodes a functional relaxase involved in its transfer

    PubMed Central

    Lorenzo-Diaz, Fabian; Fernández-Lopez, Cris; Douarre, Pierre-Emmanuel; Baez-Ortega, Adrian; Flores, Carlos; Glaser, Philippe

    2016-01-01

    Streptococcus agalactiae or Group B Streptococcus (GBS) are opportunistic bacteria that can cause lethal sepsis in children and immuno-compromised patients. Their genome is a reservoir of mobile genetic elements that can be horizontally transferred. Among them, integrative and conjugative elements (ICEs) and the smaller integrative and mobilizable elements (IMEs) primarily reside in the bacterial chromosome, yet have the ability to be transferred between cells by conjugation. ICEs and IMEs are therefore a source of genetic variability that participates in the spread of antibiotic resistance. Although IMEs seem to be the most prevalent class of elements transferable by conjugation, they are poorly known. Here, we have studied a GBS-IME, termed IMESag-rpsI, which is widely distributed in GBS despite not carrying any apparent virulence trait. Analyses of 240 whole genomes showed that IMESag-rpsI is present in approximately 47% of the genomes, has a roughly constant size (approx. 9 kb) and is always integrated at a single location, the 3′-end of the gene encoding the ribosomal protein S9 (rpsI). Based on their genetic variation, several IMESag-rpsI types were defined (A–J) and classified in clonal complexes (CCs). CC1 was the most populated by IMESag-rpsI (more than 95%), mostly of type-A (71%). One CC1 strain (S. agalactiae HRC) was deep-sequenced to understand the rationale underlying type-A IMESag-rpsI enrichment in GBS. Thirteen open reading frames were identified, one of them encoding a protein (MobSag) belonging to the broadly distributed family of relaxases MOBV1. Protein MobSag was purified and, by a newly developed method, shown to cleave DNA at a specific dinucleotide. The S. agalactiae HRC-IMESag-rpsI is able to excise from the chromosome, as shown by the presence of circular intermediates, and it harbours a fully functional mobilization module. Further, the mobSag gene encoded by this mobile element is able to promote plasmid transfer among pneumococcal

  19. 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.

  20. 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

  1. 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…

  2. 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.

  3. Intermolecular vibrations in hydrophobic amino acid crystals: experiments and calculations.

    PubMed

    Williams, Michael R C; Aschaffenburg, Daniel J; Ofori-Okai, Benjamin K; Schmuttenmaer, Charles A

    2013-09-12

    Intermolecular vibrations of amino acid crystals occur in the THz, or far-infrared, region of the electromagnetic spectrum. We have measured the THz and Raman spectra of DL-leucine as well as two polymorphs of DL-valine, the spectroscopic properties of which have not previously been compared. Theoretical modeling of intermolecular vibrations in hydrophobic amino acids is challenging because the van der Waals interactions between molecules are not accounted for in standard density functional theory. Therefore, to calculate the vibrational modes, we used a recently developed approach that includes these nonlocal electron correlation forces. We discuss methods for comparing results from different theoretical models using metrics other than calculated vibrational frequency and intensity, and we also report a new approach enabling concise comparison of vibrational modes that involve complicated mixtures of inter- and intramolecular displacements.

  4. Intramolecular versus intermolecular disulfide bonds in prion proteins.

    PubMed

    Welker, Ervin; Raymond, Lynne D; Scheraga, Harold A; Caughey, Byron

    2002-09-01

    Prion protein (PrP) is the major component of the partially protease-resistant aggregate that accumulates in mammals with transmissible spongiform encephalopathies. The two cysteines of the scrapie form, PrP(Sc), were found to be in their oxidized (i.e. disulfide) form (Turk, E., Teplow, D. B., Hood, L. E., and Prusiner, S. B. (1988) Eur. J. Biochem. 176, 21-30); however, uncertainty remains as to whether the disulfide bonds are intra- or intermolecular. It is demonstrated here that the monomers of PrP(Sc) are not linked by intermolecular disulfide bonds. Furthermore, evidence is provided that PrP(Sc) can induce the conversion of the oxidized, disulfide-intact form of the monomeric cellular prion protein to its protease-resistant form without the temporary breakage and subsequent re-formation of the disulfide bonds in cell-free reactions.

  5. Benefits and Challenges of Using Live Modeling to Help Preservice Teachers Transfer Technology Integration Principles

    ERIC Educational Resources Information Center

    West, Richard E.; Graham, Charles R.

    2007-01-01

    One method underutilized in training teachers to use technology is to use live modeling sessions. This study qualitatively investigates how the use of modeling sessions impacted students. In this study we found that modeling was perceived by most students to be effective at teaching technology skills and ideas for integrating technology as…

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. Phosphorescence and Energy Transfer in Rigid Solutions.

    ERIC Educational Resources Information Center

    Enciso, E.; Cabello, A.

    1980-01-01

    Describes an experiment which illustrates the general aspects of intermolecular energy transfer between triplet states in rigid solutions of organic compounds solved in an ethanol-ether mixture. Measurements of quenching and energy transfer processes are made using the chemicals of benzophenone and naphthalene. (CS)

  11. Transient grating study of the intermolecular dynamics of liquid nitrobenzene

    NASA Astrophysics Data System (ADS)

    Wu, Hong-Lin; Song, Yun-Fei; Yu, Guo-Yang; Yang, Yan-Qiang

    2016-10-01

    Femtosecond time-resolved transient grating (TG) technique is used to study the intermolecular dynamics in liquid phase. Non-resonant excitation of the sample by two crossing laser pulses results in a transient Kerr grating, and the molecular motion of liquid can be detected by monitoring the diffraction of a third time-delayed probe pulse. In liquid nitrobenzene (NB), three intermolecular processes are observed with lifetimes of 37.9±1.4 ps, 3.28±0.11 ps, and 0.44±0.03 ps, respectively. These relaxations are assigned to molecular orientational diffusion, dipole/induced dipole interaction, and libration in liquid cage, respectively. Such a result is slightly different from that obtained from OKE experiment in which the lifetime of the intermediate process is measured to be 1.9 ps. The effects of electric field on matter are different in TG and optical Kerr effect (OKE) experiments, which should be responsible for the difference between the results of these two types of experiments. The present work demonstrates that TG technique is a useful alternative in the study of intermolecular dynamics. Project supported by the National Natural Science Foundation of China (Grant Nos. 11304058 and 11404307) and NSAF (Grant No. U1330106).

  12. Morphology development in polymer blends exhibiting strong intermolecular interactions

    SciTech Connect

    Weiss, R.A.; Feng, Y.; Han, C.C.; Karim, A.

    1996-12-31

    He et al. measured the spinodal decomposition (SD) kinetics of a blend of poly(butyl methacrylate) with a polystyrene modified with 1.5 mol% of a hydroxy-containing comonomer that exhibited intermolecular hydrogen bonding, who studied blends. For small excursions into the spinodal region, multiple structures developed in the blend, which suggested that multiple mechanisms may be involved in the phase separation process. For most cases, however, the kinetics of phase separation followed Cahn-Hilliard theory in the early stage of spinodal decomposition and a self-similar mechanism in the later stages, similar to non-associating polymer blends such as PS/PVME. The failure to observe an effect of a specific intermolecular interaction on SD kinetics may be a consequence of the low concentration of hydroxyl groups on the polystyrene, ca. five per chain, and the weakening of the hydrogen bond at the elevated temperatures used to study phase separation where the crosslink effect of hydrogen bonding may not be significant. At elevated temperatures, the association-dissociation equilibrium shifts towards non-associated hydroxyl and ester groups. An objective of the present study was to use a polymer blend having a relatively higher degree of intermolecular association at the phase separation temperature and to investigate how physical crosslinks affect the phase separation kinetics accompanying spinodal decomposition.

  13. 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

  14. Differential integrity of TALE nuclease genes following adenoviral and lentiviral vector gene transfer into human cells.

    PubMed

    Holkers, Maarten; Maggio, Ignazio; Liu, Jin; Janssen, Josephine M; Miselli, Francesca; Mussolino, Claudio; Recchia, Alessandra; Cathomen, Toni; Gonçalves, Manuel A F V

    2013-03-01

    The array of genome editing strategies based on targeted double-stranded DNA break formation have recently been enriched through the introduction of transcription activator-like type III effector (TALE) nucleases (TALENs). To advance the testing of TALE-based approaches, it will be crucial to deliver these custom-designed proteins not only into transformed cell types but also into more relevant, chromosomally stable, primary cells. Viral vectors are among the most effective gene transfer vehicles. Here, we investigated the capacity of human immunodeficiency virus type 1- and adenovirus-based vectors to package and deliver functional TALEN genes into various human cell types. To this end, we attempted to assemble particles of these two vector classes, each encoding a monomer of a TALEN pair targeted to a bipartite sequence within the AAVS1 'safe harbor' locus. Vector DNA analyses revealed that adenoviral vectors transferred intact TALEN genes, whereas lentiviral vectors failed to do so, as shown by their heterogeneously sized proviruses in target cells. Importantly, adenoviral vector-mediated TALEN gene delivery resulted in site-specific double-stranded DNA break formation at the intended AAVS1 target site at similarly high levels in both transformed and non-transformed cells. In conclusion, we demonstrate that adenoviral, but not lentiviral, vectors constitute a valuable TALEN gene delivery platform.

  15. Differential integrity of TALE nuclease genes following adenoviral and lentiviral vector gene transfer into human cells

    PubMed Central

    Holkers, Maarten; Maggio, Ignazio; Liu, Jin; Janssen, Josephine M.; Miselli, Francesca; Mussolino, Claudio; Recchia, Alessandra; Cathomen, Toni; Gonçalves, Manuel A. F. V.

    2013-01-01

    The array of genome editing strategies based on targeted double-stranded DNA break formation have recently been enriched through the introduction of transcription activator-like type III effector (TALE) nucleases (TALENs). To advance the testing of TALE-based approaches, it will be crucial to deliver these custom-designed proteins not only into transformed cell types but also into more relevant, chromosomally stable, primary cells. Viral vectors are among the most effective gene transfer vehicles. Here, we investigated the capacity of human immunodeficiency virus type 1- and adenovirus-based vectors to package and deliver functional TALEN genes into various human cell types. To this end, we attempted to assemble particles of these two vector classes, each encoding a monomer of a TALEN pair targeted to a bipartite sequence within the AAVS1 ‘safe harbor’ locus. Vector DNA analyses revealed that adenoviral vectors transferred intact TALEN genes, whereas lentiviral vectors failed to do so, as shown by their heterogeneously sized proviruses in target cells. Importantly, adenoviral vector-mediated TALEN gene delivery resulted in site-specific double-stranded DNA break formation at the intended AAVS1 target site at similarly high levels in both transformed and non-transformed cells. In conclusion, we demonstrate that adenoviral, but not lentiviral, vectors constitute a valuable TALEN gene delivery platform. PMID:23275534

  16. 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.

  17. State feedback with fractional integral control design based on the Bode's ideal transfer function

    NASA Astrophysics Data System (ADS)

    Al-Saggaf, U. M.; Mehedi, I. M.; Mansouri, R.; Bettayeb, M.

    2016-01-01

    State feedback technique through a gain matrix has been a well-known method for pole assignment of a linear system. The technique could encounter a difficulty in eliminating the steady-state errors in some states. Introducing an integral element can effectively eliminate these errors. State feedback with fractional integral control is proposed, in this work, for pole placement of a linear time invariant system. The proposed method yields simple gain formulae. The paper presents the derivation of the design formulae. The method is applied to stabilise an inherently unstable inverted pendulum-cart system. Simulation and experimental results show the effectiveness of the proposed method for set-point tracking, disturbance rejection and stabilising the inverted pendulum. Comparison with the results obtained from applying Achermann's formula is also presented.

  18. Data Transfer Software-SAS MetaData Server & Phoenix Integration Model Center

    SciTech Connect

    2010-04-15

    This software is a plug-in that interfaces between the Phoenix Integration's Model Center and the Base SAS 9.2 applications. The end use of the plug-in is to link input and output data that resides in SAS tables or MS SQL to and from "legacy" software programs without recoding. The potential end users are users who need to run legacy code and want data stored in a SQL database.

  19. Intermolecular interactions at early stage of protein/detergent particle association induced by salt/polyethylene glycol mixtures.

    PubMed

    Odahara, Takayuki; Odahara, Koji

    2016-04-01

    Mixtures of neutral salts and polyethylene glycol are used for various purposes in biological studies. Although the effects of each component of the mixtures are theoretically well investigated, comprehension of their integrated effects remains insufficient. In this work, their roles and effects as a precipitant were clarified by studying dependence of precipitation curves on salt concentration for integral membrane protein/detergent particles of different physicochemical properties. The dependence of precipitation curves was reasonably related to intermolecular interactions among relevant molecules such as protein, detergent and polyethylene glycol by considering their physicochemical properties. The obtained relationships are useful as basic information to learn the early stage of biological macromolecular associations.

  20. Time delay and integration array (TDI) using charge transfer device technology. Phase 2, volume 1: Technical

    NASA Technical Reports Server (NTRS)

    1977-01-01

    The 20x9 TDI array was developed to meet the LANDSAT Thematic Mapper Requirements. This array is based upon a self-aligned, transparent gate, buried channel process. The process features: (1) buried channel, four phase, overlapping gate CCD's for high transfer efficiency without fat zero; (2) self-aligned transistors to minimize clock feedthrough and parasitic capacitance; and (3) transparent tin oxide electrode for high quantum efficiency with front surface irradiation. The requirements placed on the array and the performance achieved are summarized. This data is the result of flat field measurements only, no imaging or dynamic target measurements were made during this program. Measurements were performed with two different test stands. The bench test equipment fabricated for this program operated at the 8 micro sec line time and employed simple sampling of the gated MOSFET output video signal. The second stand employed Correlated Doubled Sampling (CDS) and operated at 79.2 micro sec line time.

  1. Heterogeneous integration of gallium nitride light-emitting diodes on diamond and silica by transfer printing.

    PubMed

    Trindade, A J; Guilhabert, B; Xie, E Y; Ferreira, R; McKendry, J J D; Zhu, D; Laurand, N; Gu, E; Wallis, D J; Watson, I M; Humphreys, C J; Dawson, M D

    2015-04-01

    We report the transfer printing of blue-emitting micron-scale light-emitting diodes (micro-LEDs) onto fused silica and diamond substrates without the use of intermediary adhesion layers. A consistent Van der Waals bond was achieved via liquid capillary action, despite curvature of the LED membranes following release from their native silicon growth substrates. The excellence of diamond as a heat-spreader allowed the printed membrane LEDs to achieve optical power output density of 10 W/cm(2) when operated at a current density of 254 A/cm(2). This high-current-density operation enabled optical data transmission from the LEDs at 400 Mbit/s.

  2. Enantioselective Intermolecular [2 + 2] Photocycloaddition Reactions of 2(1H)-Quinolones Induced by Visible Light Irradiation

    PubMed Central

    2016-01-01

    In the presence of a chiral thioxanthone catalyst (10 mol %) the title compounds underwent a clean intermolecular [2 + 2] photocycloaddition with electron-deficient olefins at λ = 419 nm. The reactions not only proceeded with excellent regio- and diastereoselectivity but also delivered the respective cyclobutane products with significant enantiomeric excess (up to 95% ee). Key to the success of the reactions is a two-point hydrogen bonding between quinolone and catalyst enabling efficient energy transfer and high enantioface differentiation. Preliminary work indicated that solar irradiation can be used for this process and that the substrate scope can be further expanded to isoquinolones. PMID:27268908

  3. Enantioselective Intermolecular [2 + 2] Photocycloaddition Reactions of 2(1H)-Quinolones Induced by Visible Light Irradiation.

    PubMed

    Tröster, Andreas; Alonso, Rafael; Bauer, Andreas; Bach, Thorsten

    2016-06-29

    In the presence of a chiral thioxanthone catalyst (10 mol %) the title compounds underwent a clean intermolecular [2 + 2] photocycloaddition with electron-deficient olefins at λ = 419 nm. The reactions not only proceeded with excellent regio- and diastereoselectivity but also delivered the respective cyclobutane products with significant enantiomeric excess (up to 95% ee). Key to the success of the reactions is a two-point hydrogen bonding between quinolone and catalyst enabling efficient energy transfer and high enantioface differentiation. Preliminary work indicated that solar irradiation can be used for this process and that the substrate scope can be further expanded to isoquinolones. PMID:27268908

  4. Strong intermolecular vibrational coupling through cyclic hydrogen-bonded structures revealed by ultrafast continuum mid-IR spectroscopy.

    PubMed

    Stingel, Ashley M; Calabrese, Carmella; Petersen, Poul B

    2013-12-12

    Cyclic hydrogen-bonded structures are common motifs in biological systems, providing structural stability and mediating proton transfer for redox reactions. The mechanism of proton transfer across hydrogen-bonded interfaces depends on the strength of the intermolecular coupling between bridging OH/NH vibrational modes. Here we present a novel ultrafast continuum mid-IR spectroscopy experiment to study the vibrational dynamics of the 7-azaindole-acetic acid (7AI-Ac) heterodimer as a model system for asymmetric cyclic hydrogen-bonded structures. In addition to spreading of the excitation across the whole OH band within the time resolution of the experiment, excitation of a 300 cm(-1) region of the ∼1000 cm(-1) broad OH stretching mode of the acetic acid monomer leads to a frequency shift in the NH stretching mode of the 7AI monomer. This indicates that the NH and OH stretching modes located on the two monomers are strongly coupled despite being separated by 750 cm(-1). The strong coupling further causes the OH and NH bands to decay with a common decay time of ∼2.5 ps. This intermolecular coupling is mediated through the hydrogen-bonded structure of the 7AI-Ac heterodimer and is likely a general property of cyclic hydrogen-bonded structures. Characterizing the vibrational dynamics of and the coupling between the high-frequency OH/NH modes will be important for understanding proton transfer across such molecular interfaces.

  5. Analysis of Hydrodynamics and Heat Transfer in a Thin Liquid Film Flowing over a Rotating Disk by Integral Method

    NASA Technical Reports Server (NTRS)

    Basu, S.; Cetegen, B. M.

    2005-01-01

    An integral analysis of hydrodynamics and heat transfer in a thin liquid film flowing over a rotating disk surface is presented for both constant temperature and constant heat flux boundary conditions. The model is found to capture the correct trends of the liquid film thickness variation over the disk surface and compare reasonably well with experimental results over the range of Reynolds and Rossby numbers covering both inertia and rotation dominated regimes. Nusselt number variation over the disk surface shows two types of behavior. At low rotation rates, the Nusselt number exhibits a radial decay with Nusselt number magnitudes increasing with higher inlet Reynolds number for both constant wall temperature and heat flux cases. At high rotation rates, the Nusselt number profiles exhibit a peak whose location advances radially outward with increasing film Reynolds number or inertia. The results also compare favorably with the full numerical simulation results from an earlier study as well as with the reported experimental results.

  6. A Small Molecule That Protects the Integrity of the Electron Transfer Chain Blocks the Mitochondrial Apoptotic Pathway.

    PubMed

    Jiang, Xian; Li, Li; Ying, Zhengxin; Pan, Chenjie; Huang, Shaoqiang; Li, Lin; Dai, Miaomiao; Yan, Bo; Li, Ming; Jiang, Hui; Chen, She; Zhang, Zhiyuan; Wang, Xiaodong

    2016-07-21

    In response to apoptotic stimuli, mitochondria in mammalian cells release cytochrome c and other apoptogenic proteins, leading to the subsequent activation of caspases and apoptotic cell death. This process is promoted by the pro-apoptotic members of the Bcl-2 family of proteins, such as Bim and Bax, which, respectively, initiate and execute cytochrome c release from the mitochondria. Here we report the discovery of a small molecule that efficiently blocks Bim-induced apoptosis after Bax is activated on the mitochondria. The cellular target of this small molecule was identified to be the succinate dehydrogenase subunit B (SDHB) protein of complex II of the mitochondrial electron transfer chain (ETC). The molecule protects the integrity of the ETC and allows treated cells to continue to proliferate after apoptosis induction. Moreover, this molecule blocked dopaminergic neuron death and reversed Parkinson-like behavior in a rat model of Parkinson's disease. PMID:27447985

  7. Space transfer vehicle concepts and requirements study. Volume 2, book 4: Integrated advanced technology development

    NASA Technical Reports Server (NTRS)

    Weber, Gary A.

    1991-01-01

    The Space Transfer Vehicle (STV) program provides both an opportunity and a requirement to increase our upper stage capabilities with the development and applications of new technologies. Issues such as man rating, space basing, reusability, and long lunar surface storage times drive the need for new technology developments and applications. In addition, satisfaction of mission requirements such as lunar cargo delivery capability and lunar landing either require new technology development or can be achieved in a more cost-effective manner with judicious applications of advanced technology. During the STV study, advanced technology development requirements and plans have been addressed by the Technology/Advanced Development Working Group composed of NASA and contractor representatives. This report discusses the results to date of this working group. The first section gives an overview of the technologies that have potential or required applications for the STV and identifies those technologies baselined for the STV. Figures are provided that list the technology categories and show the priority placed on those technology categories for either the space-based or ground-based options. The second section covers the plans and schedules for incorporating the technologies into the STV program.

  8. Integration of radiative transfer into satellite models of ocean primary production

    NASA Astrophysics Data System (ADS)

    Smyth, T. J.; Tilstone, G. H.; Groom, S. B.

    2005-10-01

    A major goal of ocean color observations from space is the determination of phytoplankton primary productivity (PP) and hence oceanic carbon uptake. Results of a PP model implemented to use satellite-derived fields of chlorophyll, photosynthetically available radiation (PAR) and sea-surface temperature (SST) are presented. The model gave a global estimate of PP of around 57 Gt C yr-1 and gives a low RMS (0.16) when compared with in situ data. However, as the model's in-water light field parameterization only considers attenuation by pure water and chlorophyll, PP is overestimated in case II waters where other optically important constituents such as colored dissolved organic matter (CDOM) and suspended particulate matter (SPM) are also present. This paper develops a novel technique to determine PP by coupling a radiative transfer code, which allows the inclusion of CDOM and SPM, to the original photosynthesis model. For the global calculations, a look-up table has been generated using chlorophyll, CDOM, SST, PAR and day length as inputs. The resultant 364,500 element look-up table has been applied to data from the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) and Moderate-Resolution Imaging Spectroradiometer (MODIS). PP retrievals are improved in case II waters and global estimates are reduced to between 52 and 55 Gt C yr-1.

  9. Space transfer vehicle concepts and requirements study. Volume 2, book 4: Integrated advanced technology development

    NASA Astrophysics Data System (ADS)

    Weber, Gary A.

    1991-04-01

    The Space Transfer Vehicle (STV) program provides both an opportunity and a requirement to increase our upper stage capabilities with the development and applications of new technologies. Issues such as man rating, space basing, reusability, and long lunar surface storage times drive the need for new technology developments and applications. In addition, satisfaction of mission requirements such as lunar cargo delivery capability and lunar landing either require new technology development or can be achieved in a more cost-effective manner with judicious applications of advanced technology. During the STV study, advanced technology development requirements and plans have been addressed by the Technology/Advanced Development Working Group composed of NASA and contractor representatives. This report discusses the results to date of this working group. The first section gives an overview of the technologies that have potential or required applications for the STV and identifies those technologies baselined for the STV. Figures are provided that list the technology categories and show the priority placed on those technology categories for either the space-based or ground-based options. The second section covers the plans and schedules for incorporating the technologies into the STV program.

  10. Integration of Ultraviolet Photodissociation with Proton Transfer Reactions and Ion Parking for Analysis of Intact Proteins.

    PubMed

    Holden, Dustin D; McGee, William M; Brodbelt, Jennifer S

    2016-01-01

    We report the implementation of proton transfer reactions (PTR) and ion parking on an Orbitrap mass spectrometer. PTR/ion parking allows charge states of proteins to be focused into a single lower charge state via sequential deprotonation reactions with a proton scavenging reagent, in this case, a nitrogen-containing adduct of fluoranthene. Using PTR and ion parking, we evaluate the charge state dependence of fragmentation of ubiquitin (8.6 kDa), myoglobin (17 kDa), and carbonic anhydrase (29 kDa) upon higher energy collisional dissociation (HCD) or ultraviolet photodissociation (UVPD). UVPD exhibited less charge state dependence, thus yielding more uniform distributions of cleavages along the protein backbone and consequently higher sequence coverage than HCD. HCD resulted in especially prominent cleavages C-terminal to amino acids containing acidic side-chains and N-terminal to proline residues; UVPD did not exhibit preferential cleavage adjacent to acidic residues but did show enhancement next to proline and phenylalanine. PMID:26633754

  11. Density-based Energy Decomposition Analysis for Intermolecular Interactions with Variationally Determined Intermediate State Energies

    SciTech Connect

    Wu, Q.; Ayers, P.W.; Zhang, Y.

    2009-10-28

    The first purely density-based energy decomposition analysis (EDA) for intermolecular binding is developed within the density functional theory. The most important feature of this scheme is to variationally determine the frozen density energy, based on a constrained search formalism and implemented with the Wu-Yang algorithm [Q. Wu and W. Yang, J. Chem. Phys. 118, 2498 (2003) ]. This variational process dispenses with the Heitler-London antisymmetrization of wave functions used in most previous methods and calculates the electrostatic and Pauli repulsion energies together without any distortion of the frozen density, an important fact that enables a clean separation of these two terms from the relaxation (i.e., polarization and charge transfer) terms. The new EDA also employs the constrained density functional theory approach [Q. Wu and T. Van Voorhis, Phys. Rev. A 72, 24502 (2005)] to separate out charge transfer effects. Because the charge transfer energy is based on the density flow in real space, it has a small basis set dependence. Applications of this decomposition to hydrogen bonding in the water dimer and the formamide dimer show that the frozen density energy dominates the binding in these systems, consistent with the noncovalent nature of the interactions. A more detailed examination reveals how the interplay of electrostatics and the Pauli repulsion determines the distance and angular dependence of these hydrogen bonds.

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

    SciTech Connect

    Wang, Hanyu; Wang, Xu; Yu, Junsheng E-mail: jsyu@uestc.edu.cn; Zhou, Jie; Lu, Zhiyun E-mail: jsyu@uestc.edu.cn

    2014-08-11

    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 × 10{sup 11} Jones at −3 V under the UV-350 nm illumination with an intensity of 0.6 mW/cm{sup 2}, and yielded an exciplex EL light emission with a maximum brightness of 1437 cd/m{sup 2}. 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.

  13. Organic nanofibers integrated by transfer technique in field-effect transistor devices

    PubMed Central

    2011-01-01

    The electrical properties of self-assembled organic crystalline nanofibers are studied by integrating these on field-effect transistor platforms using both top and bottom contact configurations. In the staggered geometries, where the nanofibers are sandwiched between the gate and the source-drain electrodes, a better electrical conduction is observed when compared to the coplanar geometry where the nanofibers are placed over the gate and the source-drain electrodes. Qualitatively different output characteristics were observed for top and bottom contact devices reflecting the significantly different contact resistances. Bottom contact devices are dominated by contact effects, while the top contact device characteristics are determined by the nanofiber bulk properties. It is found that the contact resistance is lower for crystalline nanofibers when compared to amorphous thin films. These results shed light on the charge injection and transport properties for such organic nanostructures and thus constitute a significant step forward toward a nanofiber-based light-emitting device. PMID:21711821

  14. Structural and functional investigation of the intermolecular interaction between NRPS adenylation and carrier protein domains

    PubMed Central

    Sundlov, Jesse A.; Shi, Ce; Wilson, Daniel J.; Aldrich, Courtney C.; Gulick, Andrew M.

    2012-01-01

    Summary Non-ribosomal peptide synthetases (NRPSs) are modular proteins that produce peptide antibiotics and siderophores. These enzymes act as catalytic assembly lines where substrates, covalently bound to integrated carrier domains, are delivered to adjacent catalytic domains. The carrier domains are initially loaded by adenylation domains, which use two distinct conformations to catalyze sequentially the adenylation of the substrate and the thioesterification of the pantetheine cofactor. We have used a mechanism-based inhibitor to determine the crystal structure of an engineered adenylation-carrier domain protein illustrating the intermolecular interaction between the adenylation and carrier domains. This structure enabled directed mutations to improve the interaction between non-native partner proteins. Comparison with prior NRPS adenylation domain structures provides insights into the assembly line dynamics of these modular enzymes. PMID:22365602

  15. Computing free energy hypersurfaces for anisotropic intermolecular associations.

    PubMed

    Strümpfer, Johan; Naidoo, Kevin J

    2010-01-30

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  17. Integrating Horizontal Gene Transfer and Common Descent to Depict Evolution and Contrast It with “Common Design”1

    PubMed Central

    GUILLERMO PAZ-Y-MIÑO-C; ESPINOSA, AVELINA

    2016-01-01

    Horizontal gene transfer (HGT) and common descent interact in space and time. Because events of HGT co-occur with phylogenetic evolution, it is difficult to depict evolutionary patterns graphically. Tree-like representations of life’s diversification are useful, but they ignore the significance of HGT in evolutionary history, particularly of unicellular organisms, ancestors of multicellular life. Here we integrate the reticulated-tree model, ring of life, symbiogenesis whole-organism model, and eliminative pattern pluralism to represent evolution. Using Entamoeba histolytica alcohol dehydrogenase 2 (EhADH2), a bifunctional enzyme in the glycolytic pathway of amoeba, we illustrate how EhADH2 could be the product of both horizontally acquired features from ancestral prokaryotes (i.e. aldehyde dehydrogenase [ALDH] and alcohol dehydrogenase [ADH]), and subsequent functional integration of these enzymes into EhADH2, which is now inherited by amoeba via common descent. Natural selection has driven the evolution of EhADH2 active sites, which require specific amino acids (cysteine 252 in the ALDH domain; histidine 754 in the ADH domain), iron- and NAD+ as cofactors, and the substrates acetyl-CoA for ALDH and acetaldehyde for ADH. Alternative views invoking “common design” (i.e. the non-naturalistic emergence of major taxa independent from ancestry) to explain the interaction between horizontal and vertical evolution are unfounded. PMID:20021546

  18. Radiative transfer in a sphere illuminated by a parallel beam - An integral equation approach. [in planetary atmosphere

    NASA Technical Reports Server (NTRS)

    Shia, R.-L.; Yung, Y. L.

    1986-01-01

    The problem of multiple scattering of nonpolarized light in a planetary body of arbitrary shape illuminated by a parallel beam is formulated using the integral equation approach. There exists a simple functional whose stationarity condition is equivalent to solving the equation of radiative transfer and whose value at the stationary point is proportional to the differential cross section. The analysis reveals a direct relation between the microscopic symmetry of the phase function for each scattering event and the macroscopic symmetry of the differential cross section for the entire planetary body, and the interconnection of these symmetry relations and the variational principle. The case of a homogeneous sphere containing isotropic scatterers is investigated in detail. It is shown that the solution can be expanded in a multipole series such that the general spherical problem is reduced to solving a set of decoupled integral equations in one dimension. Computations have been performed for a range of parameters of interest, and illustrative examples of applications to planetary problems as provided.

  19. Photon Antibunching in Complex Intermolecular Fluorescence Quenching Kinetics.

    PubMed

    Sharma, Arjun; Enderlein, Jörg; Kumbhakar, Manoj

    2016-08-18

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

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

    PubMed Central

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

    2015-01-01

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

  1. Integration of energy and electron transfer processes in the photosynthetic membrane of Rhodobacter sphaeroides

    PubMed Central

    Cartron, Michaël L.; Olsen, John D.; Sener, Melih; Jackson, Philip J.; Brindley, Amanda A.; Qian, Pu; Dickman, Mark J.; Leggett, Graham J.; Schulten, Klaus; Hunter, C. Neil

    2014-01-01

    Photosynthesis converts absorbed solar energy to a protonmotive force, which drives ATP synthesis. The membrane network of chlorophyll–protein complexes responsible for light absorption, photochemistry and quinol (QH2) production has been mapped in the purple phototrophic bacterium Rhodobacter (Rba.) sphaeroides using atomic force microscopy (AFM), but the membrane location of the cytochrome bc1 (cytbc1) complexes that oxidise QH2 to quinone (Q) to generate a protonmotive force is unknown. We labelled cytbc1 complexes with gold nanobeads, each attached by a Histidine10 (His10)-tag to the C-terminus of cytc1. Electron microscopy (EM) of negatively stained chromatophore vesicles showed that the majority of the cytbc1 complexes occur as dimers in the membrane. The cytbc1 complexes appeared to be adjacent to reaction centre light-harvesting 1-PufX (RC-LH1-PufX) complexes, consistent with AFM topographs of a gold-labelled membrane. His-tagged cytbc1 complexes were retrieved from chromatophores partially solubilised by detergent; RC-LH1-PufX complexes tended to co-purify with cytbc1, whereas LH2 complexes became detached, consistent with clusters of cytbc1 complexes close to RC-LH1-PufX arrays, but not with a fixed, stoichiometric cytbc1-RC-LH1-PufX supercomplex. This information was combined with a quantitative mass spectrometry (MS) analysis of the RC, cytbc1, ATP synthase, cytaa3 and cytcbb3 membrane protein complexes, to construct an atomic-level model of a chromatophore vesicle comprising 67 LH2 complexes, 11 LH1-RC-PufX dimers & 2 RC-LH1-PufX monomers, 4 cytbc1 dimers and 2 ATP synthases. Simulation of the interconnected energy, electron and proton transfer processes showed a half-maximal ATP turnover rate for a light intensity equivalent to only 1% of bright sunlight. Thus, the photosystem architecture of the chromatophore is optimised for growth at low light intensities. PMID:24530865

  2. Integrated smartphone imaging of quantum dot photoluminescence and Förster resonance energy transfer

    NASA Astrophysics Data System (ADS)

    Petryayeva, Eleonora; Algar, W. Russ

    2015-06-01

    Smartphones and other mobile devices are emerging as promising analytical platforms for point-of-care diagnostics, particularly when combined with nanotechnology. For example, we have shown that the optical properties of semiconductor quantum dots (QDs) are well suited to photoluminescence (PL) detection with a smartphone camera. However, this previous work has utilized an external excitation source for interrogation of QD PL. In this proceeding, we demonstrate that the white-light LED photographic flashes built into smartphones can be optically filtered to yield blue light suitable for excitation of QD PL. Measurements were made by recording video with filtered flash illumination and averaging the frames of the video to obtain images with good signal-to-background ratios. These images permitted detection of green-emitting and red-emitting QDs at levels comparable to those possible with excitation using an external long-wave UV lamp. The optical properties of QDs proved to be uniquely suited to smartphone PL imaging, exhibiting emission that was 1-2 orders magnitude brighter than that of common fluorescent dyes under the same conditions. Excitation with the smartphone flash was also suitable for imaging of FRET between green-emitting QD donors and Alexa Fluor 555 (A555) fluorescent dye acceptors. No significant difference in FRET imaging capability was observed between excitation with the smartphone flash and a long-wave UV lamp. Although the smartphone flash did have some disadvantages compared to an external UV lamp, these disadvantages are potentially offset by the benefit of having excitation and detection integrated into the smartphone.

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

    PubMed

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

    2014-07-01

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

  4. Design, fabrication, and calibration of curved integral coils for measuring transfer function, uniformity, and effective length of LBL ALS (Lawrence Berkeley Laboratory Advanced Light Source) Booster Dipole Magnets

    SciTech Connect

    Green, M.I.; Nelson, D.; Marks, S.; Gee, B.; Wong, W.; Meneghetti, J.

    1989-03-01

    A matched pair of curved integral coils has been designed, fabricated and calibrated at Lawrence Berkeley Laboratory for measuring Advanced Light Source (ALS) Booster Dipole Magnets. Distinctive fabrication and calibration techniques are described. The use of multifilar magnet wire in fabrication integral search coils is described. Procedures used and results of AC and DC measurements of transfer function, effective length and uniformity of the prototype booster dipole magnet are presented in companion papers. 8 refs.

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

    PubMed

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

    2016-07-13

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

  6. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    SciTech Connect

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

    2015-08-14

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

  7. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    PubMed Central

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

    2015-01-01

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

  8. Quantitative analysis of intermolecular interactions in orthorhombic rubrene

    DOE PAGES

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

    2015-08-14

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

  9. Quantitative analysis of intermolecular interactions in orthorhombic rubrene.

    PubMed

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

    2015-09-01

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

  10. 3D CFD Electrochemical and Heat Transfer Model of an Integrated-Planar Solid Oxide Electrolysis Cells

    SciTech Connect

    Grant Hawkes; James E. O'Brien

    2008-10-01

    A three-dimensional computational fluid dynamics (CFD) electrochemical model has been created to model high-temperature electrolysis cell performance and steam electrolysis in a new novel integrated planar porous-tube supported solid oxide electrolysis cell (SOEC). The model is of several integrated planar cells attached to a ceramic support tube. This design is being evaluated with modeling at the Idaho National Laboratory. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user-defined subroutine was modified for this work to allow for operation in the SOEC mode. Model results provide detailed profiles of temperature, Nernst potential, operating potential, activation over-potential, anode-side gas composition, cathode-side gas composition, current density and hydrogen production over a range of stack operating conditions. Mean per-cell area-specific-resistance (ASR) values decrease with increasing current density. Predicted mean outlet hydrogen and steam concentrations vary linearly with current density, as expected. Effects of variations in operating temperature, gas flow rate, cathode and anode exchange current density, and contact resistance from the base case are presented. Contour plots of local electrolyte temperature, current density, and Nernst potential indicated the effects of heat transfer, reaction cooling/heating, and change in local gas composition. Results are discussed for using this design in the electrolysis mode. Discussion of thermal neutral voltage, enthalpy of reaction, hydrogen production, cell thermal efficiency, cell electrical efficiency, and Gibbs free energy are discussed and reported herein.

  11. Definition, technology readiness, and development cost of the orbit transfer vehicle engine integrated control and health monitoring system elements

    NASA Technical Reports Server (NTRS)

    Cannon, I.; Balcer, S.; Cochran, M.; Klop, J.; Peterson, S.

    1991-01-01

    An Integrated Control and Health Monitoring (ICHM) system was conceived for use on a 20 Klb thrust baseline Orbit Transfer Vehicle (OTV) engine. Considered for space used, the ICHM was defined for reusability requirements for an OTV engine service free life of 20 missions, with 100 starts and a total engine operational time of 4 hours. Functions were derived by flowing down requirements from NASA guidelines, previous OTV engine or ICHM documents, and related contracts. The elements of an ICHM were identified and listed, and these elements were described in sufficient detail to allow estimation of their technology readiness levels. These elements were assessed in terms of technology readiness level, and supporting rationale for these assessments presented. The remaining cost for development of a minimal ICHM system to technology readiness level 6 was estimated. The estimates are within an accuracy range of minus/plus 20 percent. The cost estimates cover what is needed to prepare an ICHM system for use on a focussed testbed for an expander cycle engine, excluding support to the actual test firings.

  12. Integral cross section measurements and product recoil velocity distributions of Xe(2+) + N2 hyperthermal charge-transfer collisions.

    PubMed

    Hause, Michael L; Prince, Benjamin D; Bemish, Raymond J

    2016-07-28

    Charge exchange from doubly charged rare gas cations to simple diatomics proceeds with a large cross section and results in populations of many vibrational and electronic product states. The charge exchange between Xe(2+) and N2, in particular, is known to create N2 (+) in both the A and B electronic states. In this work, we present integral charge exchange cross section measurements of the Xe(2+) + N2 reaction as well as axial recoil velocity distributions of the Xe(+) and N2 (+) product ions for collision energies between 0.3 and 100 eV in the center-of-mass (COM) frame. Total charge-exchange cross sections decrease from 70 Å(2) to about 40 Å(2) with increasing collision energy through this range. Analysis of the axial velocity distributions indicates that a Xe(2+) - N2 complex exists at low collision energies but is absent by 17.6 eV COM. Analysis of the axial velocity distributions reveals evidence for complexes with lifetimes comparable to the rotational period at low collision energies. The velocity distributions are consistent with quasi-resonant single charge transfer at high collision energies. PMID:27475363

  13. Quantum dots for single-pair fluorescence resonance energy transfer in membrane- integrated EFoF1.

    PubMed

    Galvez, Eva; Düser, Monika; Börsch, Michael; Wrachtrup, Jörg; Gräber, Peter

    2008-10-01

    spFRET (single-pair fluorescence resonance energy transfer) with organic fluorophores has been used to demonstrate rotation of the subunits gamma and epsilon in membrane-integrated FoF1 during proton transport-coupled ATP synthesis. Owing to the high light intensities used in single-molecule spectroscopy, organic fluorophores show a high probability for photobleaching. Luminescent CdSe/ZnS nanocrystals with a hydrophilic shell have been covalently bound to FoF1 either to the stator subunit b or to the rotor subunit c. TIRFM (total internal reflection microscopy) shows that covalent binding of the QD (quantum dot) via cysteine to FoF1 leads to a significant decrease in the blinking probability in the microsecond-to-second time range. This effect allows the observation of subunit movements in an extended time range. If the QD is bound to the rotor subunit c, the fluorescence anisotropy shows fluctuations in the presence of ATP, in contrast with the constant anisotropy observed in the absence of ATP.

  14. Integral cross section measurements and product recoil velocity distributions of Xe2+ + N2 hyperthermal charge-transfer collisions

    NASA Astrophysics Data System (ADS)

    Hause, Michael L.; Prince, Benjamin D.; Bemish, Raymond J.

    2016-07-01

    Charge exchange from doubly charged rare gas cations to simple diatomics proceeds with a large cross section and results in populations of many vibrational and electronic product states. The charge exchange between Xe2+ and N2, in particular, is known to create N2 + in both the A and B electronic states. In this work, we present integral charge exchange cross section measurements of the Xe2+ + N2 reaction as well as axial recoil velocity distributions of the Xe+ and N2 + product ions for collision energies between 0.3 and 100 eV in the center-of-mass (COM) frame. Total charge-exchange cross sections decrease from 70 Å2 to about 40 Å2 with increasing collision energy through this range. Analysis of the axial velocity distributions indicates that a Xe2+ - N2 complex exists at low collision energies but is absent by 17.6 eV COM. Analysis of the axial velocity distributions reveals evidence for complexes with lifetimes comparable to the rotational period at low collision energies. The velocity distributions are consistent with quasi-resonant single charge transfer at high collision energies.

  15. Thermodynamic curvature for attractive and repulsive intermolecular forces.

    PubMed

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

    2013-09-01

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

  16. Atomic force microscopy measurements of intermolecular binding forces.

    PubMed

    Misevic, Gradimir N; Karamanos, Yannis; Misevic, Nikola J

    2009-01-01

    Atomic force microscopy (AFM) measurements of intermolecular binding strength between a single pair of complementary cell adhesion molecules in physiological solutions provided the first quantitative evidence for their cohesive function. This novel AFM-based nanobiotechnology opens a molecular mechanic approach for studying structure- to function-related properties of any type of individual biological macromolecules. The presented example of Porifera cell adhesion glyconectin proteoglycans showed that homotypic carbohydrate to carbohydrate interactions between two primordial proteoglycans can hold the weight of 1,600 cells. Thus, glyconectin type carbohydrates, as the most peripheral cell surface molecules of sponges (today's simplest living Metazoa), are proposed to be the primary cell adhesive molecules essential for the evolution of the multicellularity.

  17. Visualizing the orientational dependence of an intermolecular potential

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Kannemann, Felix; Becke, Axel

    2010-03-01

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

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

    PubMed Central

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

    2014-01-01

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

  20. Visualizing the orientational dependence of an intermolecular potential

    PubMed Central

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

    2016-01-01

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

  1. An assay for intermolecular exchange of alpha crystallin

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  2. Evaluation of intermolecular forces in a circulating system.

    PubMed

    Guo, Qiuquan; Liu, Mei; Yang, Jun

    2011-11-01

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

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

    SciTech Connect

    Muenter, J.S.

    1992-01-01

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

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

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  5. Synergy between twisted conformation and effective intermolecular interactions: strategy for efficient mechanochromic luminogens with high contrast.

    PubMed

    Yuan, Wang Zhang; Tan, Yeqiang; Gong, Yongyang; Lu, Ping; Lam, Jacky W Y; Shen, Xiao Yuan; Feng, Cunfang; Sung, Herman H-Y; Lu, Yawei; Williams, Ian D; Sun, Jing Zhi; Zhang, Yongming; Tang, Ben Zhong

    2013-05-28

    A strategy towards efficient mechanochromic luminogens with high contrast is developed. The twisted propeller-like conformations and effective intermolecular interactions not only endow the luminogens with AIE characteristics and high efficiency in the crystalline state, but also render them to undergo conformational planarization and disruption in intermolecular interactions upon mechanical stimuli, resulting in remarkable changes in emission wavelength and efficiency.

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

    PubMed Central

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

    2014-01-01

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

  7. Accompanying coordinate expansion and recurrence relation method using a transfer relation scheme for electron repulsion integrals with high angular momenta and long contractions

    SciTech Connect

    Hayami, Masao; Seino, Junji; Nakai, Hiromi

    2015-05-28

    An efficient algorithm for the rapid evaluation of electron repulsion integrals is proposed. The present method, denoted by accompanying coordinate expansion and transferred recurrence relation (ACE-TRR), is constructed using a transfer relation scheme based on the accompanying coordinate expansion and recurrence relation method. Furthermore, the ACE-TRR algorithm is extended for the general-contraction basis sets. Numerical assessments clarify the efficiency of the ACE-TRR method for the systems including heavy elements, whose orbitals have long contractions and high angular momenta, such as f- and g-orbitals.

  8. Modelling past and future sediment transfer in catchment-lake systems using integrated records of environmental change

    NASA Astrophysics Data System (ADS)

    Smith, Hugh; Sellami, Haykel; Sangster, Heather; Riley, Mark; Chiverrell, Richard; Boyle, John

    2016-04-01

    Agricultural change has caused significant environmental impacts with the onset of modern practices and intensification over the past century. In response, many current policy and management initiatives aim to reduce soil erosion and river pollution by fine sediment. However, there is a lack of detailed, longer-term baseline information extending beyond the instrumental record against which to measure the success or otherwise of such efforts. Furthermore, future reductions in the magnitude of impacts on soil erosion achievable under a changing climate remain unclear. Here, we provide an overview of an integrated approach for reconstructing impacts from past agricultural change based on social and environmental records coupled with multi-model simulations of catchment erosion and lake sediment dating. We aim to model soil erosion and sediment transfer responses to climatic variability and land use changes spanning the last ca. 100 years using variants of the RUSLE and Morgan-Morgan-Finney models. The study focuses on six lake catchments in Britain which cover a range of agricultural environments from intensively-farmed lowlands to upland catchments subject to lower-intensity livestock grazing. Land use reconstructions are based on historic aerial photography (1940s-2000s) and satellite-derived land cover maps (1990-2007) in combination with annual parish-level agricultural census data (1890s-1970s) and farmer interviews. Radionuclide dating of lake sediments coupled with pollen analysis provides independent data on decadal sedimentation rates and vegetation cover for comparison with model outputs and land use reconstructions. This combination of social and environmental records, soil erosion modelling and dating of lake sedimentary archives forms a powerful platform from which to project impacts from future agricultural scenarios under a changing climate.

  9. Intermolecular interaction of prednisolone with bovine serum albumin: spectroscopic and molecular docking methods.

    PubMed

    Shi, Jie-hua; Zhu, Ying-Yao; Wang, Jing; Chen, Jun; Shen, Ya-Jing

    2013-02-15

    The intermolecular interaction of prednisolone with bovine serum albumin (BSA) was studied using fluorescence, circular dichroism (CD) and molecular docking methods. The experimental results showed that the fluorescence quenching of the BSA at 338 nm by prednisolone resulted from the formation of prednisolone-BSA complex. The number of binding sites (n) for prednisolone binding on BSA was approximately equal to 1. Base on the sign and magnitude of the enthalpy and entropy changes (ΔH(0)=-149.6 kJ mol(-1) and ΔS(0)=-370.7 J mol(-1)K(-1)) and the results of molecular docking, it could be suggested that the interaction forces were mainly Van der Waals and hydrogen bonding interactions. Moreover, in the binding process of BSA with prednisolone, prednisolone molecule can be inserted into the hydrophobic cavity of subdomain IIIA (site II) of BSA. The distance between prednisolone and Trp residue of BSA was calculated as 2.264 nm according to Forster's non-radiative energy transfer theory.

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

    SciTech Connect

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

    2011-12-21

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

  11. Integrating energy planning and techno-economic development: A solid basis for the assessment and transfer of energy technology to developing countries

    SciTech Connect

    Kahen, G.

    1998-05-01

    Developing countries not only suffer from technical and technological weaknesses and underdeveloped socioeconomic systems, but also face energy shortages and inefficient energy systems. This article explains the major issues of energy systems and technology transfer to developing countries and their constraints for energy planning. It then introduces a comprehensive approach for integrating techno-economic development and energy planning, leading to a proposal of a smooth context for the assessment of candidate energy technology for underdeveloped countries. The article describes the reason for integrating development goals and energy planning within an interrelated demand-supply perspective in order to underline crucial variables (qualitative, quantitative, and knowledge-based). The analytic hierarchy process is addressed as an appropriate technique for setting energy planning goals and also for the assessment of candidate energy technology to be transferred to the Third World.

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

    PubMed

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

    2016-01-01

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

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

    SciTech Connect

    Venkattraman, Ayyaswamy

    2014-12-09

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

  14. Carbon dioxide-methanol intermolecular complexes in interstellar grain mantles

    NASA Astrophysics Data System (ADS)

    Dartois, E.; Demyk, K.; d'Hendecourt, L.; Ehrenfreund, P.

    1999-11-01

    We present new laboratory data to interpret the Infrared Space Observatory (ISO) spectra of protostellar objects, and particularly RAFGL7009S. Our experimental results show that solid methanol and carbon dioxide exhibit specific intermolecular interactions. We propose the formation of a Lewis acid-base complex between carbon dioxide and methanol molecules to explain specific substructure of the 15.2 mu m CO_2 bending mode observed in different objects. The various CO_2 bending mode patterns observed in many lines of sight can be interpreted as a combination of both this complex formation and the temperature evolution of the ices. The temperature induced segregation of ice mantles containing CO_2 can be monitored by the 13CO_2 stretching mode shift toward the pure CO_2 ice position. The large width observed for this mode towards interstellar sources partly results from the different temperatures sampled along the line of sight. Given the amount of methanol involved in RAFGL7009S, on the basis of ground based observations, we derive that about half of the so called ``6.85 mu m'' band and a quarter of the 4.9 mu m bands can be accounted for by the deformation modes and 2nu_8 transitions of CH_3OH. Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, the Netherlands and the United Kingdom) and with the participation of ISAS and NASA

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  16. Intermolecular interactions, nucleation, and thermodynamics of crystallization of hemoglobin C.

    PubMed Central

    Vekilov, Peter G; Feeling-Taylor, Angela R; Petsev, Dimiter N; Galkin, Oleg; Nagel, Ronald L; Hirsch, Rhoda Elison

    2002-01-01

    The mutated hemoglobin HbC (beta 6 Glu-->Lys), in the oxygenated (R) liganded state, forms crystals inside red blood cells of patients with CC and SC diseases. Static and dynamic light scattering characterization of the interactions between the R-state (CO) HbC, HbA, and HbS molecules in low-ionic-strength solutions showed that electrostatics is unimportant and that the interactions are dominated by the specific binding of solutions' ions to the proteins. Microscopic observations and determinations of the nucleation statistics showed that the crystals of HbC nucleate and grow by the attachment of native molecules from the solution and that concurrent amorphous phases, spherulites, and microfibers are not building blocks for the crystal. Using a novel miniaturized light-scintillation technique, we quantified a strong retrograde solubility dependence on temperature. Thermodynamic analyses of HbC crystallization yielded a high positive enthalpy of 155 kJ mol(-1), i.e., the specific interactions favor HbC molecules in the solute state. Then, HbC crystallization is only possible because of the huge entropy gain of 610 J mol(-1) K(-1), likely stemming from the release of up to 10 water molecules per protein intermolecular contact-hydrophobic interaction. Thus, the higher crystallization propensity of R-state HbC is attributable to increased hydrophobicity resulting from the conformational changes that accompany the HbC beta 6 mutation. PMID:12124294

  17. Thermal selectivity of intermolecular versus intramolecular reactions on surfaces

    PubMed Central

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

    2016-01-01

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

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

    PubMed

    Lynch, Michael; Hagner, Kyle

    2015-01-01

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

  19. Integrated transfers of terrigenous organic matter to lakes at their watershed level: A combined biomarker and GIS analysis

    NASA Astrophysics Data System (ADS)

    Teisserenc, Roman; Lucotte, Marc; Houel, Stéphane; Carreau, Jean

    2010-11-01

    Terrigenous organic matter (TOM) transfer from a watershed to a lake plays a key role in contaminants fate and greenhouse gazes emission in these aquatic ecosystems. In this study, we linked physiographic and vegetation characteristics of a watershed with TOM nature deposited in lake sediments. TOM was characterized using lignin biomarkers as indicators of TOM sources and state of degradation. Geographical information system (GIS) also allowed us to integrate and describe the landscape morpho-edaphic characteristics of a defined drainage basin. Combining these tools we found a significant and positive relationship ( R2 = 0.65, p < 0.002) between mean slope of the watershed and the terrigenous fraction estimated by Λ8 in recent sediments. The mean slope also correlated with the composition of TOM in recent sediments as P/(V + S) and 3,5Bd/V ratios significantly decreased with the steepness of the watersheds ( R2 = 0.57, p < 0.021 and R2 = 0.71, p < 0.004, respectively). More precisely, areas with slopes comprised between 4° and 10° have a major influence on TOM inputs to lakes. The vegetation composition of each watershed influenced the composition of recent sediments of the sampled lakes. The increasing presence of angiosperm trees in the watershed influenced the export of TOM to the lake as Λ8 increased significantly with the presence of this type of vegetation ( R2 = 0.44, p < 0.019). A similar relationship was also observed with S/V ratios, an indicator of angiosperm sources for TOM. The type of vegetation also greatly influenced the degradation state of OM. In this study, we were able to determine that low-sloped areas (0-2°) act as buffer zones for lignin inputs and by extension for TOM loading to sediments. The relative contribution of TOM from the soil organic horizons also increased in steeper watersheds. This study has significant implications in our understanding of the fate of TOM in lacustrine ecosystems.

  20. The fragment spin difference scheme for triplet-triplet energy transfer coupling

    NASA Astrophysics Data System (ADS)

    You, Zhi-Qiang; Hsu, Chao-Ping

    2010-08-01

    To calculate the electronic couplings in both inter- and intramolecular triplet energy transfer (TET), we have developed the "fragment spin difference" (FSD) scheme. The FSD was a generalization from the "fragment charge difference" (FCD) method of Voityuk et al. [J. Chem. Phys. 117, 5607 (2002)] for electron transfer (ET) coupling. In FSD, the spin population difference was used in place of the charge difference in FCD. FSD is derived from the eigenstate energies and populations, and therefore the FSD couplings contain all contributions in the Hamiltonian as well as the potential overlap effect. In the present work, two series of molecules, all-trans-polyene oligomers and polycyclic aromatic hydrocarbons, were tested for intermolecular TET study. The TET coupling results are largely similar to those from the previously developed direct coupling scheme, with FSD being easier and more flexible in use. On the other hand, the Dexter's exchange integral value, a quantity that is often used as an approximate for the TET coupling, varies in a large range as compared to the corresponding TET coupling. To test the FSD for intramolecular TET, we have calculated the TET couplings between zinc(II)-porphyrin and free-base porphyrin separated by different numbers of p-phenyleneethynylene bridge units. Our estimated rate constants are consistent with experimentally measured TET rates. The FSD method can be used for both intermolecular and intramolecular TET, regardless of their symmetry. This general applicability is an improvement over most existing methodologies.

  1. Na + concentration dependence of intermolecular distance in 3,4,9,10-perylenetetracarboxylic dianhydride dimer

    NASA Astrophysics Data System (ADS)

    Fujii, Kazuhito

    2010-01-01

    We have discussed the Na + concentration dependence of the intermolecular distance of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) dimers in aqueous solution of NaOH. We have particularly focused on the S10-S00 transition of the PTCDA dimers which is sensitive to the intermolecular distance and we have found that the S10 state is split for the higher lying sublevel and the lower lying sublevel with the increase of the Na + concentrations. From the energy shift of the lower lying sublevel, we have estimated the intermolecular distance of the PTCDA dimer, that changes from 7.5 to 4.9 Å by the Na + concentration.

  2. Structurally dependent thermochromism of two iodoargentate hybrids based on the intermolecular charge transfer

    NASA Astrophysics Data System (ADS)

    Zhang, Caifeng; Shen, Junju; Guan, Qi; Yu, Tanlai; Fu, Yunlong

    2015-08-01

    Two iodoargentates directed by N-alkylated 3-cyanopyridiniums, [(EC) (Ag2I3)]n (1) and [(PC) (Ag5I6)]n (2) (EC = N-ethyl-3-cyanopyridinium, PC = N-propyl-3-cyanopyridinium) have been solvothermally synthesized. Structural analysis reveals that the variation of N-substituents on 3-cyanopyridinium is responsible for change of the inorganic moieties (belt-like chain for 1 and columnar chain for 2) and consequent packing modes, which further results in the shift of absorption edges and different thermochromic behavior (from yellow at room temperature to almost colorless for 1 and pale yellow for 2 at liquid nitrogen temperature), as proved by UV-vis spectra.

  3. The asymmetric alkylation of dimethylhydrazones; intermolecular chirality transfer using sparteine as chiral ligand.

    PubMed

    McSweeney, Christina M; Foley, Vera M; McGlacken, Gerard P

    2014-12-01

    The asymmetric alkylation of ketones represents a fundamental transformation in organic chemistry. Chiral auxiliaries have been used almost exclusively for this transformation. Herein we describe a strategy for the generation of enantiomerically enriched α-alkylated ketones up to an er of 83 : 17, using a chiral ligand protocol.

  4. The ``primitive'' wave function in the theory of intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Kutzelnigg, Werner

    1980-07-01

    The concept of the primitive wave function for a supermolecule consisting of interacting subsystems is critically analyzed. The distinction between formal and genuine primitive functions is stressed. The concept of uniformly complete basis sets as contrasted to simply complete basis is introduced. Primitive basis sets are defined and shown not to be uniformly complete for the expansion of the supersystem wave function while 'full supersystem basis sets' are. The conditions are specified under which a supersystem wave function can be decomposed into its 'primitive components' corresponding to different partitions of the electrons among the subsystems. These primitive components satisfy the Schrödinger equation asymptotically. The matrix representation of the Hamiltonian (both the full supersystem Hamiltonian H and the zeroth order Hamiltonian Ho) in terms of these partitions is analyzed. It is shown that in the standard application of RS-perturbation theory to intermolecular forces (the polarization approximation) the limiting processes λ→1 and R→∞ do not commute, that the λ-series is not uniformly convergent with respect to R and that the wave function to any finite order in λ is genuinely primitive. The symmetrized polarization approximation is justified for the 'coasymptotic ground state' in certain cases and a 'symmetrized polarization approximation with shifted eigenvalues' is proposed that connects the lowest eigenvalue of Ho with the physical ground state. A justification of simplified schemes in the region of 'small exchange' is given and alternative perturbation schemes are discussed. Finally the use of the primitive function in variational treatments is outlined. One advantage is that a genuinely (not a formally) primitive function is uniformly expandable in a primitive basis set.

  5. Interpretation of intermolecular geometric isotope effect in hydrogen bonds: nuclear orbital plus molecular orbital study.

    PubMed

    Ikabata, Yasuhiro; Imamura, Yutaka; Nakai, Hiromi

    2011-03-01

    The intermolecular geometric isotope effect (GIE) in hydrogen bond A-X···B (X = H and D) is investigated theoretically using the nuclear orbital plus molecular orbital (NOMO) theory. To interpret the GIE in terms of physically meaningful energy components such as electrostatic and exchange-repulsion interactions, the reduced variational space self-consistent-field method is extended to the NOMO scheme. The intermolecular GIE is analyzed as a two-stage process: the intramolecular bond shrinkage and the intermolecular bond elongation. According to the isotopic shifts of energy components described by the NOMO/MP2 method, the intermolecular GIE is approximately interpreted as a process reducing the exchange-repulsion interaction after the decrease of electrostatic interaction. PMID:21306139

  6. The palladium-catalyzed intermolecular C-H chalcogenation of arenes.

    PubMed

    Qiu, Renhua; Reddy, Vutukuri Prakash; Iwasaki, Takanori; Kambe, Nobuaki

    2015-01-01

    Palladium catalyzes the intermolecular chalcogenation of carbazole, 2-phenylpyridine, benzo[h]quinolone, and indole derivatives with disulfides and diselenides via selective C-H bond cleavage, providing a convenient route to thio and selenoethers. PMID:25437148

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    ERIC Educational Resources Information Center

    Olbregts, J.; Walgraeve, J. P.

    1976-01-01

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

  9. Quantum free energy landscapes from ab initio path integral metadynamics: Double proton transfer in the formic acid dimer is concerted but not correlated

    SciTech Connect

    Ivanov, Sergei D. Grant, Ian M.; Marx, Dominik

    2015-09-28

    With the goal of computing quantum free energy landscapes of reactive (bio)chemical systems in multi-dimensional space, we combine the metadynamics technique for sampling potential energy surfaces with the ab initio path integral approach to treating nuclear quantum motion. This unified method is applied to the double proton transfer process in the formic acid dimer (FAD), in order to study the nuclear quantum effects at finite temperatures without imposing a one-dimensional reaction coordinate or reducing the dimensionality. Importantly, the ab initio path integral metadynamics technique allows one to treat the hydrogen bonds and concomitant proton transfers in FAD strictly independently and thus provides direct access to the much discussed issue of whether the double proton transfer proceeds via a stepwise or concerted mechanism. The quantum free energy landscape we compute for this H-bonded molecular complex reveals that the two protons move in a concerted fashion from initial to product state, yet world-line analysis of the quantum correlations demonstrates that the protons are as quantum-uncorrelated at the transition state as they are when close to the equilibrium structure.

  10. Recombinant adeno-associated virus mediates a high level of gene transfer but less efficient integration in the K562 human hematopoietic cell line.

    PubMed Central

    Malik, P; McQuiston, S A; Yu, X J; Pepper, K A; Krall, W J; Podsakoff, G M; Kurtzman, G J; Kohn, D B

    1997-01-01

    We tested the ability of a recombinant adeno-associated virus (rAAV) vector to express and integrate exogenous DNA into human hematopoietic cells in the absence of selection. We developed an rAAV vector, AAV-tNGFR, carrying a truncated rat nerve growth factor receptor (tNGFR) cDNA as a cell surface reporter under the control of the Moloney murine leukemia virus (MoMuLV) long terminal repeat. An analogous MoMuLV-based retroviral vector (L-tNGFR) was used in parallel, and gene transfer and expression in human hematopoietic cells were assessed by flow cytometry and DNA analyses. Following gene transfer into K562 cells with AAV-tNGFR at a multiplicity of infection (MOI) of 13 infectious units (IU), 26 to 38% of cells expressed tNGFR on the surface early after transduction, but the proportion of tNGFR expressing cells steadily declined to 3.0 to 3.5% over 1 month of culture. At an MOI of 130 IU, nearly all cells expressed tNGFR immediately posttransduction, but the proportion of cells expressing tNGFR declined to 62% over 2 months of culture. The decline in the proportion of AAV-tNGFR-expressing cells was associated with ongoing losses of vector genomes. In contrast, K562 cells transduced with the retroviral vector L-tNGFR expressed tNGFR in a constant fraction. Integration analyses on clones showed that integration occurred at different sites. Integration frequencies were estimated at about 49% at an MOI of 130 and 2% at an MOI of 1.3. Transduction of primary human CD34+ progenitor cells by AAV-tNGFR was less efficient than with K562 cells and showed a declining percentage of cells expressing tNGFR over 2 weeks of culture. Thus, purified rAAV caused very high gene transfer and expression in human hematopoietic cells early after transduction, which steadily declined during cell passage in the absence of selection. Although the efficiency of integration was low, overall integration was markedly improved at a high MOI. While prolonged episomal persistence may be adequate

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  12. Proton-transfer dynamics in the (HCO3-)2 dimer of KHCO3 from Car-Parrinello and path-integrals molecular dynamics calculations.

    PubMed

    Dopieralski, Przemyslaw D; Latajka, Zdzislaw; Olovsson, Ivar

    2010-04-01

    The proton motion in the (HCO(3)(-))(2) dimer of KHCO(3) at 298 K has been studied with Car-Parrinello molecular dynamics (CPMD) and path-integrals molecular dynamics (PIMD) simulations. According to earlier neutron diffraction studies at 298 K hydrogen is disordered and occupies two positions with an occupancy ratio of 0.804/0.196. A simulation with only one unit cell is not sufficient to reproduce the disorder of the protons found in the experiments. The CPMD results with four cells, 0.783/0.217, are in close agreement with experiment. The motion of the two protons along the O...O bridge is highly correlated inside one dimer, but strongly uncoupled between different dimers. The present results support a mechanism for the disorder which involves proton transfer from donor to acceptor and not orientational disordering of the entire dimer. The question of simultaneous or successive proton transfer in the two hydrogen bonds in the dimer remains unanswered. During the simulation situations with almost simultaneous proton transfer with a time gap of around 1 fs were observed, as well as successive processes where first one proton is transferred and then the second one with a time gap of around 20 fs. The calculated vibrational spectrum is in good agreement with the experimental IR spectrum, but a slightly different assignment of the bands is indicated by the present simulations. PMID:20305356

  13. Molecular dynamics study of solubilization of immiscible solutes by a micelle: Free energy of transfer of alkanes from water to the micelle core by thermodynamic integration method.

    PubMed

    Fujimoto, K; Yoshii, N; Okazaki, S

    2010-08-21

    Free energy of transfer, DeltaG(w-->m), from water phase to a sodium dodecyl sulfate (SDS) micelle core has been calculated for a series of hydrophobic solutes originally immiscible with water by thermodynamic integration method combined with molecular dynamics calculations. The calculated free energy of transfer is in good correspondence to the experiment as well as the theoretical free energy of transfer. The calculated DeltaG(w-->m)'s are all negative, implying that the alkane molecules are more stable in the micelle than in the water phase. It decreases almost linearly as a function of the number of carbon atoms of the alkanes longer than methane with a decrement of 3.3 kJ mol(-1) per one methylene group. The calculated free energy of transfer indicates that, for example, at the micelle concentration of 50 CMC (critical micelle concentration), about only 1 of 6 micelles or 1 of 32 000 micelles does not contain a solute methane or n-octane molecule, respectively. PMID:20726656

  14. Molecular dynamics study of solubilization of immiscible solutes by a micelle: Free energy of transfer of alkanes from water to the micelle core by thermodynamic integration method

    NASA Astrophysics Data System (ADS)

    Fujimoto, K.; Yoshii, N.; Okazaki, S.

    2010-08-01

    Free energy of transfer, ΔGw→m, from water phase to a sodium dodecyl sulfate (SDS) micelle core has been calculated for a series of hydrophobic solutes originally immiscible with water by thermodynamic integration method combined with molecular dynamics calculations. The calculated free energy of transfer is in good correspondence to the experiment as well as the theoretical free energy of transfer. The calculated ΔGw→m's are all negative, implying that the alkane molecules are more stable in the micelle than in the water phase. It decreases almost linearly as a function of the number of carbon atoms of the alkanes longer than methane with a decrement of 3.3 kJ mol-1 per one methylene group. The calculated free energy of transfer indicates that, for example, at the micelle concentration of 50 CMC (critical micelle concentration), about only 1 of 6 micelles or 1 of 32 000 micelles does not contain a solute methane or n-octane molecule, respectively.

  15. Integrating a 250 mL-spinner flask with other stirred bench-scale cell culture devices: a mass transfer perspective.

    PubMed

    Vallejos, Jose R; Brorson, Kurt A; Moreira, Antonio R; Rao, Govind

    2011-01-01

    The bioprocess development cycle is a complex task that requires a complete understanding of the engineering of the process (e.g., mass transfer, mixing, CO(2) removal, process monitoring, and control) and its affect on cell biology and product quality. Despite their widespread use in bioprocess development, spinner flasks generally lack engineering characterization of critical physical parameters such as k(L)a, P/V, or mixing time. In this study, mass transfer characterization of a 250-mL spinner flask using optical patch-based sensors is presented. The results quantitatively show the effect of the impeller type, liquid filling volume, and agitation speed on the volumetric mass transfer coefficient (k(L)a) in a 250-mL spinner flask, and how they can be manipulated to match mass transfer capability at large culture devices. Thus, process understanding in spinner flasks can be improved, and these devices can be seamlessly integrated in a rational scale-up strategy from cell thawing to bench-scale bioreactors (and beyond) in biomanufacturing. PMID:21523928

  16. Evaluation of gas radiation heat transfer in a 2D axisymmetric geometry using the line-by-line integration and WSGG models

    NASA Astrophysics Data System (ADS)

    Centeno, Felipe Roman; Brittes, Rogério; França, Francis. H. R.; Ezekoye, Ofodike A.

    2015-05-01

    The weighted-sum-of-gray-gases (WSGG) model is widely used in engineering computations of radiative heat transfer due to its relative simplicity, robustness and flexibility. This paper presents the computation of radiative heat transfer in a 2D axisymmetric chamber using two WSGG models to compute radiation in H2O and CO2 mixtures. The first model considers a fixed ratio between the molar concentrations of H2O and CO2, while the second allows the solution for arbitrary ratios. The correlations for both models are based on the HITEMP2010 database. The test case considers typical conditions found in turbulent methane flames, with steep variations in the temperature field as well as in the molar concentrations of the participating species. To assess the accuracy of the WSGG model, the results are compared with a solution obtained by line-by-line integration (LBL) of the spectrum.

  17. Transfer of Learning as a Specific Case of Transition between Learning Contexts in a French Work-Integrated Learning Programme

    ERIC Educational Resources Information Center

    Veillard, Laurent

    2012-01-01

    The aim of this article is to discuss transfer of learning in a tertiary technical course in the French educational context. The focus is on a pedagogical sequence (i.e. a complex problem-solving activity) requiring different types of knowledge that students are expected to have learnt previously in the different parts of their training course…

  18. Single-molecule studies of DNA dynamics and intermolecular forces

    NASA Astrophysics Data System (ADS)

    Robertson, Rae Marie

    DNA molecules were used as a model system to investigate fundamental problems in polymer physics; namely, how molecular length, topology and concentration influence the dynamical properties of polymers. A set of DNA molecules suitable for polymer studies was prepared using molecular biology techniques. Video fluorescence microscopy and single-molecule tracking were used to determine self-diffusion coefficients of DNA molecules. Optical tweezers were used to measure the intermolecular forces confining entangled DNA molecules. Scaling of diffusion with molecular length was in agreement with the Zimm model for dilute solutions of linear and circular DNA, indicating that excluded volume effects are appreciable for both topologies. Scaling of diffusion with concentration was also determined for the four possible topological combinations of linear and circular molecules: linear DNA diffusing in a solution of linear DNA, linear DNA in circular DNA, circular in circular, and circular in linear. For lower concentrations molecular topology had little effect and scaling was in agreement with that of the Rouse model. As concentration was increased topology played a much larger role and scaling crossed over to that of the reptation model, predicted to describe the dynamics of entangled polymers. The notable exception was the strongly hindered diffusion observed for a circular molecule diffusing in an entangled linear solution, suggesting the importance of constraint release. Using a new experimental approach with optical tweezers, a tube-like field confining a single entangled molecule was measured, in accord with the key assumption of the reptation model. A time-dependent harmonic potential opposed displacement transverse to the molecular contour, and the force relaxations following displacement were composed of three distinct modes. A characteristic tube radius of the entangled solution was also determined, close to the classically predicted value. The dependence of the above

  19. Intermolecular Interactions and Electrostatic Properties of the [beta]-Hydroquinone Apohost: Implications for Supramolecular Chemistry

    SciTech Connect

    Clausen, Henrik F.; Chen, Yu-Sheng; Jayatilaka, Dylan; Overgaard, Jacob; Koutsantonis, George A.; Spackman, Mark A.; Iversen, Bo B.

    2012-02-07

    The crystal structure of the {beta}-polymorph of hydroquinone ({beta}-HQ), the apohost of a large family of clathrates, is reported with a specific focus on intermolecular interactions and the electrostatic nature of its cavity. Hirshfeld surface analysis reveals subtle close contacts between two interconnecting HQ networks, and the local packing and related close contacts were examined by breakdown of the fingerprint plot. An experimental multipole model containing anisotropic thermal parameters for hydrogen atoms has been successfully refined against 15(2) K single microcrystal synchrotron X-ray diffraction data. The experimental electron density model has been compared with a theoretical electron density calculated with the molecule embedded in its own crystal field. Hirshfeld charges, interaction energies and the electrostatic potential calculated for both models are qualitatively in good agreement, but small differences in the electrostatic potential persist due to charge transfer from all hydrogen atoms to the oxygen atoms in the theoretical model. The electrostatic potential in the center of the cavity is positive, very shallow and highly symmetric, suggesting that the inclusion of polar molecules in the void will involve a balance between opposing effects. The electric field is by symmetry zero in the center of the cavity, increasing to a value of 0.0185 e/{angstrom}{sup 2} (0.27 V/{angstrom}) 1 {angstrom} along the 3-fold axis and 0.0105 e/{angstrom}{sup 2} (0.15 V/{angstrom}) 1 {angstrom} along the perpendicular direction. While these values are substantial in a macroscopic context, they are quite small for a molecular cavity and are not expected to strongly polarize a guest molecule.

  20. Intermolecular interactions and electrostatic properties of the β-hydroquinone apohost: implications for supramolecular chemistry.

    PubMed

    Clausen, Henrik F; Chen, Yu-Sheng; Jayatilaka, Dylan; Overgaard, Jacob; Koutsantonis, George A; Spackman, Mark A; Iversen, Bo B

    2011-11-17

    The crystal structure of the β-polymorph of hydroquinone (β-HQ), the apohost of a large family of clathrates, is reported with a specific focus on intermolecular interactions and the electrostatic nature of its cavity. Hirshfeld surface analysis reveals subtle close contacts between two interconnecting HQ networks, and the local packing and related close contacts were examined by breakdown of the fingerprint plot. An experimental multipole model containing anisotropic thermal parameters for hydrogen atoms has been successfully refined against 15(2) K single microcrystal synchrotron X-ray diffraction data. The experimental electron density model has been compared with a theoretical electron density calculated with the molecule embedded in its own crystal field. Hirshfeld charges, interaction energies and the electrostatic potential calculated for both models are qualitatively in good agreement, but small differences in the electrostatic potential persist due to charge transfer from all hydrogen atoms to the oxygen atoms in the theoretical model. The electrostatic potential in the center of the cavity is positive, very shallow and highly symmetric, suggesting that the inclusion of polar molecules in the void will involve a balance between opposing effects. The electric field is by symmetry zero in the center of the cavity, increasing to a value of 0.0185 e/Å(2) (0.27 V/Å) 1 Å along the 3-fold axis and 0.0105 e/Å(2) (0.15 V/Å) 1 Å along the perpendicular direction. While these values are substantial in a macroscopic context, they are quite small for a molecular cavity and are not expected to strongly polarize a guest molecule. PMID:21809888

  1. Crystal packing of TCNQ anion pi-radicals governed by intermolecular covalent pi-pi bonding: DFT calculations and statistical analysis of crystal structures.

    PubMed

    Huang, Jingsong; Kingsbury, Stephanie; Kertesz, Miklos

    2008-05-21

    On the basis of a thorough Cambridge Structural Database survey, we present a statistical analysis of the packing of TCNQ anion pi-radicals in TCNQ charge transfer salts, which reveals three packing motifs between neighboring TCNQs: one with a zero longitudinal offset and an approximate 1 A transversal offset, another with an approximate 2 A longitudinal offset and zero transversal offset, and the third with a relatively long sigma-bond in the length of r = 1.6-1.7 A connecting two TCNQ fragments. Along with the statistical analysis of the crystal structures, we also present density functional theory calculations of the total energy, covalent pi-pi bonding interaction energy, and Coulombic repulsion energy for the [TCNQ](2)(2-)pi-dimers with various packing geometries. We find that the interactions between TCNQ anion pi-radicals include contributions from intermolecular covalent pi-pi bonding interaction and local dipole repulsions, in addition to Coulombic repulsion, van der Waals and the attractive electrostatic forces between counter-cations and TCNQ anions pointed out recently by other groups for TCNE anion radicals. We describe an approximate formula for intermolecular interaction energy, E(int) = E(coul) + E(bond) + E(vdW), for systems in vacuum, while in the solid state E(coul) is compensated by the attractive electrostatic forces between counter-cations and TCNQ anions. We conclude that the crystal packing of TCNQ molecules in their charge transfer salts is predominantly determined by the intermolecular covalent pi-pi bonding term, E(bond).

  2. Calibration chain design based on integrating sphere transfer radiometer for SI-traceable on-orbit spectral radiometric calibration and its uncertainty analysis

    NASA Astrophysics Data System (ADS)

    Zhao, Wei-Ning; Fang, Wei; Sun, Li-Wei; Cui, Li-Hong; Wang, Yu-Peng

    2016-09-01

    In order to satisfy the requirement of SI-traceable on-orbit absolute radiation calibration transfer with high accuracy for satellite remote sensors, a transfer chain consisting of a fiber coupling monochromator (FBM) and an integrating sphere transfer radiometer (ISTR) was designed in this paper. Depending on the Sun, this chain based on detectors provides precise spectral radiometric calibration and measurement to spectrometers in the reflective solar band (RSB) covering 300-2500 nm with a spectral bandwidth of 0.5-6 nm. It shortens the traditional chain based on lamp source and reduces the calibration uncertainty from 5% to 0.5% by using the cryogenic radiometer in space as a radiometric benchmark and trap detectors as secondary standard. This paper also gives a detailed uncertainty budget with reasonable distribution of each impact factor, including the weak spectral signal measurement with uncertainty of 0.28%. According to the peculiar design and comprehensive uncertainty analysis, it illustrates that the spectral radiance measurement uncertainty of the ISTR system can reach to 0.48%. The result satisfies the requirements of SI-traceable on-orbit calibration and has wider significance for expanding the application of the remote sensing data with high-quality. Project supported by the National Natural Science Foundation of China (Grant No. 41474161) and the National High-Technology Program of China (Grant No. 2015AA123703).

  3. Calibration chain design based on integrating sphere transfer radiometer for SI-traceable on-orbit spectral radiometric calibration and its uncertainty analysis

    NASA Astrophysics Data System (ADS)

    Zhao, Wei-Ning; Fang, Wei; Sun, Li-Wei; Cui, Li-Hong; Wang, Yu-Peng

    2016-09-01

    In order to satisfy the requirement of SI-traceable on-orbit absolute radiation calibration transfer with high accuracy for satellite remote sensors, a transfer chain consisting of a fiber coupling monochromator (FBM) and an integrating sphere transfer radiometer (ISTR) was designed in this paper. Depending on the Sun, this chain based on detectors provides precise spectral radiometric calibration and measurement to spectrometers in the reflective solar band (RSB) covering 300–2500 nm with a spectral bandwidth of 0.5–6 nm. It shortens the traditional chain based on lamp source and reduces the calibration uncertainty from 5% to 0.5% by using the cryogenic radiometer in space as a radiometric benchmark and trap detectors as secondary standard. This paper also gives a detailed uncertainty budget with reasonable distribution of each impact factor, including the weak spectral signal measurement with uncertainty of 0.28%. According to the peculiar design and comprehensive uncertainty analysis, it illustrates that the spectral radiance measurement uncertainty of the ISTR system can reach to 0.48%. The result satisfies the requirements of SI-traceable on-orbit calibration and has wider significance for expanding the application of the remote sensing data with high-quality. Project supported by the National Natural Science Foundation of China (Grant No. 41474161) and the National High-Technology Program of China (Grant No. 2015AA123703).

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

    PubMed

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

    2014-08-12

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

  5. Integrating Communication into Engineering Curricula: An Interdisciplinary Approach to Facilitating Transfer at New Mexico Institute of Mining and Technology

    ERIC Educational Resources Information Center

    Ford, Julie Dyke

    2012-01-01

    This program profile describes a new approach towards integrating communication within Mechanical Engineering curricula. The author, who holds a joint appointment between Technical Communication and Mechanical Engineering at New Mexico Institute of Mining and Technology, has been collaborating with Mechanical Engineering colleagues to establish a…

  6. Integrating Metacognition into a Developmental Reading and Writing Course to Promote Skill Transfer: An Examination of Student Perceptions and Experiences

    ERIC Educational Resources Information Center

    Pacello, James

    2014-01-01

    This qualitative research study was aimed at examining the experiences and perceptions of students at a four-year college in New York City who were enrolled in an integrated reading and writing course designed to help students connect the literacy skills learned in the course to other contexts. Focusing on three students enrolled in the course,…

  7. The role of entropy and polarity in intermolecular contacts in protein crystals

    SciTech Connect

    Cieślik, Marcin; Derewenda, Zygmunt S.

    2009-05-01

    Logistic regression was used to study the amino-acid composition and structure of crystal contacts in monomeric proteins. Crystal contacts are generally depleted of large flexible amino acids and enriched in small and hydrophobic residues such as Gly and Leu; additionally, larger contacts have cores depleted of polar residues. The integrity and X-ray diffraction quality of protein crystals depend on the three-dimensional order of relatively weak but reproducible intermolecular contacts. Despite their importance, relatively little attention has been paid to the chemical and physical nature of these contacts, which are often regarded as stochastic and thus not different from randomly selected protein surface patches. Here, logistic regression was used to analyze crystal contacts in a database of 821 unambiguously monomeric proteins with structures determined to 2.5 Å resolution or better. It is shown that the propensity of a surface residue for incorporation into a crystal contact is not a linear function of its solvent-accessible surface area and that amino acids with low exposed surfaces, which are typically small and hydrophobic, have been underestimated with respect to their contact-forming potential by earlier area-based calculations. For any given solvent-exposed surface, small and hydrophobic residues are more likely to be involved in crystal contacts than large and charged amino acids. Side-chain entropy is the single physicochemical property that is most negatively correlated with the involvement of amino acids in crystal contacts. It is also shown that crystal contacts with larger buried surfaces containing eight or more amino acids have cores that are depleted of polar amino acids.

  8. Comment on 'Intermolecular interaction potentials of the methane dimer from the local density approximation'

    SciTech Connect

    Li, Arvin H.-T.; Chao, S.D.

    2006-01-15

    To verify the recently calculated intermolecular interaction potentials of the methane dimer within the density functional theory using the (Perdew) local density approximation (LDA) [Chen et al., Phys. Rev. A 69, 034701 (2004)], we have performed a parallel series of calculations using the LDA/6-311++G (3df, 3pd) level of theory with selected exchange functionals (B, G96, MPW, O, PBE, PW91, S, and XA). None of the above calculated intermolecular interaction potentials from the local density approximation reproduce the results reported in the commented paper. In addition, we point out the inappropriateness of using the Lennard-Jones function to model the long-range parts of the calculated intermolecular interaction potentials, as suggested positively by Chen et al.

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

    PubMed

    Chiue, Hiroko; Yamazoye, Tsutako; Matsumura, Sueo

    2015-06-01

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

  10. Intermolecular and intramolecular contributions to the relaxation process in sorbitol and maltitol

    NASA Astrophysics Data System (ADS)

    Sixou, B.; Faivre, A.; David, L.; Vigier, G.

    Molecular mobility in sorbitol and maltitol is studied with spectroscopic techniques and molecular dynamics simulations in order to evaluate the relative contributions of the intermolecular and intramolecular interactions involved in the relaxation processes. The results of the molecular dynamics simulations performed on the polyols in the bulk or in vacuum compares well with the results of the analysis of the relaxation diagrams in the framework of the Perez et al . model. They both imply that the difference in the relative contributions of the intermolecular and intramolecular interactions associated with the different chemical architectures of the two polyols must be taken into account. The intermolecular interactions cannot be neglected and they are stronger in sorbitol than in maltitol in relation with the linear structure of this polyol. The intramolecular barrier, higher in the maltitol molecule with a more complex structure, could be at the origin of the higher junction temperature between the αand βrelaxation processes.

  11. Photoinduced electron transfer in binary blends of conjugated polymers

    SciTech Connect

    Jenekhe, A.A.; Paor, L.R. de; Chen, X.L.; Tarkka, R.M.

    1996-10-01

    The authors report observations concerning the intermolecular photoinduced electron transfer through blends of n-type/p-type {pi}-conjugated organic polymers. The results of transient absorption spectroscopy, fluorescence quenching analysis, and delocalized radical ion pair generation studies imply that these materials are supramolecular materials.

  12. Integration of Artificial Photosynthesis System for Enhanced Electronic Energy-Transfer Efficacy: A Case Study for Solar-Energy Driven Bioconversion of Carbon Dioxide to Methanol.

    PubMed

    Ji, Xiaoyuan; Su, Zhiguo; Wang, Ping; Ma, Guanghui; Zhang, Songping

    2016-09-01

    Biocatalyzed artificial photosynthesis systems provide a promising strategy to store solar energy in a great variety of chemicals. However, the lack of direct interface between the light-capturing components and the oxidoreductase generally hinders the trafficking of the chemicals and photo-excited electrons into the active center of the redox biocatalysts. To address this problem, a completely integrated artificial photosynthesis system for enhanced electronic energy-transfer efficacy is reported by combining co-axial electrospinning/electrospray and layer-by-layer (LbL) self-assembly. The biocatalysis part including multiple oxidoreductases and coenzymes NAD(H) was in situ encapsulated inside the lumen polyelectrolyte-doped hollow nanofibers or microcapsules fabricated via co-axial electrospinning/electrospray; while the precise and spatial arrangement of the photocatalysis part, including electron mediator and photosensitizer for photo-regeneration of the coenzyme, was achieved by ion-exchange interaction-driven LbL self-assembly. The feasibility and advantages of this integrated artificial photosynthesis system is fully demonstrated by the catalyzed cascade reduction of CO2 to methanol by three dehydrogenases (formate, formaldehyde, and alcohol dehydrogenases), incorporating the photo-regeneration of NADH under visible-light irradiation. Compared to solution-based systems, the methanol yield increases from 35.6% to 90.6% using the integrated artificial photosynthesis. This work provides a novel platform for the efficient and sustained production of a broad range of chemicals and fuels from sunlight.

  13. Integration of Artificial Photosynthesis System for Enhanced Electronic Energy-Transfer Efficacy: A Case Study for Solar-Energy Driven Bioconversion of Carbon Dioxide to Methanol.

    PubMed

    Ji, Xiaoyuan; Su, Zhiguo; Wang, Ping; Ma, Guanghui; Zhang, Songping

    2016-09-01

    Biocatalyzed artificial photosynthesis systems provide a promising strategy to store solar energy in a great variety of chemicals. However, the lack of direct interface between the light-capturing components and the oxidoreductase generally hinders the trafficking of the chemicals and photo-excited electrons into the active center of the redox biocatalysts. To address this problem, a completely integrated artificial photosynthesis system for enhanced electronic energy-transfer efficacy is reported by combining co-axial electrospinning/electrospray and layer-by-layer (LbL) self-assembly. The biocatalysis part including multiple oxidoreductases and coenzymes NAD(H) was in situ encapsulated inside the lumen polyelectrolyte-doped hollow nanofibers or microcapsules fabricated via co-axial electrospinning/electrospray; while the precise and spatial arrangement of the photocatalysis part, including electron mediator and photosensitizer for photo-regeneration of the coenzyme, was achieved by ion-exchange interaction-driven LbL self-assembly. The feasibility and advantages of this integrated artificial photosynthesis system is fully demonstrated by the catalyzed cascade reduction of CO2 to methanol by three dehydrogenases (formate, formaldehyde, and alcohol dehydrogenases), incorporating the photo-regeneration of NADH under visible-light irradiation. Compared to solution-based systems, the methanol yield increases from 35.6% to 90.6% using the integrated artificial photosynthesis. This work provides a novel platform for the efficient and sustained production of a broad range of chemicals and fuels from sunlight. PMID:27273818

  14. Computational Analysis of Intermolecular Coulombic Decay Effects in DNA nucleotide Photoionization

    NASA Astrophysics Data System (ADS)

    Vargas, E. L.; Robertson, J.; Andrianarijaona, V. M.

    2016-03-01

    Intermolecular Coulombic Decay (ICD) is the process of how electrons return to their original state after excitation and how this affects their immediate environment. In a previous research presentationwe had considered the hypothetical applications of Intermolecular Coulombic Decay on the adhesiveness of coding proteins within DNA molecules. This presentation is a continuation of the previous in that the results of our DFT-based computational calculations of the ionization potentials of nucleotides and their excitation energies will be presented, as well as how they influence their surroundings. Author would like to acknowledge the PUC Student Senate for financial assistance.

  15. Study of gelatin-agar intermolecular aggregates in the supernatant of its coacervate.

    PubMed

    Singh, S Santinath; Bohidar, H B; Bandyopadhyay, S

    2007-05-15

    Intermolecular interaction leading to formation of aggregates between gelatin, a polyampholyte, and agar, a polysaccharide was studied in the supernatant of the complex coacervate formed by these biopolymers. Electrophoresis, laser light scattering and viscometry data were used to determine the interaction and the physical structure of these intermolecular soluble complexes by modeling these to be prolate ellipsoids of revolution (rod-like structures with well defined axial ratio and Perrin's factor). Solution ionic strength was found to reduce the axial ratio of these complexes implying the presence of screened polarization-induced electrostatic interaction between the two biopolymers.

  16. Intermolecular potential functions and high resolution molecular spectroscopy of weakly bound complexes. Final progress report

    SciTech Connect

    Muenter, J.S.

    1997-04-01

    This report describes accomplishments over the past year in research supported by this grant. Two papers published in this period are briefly discussed. The general goal of the work is to consolidate the understanding of experimental results through a theoretical model of intermolecular potential energy surfaces. Progress in the experimental and theoretical phases of the program are presented and immediate goals outlined. The ability to construct analytic intermolecular potential functions that accurately predict the energy of interaction between small molecules will have great impact in many areas of chemistry, biochemistry, and biology.

  17. Addressable test matrix for measuring analog transfer characteristics of test elements used for integrated process control and device evaluation

    NASA Technical Reports Server (NTRS)

    Buehler, Martin G. (Inventor)

    1988-01-01

    A set of addressable test structures, each of which uses addressing schemes to access individual elements of the structure in a matrix, is used to test the quality of a wafer before integrated circuits produced thereon are diced, packaged and subjected to final testing. The electrical characteristic of each element is checked and compared to the electrical characteristic of all other like elements in the matrix. The effectiveness of the addressable test matrix is in readily analyzing the electrical characteristics of the test elements and in providing diagnostic information.

  18. Intermolecula transfer and elimination of molecular hydrogen in thermal reactions of unsaturated organic compounds

    SciTech Connect

    Suria, S.

    1995-02-10

    Two reactions which are important to coal liquefaction include intermolecular transfer and the elimination of two hydrogen atoms. We have designed several model reactions to probe the viability of several hydrogen transfer and elimination pathways. This report described studies on these reactions using organic model compounds.

  19. Accurate first principles model potentials for intermolecular interactions.

    PubMed

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

    2013-01-01

    The general effective fragment potential (EFP) method provides model potentials for any molecule that is derived from first principles, with no empirically fitted parameters. The EFP method has been interfaced with most currently used ab initio single-reference and multireference quantum mechanics (QM) methods, ranging from Hartree-Fock and coupled cluster theory to multireference perturbation theory. The most recent innovations in the EFP model have been to make the computationally expensive charge transfer term much more efficient and to interface the general EFP dispersion and exchange repulsion interactions with QM methods. Following a summary of the method and its implementation in generally available computer programs, these most recent new developments are discussed.

  20. A reduced-order integral formulation to account for the finite size effect of isotropic square panels using the transfer matrix method.

    PubMed

    Bonfiglio, Paolo; Pompoli, Francesco; Lionti, Riccardo

    2016-04-01

    The transfer matrix method is a well-established prediction tool for the simulation of sound transmission loss and the sound absorption coefficient of flat multilayer systems. Much research has been dedicated to enhancing the accuracy of the method by introducing a finite size effect of the structure to be simulated. The aim of this paper is to present a reduced-order integral formulation to predict radiation efficiency and radiation impedance for a panel with equal lateral dimensions. The results are presented and discussed for different materials in terms of radiation efficiency, sound transmission loss, and the sound absorption coefficient. Finally, the application of the proposed methodology for rectangular multilayer systems is also investigated and validated against experimental data. PMID:27106325

  1. The role of charge-transfer integral in determining and engineering the carrier mobilities of 9,10-di(2-naphthyl)anthracene compounds

    NASA Astrophysics Data System (ADS)

    Tse, S. C.; So, S. K.; Yeung, M. Y.; Lo, C. F.; Wen, S. W.; Chen, C. H.

    2006-05-01

    The charge transporting properties of t-butylated 9,10-di(2-naphthyl)anthracene (ADN) compounds have been investigated experimentally and computationally in relation to their molecular structures. The ADN compounds are found to be ambipolar with both electron and hole mobilities in the range of 1-4 × 10 -7 cm 2 V -1 s -1 (electric field 0.5-0.8 MV/cm). As the degree of t-butylation increases, the carrier mobility decreases progressively. The mobility reduction was examined by Marcus theory of reorganization energies. All ADN compounds possess similar reorganization energies of ˜0.3 eV. The reduction of carrier mobilities with increasing t-butylation can be attributed to a decrease in the charge-transfer integral or the wavefunction overlap.

  2. A reduced-order integral formulation to account for the finite size effect of isotropic square panels using the transfer matrix method.

    PubMed

    Bonfiglio, Paolo; Pompoli, Francesco; Lionti, Riccardo

    2016-04-01

    The transfer matrix method is a well-established prediction tool for the simulation of sound transmission loss and the sound absorption coefficient of flat multilayer systems. Much research has been dedicated to enhancing the accuracy of the method by introducing a finite size effect of the structure to be simulated. The aim of this paper is to present a reduced-order integral formulation to predict radiation efficiency and radiation impedance for a panel with equal lateral dimensions. The results are presented and discussed for different materials in terms of radiation efficiency, sound transmission loss, and the sound absorption coefficient. Finally, the application of the proposed methodology for rectangular multilayer systems is also investigated and validated against experimental data.

  3. Spectroscopic and computational studies of a Ru(II) terpyridine complex: the importance of weak intermolecular forces to photophysical properties.

    PubMed

    Garino, Claudio; Gobetto, Roberto; Nervi, Carlo; Salassa, Luca; Rosenberg, Edward; Ross, J B Alexander; Chu, Xi; Hardcastle, Kenneth I; Sabatini, Cristiana

    2007-10-15

    The complex [Ru(tpy)(CO)(2)TFA]+[PF(6)]- (where tpy = 2,2':6',2' '-terpyridine and TFA = CF(3)CO(2)-) (1) has been synthesized and fully characterized spectroscopically. The X-ray structure of the complex has been determined. The photopysical properties of the ruthenium complex and the free ligand tpy have been investigated at room temperature and at 77 K in acetonitrile solution and in the solid state. Their electronic spectra are highly influenced by intermolecular stacking interactions, both in solution and in the solid state. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed to characterize the electronic structure and the excited states of [Ru(tpy)(CO)(2)TFA]+[PF(6)]- and tpy. TDDFT calculations on three different conformations of free ligand have been performed as well. Absorption and emission spectra of tpy have been studied at different temperatures and concentrations in order to have a better understanding of this ruthenium derivative's properties. The absorption spectrum of 1 is characterized by metal-perturbed ligand-centered (LC) bands in the UV region. No metal-to-ligand charge transfer (MLCT) bands are observed in the visible for the complex. Only at high concentrations (10(-4) M) does a very weak band appear at 470 nm. At 77 K and low concentrations, solutions of 1 exhibit a major 3LC emission band centered at 468 nm (21.4 x 10(-3) cm(-1)). When the concentration of the complex is increased, an unstructured narrow emission at 603 nm (16.6 x 10(-3) cm(-1)), with a lifetime of 10 micros, dominates the emission spectrum in glassy acetonitrile. This emission originates from a pi-pi stacked dimeric (or oligomeric) species. TDDFT calculations performed on a tail-to-tail dimer structure, similar to that seen in the solid state, ascribe the transition to a triplet excited state, where intermolecular metal (d) --> ligand (pi*, polypyridine) charge transfer occurs. A good estimate of the transition energy is also

  4. How dangerous are phthalate plasticizers? Integrated approach to toxicity based on metabolism, electron transfer, reactive oxygen species and cell signaling.

    PubMed

    Kovacic, Peter

    2010-04-01

    Phthalate plasticizers are the most abundant man-made pollutants that have recently received wide-spread attention. There is uncertainty concerning the toxicity to humans. During the debate, scant attention has been paid to adverse effects at the molecular level which is the focus of this article. Most metabolic reports are concerned only with ester hydrolysis. In addition to that aspect, an important study deals with formation of catechol carboxylic acids which have the potential to redox cycle with the o-quinone counterparts. This electron transfer (ET) process is capable of generating reactive oxygen species (ROS) which are well known toxic agents at elevated levels. Substantial numbers of investigations find the presence of ROS leading to oxidative stress (OS) in living systems containing phthalates. Insults occur to various organs, including the reproductive system, pulmonary, central nervous system, immune system and liver. Toxic reactions are also reported involving inflammation, mitochondria and carcinogenicity. Generally, OS evidently plays a role. Of relevance are prior reviews which document extensive evidence for association of ET-ROS-OS with organ toxicity, and other deleterious reactions. In addition, cell signaling has been related to the physiological effects of phthalates. Various signaling processes participate together with involvement of ROS and association with biological effects. Suggestions for future work are offered.

  5. Control of volatile organic compounds indoors—Development of an integrated mass-transfer-based model and its application

    NASA Astrophysics Data System (ADS)

    Li, Feng; Niu, Jianlei

    Building envelopes are usually comprised of several different layers of building materials, which may alternatively act as VOC sources or sinks depending on their emission and sorption potentials and the indoor environmental conditions as well. In this research, a whole room IAQ model consisting of multi-phase emission/sorption model for wall materials and room volume mass balance model catering for practical ventilation schemes was developed. The interactions of VOC and building materials composing different building components can be modeled based on fundamental mass transfer theories. The effects of various construction materials and ventilation strategies on the emission characteristics were investigated. Results show that measures like pre-occupancy flush-out, lead-time ventilation, etc. have substantial impacts on indoor VOC concentration and the model can successfully handle different building scenarios. Although more rigorous validation, in particular more experimental verification, is needed, the proposed model has proven to be valuable in handling different building scenarios. It is useful in analyzing the levels of contaminant buildup that would occur during no ventilation period for intermittent ventilation situations and in determining the amount of outdoor air and the lead-time period required to flush out the contaminants prior to occupancy. It is likely to be a simple routine tool for building owners, designers and operators to attain acceptable indoor VOC concentration level.

  6. A new V-shaped organic fluorescent compound integrated with crystallization-induced emission enhancement and intramolecular charge transfer.

    PubMed

    Gu, Pei-Yang; Zhang, You-Hao; Liu, Gao-Yan; Ge, Jian-Feng; Xu, Qing-Feng; Zhang, Qichun; Lu, Jian-Mei

    2013-09-01

    The emission behavior of a new V-shaped organic fluorescent compound (p,p′-bis(2-aryl-1,3,4-oxadiazol-5-yl)diphenyl sulfone (OZA-SO)), consisting of diethylamino (donor) and sulfone (acceptor) units, has been studied in various polar solvents and with different morphologies. As expected, there is the gradual transition from the locally excited state to the intramolecular charge-transfer (ICT) state with the increasing solvent polarity. The photoluminescence intensity of OZA-SO initially decreases with a low water fraction (f(w)), owing to ICT effect, and then increases with a high f(w), owing to crystallization-induced emission enhancement. At the same time, the fluorescence lifetime of OZA-SO increases from 0.062 ns in dimethylformamide (DMF) to 5.80 ns in a solution containing 90 % water, and then to 7.49 ns in a solution containing 60 % water. Furthermore, the solid-state emission of OZA-SO can be tuned reversibly from green to yellow by fuming/grinding or fuming/heating owing to morphological changes. This color-switchable feature of OZA-SO may have potential applications in optical-recording and temperature-sensing materials.

  7. Evaluation of the heat transfer module (FAHT) of Failure Analysis Nonlinear Thermal And Structural Integrated Code (FANTASTIC)

    NASA Technical Reports Server (NTRS)

    Keyhani, Majid

    1989-01-01

    The heat transfer module of FANTASTIC Code (FAHT) is studied and evaluated to the extend possible during the ten weeks duration of this project. A brief background of the previous studies is given and the governing equations as modeled in FAHT are discussed. FAHT's capabilities and limitations based on these equations and its coding methodology are explained in detail. It is established that with improper choice of element size and time step FAHT's temperature field prediction at some nodes will be below the initial condition. The source of this unrealistic temperature prediction is identified and a procedure is proposed for avoiding this phenomenon. It is further shown that the proposed procedure will converge to an accurate prediction upon mesh refinement. Unfortunately due to lack of time FAHT's ability to accurately account for pyrolysis and surface ablation has not been verified. Therefore, at the present time it can be stated with confidence that FAHT can accurately predict the temperature field for a transient multi-dimensional, orthotropic material with directional dependence, variable property, with nonlinear boundary condition. Such a prediction will provide an upper limit for the temperature field in an ablating decomposing nozzle liner. The pore pressure field, however, will not be known.

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

    SciTech Connect

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

    2014-10-07

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

  9. Nutrient dynamics, transfer and retention along the aquatic continuum from land to ocean: towards integration of ecological and biogeochemical models

    NASA Astrophysics Data System (ADS)

    Bouwman, A. F.; Bierkens, M. F. P.; Griffioen, J.; Hefting, M. M.; Middelburg, J. J.; Middelkoop, H.; Slomp, C. P.

    2013-01-01

    In river basins, soils, groundwater, riparian zones and floodplains, streams, rivers, lakes and reservoirs act as successive filters in which the hydrology, ecology and biogeochemical processing are strongly coupled and together act to retain a significant fraction of the nutrients transported. This paper compares existing river ecology concepts with current approaches to describe river biogeochemistry, and assesses the value of these concepts and approaches for understanding the impacts of interacting global change disturbances on river biogeochemistry. Through merging perspectives, concepts, and modeling techniques, we propose integrated model approaches that encompass both aquatic and terrestrial components in heterogeneous landscapes. In this model framework, existing ecological and biogeochemical concepts are extended with a balanced approach for assessing nutrient and sediment delivery, on the one hand, and nutrient in-stream retention on the other hand.

  10. Nutrient dynamics, transfer and retention along the aquatic continuum from land to ocean: towards integration of ecological and biogeochemical models

    NASA Astrophysics Data System (ADS)

    Bouwman, A. F.; Bierkens, M. F. P.; Griffioen, J.; Hefting, M. M.; Middelburg, J. J.; Middelkoop, H.; Slomp, C. P.

    2012-07-01

    In river basins, soils, groundwater, riparian zones, streams, rivers, lakes and reservoirs act as successive filters in which the hydrology, ecology and biogeochemical processing are strongly coupled and together act to retain a significant fraction of the nutrients transported. This paper compares existing river ecology concepts with current approaches to describe river biogeochemistry, and assesses the value of these concepts and approaches for understanding the impacts of interacting global change disturbances on river biogeochemistry. Through merging perspectives, concepts, modeling techniques, we propose integrated model approaches that encompass both aquatic and terrestrial components in heterogeneous landscapes. In this model framework, existing ecological and biogeochemistry concepts are extended with a balanced approach for assessing nutrient and sediment delivery on the one hand, and nutrient in-stream retention on the other hand.

  11. Copper-catalyzed intermolecular chloroazidation of α,β-unsaturated amides.

    PubMed

    Chen, Long; Xing, Haotian; Zhang, Huaibin; Jiang, Zhong-Xing; Yang, Zhigang

    2016-08-21

    A highly practical copper-catalyzed intermolecular chloroazidation of α,β-unsaturated amides has been described, giving a series of azidochlorides in good-to-excellent yields. The stable azidoiodine(iii) reagent and SOCl2 were used as azide and chlorine sources, respectively. The synthetic applications of this protocol were also explored by a variety of synthetically useful transformations. PMID:27462802

  12. An Analysis of Two Textbooks on the Topic of Intermolecular Forces

    ERIC Educational Resources Information Center

    Tan, Daniel Kim Chwee; Seng, Chan Kim

    2004-01-01

    This paper describes the analysis of two commonly used high school (Grades 11 and 12) chemistry textbooks in Singapore to determine if the content presented in the topic of intermolecular forces is consistent with the concepts and propositional knowledge identified by the authors as essential for the learning and understanding of the topic…

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

    PubMed

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

    2013-08-14

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

  14. Intermolecular forces and nonbonded interactions: Superoperator nonlinear time-dependent density-functional-theory response approach

    SciTech Connect

    Harbola, Upendra; Mukamel, Shaul

    2004-11-01

    Electrostatic and dispersive interactions of polarizable molecules are expressed in terms of generalized (nonretarded) charge-density response functions of the isolated molecules, which in turn are expanded using the collective electronic oscillator (CEO) eigenmodes of linearized time-dependent density-functional theory. Closed expressions for the intermolecular energy are derived to sixth order in charge fluctuation amplitudes.

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

    PubMed Central

    Jarvis, Samuel Paul

    2015-01-01

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

  16. Salting Effects as an Illustration of the Relative Strength of Intermolecular Forces

    ERIC Educational Resources Information Center

    Person, Eric C.; Golden, Donnie R.; Royce, Brenda R.

    2010-01-01

    This quick and inexpensive demonstration of the salting of an alcohol out of an aqueous solution illustrates the impact of intermolecular forces on solubility using materials familiar to many students. Ammonium sulfate (fertilizer) is added to an aqueous 35% solution of isopropyl alcohol (rubbing alcohol and water) containing food coloring as a…

  17. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view

    SciTech Connect

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-28

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  18. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view.

    PubMed

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-28

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  19. The acid free asymmetric intermolecular α-alkylation of aldehydes in fluorinated alcohols.

    PubMed

    Xiao, Jian; Zhao, Kai; Loh, Teck-Peng

    2012-04-11

    The acid free asymmetric intermolecular α-alkylation of aldehydes with alcohols has been discovered using trifluoroethanol as solvent. This unprecedented system affords the enantioenriched functionalized primary alcohols (after NaBH(4) reduction) in high yields and good to excellent enantioselectivities with wide substrate scope in the absence of any acid additive.

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

    PubMed

    Jarvis, Samuel Paul

    2015-08-21

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

  1. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-01

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  2. Using Molecular Dynamics Simulation to Reinforce Student Understanding of Intermolecular Forces

    ERIC Educational Resources Information Center

    Burkholder, Phillip R.; Purser, Gordon H.; Cole, Renee S.

    2008-01-01

    Intermolecular forces play an important role in many aspects of chemistry ranging from inorganic to biological chemistry. These forces dictate molecular conformation, species aggregation (including self-assembly), trends in solubility and boiling points, adsorption characteristics, viscosity, phase changes, surface tension, capillary action, vapor…

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

    PubMed

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

    2016-09-16

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

  4. Energy Transfer Involving Diatomic Molecules.

    NASA Astrophysics Data System (ADS)

    Gibbons, John Paul

    A three-dimensional, Monte Carlo model for the calculation of vibrational energy relaxation and transfer rates for both diatomic-monatomic and diatomic-diatomic systems was developed, analyzed and implemented. Mediation by internal angular momentum was demonstrated to be important in these energy transfer processes. This was named the TLV mechanism for translation to vibration flow through changes in angular momentum. The equations for the component of vibrational energy change due to the TLV mechanism for the two extreme cases of very hard or very soft collisions were derived. Results of using these equations were compared with those obtained by direct integration of the differential equations of motion and in many cases were found to agree. This mechanism was incorporated into the model in order to achieve statistically significant results within reasonable computer running times. When this was done the variance of a result was frequently reduced by a factor of thirty to fifty or more with little or no increase in the computer times required. This made possible a meaningful study of the full three-dimensional diatomic-diatomic collisional processes and also permitted extension of the mono-diatomic model calculations to much lower temperatures than had been previously investigated. After this calculational procedure was developed for Ar - O(,2) collisions, it was also applied to He - O(,2) and to the near resonant vibration energy exchange process:. CO ((nu)=0)+N(,2)((nu)=1)(--->)CO((nu)=1)+N(,2)((nu)=0). These three processes were investigated at several temperatures between room temperature and 4000K. Exponential repulsive intermolecular potentials were used. The values for the coefficients and characteristic lengths for these potentials were obtained from independent sources both experimental and theoretical. In general, the results, when compared to experiment, are very consistent relative to their dependence on the potential parameters. In every case for all

  5. Time dependence of donor-acceptor electron transfer and back transfer in solid solution

    NASA Astrophysics Data System (ADS)

    Lin, Y.; Dorfman, R. C.; Fayer, M. D.

    1989-01-01

    Electron transfer from an optically excited donor to randomly distributed acceptors followed by electron back transfer is treated theoretically for donors and acceptors in a rigid solution. The forward electron transfer process is described in terms of the excited state population probabilityPex(t) of the donor molecules, while the electron back transfer from the radical anion to the radical cation is characterized by Pct(t), the donor cation state population probability. Exact expressions for the ensemble averages and are derived. Numerical calulations are presented for the cation probabilities, the average cation-anion separation distance , and the average cation existence time <τ(R)>, using parameters which characterize the forward and back transfer distance dependent rates. Relationships among , and the intermolecular interaction parameters provide detailed insights into the distance and time dependence of the flow of electron probability in an ensemble of donors and acceptors. The theoretical expressions can be used to calculate experimental observables. In particular, picosecond transient grating experiments are analyzed, and it is shown that by combining grating experiments (or other ground state recovery experiments) with fluorescence experiments it is possible to obtain the intermolecular interaction parameters for both forward and back transfer and a detailed description of the dynamics. The calculations presented here for rigid solutions are the precursor to the inclusion of diffusive motion of donors and acceptors to describe the dynamics of coupled electron transfer and back transfer in liquid solutions.

  6. Impact of an integrated science and reading intervention (INSCIREAD) on bilingual students' misconceptions, reading comprehension, and transferability of strategies

    NASA Astrophysics Data System (ADS)

    Martinez, Patricia

    This thesis describes a research study that resulted in an instructional model directed at helping fourth grade diverse students improve their science knowledge, their reading comprehension, their awareness of the relationship between science and reading, and their ability to transfer strategies. The focus of the instructional model emerged from the intersection of constructs in science and reading literacy; the model identifies cognitive strategies that can be used in science and reading, and inquiry-based instruction related to the science content read by participants. The intervention is termed INSCIREAD (Instruction in Science and Reading). The GoInquire web-based system (2006) was used to develop students' content knowledge in slow landform change. Seventy-eight students participated in the study. The treatment group comprised 49 students without disabilities and 8 students with disabilities. The control group comprised 21 students without disabilities. The design of the study is a combination of a mixed-methods quasi-experimental design (Study 1), and a single subject design with groups as the unit of analysis (Study 2). The results from the quantitative measures demonstrated that the text recall data analysis from Study 1 yielded near significant statistical levels when comparing the performance of students without disabilities in the treatment group to that of the control group. Visual analyses of the results from the text recall data from Study 2 showed at least minimal change in all groups. The results of the data analysis of the level of the generated questions show there was a statistically significant increase in the scores students without disabilities obtained in the questions they generated from the pre to the posttest. The analyses conducted to detect incongruities, to summarize and rate importance, and to determine the number of propositions on a science and reading concept map data showed a statistically significant difference between students

  7. α- And β Pahases of oxalic acid, H 2C 2O 4: Vibrational spectra, normal-coordinate calculations, and intermolecular forces

    NASA Astrophysics Data System (ADS)

    De Villepin, J.; Novak, A.; Bougeard, D.

    1982-12-01

    Infrared (4000-30 cm -1) and Raman (4000-0 cm -) spectra of single crystals of α-oxalic acid (Pcab, Z=4) have been investigated at 100 and 300 K. A complete assignment of all modes in terms of symmetry species and to internal, librational, translational, and hydrogen bond motions is given. In order to interpret the spectra and to determine the crystal field, several normal-coordinate calculations (free molecule, rigid body model, unit cell as a supermolecule) have been carried out. The calculations are in good agreement with the experimental results and show the importance of different intermolecular forces: OH … O hydrogen bonds and very short C … O interactions lead to both unusually strong correlation field splitting and high lattice frequencies while quadrupole-quadrupole and CO dipole-dipole interactions influence lattice and some internal vibrations, respectively. The intermolecular potentials obtained for α-oxalic acid are transferable to the β form having a different crystal structure (P2 1/c, Z = 2) and stronger hydrogen bonds.

  8. Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds.

    PubMed

    Hestand, Nicholas J; Kazantsev, Roman V; Weingarten, Adam S; Palmer, Liam C; Stupp, Samuel I; Spano, Frank C

    2016-09-14

    Coupling among chromophores in molecular assemblies is responsible for phenomena such as resonant energy transfer and intermolecular charge transfer. These processes are central to the fields of organic photovoltaics and photocatalysis, where it is necessary to funnel energy or charge to specific regions within the system. As such, a fundamental understanding of these transport processes is essential for developing new materials for photovoltaic and photocatalytic applications. Recently, photocatalytic systems based on photosensitizing perylene monomimide (PMI) chromophore amphiphiles were found to show variation in hydrogen gas (H2) production as a function of nanostructure crystallinity. The 2D crystalline systems form in aqueous electrolyte solution, which provides a high dielectric environment where the Coulomb potential between charges is mitigated. This results in relatively weakly bound excitons that are ideal for reducing protons. In order to understand how variations in crystalline structure affect H2 generation, two representative PMI systems are investigated theoretically using a modified Holstein Hamiltonian. The Hamiltonian includes both molecular Frenkel excitations (FE) and charge-transfer excitations (CTE) coupled nonadiabatically to local intramolecular vibrations. Signatures of FE/CTE mixing and the extent of electron/hole separation are identified in the optical absorption spectrum and are found to correlate strongly to the observed H2 production rates. The absorption spectral signatures are found to sensitively depend on the relative phase between the electron and hole transfer integrals, as well as the diabatic energy difference between the Frenkel and CT exciton bands. Our analysis provides design rules for artificial photosynthetic systems based on organic chromophore arrays. PMID:27589150

  9. Intermolecular interactions in ternary solutions of some 1,2,4-triazolium ylids studied by spectral means

    NASA Astrophysics Data System (ADS)

    Closca, Valentina; Melniciuc-Puica, Nicoleta; Dorohoi, Dana Ortansa; Benchea, A. C.

    2014-08-01

    Triazolium ylids are dipolar molecules with separated charges in their ground electronic state; the positive charge is located on one Nitrogen atom belonging to the heterocycle and the negative charge is located near the ylid carbanion. The intramolecular charge transfer from the carbanion to heterocycle gives a visible electronic absorption band, very sensitive to the solvent nature. Its position in the wavenumber scale offers information about the intermolecular interactions in which the ylid molecules are engaged. The spectral study revealed the presence of both universal and specific interactions in solutions of 1,2,4-triazolium ylids with protic solvents. By choosing adequate binary solvents, the contribution of the specific interaction of the weak hydrogen bond between the -OH atomic group of the protic solvents and the ylid carbanion can be estimated. Ternary solutions of the studied ylids achieved with Methanol +Benzene, Water + Ethanol and 1,3 Propanediol + Dimethyl formamide binary solvents are analyzed from spectral point of view and the difference between the potential energies in molecular pairs of the types: 1,2,4-triazolium ylid-protic solvent and 1,2,4-triazolium ylid-non protic were estimated on the basis of the statistic cell model of ternary solutions.

  10. Rotational Energy Transfer in N2

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.

    1994-01-01

    Using the N2-N2 intermolecular potential of van der Avoird et al. rotational energy transfer cross sections have been calculated using both the coupled state (CS) and infinite order sudden (IOS) approximations. The rotational energy transfer rate constants at 300 K, calculated in the CS approximation, are in reasonable agreement with the measurements of Sitz and Farrow. The IOS approximation qualitatively reproduces the dependence of the rate constants on the rotational quantum numbers, but consistently overestimates their magnitudes. The treatment of exchange symmetry will be discussed.

  11. Intramolecular and intermolecular hydrogen-bonding effects on photophysical properties of 2'-aminoacetophenone and its derivatives in solution.

    PubMed

    Shimada, Hirofumi; Nakamura, Akihito; Yoshihara, Toshitada; Tobita, Seiji

    2005-04-01

    Effects of intra- and intermolecular hydrogen-bonds on the photophysical properties of 2'-aminoacetophenone derivatives (X-C6H4-COCH3) having a substituted amino group (X) with different hydrogen-bonding ability to the carbonyl oxygen (X: NH2(AAP), NHCH3(MAAP), N(CH3)2(DMAAP), NHCOCH3(AAAP), NHCOCF3(TFAAP)) are investigated by means of steady-state and time-resolved fluorescence spectroscopy and time-resolved thermal lensing. Based on the photophysical parameters obtained in aprotic solvents with different polarity and protic solvents with different hydrogen-bonding ability, the characteristic photophysical behavior of the 2'-aminoacetophenone derivatives is discussed in terms of hydrogen-bonding and n,pi*-pi,pi* vibronic coupling. The dominant deactivation process of AAP and MAAP in nonpolar aprotic solvents is the extremely fast internal conversion (k(ic)= 1.0 x 10(11) s(-1) for AAP and 3.9 x 10(10) s(-1) for MAAP in n-hexane). The internal conversion rates of both compounds decrease markedly with increasing solvent polarity, suggesting that vibronic interactions between close-lying S1(pi,pi*) and S2(n,pi*) states lead to the large increase in the non-radiative decay rate of the lowest excited singlet state. It is also suggested that for MAAP, which has a stronger hydrogen-bond as compared to AAP, an intramolecular hydrogen-bonding induced deactivation is involved in the dissipation of the S1 state. For DMAAP, which cannot possess an intramolecular hydrogen-bond, the primary relaxation mechanism of the S1 state in nonpolar aprotic solvents is the intersystem crossing to the triplet state, whereas in protic solvents very efficient internal conversion due to intermolecular hydrogen-bonding is induced. In contrast, the fluorescence spectra of AAAP and TFAAP, which have an amino group with a much stronger hydrogen-bonding ability, give strongly Stokes-shifted fluorescence, indicating that these compounds undergo excited-state intramolecular proton transfer reaction

  12. Car-Parrinello and path integral molecular dynamics study of the hydrogen bond in the chloroacetic acid dimer system

    NASA Astrophysics Data System (ADS)

    Durlak, Piotr; Morrison, Carole A.; Middlemiss, Derek S.; Latajka, Zdzislaw

    2007-08-01

    We have studied the double proton transfer (DPT) reaction in the cyclic dimer of chloroacetic acid using both classical and path integral Car-Parrinello molecular dynamics. We also attempt to quantify the errors in the potential energy surface that arise from the use of a pure density functional. In the classical dynamics a clear reaction mechanism can be identified, where asynchronized DPT arises due to coupling between the O-H stretching oscillator and several low energy intermolecular vibrational modes. This mechanism is considerably altered when quantum tunneling is permitted in the simulation. The introduction of path integrals leads to considerable changes in the thermally averaged molecular geometry, leading to shorter and more centered hydrogen bond linkages.

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

    PubMed

    Xia, Wenjie; Keten, Sinan

    2013-10-15

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

  14. Changes of microstructure characteristics and intermolecular interactions of preserved egg white gel during pickling.

    PubMed

    Zhao, Yan; Chen, Zhangyi; Li, Jianke; Xu, Mingsheng; Shao, Yaoyao; Tu, Yonggang

    2016-07-15

    Changes in gel microstructure characteristics and in intermolecular interactions of preserved egg whites during pickling were investigated. Spin-spin relaxation times of preserved egg whites significantly decreased in the first 8 days and remained unchanged after the 16th day. SEM images revealed a three-dimensional gel network, interwoven with a loose linear fibrous mesh structure. The protein gel mesh structure became more regular, smaller, and compacted with pickling time. Free sulfhydryl contents in the egg whites increased significantly, while total sulfhydryl contents dramatically decreased during pickling. The primary intermolecular forces in the preserved egg white gels were ionic and disulfide bonds. Secondary forces included hydrophobic interaction and relatively few hydrogen bonds. During the first 8 days, the proportion of ionic bonds sharply decreased, and that of disulfide bonds increased over the first 24 days.

  15. Cation-π interactions: accurate intermolecular potential from symmetry-adapted perturbation theory.

    PubMed

    Ansorg, Kay; Tafipolsky, Maxim; Engels, Bernd

    2013-09-01

    Symmetry-adapted perturbation theory (SAPT) is used to decompose the total intermolecular interaction energy between the ammonium cation and a benzene molecule into four physically motivated individual contributions: electrostatics, exchange, dispersion, and induction. Based on this rigorous decomposition, it is shown unambiguously that both the electrostatic and the induction energy components contribute almost equally to the attractive forces stabilizing the dimer with a nonnegligible contribution coming from the dispersion term. A polarizable potential model for the interaction of ammonium cation with benzene is parametrized by fitting these four energy components separately using the functional forms of the AMOEBA force field augmented with the missing charge penetration energy term calculated as a sum over pairwise electrostatic energies between spherical atoms. It is shown that the proposed model is able to produce accurate intermolecular interaction energies as compared to ab initio results, thus avoiding error compensation to a large extent.

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

    SciTech Connect

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

    2014-05-28

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

  17. Charge dependence of solvent-mediated intermolecular Coster-Kronig decay dynamics of aqueous ions.

    PubMed

    Ohrwall, G; Ottosson, N; Pokapanich, W; Legendre, S; Svensson, S; Björneholm, O

    2010-12-30

    The 2s and 2p photoelectron spectra have been measured for Na(+), Mg(2+), and Al(3+) ions in aqueous solution. In all cases, the 2s lines are significantly broader than the 2p features, which is attributed to a shorter lifetime of the respective 2s hole. Since intraionic Coster-Kronig decay channels from the (2s)(-1) state are closed for free Na(+), Mg(2+), and Al(3+) ions, this is evidence for an intermolecular Coster-Kronig-like process, reminiscent of intermolecular Coulombic decay (ICD), involving neighboring water solvent molecules. The observed 2s Lorentzian line widths correspond to lifetimes of the (2s)(-1) state of 3.1, 1.5, and 0.98 fs for the solvated Na, Mg, and Al ions, respectively.

  18. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    NASA Astrophysics Data System (ADS)

    Chavda, Bhavin R.; Gandhi, Sahaj A.; Dubey, Rahul P.; Patel, Urmila H.; Barot, Vijay M.

    2016-05-01

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb -London -Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

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

    NASA Astrophysics Data System (ADS)

    Chaudhari, Sachin Rama; Suryaprakash, N.

    2012-05-01

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

  20. Changes of microstructure characteristics and intermolecular interactions of preserved egg white gel during pickling.

    PubMed

    Zhao, Yan; Chen, Zhangyi; Li, Jianke; Xu, Mingsheng; Shao, Yaoyao; Tu, Yonggang

    2016-07-15

    Changes in gel microstructure characteristics and in intermolecular interactions of preserved egg whites during pickling were investigated. Spin-spin relaxation times of preserved egg whites significantly decreased in the first 8 days and remained unchanged after the 16th day. SEM images revealed a three-dimensional gel network, interwoven with a loose linear fibrous mesh structure. The protein gel mesh structure became more regular, smaller, and compacted with pickling time. Free sulfhydryl contents in the egg whites increased significantly, while total sulfhydryl contents dramatically decreased during pickling. The primary intermolecular forces in the preserved egg white gels were ionic and disulfide bonds. Secondary forces included hydrophobic interaction and relatively few hydrogen bonds. During the first 8 days, the proportion of ionic bonds sharply decreased, and that of disulfide bonds increased over the first 24 days. PMID:26948621

  1. Optical Activity Enhanced by Strong Inter-molecular Coupling in Planar Chiral Metamaterials

    PubMed Central

    Kim, Teun-Teun; Oh, Sang Soon; Park, Hyun-Sung; Zhao, Rongkuo; Kim, Seong-Han; Choi, Wonjune; Min, Bumki; Hess, Ortwin

    2014-01-01

    The polarization of light can be rotated in materials with an absence of molecular or structural mirror symmetry. While this rotating ability is normally rather weak in naturally occurring chiral materials, artificial chiral metamaterials have demonstrated extraordinary rotational ability by engineering intra-molecular couplings. However, while in general, chiral metamaterials can exhibit strong rotatory power at or around resonances, they convert linearly polarized waves into elliptically polarized ones. Here, we demonstrate that strong inter-molecular coupling through a small gap between adjacent chiral metamolecules can lead to a broadband enhanced rotating ability with pure rotation of linearly polarized electromagnetic waves. Strong inter-molecular coupling leads to nearly identical behaviour in magnitude, but engenders substantial difference in phase between transmitted left and right-handed waves. PMID:25209452

  2. S- to N-Palmitoyl Transfer During Proteomic Sample Preparation

    NASA Astrophysics Data System (ADS)

    Ji, Yuhuan; Bachschmid, Markus M.; Costello, Catherine E.; Lin, Cheng

    2016-04-01

    N-palmitoylation has been reported in a number of proteins and suggested to play an important role in protein localization and functions. However, it remains unclear whether N-palmitoylation is a direct enzyme-catalyzed process, or results from intramolecular S- to N-palmitoyl transfer. Here, using the S-palmitoyl peptide standard, GCpalmLGNAK, as the model system, we observed palmitoyl migration from the cysteine residue to either the peptide N-terminus or the lysine side chain during incubation in both neutral and slightly basic buffers commonly used in proteomic sample preparation. Palmitoyl transfer can take place either intra- or inter-molecularly, with the peptide N-terminus being the preferred migration site, presumably because of its lower basicity. The extent of intramolecular palmitoyl migration was low in the system studied, as it required the formation of an entropically unfavored macrocycle intermediate. Intermolecular palmitoyl transfer, however, remained a tangible problem, and may lead to erroneous reporting of in vivo N-palmitoylation. It was found that addition of the MS-compatible detergent RapiGest could significantly inhibit intermolecular palmitoyl transfer, as well as thioester hydrolysis and DTT-induced thioester cleavage. Finally, palmitoyl transfer from the cysteine residue to the peptide N-terminus can also occur in the gas phase, during collision-induced dissociation, and result in false identification of N-palmitoylation. Therefore, one must be careful with both sample preparation and interpretation of tandem mass spectra in the study of N-palmitoylation.

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

    PubMed

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

    2016-09-16

    The intermolecular direct C-H alkylation of aniline derivatives with α-bromo ketones to build a quaternary carbon center was reported with a visible-light catalysis procedure. The reaction covers a variety of functional groups with good to excellent yields. A regioselectivity favoring the ortho position for the amine group was observed and investigated with Fukui indices and spectral methods. PMID:27571116

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  5. Estimation of Some Parameters from Morse-Morse-Spline-Van Der Waals Intermolecular Potential

    SciTech Connect

    Coroiu, I.

    2007-04-23

    Some parameters such as transport cross-sections and isotopic thermal diffusion factor have been calculated from an improved intermolecular potential, Morse-Morse-Spline-van der Waals (MMSV) potential proposed by R.A. Aziz et al. The treatment was completely classical and no corrections for quantum effects were made. The results would be employed for isotope separations of different spherical and quasi-spherical molecules.

  6. Enantioselective Intermolecular Cyclopropanations for the Synthesis of Chiral Pyrimidine Carbocyclic Nucleosides.

    PubMed

    Xie, Ming-Sheng; Zhou, Peng; Niu, Hong-Ying; Qu, Gui-Rong; Guo, Hai-Ming

    2016-09-01

    A direct route to chiral cyclopropylpyrimidine carbocyclic nucleoside analogues has been reported via highly enantioselective intermolecular cyclopropanation reactions of N1-vinylpyrimidines with α-diazoesters. With chiral ruthenium(II)-phenyloxazoline complex (2 mol %) as the catalyst, cyclopropyl pyrimidine nucleoside analogues could be obtained in good yields (71-96% yields) with high levels of diastereo- and enantioselectivities (10:1 to >20:1 dr and 96-99% ee) in 1 min. PMID:27526779

  7. Cupric-Superoxo Mediated Inter-Molecular C-H Activation Chemistry

    PubMed Central

    Peterson, Ryan L.; Himes, Richard A.; Kotani, Hiroaki; Suenobu, Tomoyoshi; Tian, Li; Siegler, Maxime A.; Solomon, Edward I.; Fukuzumi, Shunichi; Karlin, Kenneth D.

    2011-01-01

    A new cupric-superoxo complex [LCuII(O2•−)]+, which possesses particularly strong O–O and Cu–O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicate a first-order dependence on both the Cu-complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases. PMID:21265534

  8. Copper-catalyzed regio- and stereoselective intermolecular three-component oxyarylation of allenes.

    PubMed

    Itoh, Taisuke; Shimizu, Yohei; Kanai, Motomu

    2014-05-16

    A copper(II)-catalyzed intermolecular three-component oxyarylation of allenes using arylboronic acids as a carbon source and TEMPO as an oxygen source is described. The reaction proceeded under mild conditions with high regio- and stereoselectivity and functional group tolerance. A plausible reaction mechanism is proposed, involving carbocupration of allenes, homolysis of the intervening allylcopper(II), and a radical TEMPO trap. PMID:24766635

  9. Metal-free intermolecular formal cycloadditions enable an orthogonal access to nitrogen heterocycles

    PubMed Central

    Xie, Lan-Gui; Niyomchon, Supaporn; Mota, Antonio J.; González, Leticia; Maulide, Nuno

    2016-01-01

    Nitrogen-containing heteroaromatic cores are ubiquitous building blocks in organic chemistry. Herein, we present a family of metal-free intermolecular formal cycloaddition reactions that enable highly selective and orthogonal access to isoquinolines and pyrimidines at will. Applications of the products are complemented by a density functional theory mechanistic analysis that pinpoints the crucial factors responsible for the selectivity observed, including stoichiometry and the nature of the heteroalkyne. PMID:26975182

  10. Blind test of density-functional-based methods on intermolecular interaction energies

    NASA Astrophysics Data System (ADS)

    Taylor, DeCarlos E.; Ángyán, János G.; Galli, Giulia; Zhang, Cui; Gygi, Francois; Hirao, Kimihiko; Song, Jong Won; Rahul, Kar; Anatole von Lilienfeld, O.; Podeszwa, Rafał; Bulik, Ireneusz W.; Henderson, Thomas M.; Scuseria, Gustavo E.; Toulouse, Julien; Peverati, Roberto; Truhlar, Donald G.; Szalewicz, Krzysztof

    2016-09-01

    In the past decade, a number of approaches have been developed to fix the failure of (semi)local density-functional theory (DFT) in describing intermolecular interactions. The performance of several such approaches with respect to highly accurate benchmarks is compared here on a set of separation-dependent interaction energies for ten dimers. Since the benchmarks were unknown before the DFT-based results were collected, this comparison constitutes a blind test of these methods.

  11. Fully Integrated On-Chip Coil in 0.13 μm CMOS for Wireless Power Transfer Through Biological Media.

    PubMed

    Zargham, Meysam; Gulak, P Glenn

    2015-04-01

    Delivering milliwatts of wireless power at centimeter distances is advantageous to many existing and emerging biomedical applications. It is highly desirable to fully integrate the receiver on a single chip in standard CMOS with no additional post-processing steps or external components. This paper presents a 2 × 2.18 mm(2) on-chip wireless power transfer (WPT) receiver (Rx) coil fabricated in 0.13 μm CMOS. The WPT system utilizes a 14.5 × 14.5 mm(2) transmitter (Tx) coil that is fabricated on a standard FR4 substrate. The on-chip power harvester demonstrates a peak WPT efficiency of -18.47 dB , -20.96 dB and -20.15 dB at 10 mm of separation through air, bovine muscle and 0.2 molar NaCl, respectively. The achieved efficiency enables the delivery of milliwatts of power to application circuits while staying below safe power density and electromagnetic (EM) exposure limits. PMID:25099630

  12. Molecular dynamics study of free energy of transfer of alcohol and amine from water phase to the micelle by thermodynamic integration method

    NASA Astrophysics Data System (ADS)

    Fujimoto, K.; Yoshii, N.; Okazaki, S.

    2012-09-01

    Free energy of transfer of methylamine, octylamine, methanol, and octanol from water phase to sodium dodecyl sulfate (SDS) micelle has been calculated using thermodynamic integration method combined with molecular dynamics calculations. Together with the results for alkanes obtained in our previous study [K. Fujimoto, N. Yoshii, and S. Okazaki, J. Chem. Phys. 133, 074511 (2010)], 10.1063/1.3469772, the effect of polar group on the partition of hydrophilic solutes between water phase and the micelle has been investigated in detail at a molecular level. The calculations showed that the molecules with octyl group are more stable in the SDS micelle than in the water phase due to their hydrophobicity of long alkyl chain. In contrast, methanol and methylamine are stable in the water phase as well as in the micelle because of their high hydrophilicity. The spatial distribution of methylamine, octylamine, methanol, and octanol has also been evaluated as a function of the distance, R, from the center of mass of SDS micelle to the solutes. The distribution shows that the methylamine molecule is adsorbed on the SDS micelle surface, while the methanol molecule is delocalized among the whole system, i.e., in the water phase, on the surface of the micelle, and in the hydrophobic core of the micelle. The octylamine and octanol molecules are solubilized in the SDS micelle with palisade layer structure and are not found in the water phase.

  13. Evaluating the integrity of the reinforced concrete structure repaired by epoxy injection using simulated transfer function of impact-echo response

    SciTech Connect

    Cheng, Chia-Chi; Yu, Chih-peng; Wu, Jiunn-Hong; Hsu, Keng-Tsan; Ke, Ying-Tsu

    2014-02-18

    Cracks and honeycombs are often found inside reinforced concrete (RC) structure caused by excessive external force, or improper casting of concrete. The repairing method usually involves epoxy injection. The impact-echo method, which is a sensitive for detecting of the interior voids, may not be applicable to assess the integrity of the repaired member as both air and epoxy are less in acoustic impedances. In this study, the repaired RC structure was evaluated by the simulated transfer function of the IE displacement waveform where the R-wave displacement waveform is used as a base of a simulated force-time function. The effect of different thickness of the epoxy layer to the amplitude corresponding to the interface is studied by testing on specimen containing repaired naturally delaminated cracks with crack widths about 1 mm, 3 mm and 5 mm. The impact-echo responses were compared with the drilling cores at the test positions. The results showed the cracks were not fully filled with epoxy when the peak amplitude corresponding to the interface dropped less than 20%. The peak corresponding to the thicker epoxy layer tends to be larger in amplitude. A field study was also performed on a column damaged by earthquake before and after repairing.

  14. Analysis and calculation by integral methods of laminar compressible boundary-layer with heat transfer and with and without pressure gradient

    NASA Technical Reports Server (NTRS)

    Morduchow, Morris

    1955-01-01

    A survey of integral methods in laminar-boundary-layer analysis is first given. A simple and sufficiently accurate method for practical purposes of calculating the properties (including stability) of the laminar compressible boundary layer in an axial pressure gradient with heat transfer at the wall is presented. For flow over a flat plate, the method is applicable for an arbitrarily prescribed distribution of temperature along the surface and for any given constant Prandtl number close to unity. For flow in a pressure gradient, the method is based on a Prandtl number of unity and a uniform wall temperature. A simple and accurate method of determining the separation point in a compressible flow with an adverse pressure gradient over a surface at a given uniform wall temperature is developed. The analysis is based on an extension of the Karman-Pohlhausen method to the momentum and the thermal energy equations in conjunction with fourth- and especially higher degree velocity and stagnation-enthalpy profiles.

  15. Stereodynamics in the Collisional Autoionization of Water, Ammonia, and Hydrogen Sulfide with Metastable Rare Gas Atoms: Competition Between Intermolecular Halogen and Hydrogen Bonds.

    PubMed

    Falcinelli, Stefano; Bartocci, Alessio; Cavalli, Simonetta; Pirani, Fernando; Vecchiocattivi, Franco

    2016-01-11

    Recent experiments on the title subject, performed with a high-resolution crossed-beam apparatus, have provided the total ionization cross sections as a function of the collision energy between noble gas atoms, electronically excited in their metastable states (Ng*), and H2 O, H2 S, and NH3 reagents, as well as the emitted electron energy spectra. This paper presents a rationalization of all the experimental findings in a unifying picture to cast light on the basic chemical properties of Ng* under conditions of great relevance both from a fundamental and from an applied point of view. The importance of this investigation is that it isolates the selective role of the intermolecular halogen and hydrogen bonds, to assess their anisotropic effects on the stereodynamics of the promoted ionization reactions, and to model energy transfer and reactivity in systems of applied interest, such as planetary atmospheres, plasmas, lasers, and flames.

  16. Inelastic x-ray scattering of dense solid oxygen: Evidence for intermolecular bonding

    SciTech Connect

    Meng, Yue; Eng, Peter J.; Tse, John S.; Shaw, Dawn M.; Hu, Michael Y.; Shu, Jinfu; Gramsch, Stephen A.; Kao, Chichang; Hemley, Russell J.; Mao, Ho-kwang

    2008-08-14

    The detailing of the intermolecular interactions in dense solid oxygen is essential for an understanding of the rich polymorphism and remarkable properties of this element at high pressure. Synchrotron inelastic x-ray scattering measurements of oxygen K-edge excitations to 38 GPa reveal changes in electronic structure and bonding on compression of the molecular solid. The measurements show that O{sub 2} molecules interact predominantly through the half-filled 1{pi}{sub g}* orbital <10 GPa. Enhanced intermolecular interactions develop because of increasing overlap of the 1{pi}{sub g}* orbital in the low-pressure phases, leading to electron delocalization and ultimately intermolecular bonding between O{sub 2} molecules at the transition to the {epsilon}-phase. The {epsilon}-phase, which consists of (O{sub 2}){sub 4} clusters, displays the bonding characteristics of a closed-shell system. Increasing interactions between (O{sub 2}){sub 4} clusters develop upon compression of the {epsilon}-phase, and provide a potential mechanism for intercluster bonding in still higher-pressure phases.

  17. Intermolecular interactions in multi-component crystals of acridinone/thioacridinone derivatives: Structural and energetics investigations

    NASA Astrophysics Data System (ADS)

    Wera, Michał; Storoniak, Piotr; Trzybiński, Damian; Zadykowicz, Beata

    2016-12-01

    A single crystal X-ray analysis of two multi-component crystals consisting of an acridinone/thioacridinone moiety and a solvent moiety - water and ammonia (1 and 2), respectively, was carried out to determine the crystal structures of obtained crystals. A theoretical approach was undertaken - using the DFT method, lattice energies calculations and Hirshfeld surfaces (HS) - to qualitatively and quantitatively assess the intermolecular interactions within the crystal. HS analysis was showed that the H⋯H, C⋯H/H⋯C and C⋯C contacts for both structures (altogether 81.6% of total Hirshfeld surface area for 1 and 79.3% for 2) and the O⋯H/H⋯O (14.3%) for 1 and the S⋯H/H⋯S (15.2%) contacts for 2 were the characteristic intermolecular contacts in the related crystal structures. Using a computational methods were confirmed that the main contribution to the stabilization of the crystal lattice of compound 1 comes from the Coulombic interactions, whereas in compound 2 electrostatic and van der Waals appear to have similar contribution to the crystal lattice energy. Theoretical calculations of the investigated compounds have also allowed to determine the energy of a single specific intermolecular interaction.

  18. Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

    PubMed

    Beauchamp, Guy

    2008-10-23

    This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

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

    NASA Astrophysics Data System (ADS)

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

    1994-11-01

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

  20. Human DNA ligase III bridges two DNA ends to promote specific intermolecular DNA end joining

    PubMed Central

    Kukshal, Vandna; Kim, In-Kwon; Hura, Gregory L.; Tomkinson, Alan E.; Tainer, John A.; Ellenberger, Tom

    2015-01-01

    Mammalian DNA ligase III (LigIII) functions in both nuclear and mitochondrial DNA metabolism. In the nucleus, LigIII has functional redundancy with DNA ligase I whereas LigIII is the only mitochondrial DNA ligase and is essential for the survival of cells dependent upon oxidative respiration. The unique LigIII zinc finger (ZnF) domain is not required for catalytic activity but senses DNA strand breaks and stimulates intermolecular ligation of two DNAs by an unknown mechanism. Consistent with this activity, LigIII acts in an alternative pathway of DNA double strand break repair that buttresses canonical non-homologous end joining (NHEJ) and is manifest in NHEJ-defective cancer cells, but how LigIII acts in joining intermolecular DNA ends versus nick ligation is unclear. To investigate how LigIII efficiently joins two DNAs, we developed a real-time, fluorescence-based assay of DNA bridging suitable for high-throughput screening. On a nicked duplex DNA substrate, the results reveal binding competition between the ZnF and the oligonucleotide/oligosaccharide-binding domain, one of three domains constituting the LigIII catalytic core. In contrast, these domains collaborate and are essential for formation of a DNA-bridging intermediate by adenylated LigIII that positions a pair of blunt-ended duplex DNAs for efficient and specific intermolecular ligation. PMID:26130724

  1. Transfer and partitioning of energy and mass through seafloor hydrothermal systems: comparative studies at the Ridge2000 Integrated Study Sites (ISS) (Invited)

    NASA Astrophysics Data System (ADS)

    Tivey, M. K.

    2010-12-01

    Seafloor hydrothermal systems are major players in the transfer of mass and energy from the mantle and crust to the ocean and biosphere. Over the past thirty years, much has been learned about this transfer to the ocean, but considerably less is known about the transfer to the biosphere. Study of hydrothermal systems in a diverse range of geologic settings has shown relationships between spreading rate and hydrothermal heat flux, substrate composition (including rock geochemistry, presence/absence of sediment) and hydrothermal fluid composition, and magmatic/tectonic events and temporal variability of fluid composition (e.g., German and Von Damm, Treatise On Geochemistry, 2004; Baker et al. AGU Monograph Series 91, 1995). Studies in arc and back-arc settings are documenting the effects of magmatic acid volatiles on fluid-rock reaction and fluid and vent deposit compositions (e.g., Ishibashi and Urabe, Backarc Basins: Tectonics and Magmatism, 1995). These comparative studies in a wide range of geologic settings, including at the three Ridge2000 ISS, have provided a fairly good understanding of the flux of heat and many elements to the ocean associated with high temperature seafloor hydrothermal systems. Considerably less is known, however, about the partitioning of heat and mass (particularly metals and sulfur) in hydrothermal systems. The deposits that form at vent sites are intimately linked within paths of energy and mass transport from the mantle and crust to the oceans. Transport differs greatly through different types of deposits (e.g., black smokers, white smokers/diffusers, flanges). Estimates of heat flux from measured temperatures of flow (unless integrated over and around an entire vent field) require an understanding of the partitioning of flow between focused black smokers and more diffuse flow from diffusers, flanges, and surfaces of deposits, and from the igneous substrate. Estimates of mass flux into the ocean require an understanding of the

  2. Molecular orientation transition of organic thin films on graphite: the effect of intermolecular electrostatic and interfacial dispersion forces.

    PubMed

    Chen, Wei; Huang, Han; Thye, Andrew; Wee, Shen

    2008-09-28

    In situ low-temperature scanning tunnelling microscopy investigation reveals a molecular orientation transition of organic thin films of pentacene and p-sexiphenyl on graphite, arising from the delicate balance between the intermolecular electrostatic and interfacial dispersion forces.

  3. Interplay between molecular conformation and intermolecular interactions in conformational polymorphism: a molecular perspective from electronic calculations of tolfenamic acid.

    PubMed

    Mattei, Alessandra; Li, Tonglei

    2011-10-14

    Tolfenamic acid exhibits conformational polymorphism. The molecules in its two commonly occurred crystal structures form similar hydrogen-bonded dimers but differ in conformation. The conformational variance was analyzed by electronic calculation methods with the aim to unravel intrinsic connection between the conformational flexibility and intermolecular interactions in the polymorphs. The study was conducted mainly by conceptual density functional theory (DFT) and natural bond orbital (NBO) analysis. It is found that the conformational polymorphism is resulted from the energy competition between intramolecular π-conjugation and intermolecular hydrogen bonding. By adapting conformation that departs from being the most energetically stable, tolfenamic acid molecules can strengthen the intermolecular hydrogen-bonding interactions in the crystals. The study illustrates how the molecule's electronic properties are influenced by conformational variation and, inherently, how the intermolecular interactions become regulated. Moreover, understanding molecular interaction and crystal packing necessitates electronic structure calculation and analysis, which can be further facilitated by utilizing DFT and NBO concepts.

  4. 15N-15N spin-spin coupling constants through intermolecular hydrogen bonds in the solid state.

    PubMed

    Claramunt, Rosa M; Pérez-Torralba, Marta; María, Dolores Santa; Sanz, Dionisia; Elena, Bénédicte; Alkorta, Ibon; Elguero, José

    2010-10-01

    A 2hJNN intermolecular spin-spin coupling constant (SSCC) of 10.2±0.4 Hz has been measured for the powdered tetrachlorogallate salt of pyridinium solvated by pyridine (pyridine-H+⋯pyridine cation 3). Density Functional Theory (DFT) calculations at the B3LYP/6-311++G(d,p) level reproduced this value and two others reported in the literature for 2hJ intermolecular SSCCs, which were measured for complexes in solution.

  5. Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

    SciTech Connect

    Bartocci, Alessio; Cappelletti, David; Pirani, Fernando; Belpassi, Leonardo; Falcinelli, Stefano; Grandinetti, Felice; Tarantelli, Francesco

    2015-05-14

    The systems studied in this work are gas-phase weakly bound adducts of the noble-gas (Ng) atoms with CCl{sub 4} and CF{sub 4}. Their investigation was motivated by the widespread current interest for the intermolecular halogen bonding (XB), a structural motif recognized to play a role in fields ranging from elementary processes to biochemistry. The simulation of the static and dynamic behaviors of complex systems featuring XB requires the formulation of reliable and accurate model potentials, whose development relies on the detailed characterization of strength and nature of the interactions occurring in simple exemplary halogenated systems. We thus selected the prototypical Ng-CCl{sub 4} and Ng-CF{sub 4} and performed high-resolution molecular beam scattering experiments to measure the absolute scale of their intermolecular potentials, with high sensitivity. In general, we expected to probe typical van der Waals interactions, consisting of a combination of size (exchange) repulsion with dispersion/induction attraction. For the He/Ne-CF{sub 4}, the analysis of the glory quantum interference pattern, observable in the velocity dependence of the integral cross section, confirmed indeed this expectation. On the other hand, for the He/Ne/Ar-CCl{sub 4}, the scattering data unravelled much deeper potential wells, particularly for certain configurations of the interacting partners. The experimental data can be properly reproduced only including a shifting of the repulsive wall at shorter distances, accompanied by an increased role of the dispersion attraction, and an additional short-range stabilization component. To put these findings on a firmer ground, we performed, for selected geometries of the interacting complexes, accurate theoretical calculations aimed to evaluate the intermolecular interaction and the effects of the complex formation on the electron charge density of the constituting moieties. It was thus ascertained that the adjustments of the potential

  6. Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

    NASA Astrophysics Data System (ADS)

    Bartocci, Alessio; Belpassi, Leonardo; Cappelletti, David; Falcinelli, Stefano; Grandinetti, Felice; Tarantelli, Francesco; Pirani, Fernando

    2015-05-01

    The systems studied in this work are gas-phase weakly bound adducts of the noble-gas (Ng) atoms with CCl4 and CF4. Their investigation was motivated by the widespread current interest for the intermolecular halogen bonding (XB), a structural motif recognized to play a role in fields ranging from elementary processes to biochemistry. The simulation of the static and dynamic behaviors of complex systems featuring XB requires the formulation of reliable and accurate model potentials, whose development relies on the detailed characterization of strength and nature of the interactions occurring in simple exemplary halogenated systems. We thus selected the prototypical Ng-CCl4 and Ng-CF4 and performed high-resolution molecular beam scattering experiments to measure the absolute scale of their intermolecular potentials, with high sensitivity. In general, we expected to probe typical van der Waals interactions, consisting of a combination of size (exchange) repulsion with dispersion/induction attraction. For the He/Ne-CF4, the analysis of the glory quantum interference pattern, observable in the velocity dependence of the integral cross section, confirmed indeed this expectation. On the other hand, for the He/Ne/Ar-CCl4, the scattering data unravelled much deeper potential wells, particularly for certain configurations of the interacting partners. The experimental data can be properly reproduced only including a shifting of the repulsive wall at shorter distances, accompanied by an increased role of the dispersion attraction, and an additional short-range stabilization component. To put these findings on a firmer ground, we performed, for selected geometries of the interacting complexes, accurate theoretical calculations aimed to evaluate the intermolecular interaction and the effects of the complex formation on the electron charge density of the constituting moieties. It was thus ascertained that the adjustments of the potential suggested by the analysis of the

  7. Electron collisions with phenol: Total, integral, differential, and momentum transfer cross sections and the role of multichannel coupling effects on the elastic channel

    NASA Astrophysics Data System (ADS)

    da Costa, Romarly F.; de Oliveira, Eliane M.; Bettega, Márcio H. F.; Varella, Márcio T. do N.; Jones, Darryl B.; Brunger, Michael J.; Blanco, Francisco; Colmenares, Rafael; Limão-Vieira, Paulo; García, Gustavo; Lima, Marco A. P.

    2015-03-01

    We report theoretical and experimental total cross sections for electron scattering by phenol (C6H5OH). The experimental data were obtained with an apparatus based in Madrid and the calculated cross sections with two different methodologies, the independent atom method with screening corrected additivity rule (IAM-SCAR), and the Schwinger multichannel method with pseudopotentials (SMCPP). The SMCPP method in the Nopen-channel coupling scheme, at the static-exchange-plus-polarization approximation, is employed to calculate the scattering amplitudes at impact energies ranging from 5.0 eV to 50 eV. We discuss the multichannel coupling effects in the calculated cross sections, in particular how the number of excited states included in the open-channel space impacts upon the convergence of the elastic cross sections at higher collision energies. The IAM-SCAR approach was also used to obtain the elastic differential cross sections (DCSs) and for correcting the experimental total cross sections for the so-called forward angle scattering effect. We found a very good agreement between our SMCPP theoretical differential, integral, and momentum transfer cross sections and experimental data for benzene (a molecule differing from phenol by replacing a hydrogen atom in benzene with a hydroxyl group). Although some discrepancies were found for lower energies, the agreement between the SMCPP data and the DCSs obtained with the IAM-SCAR method improves, as expected, as the impact energy increases. We also have a good agreement among the present SMCPP calculated total cross section (which includes elastic, 32 inelastic electronic excitation processes and ionization contributions, the latter estimated with the binary-encounter-Bethe model), the IAM-SCAR total cross section, and the experimental data when the latter is corrected for the forward angle scattering effect [Fuss et al., Phys. Rev. A 88, 042702 (2013)].

  8. Assimilation of SMOS-derived soil moisture in a fully integrated hydrological and soil-vegetation-atmosphere transfer model in Western Denmark

    NASA Astrophysics Data System (ADS)

    Ridler, Marc-Etienne; Madsen, Henrik; Stisen, Simon; Bircher, Simone; Fensholt, Rasmus

    2014-11-01

    Real surface soil moisture retrieved from the Soil Moisture and Ocean Salinity (SMOS) satellite is downscaled and assimilated in a fully integrated hydrological and soil-vegetation-atmosphere transfer (MIKE SHE SW-ET) model using a bias aware ensemble transform Kalman filter (Bias-ETKF). Satellite-derived soil moisture assimilation in a catchment scale model is typically restricted by two challenges: (1) passive microwave is too coarse for direct assimilation and (2) the data tend to be biased. The solution proposed in this study is to disaggregate the SMOS bias using a higher resolution land cover classification map that was derived from Landsat thermal images. Using known correlations between SMOS bias and vegetation type, the assimilation filter is adapted to calculate biases online, using an initial bias estimate. Real SMOS-derived soil moisture is assimilated in a precalibrated catchment model in Denmark. The objective is to determine if any additional gains can be achieved by SMOS surface soil moisture assimilation beyond the optimized model. A series of assimilation experiments were designed to (1) determine how effectively soil moisture corrections propagate downward in the soil column, (2) compare the efficacy of in situ versus SMOS assimilation, and (3) determine how soil moisture assimilation affects fluxes and discharge in the catchment. We find that assimilation of SMOS improved R2 soil moisture correlations in the upper 5 cm compared to a network of 30 in situ sensors for most land cover classes. Assimilation also brought modest gains in R2 at 25 cm depth but slightly degraded the correlation at 50 cm depth. Assimilation overcorrected discharge peaks.

  9. Electron collisions with phenol: Total, integral, differential, and momentum transfer cross sections and the role of multichannel coupling effects on the elastic channel

    SciTech Connect

    Costa, Romarly F. da; Oliveira, Eliane M. de; Lima, Marco A. P.; Bettega, Márcio H. F.; Varella, Márcio T. do N.; Jones, Darryl B.; Brunger, Michael J.; Blanco, Francisco; Colmenares, Rafael; and others

    2015-03-14

    We report theoretical and experimental total cross sections for electron scattering by phenol (C{sub 6}H{sub 5}OH). The experimental data were obtained with an apparatus based in Madrid and the calculated cross sections with two different methodologies, the independent atom method with screening corrected additivity rule (IAM-SCAR), and the Schwinger multichannel method with pseudopotentials (SMCPP). The SMCPP method in the N{sub open}-channel coupling scheme, at the static-exchange-plus-polarization approximation, is employed to calculate the scattering amplitudes at impact energies ranging from 5.0 eV to 50 eV. We discuss the multichannel coupling effects in the calculated cross sections, in particular how the number of excited states included in the open-channel space impacts upon the convergence of the elastic cross sections at higher collision energies. The IAM-SCAR approach was also used to obtain the elastic differential cross sections (DCSs) and for correcting the experimental total cross sections for the so-called forward angle scattering effect. We found a very good agreement between our SMCPP theoretical differential, integral, and momentum transfer cross sections and experimental data for benzene (a molecule differing from phenol by replacing a hydrogen atom in benzene with a hydroxyl group). Although some discrepancies were found for lower energies, the agreement between the SMCPP data and the DCSs obtained with the IAM-SCAR method improves, as expected, as the impact energy increases. We also have a good agreement among the present SMCPP calculated total cross section (which includes elastic, 32 inelastic electronic excitation processes and ionization contributions, the latter estimated with the binary-encounter-Bethe model), the IAM-SCAR total cross section, and the experimental data when the latter is corrected for the forward angle scattering effect [Fuss et al., Phys. Rev. A 88, 042702 (2013)].

  10. Phosphorus transfer from agricultural areas and its impact on the eutrophication of lakes—two long-term integrated studies from Norway

    NASA Astrophysics Data System (ADS)

    Bechmann, M. E.; Berge, D.; Eggestad, H. O.; Vandsemb, S. M.

    2005-03-01

    Eutrophication of most fresh water systems is limited by phosphorus (P) concentration. High P concentrations originate from external and internal sources. In most Norwegian lakes, agriculture is a main external contributor of P. Two long-term, integrated studies of the relationship between agricultural management, transfer of P and suspended sediments (SS) from agricultural areas and the total P (TP) and chlorophyll-a (Chl-a) concentrations of the receiving lake were carried out in Norway. The Grimestad subcatchment/Aker Lake system (1993-2000) represents a cereal-growing area with mixed livestock production, while the Time subcatchment/Frøyland Lake (1986-2000) system represents a grass and dairy cow production system. A comparison of the two systems showed that the mean annual concentration of SS in the Grimestad Stream was 20 times the corresponding concentration in the Time stream. The difference in transparency (secchi depth) of the two lakes reflected this difference. The losses of TP and SS from the Grimestad subcatchment increased significantly during the monitoring period. In the Time stream, there was a significant downward trend in concentrations of TP. Corresponding to the measured inputs, the TP concentration of the Aker Lake (recipient of Grimestad Stream) increased slightly during the monitoring period, while the TP concentration of the Frøyland Lake (recipient of Time Stream) showed a slightly decreasing trend. Loads of TP from the Grimestad subcatchment during spring (March-April) described 70% of the variation in TP concentration of the Aker Lake the following summer. The TP concentration in the Time stream in November-December also were correlated ( r2=0.6) to the TP concentration in the Frøyland Lake the following summer. The annual TP concentrations of the lakes were not very well correlated to the measured Chl-a in the lakes, partly because of bio-manipulation, which was performed in both lakes during the monitoring period.

  11. Analysis of saturation transfer electron paramagnetic resonance spectra of a spin-labeled integral membrane protein, band 3, in terms of the uniaxial rotational diffusion model.

    PubMed Central

    Hustedt, E J; Beth, A H

    1995-01-01

    Algorithms have been developed for the calculation of saturation transfer electron paramagnetic resonance (ST-EPR) spectra of a nitroxide spin-label assuming uniaxial rotational diffusion, a model that is frequently used to describe the global rotational dynamics of large integral membrane proteins. One algorithm explicitly includes terms describing Zeeman overmodulation effects, whereas the second more rapid algorithm treats these effects approximately using modified electron spin-lattice and spin-spin relaxation times. Simulations are presented to demonstrate the sensitivity of X-band ST-EPR spectra to the rate of uniaxial rotational diffusion and the orientation of the nitroxide probe with respect to the diffusion axis. Results obtained by using the algorithms presented, which are based on the transition-rate formalism, are in close agreement with those obtained by using an eigenfunction expansion approach. The effects of various approximations used in the simulation algorithms are considered in detail. Optimizing the transition-rate formalism to model uniaxial rotational diffusion results in over an order of magnitude reduction in computation time while allowing treatment of nonaxial A- and g-tensors. The algorithms presented here are used to perform nonlinear least-squares analyses of ST-EPR spectra of the anion exchange protein of the human erythrocyte membrane, band 3, which has been affinity spin-labeled with a recently developed dihydrostilbene disulfonate derivative, [15N,2H13]-SL-H2DADS-MAL. These results suggest that all copies of band 3 present in intact erythrocytes undergo rotational diffusion about the membrane normal axis at a rate consistent with a band 3 dimer. PMID:8534811

  12. Transfer of a lipophilic drug (temoporfin) between small unilamellar liposomes and human plasma proteins: influence of membrane composition on vesicle integrity and release characteristics.

    PubMed

    Decker, Christiane; Steiniger, Frank; Fahr, Alfred

    2013-06-01

    The introduction of PEG lipid conjugates into lipid bilayers leads to long circulating liposomes with improved pharmacokinetics and pharmacodynamics characteristics. The concentration range of PEG-lipids is limited by their micelle forming properties. We investigated two phosphatidyl oligoglycerols as potential alternatives to PEG-lipid conjugates and compared their micelle forming properties after incorporation of increasing amounts of oligoglycerols into gel-phase liposomes via cryo-transmission electron microscopy. The incorporation of highly hydrophobic drugs into liposomes makes water soluble formulations possible and improves the therapeutic properties of the drug. We incorporated the hydrophobic photosensitizer temoporfin into liposomes varying in membrane fluidity and nature of surface modifying agents. The main purpose of this study was the investigation of liposome integrity and temoporfin incorporation stability in the presence of plasma. After incubation of temoporfin-loaded liposomes with human plasma for different time intervals, liposomes and the single lipoprotein fractions were separated via size-exclusion chromatography. Liposome stability and temoporfin distribution profile over the lipoprotein fractions were determined with the help of a non-exchangeable ³H-lipid label and ¹⁴C-labeled temoporfin. The results demonstrate that both oligoglycerols are suitable alternatives to PEG-lipid conjugates because of the lack of micelle forming properties, comparable liposome stability, and a reduced temoporfin transfer rate compared to PEG-lipids. Furthermore, the incorporation stability of temoporfin is--at least to some extent--influenced by membrane fluidity, indicating that fluid membranes may be better suited for retention of lipophilic drugs.

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

    NASA Astrophysics Data System (ADS)

    Khalili, Behzad

    2016-03-01

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

  14. Comparison of the Effective Fragment Potential Method with Symmetry-Adapted Perturbation Theory in the Calculation of Intermolecular Energies for Ionic Liquids.

    PubMed

    Tan, Samuel Y S; Izgorodina, Ekaterina I

    2016-06-14

    The effective fragment potential (EFP) method that decomposes the interaction energy as a sum of the five fundamental forces-electrostatic, exchange-repulsion, polarization, dispersion, and charge transfer-was applied to a large test set of ionic liquid ion pairs and compared against the state-of-the-art method, Symmetry-Adapted Perturbation Theory (SAPT). The ion pairs include imidazolium and pyrrolidinium cations combined with anions that are routinely used in the field of ionic liquids. The aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(d,p) basis sets were used for EFP, while SAPT2+3/aug-cc-pVDZ provided the benchmark energies. Differences between the two methods were found to be large, and strongly dependent on the anion type. For the aug-cc-pVTZ basis set, which produced the least errors, average relative errors were between 2.3% and 18.4% for pyrrolidinium ion pairs and between 2.1% and 27.7% for imidazolium ion pairs for each individual energetic component (excluding charge transfer), as well as the total interaction energy. Charge transfer gave the largest relative errors: 56% and 63% on average for pyrrolidinium- and imidazolium-based ion pairs, respectively. Scaling of the EFP components against SAPT2+3 showed improvement for polarization (induction) and dispersion terms, thus indicating potential for the development of cost-effective alternatives for intermolecular induction and dispersion potentials for ionic liquids.

  15. Ultrafast dynamics of Förster resonance energy transfer and photo-induced charge transfer in cationic polyfluorene/dye-labeled DNA complex.

    PubMed

    Kyhm, Kwangseuk; Kim, Inhong; Kang, Mijeong; Woo, Han Young

    2012-10-01

    The ultrafast dynamics of Förster resonance energy transfer (FRET) and photo-induced charge transfer (PCT) has been investigated in an electrostatic complex of a fluorescein-labeled single-stranded DNA (as a FRET acceptor) and a cationic polyfluorene copolymer (as a FRET donor). The donor-acceptor intermolecular distance and total energy transfer efficiency are determined for a polymer/DNA complex with two different counter-ions and compared with those obtained using a theoretical model by considering the competition between FRET and PCT processes. The maximum total energy transfer efficiency (0.47) was estimated at the optimum donor-acceptor intermolecular distance of 39.6 A.

  16. Modelling organic crystal structures using distributed multipole and polarizability-based model intermolecular potentials.

    PubMed

    Price, Sarah L; Leslie, Maurice; Welch, Gareth W A; Habgood, Matthew; Price, Louise S; Karamertzanis, Panagiotis G; Day, Graeme M

    2010-08-14

    Crystal structure prediction for organic molecules requires both the fast assessment of thousands to millions of crystal structures and the greatest possible accuracy in their relative energies. We describe a crystal lattice simulation program, DMACRYS, emphasizing the features that make it suitable for use in crystal structure prediction for pharmaceutical molecules using accurate anisotropic atom-atom model intermolecular potentials based on the theory of intermolecular forces. DMACRYS can optimize the lattice energy of a crystal, calculate the second derivative properties, and reduce the symmetry of the spacegroup to move away from a transition state. The calculated terahertz frequency k = 0 rigid-body lattice modes and elastic tensor can be used to estimate free energies. The program uses a distributed multipole electrostatic model (Q, t = 00,...,44s) for the electrostatic fields, and can use anisotropic atom-atom repulsion models, damped isotropic dispersion up to R(-10), as well as a range of empirically fitted isotropic exp-6 atom-atom models with different definitions of atomic types. A new feature is that an accurate model for the induction energy contribution to the lattice energy has been implemented that uses atomic anisotropic dipole polarizability models (alpha, t = (10,10)...(11c,11s)) to evaluate the changes in the molecular charge density induced by the electrostatic field within the crystal. It is demonstrated, using the four polymorphs of the pharmaceutical carbamazepine C(15)H(12)N(2)O, that whilst reproducing crystal structures is relatively easy, calculating the polymorphic energy differences to the accuracy of a few kJ mol(-1) required for applications is very demanding of assumptions made in the modelling. Thus DMACRYS enables the comparison of both known and hypothetical crystal structures as an aid to the development of pharmaceuticals and other speciality organic materials, and provides a tool to develop the modelling of the

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

    SciTech Connect

    Hobbs, M.L.

    1997-12-01

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

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

    SciTech Connect

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

    2013-08-15

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

  19. Intermolecular disulfide bond formation promotes immunoglobulin aggregation: investigation by fluorescence correlation spectroscopy.

    PubMed

    Nag, Moupriya; Bera, Kallol; Basak, Soumen

    2015-01-01

    Protein aggregation generally results from association between hydrophobic regions of individual monomers. However, additional mechanisms arising from specific interactions, such as intermolecular disulfide bond formation, may also contribute to the process. The latter is proposed to be the initiating pathway for aggregation of immunoglobulin (IgG), which is essential for triggering its immune response. To test the veracity of this hypothesis, we have employed fluorescence correlation spectroscopy to measure the kinetics of aggregation of IgG in separate experiments either allowing or inhibiting disulfide formation. Fluorescence correlation spectroscopy measurements yielded a diffusion time (τ(D)) of ∼200 µsec for Rhodamine-labeled IgG, corresponding to a hydrodynamic radius (R(H)) of 56 Å for the IgG monomer. The aggregation kinetics of the protein was followed by monitoring the time evolution of τ(D) under conditions in which its cysteine residues were either free or blocked. In both cases, the progress curves confirmed that aggregation proceeded via the nucleation-dependent polymerization pathway. However, for aggregation in the presence of free cysteines, the lag times were shorter, and the aggregate sizes bigger, than their respective counterparts for aggregation in the presence of blocked cysteines. This result clearly demonstrates that formation of intermolecular disulfide bonds represents a preferred pathway in the aggregation process of IgG. Fluorescence spectroscopy showed that aggregates formed in experiments where disulfide formation was prevented denatured at lower concentration of guanidine hydrochloride than those obtained in experiments where the disulfides were free to form, indicating that intermolecular disulfide bridging is a valid pathway for IgG aggregation. PMID:25371040

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

    PubMed

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

    2012-09-14

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

  1. THE INTEGRITY OF THE α-HELICAL DOMAIN OF INTESTINAL FATTY ACID BINDING PROTEIN IS ESSENTIAL FOR THE COLLISION-MEDIATED TRANSFER OF FATTY ACIDS TO PHOSPHOLIPID MEMBRANES

    PubMed Central

    Franchini, G. R.; Storch, J.; Corsico, B.

    2015-01-01

    Summary Intestinal FABP (IFABP) and liver FABP (LFABP), homologous proteins expressed at high levels in intestinal absorptive cells, employ markedly different mechanisms of fatty acid transfer to acceptor model membranes. Transfer from IFABP occurs during protein-membrane-collisional interactions, while for LFABP transfer occurs by diffusion through the aqueous phase. In addition, transfer from IFABP is markedly faster than from LFABP. The overall goal of this study was to further explore the structural differences between IFABP and LFABP which underlie their large functional differences in ligand transport. In particular, we addressed the role of the αI-helix domain in the unique transport properties of intestinal FABP. A chimeric protein was engineered with the ‘body’ (ligand binding domain) of IFABP and the αI-helix of LFABP (α(I)LβIFABP), and the fatty acid transfer properties of the chimeric FABP were examined using a fluorescence resonance energy transfer assay. The results showed a significant decrease in the absolute rate of FA transfer from α(I)LβIFABP compared to IFABP. The results indicate that the αI-helix is crucial for IFABP collisional FA transfer, and further indicate the participation of the αII-helix in the formation of a protein-membrane “collisional complex”. Photo-crosslinking experiments with a photoactivable reagent demonstrated the direct interaction of IFABP with membranes and further supports the importance of the αI helix of IFABP in its physical interaction with membranes. PMID:18284926

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

    PubMed

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

    2004-01-01

    It has been recently recognized that residual intermolecular double-quantum coherences (iDQcs) provide a novel contrast mechanism to study heterogeneity in liquid systems. This is of much interest in the field of the physics of matter and biomedicine. Nowadays, literature concerning the behaviour of the iDQc signal originated by highly heterogeneous systems such as fluids in porous media is scarce. In this paper, we report and discuss our principal results about iDQc signal behaviour in confined liquid systems (trabecular bone, travertine, porous standard systems) and also some new results obtained on doped water in glass capillary pipes. PMID:14698403

  3. Direct measurement of the intermolecular forces confining a single molecule in an entangled polymer solution.

    PubMed

    Robertson, Rae M; Smith, Douglas E

    2007-09-21

    We use optical tweezers to directly measure the intermolecular forces acting on a single polymer imposed by surrounding entangled polymers (115 kbp DNA, 1 mg/ml). A tubelike confining field was measured in accord with the key assumption of reptation models. A time-dependent harmonic potential opposed transverse displacement, in accord with recent simulation findings. A tube radius of 0.8 microm was determined, close to the predicted value (0.5 microm). Three relaxation modes (approximately 0.4, 5, and 34 s) were measured following transverse displacement, consistent with predicted relaxation mechanisms.

  4. Ab Initio and Analytic Intermolecular Potentials for Ar–CH3OH

    SciTech Connect

    Tasic, Uros; Alexeev, Yuri; Vayner, Grigoriy; Crawford, T Daniel; Windus, Theresa L.; Hase, William L.

    2006-09-20

    Ab initio calculations at the CCSD(T)/aug-cc-pVTZ level of theory were used to characterize the Ar–CH₃y6tOH intermolecular potential energy surface (PES). Potential energy curves were calculated for four different Ar + CH₃OH orientations and used to derive an analytic function for the intermolecular PES. A sum of Ar–C, Ar–O, Ar–H(C), and Ar–H(O) two-body potentials gives an excellent fit to these potential energy curves up to 100 kcal mol¯¹, and adding an additional r¯¹n term to the Buckingham two-body potential results in only a minor improvement in the fit. Three Ar–CH₃OH van der Waals minima were found from the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ calculations. The structure of the global minimum is in overall good agreement with experiment (X.-C. Tan, L. Sun and R. L. Kuczkowski, J. Mol. Spectrosc., 1995, 171, 248). It is T-shaped with the hydroxyl H-atom syn with respect to Ar. Extrapolated to the complete basis set (CBS) limit, the global minimum has a well depth of 0.72 kcal mol¯¹ with basis set superposition error (BSSE) correction. The aug-cc-pVTZ basis set gives a well depth only 0.10 kcal mol¯¹ smaller than this value. The well depths of the other two minima are within 0.16 kcal mol¯¹ of the global minimum. The analytic Ar–CH₃OH intermolecular potential also identifies these three minima as the only van der Waals minima and the structures predicted by the analytic potential are similar to the ab initio structures. The analytic potential identifies the same global minimum and the predicted well depths for the minima are within 0.05 kcal mol¯1 of the ab initio values. Combining this Ar–CH₃OH intermolecular potential with a potential for a OH-terminated alkylthiolate self-assembled monolayer surface (i.e., HO-SAM) provides a potential to model Ar + HO-SAM collisions.

  5. Profile of the intermolecular forces governing the interaction of drugs with mucin.

    PubMed

    Caron, Giulia; Visentin, Sonja; Pontremoli, Carlotta; Ermondi, Giuseppe

    2015-07-01

    The study highlights the balance of the intermolecular forces governing the interaction between drugs and mucin. The interaction strength is expressed as a retention factor k (data retrieved from the literature (Gargano et al., 2014)) obtained by a new bio-affinity chromatographic method in which the stationary phase is based on covalently immobilized mucin (porcine gastric mucin, PGM). A quantitative structure-property relationship (QSPR) between logk and 82 VolSurf+ descriptors was established and mechanistically interpreted. Results evidence that all blocks contribute similarly to the model; moreover, hydrogen bonding donor (HBD) properties of solutes favor the interaction with mucin; and thus, support their detrimental role on drug permeability.

  6. Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion.

    PubMed

    Lu, Deng-Fu; Zhu, Cheng-Liang; Sears, Jeffrey D; Xu, Hao

    2016-09-01

    We herein report a new catalytic method for intermolecular olefin aminofluorination using earth-abundant iron catalysts and nucleophilic fluoride ion. This method tolerates a broad range of unfunctionalized olefins, especially nonstyrenyl olefins that are incompatible with existing olefin aminofluorination methods. This new iron-catalyzed process directly converts readily available olefins to internal vicinal fluoro carbamates with high regioselectivity (N vs F), many of which are difficult to prepare using known methods. Preliminary mechanistic studies demonstrate that it is possible to exert asymmetric induction using chiral iron catalysts and that both an iron-nitrenoid and carbocation species may be reactive intermediates. PMID:27529196

  7. Copper-catalyzed intermolecular trifluoromethylarylation of alkenes: mutual activation of arylboronic acid and CF3+ reagent.

    PubMed

    Wang, Fei; Wang, Dinghai; Mu, Xin; Chen, Pinhong; Liu, Guosheng

    2014-07-23

    A novel copper-catalyzed intermolecular trifluoromethylarylation of alkenes is developed using less active ether-type Togni's reagent under mild reaction conditions. Various alkenes and diverse arylboronic acids are compatible with these conditions. Preliminary mechanistic studies reveal that a mutual activation process between arylboronic acid and CF3(+) reagent is essential. In addition, the reaction might involve a rate-determining transmetalation, and the final aryl C-C bond is derived from reductive elimination of the aryl(alkyl)Cu(III) intermediate. PMID:24983408

  8. Flat versus twisted rotamers of 2,4-disubstituted thiazoles: the effect of intermolecular hydrogen bonds.

    PubMed

    Bernès, Sylvain; Berros, Martha I; Rodríguez de Barbarín, Cecilia; Sánchez-Viesca, Francisco

    2002-03-01

    In the title compounds, 2-amino-4-(2-chloro-4,5-dimethoxyphenyl)-1,3-thiazole, C(11)H(11)ClN(2)O(2)S, (I), and 4-(2-chloro-4,5-dimethoxyphenyl)-2-methyl-1,3-thiazole, C(12)H(12)ClNO(2)S, (II), the dihedral angles between the thiazole moiety and the chloroaryl group are 51.61 (10) and 8.44 (14), respectively. This difference is a consequence of intermolecular hydrogen bonds forcing the stabilization of a twisted rotamer in (I). Substitution of the amino function by a methyl group precludes these contacts, giving a flat rotamer in (II).

  9. Regiodivergent Intermolecular [3+2] Cycloadditions of Vinyl Aziridines and Allenes: Stereospecific Synthesis of Chiral Pyrrolidines.

    PubMed

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

    2016-08-26

    The first rhodium-catalyzed intermolecular [3+2] cycloaddition reaction of vinyl aziridines and allenes for the synthesis of enantioenriched functionalized pyrrolidines was realized. [3+2] cycloaddition with the proximal C=C bond of N-allenamides gave 3-methylene-pyrrolidines in high regio- and diastereoselectivity, whereas, 2-methylene-pyrrolidines were obtained as the major products by the cycloadditions of vinyl aziridines with the distal C=C bond of allenes. Use of readily available starting materials, a broad substrate scope, high selectivity, mild reaction conditions, as well as versatile functionalization of the cycloadducts make this approach very practical and attractive. PMID:27485044

  10. Intermolecular Interactions between Eosin Y and Caffeine Using 1H-NMR Spectroscopy

    PubMed Central

    Okuom, Macduff O.; Wilson, Mark V.; Jackson, Abby; Holmes, Andrea E.

    2014-01-01

    DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC) from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB), and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1) and the analyte (caffeine) that is responsible for the fluorescence and color changes observed in the actual array. Using 1H-NMR, 1H-COSY, and 1H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed. PMID:25018772

  11. Intermolecular Interactions between Eosin Y and Caffeine Using (1)H-NMR Spectroscopy.

    PubMed

    Okuom, Macduff O; Wilson, Mark V; Jackson, Abby; Holmes, Andrea E

    2013-12-31

    DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC) from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB), and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1) and the analyte (caffeine) that is responsible for the fluorescence and color changes observed in the actual array. Using (1)H-NMR, (1)H-COSY, and (1)H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed. PMID:25018772

  12. Catalytic Selenium-Promoted Intermolecular Friedel-Crafts Alkylation with Simple Alkenes.

    PubMed

    Tang, E; Zhao, Yinjiao; Li, Wen; Wang, Weilin; Zhang, Meng; Dai, Xin

    2016-03-01

    A method for conducting selenium-promoted intermolecular Friedel-Crafts (F-C) alkylation reactions has been developed with simple alkenes using trimethylsilyl trifluoromethanesulfonate as a catalyst and N-phenylselenophthalimide as an efficient selenium source. Electron-rich arenes smoothly underwent F-C alkylation with a variety of alkenes to afford alkylated products in good yield and with high regioselectivity and diastereoselectivity. The regioselectivity and stereoselectivity of arenes and alkenes as well as a preliminary mechanism of the F-C alkylation reaction are discussed. PMID:26882088

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

    PubMed

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

    2015-08-28

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

  14. Iridium-catalyzed intermolecular dehydrogenative silylation of polycyclic aromatic compounds without directing groups.

    PubMed

    Murai, Masahito; Takami, Keishi; Takai, Kazuhiko

    2015-03-16

    This study describes the iridium-catalyzed intermolecular dehydrogenative silylation of C(sp(2))-H bonds of polycyclic aromatic compounds without directing groups. The reaction produced various arylsilanes through both Si-H and C-H bond activation, with hydrogen as the sole byproduct. Reactivity was affected by the electronic nature of the aromatic compounds, and silylation of electron-deficient and polycyclic aromatic compounds proceeded efficiently. Site-selectivity was controlled predominantly by steric factors. Therefore, the current functionalization proceeded with opposite chemo- and site-selectivity compared to that observed for general electrophilic functionalization of aromatic compounds.

  15. DFT Study of Pd(0)-Promoted Intermolecular C-H Amination with O-Benzoyl Hydroxylamines.

    PubMed

    Zhou, Yunfei; Bao, Xiaoguang

    2016-09-16

    Computational studies were carried out to explore the mechanism of Pd-catalyzed intermolecular C-H amination with O-benzoyl hydroxylamines in which both Pd(0) and Pd(II) catalysts are effective. For the Pd(0)-catalyzed reaction, the generally assumed Pd(0)/Pd(II) catalytic cycle might not be feasible. Instead, Pd(0), being essentially a catalyst precursor, could be oxidized to Pd(II), and the C-H amination proceeds through the Pd(II)/Pd(IV) catalytic cycle. PMID:27573977

  16. Iridium(III)-Catalyzed Regioselective Intermolecular Unactivated Secondary Csp(3) -H Bond Amidation.

    PubMed

    Xiao, Xinsheng; Hou, Cheng; Zhang, Zhenhui; Ke, Zhuofeng; Lan, Jianyong; Jiang, Huanfeng; Zeng, Wei

    2016-09-19

    For the first time, a highly regioselective intermolecular sulfonylamidation unactivated secondary Csp(3) -H bond has been achieved using Ir(III) catalysts. The introduced N,N'-bichelating ligand plays a crucial role in enabling iridium-nitrene insertion into a secondary Csp(3) -H bond via an outer-sphere pathway. Mechanistic studies and density functional theory (DFT) calculations demonstrated that a two-electron concerted nitrene insertion was involved in this Csp(3) -H amidation process. This method tolerates a broad range of linear and branched-chain N-alkylamides, and provides efficient access to diverse γ-sulfonamido-substituted aliphatic amines. PMID:27561950

  17. Modification of PEGylated enzyme with glutaraldehyde can enhance stability while avoiding intermolecular crosslinking†

    PubMed Central

    McShane, M. J.

    2015-01-01

    We demonstrate an enzyme stabilization approach whereby a model enzyme is PEGylated, followed by controlled chemical modification with glutaraldehyde. Using this stabilization strategy, size increases and aggregation due to intermolecular crosslinking are avoided. Immediately following synthesis, the PEGylated enzyme with and without glutaraldehyde modification possessed specific activities of 372.9 ± 20.68 U/mg and 373.9 ± 15.14 U/mg, respectively (vs. 317.7 ± 19.31 U/mg for the native enzyme). The glutaraldehyde-modified PEGylated enzyme retains 73% original activity after 4 weeks at 37 °C (vs. 2% retention for control). PMID:26052433

  18. Intermolecular hydroaminoalkylation of alkenes and dienes using a titanium mono(formamidinate) catalyst.

    PubMed

    Dörfler, Jaika; Preuss, Till; Brahms, Christian; Scheuer, Dennis; Doye, Sven

    2015-07-21

    An easily accessible formamidinate ligand-bearing titanium complex initially synthesized by Eisen et al. is used as catalyst for intermolecular hydroaminoalkylation reactions of unactivated, sterically demanding 1,1- and 1,2-disubstituted alkenes and styrenes with secondary amines. The corresponding reactions, which have never been achieved with titanium catalysts before, take place with excellent regioselectivity (up to 99 : 1) and in addition, corresponding reactions of 1,3-butadienes with N-methylbenzylamine are also described for the first time.

  19. Polar solvation and electron transfer. Annual progress report, July 1, 1992--June 30, 1993

    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.

  20. The effect of intermolecular donor?acceptor energy transfer on emission anisotropy in uniaxially oriented polymer films

    NASA Astrophysics Data System (ADS)

    Sadownik, M.; Bojarski, Piotr

    2004-10-01

    Excitation energy transport between donors and acceptors is studied for uniaxially stretched and unstretched poly(vinyl) alcohol films. Donor emission anisotropy courses versus acceptor concentration as well as donor-acceptor emission anisotropy spectra occurred quite different in stretched and unstretched films. Upon donor excitation the total emission anisotropy rapidly decreases when passing from the donor to the acceptor fluorescence band in disordered systems. However, such a pronounced effect has not been found in partly ordered films. Donors and acceptors exhibit highly preferential mutual orientation in strongly ordered films resulting in the preservation of acceptor emission anisotropy.

  1. Vibrational energy transfer in high explosives: Nitromethane

    SciTech Connect

    Hong, X.; Hill, J.R.; Dlott, D.D.

    1996-03-01

    Time resolved vibrational spectroscopy with picosecond tunable mid-infrared pulses is used to measure the rates and investigate the detailed mechanisms of multiphonon up-pumping and vibrational cooling in a condensed high explosive, nitromethane. Both processes occur on the 100 ps time scale under ambient conditions. The mechanisms involve sequential climbing or descending the ladder of molecular vibrations. Efficient intermolecular vibrational energy transfer from various molecules to the symmetric stretching excitation of NO2 is observed. The implications of these measurements for understanding shock initiation to detonation and the sensitivities of energetic materials to shock initiation are discussed briefly.

  2. Electron Transfer Control in Soluble Methane Monooxygenase

    PubMed Central

    2015-01-01

    The hydroxylation or epoxidation of hydrocarbons by bacterial multicomponent monooxygenases (BMMs) requires the interplay of three or four protein components. How component protein interactions control catalysis, however, is not well understood. In particular, the binding sites of the reductase components on the surface of their cognate hydroxylases and the role(s) that the regulatory proteins play during intermolecular electron transfer leading to the hydroxylase reduction have been enigmatic. Here we determine the reductase binding site on the hydroxylase of a BMM enzyme, soluble methane monooxygenase (sMMO) from Methylococcus capsulatus (Bath). We present evidence that the ferredoxin domain of the reductase binds to the canyon region of the hydroxylase, previously determined to be the regulatory protein binding site as well. The latter thus inhibits reductase binding to the hydroxylase and, consequently, intermolecular electron transfer from the reductase to the hydroxylase diiron active site. The binding competition between the regulatory protein and the reductase may serve as a control mechanism for regulating electron transfer, and other BMM enzymes are likely to adopt the same mechanism. PMID:24937475

  3. Intra- and intermolecular hydrogen bonding in acetylacetone and benzoylacetone derived enaminone derivatives

    NASA Astrophysics Data System (ADS)

    Lazić, Vedrana; Jurković, Mihaela; Jednačak, Tomislav; Hrenar, Tomica; Vuković, Jelena Parlov; Novak, Predrag

    2015-01-01

    The structure and hydrogen bonding in solution of acetylacetone and benzoylacetone derived enaminone derivatives, 1a-1d and 2a-2d, have been studied by a combination of experimental (NMR and UV spectroscopies) and theoretical (PM6 and DFT) methods. It has been shown that all studied compounds predominantly existed in the localised keto-amine tautomeric form in solution as found also in the solid state. Significant line-broadening and down-field chemical shifts of NH and OH protons have strongly indicated that both groups formed hydrogen bonds, which has further been supported by quantum chemical calculations. Temperature and concentration dependent NMR measurements have pointed towards the fact that NH protons are engaged in strong intramolecular hydrogen bonds of the NH⋯Odbnd C type in both solvents. On the other hand, OH protons are involved in weaker intermolecular hydrogen bonding with solvent molecules in DMSO, while in chloroform intermolecular interactions between two molecules dominate. The results presented in this paper can be used for better understanding and further exploiting properties these ligands possess, especially their bioactivity.

  4. Intermolecular Forces as a Key to Understanding the Environmental Fate of Organic Xenobiotics

    NASA Astrophysics Data System (ADS)

    Casey, Ryan E.; Pittman, Faith A.

    2005-02-01

    Environmental education for undergraduate nonscience majors and high school students is key in fostering an increased understanding of environmental issues among the general public. We have developed an environmental chemistry module that can be used in high schools or undergraduate nonscience courses to relate chemical structures and properties to the macroscopic behavior of environmentally relevant organic chemicals like pesticides, PCBs, and solvents. The module introduces the concepts of intermolecular forces, polarity, and partitioning to explain complex phenomena such as environmental transport and biomagnification of xenobiotics (human-made chemicals). The level 1 version 2.11 model, developed by Trent University, is used in a laboratory segment that allows students to explore the relationship between chemical properties and environmental distribution. The initial material on polarity and intermolecular forces can lead to additional applications, including: bioaccumulation and biomagnification of organic chemicals; toxicology or pharmacology (ability of molecules to cross membranes); and groundwater contamination. This module can enhance chemistry courses by presenting detailed applications and allowing students to make powerful, verifiable predictions. See Featured Molecules .

  5. Relating organic fouling of reverse osmosis membranes to intermolecular adhesion forces.

    PubMed

    Lee, Sangyoup; Elimelech, Menachem

    2006-02-01

    Organic fouling of reverse osmosis (RO) membranes and its relation to foulant--foulant intermolecular adhesion forces has been investigated. Alginate and Suwannee River natural organic matter were used as model organic foulants. Atomic force microscopy was utilized to determine the adhesion force between bulk organic foulants and foulants deposited on the membrane surface under various solution chemistries. The measured adhesion force was related to the RO fouling rate determined from fouling experiments under solution chemistries similar to those used in the AFM measurements. A remarkable correlation was obtained between the measured adhesion force and the fouling rate under the solution chemistries investigated. Fouling was more severe at solution chemistries that resulted in larger adhesion forces, namely, lower pH, higher ionic strength, presence of calcium ions (but not magnesium ions), and higher mass ratio of alginate to Suwannee River natural organic matter. The significant adhesion force measured with alginate in the presence of calcium ions indicated the formation of a crossed-linked alginate gel layer during fouling through intermolecular bridging among alginate molecules.

  6. Probing the contribution of different intermolecular forces to the adsorption of spheroproteins onto hydrophilic surfaces.

    PubMed

    Borges, João; Campiña, José M; Silva, A Fernando

    2013-12-27

    Protein adsorption is a delicate process, which results from the balance between the properties of proteins and their solid supports. Although the relevance of some of these parameters has been already unveiled, the precise involvement of electrostatics and other weaker intermolecular forces requires further comprehension. Aiming to contribute to this task, this work explores the attachment, rearrangement, and surface aggregation of a model spheroprotein, such as bovine β-lactoglobulin (β-LG), onto hydrophilic substrates prefunctionalized with different alkylthiol films. Thereby, a variety of electrostatic scenarios for the adsorption of β-LG could be recreated through the variation of the pH and the functional chemistry of the surfaces. The changes in surface mass density (plus associated water) and film flexibility were followed in situ with quartz crystal microbalance with dissipation monitoring. Film packing and aggregation were assessed by faradaic electrochemical measurements and ex situ atomic force microscopy and field effect scanning electron microscopy. In contrast to previous hypotheses arguing that electrostatic interactions between charged substrates and proteins would be the only driving force, a complex interplay between Coulombic and non-Coulombic intermolecular forces (which would depend upon the experimental conditions) has been suggested to explain the results.

  7. Pressure Effects on the Intermolecular Interaction Potential of Condensed Protein Solutions.

    PubMed

    Winter, Roland

    2015-01-01

    Knowledge of the intermolecular interaction potential of proteins as a function of their solution conditions is essential for understanding protein aggregation, crystallization, and the phase behavior of proteins in general. Here, we report on a combined small-angle X-ray scattering and liquid-state theoretical approach to study dense lysozyme solutions as a function of temperature and pressure, but also in the presence of salts and osmolytes of different nature. We show that the pressure-dependent interaction potential of lysozyme changes in a nonlinear fashion over a wide range of temperatures, salt and protein concentrations, indicating that changes of the bulk water structure mediate the pressure dependence of the intermolecular forces. We present also results on the effect of high hydrostatic pressure on the phase behavior of dense lysozyme solutions in the liquid-liquid phase-coexistence region. As also shown in this study, the application of pressure can be used to fine-tune the second virial coefficient of protein solutions, which can be used to control nucleation rates and hence protein crystallization, or to prevent protein aggregation. Moreover, these results are also important for understanding the hydration behavior of biological matter under extreme environmental conditions, and the high stability of dense protein solutions (as they occur intracellularly) in organisms thriving under hydrostatic pressure conditions such as in the deep sea, where pressures up to the 100 MPa-level are reached.

  8. Terahertz notch filter using intermolecular hydrogen bonds in a sucrose crystal

    NASA Astrophysics Data System (ADS)

    Rungsawang, Rakchanok; Ueno, Yuko; Tomita, Isao; Ajito, Katsuhiro

    2006-06-01

    We propose a THz notch filter that uses the absorption of the intermolecular hydrogen bonds in a molecular crystal such as sucrose. Terahertz (THz) time-domain spectroscopy was used to investigate the absorption characteristics of a rotationally oriented sucrose single crystal in the 0.3 - 3.0 THz frequency range. The crystal was set so that the (100) face (cleavage) was normal to the THz propagation direction. The two lowest frequency intermolecular hydrogen bonding bands clearly exist at room temperature and at 1.45 and 1.64 THz when the b-axis of the crystal is parallel and perpendicular to the THz polarization, respectively. In contrast, they disappear when the b-axis is reversed. This absorption feature means that it would be possible to utilize a sucrose crystal as a notch filter with a 1.45-THz band center for the 0.1-1.7 THz range and with a 1.64-THz band center for the 0.1-1.9 THz range. When the crystal is rotated, the transmitted intensities of the frequency components near the absorption bands alternate as a sine function against angle. The spectroscopic properties of the sucrose filter were confirmed by continuous THz wave imaging.

  9. The Effect of Intermolecular Modes on the Xh-Stretching Vibrations in Hydrogen Bonded Complexes

    NASA Astrophysics Data System (ADS)

    Mackeprang, Kasper; Kjaergaard, Henrik G.

    2016-06-01

    Vibrational spectra of hydrogen bonded bimolecular complexes (XH\\cdotsY, where X is the hydrogen bond donor atom, and Y is the acceptor atom) have long been a theoretical challenge. Specifically, the XH-stretching motion is difficult to describe due to the effect of the large amplitude intermolecular modes inherent to complexes. We have developed a vibrational model, the Local Mode Perturbation Theory (LMPT) model, to accurately determine the transition wavenumber and oscillator strength of the XH-stretching transition in hydrogen bonded bimolecular complexes. The model is based on a local mode (LM) model of the XH-stretching transition and the effect of the intermolecular modes is included via Rayleigh-Schrödinger perturbation theory. Our model has significantly improved results obtained using the LM model (see Figure). Additionally, our LMPT model does not require a full-dimensional anharmonic calculation, which enables application to large systems and the usage of higher level ab initio theory for the required potential energy surfaces. This work was inspired by our recent efforts to accurately determine equilibrium constants of complex formation, which rely on an accurate determination of the oscillator strength of the XH-stretching transition.

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

    PubMed

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

    2014-08-01

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

  11. An optimized intermolecular force field for hydrogen-bonded organic molecular crystals using atomic multipole electrostatics

    PubMed Central

    Pyzer-Knapp, Edward O.; Thompson, Hugh P. G.; Day, Graeme M.

    2016-01-01

    We present a re-parameterization of a popular intermolecular force field for describing intermolecular interactions in the organic solid state. Specifically we optimize the performance of the exp-6 force field when used in conjunction with atomic multipole electrostatics. We also parameterize force fields that are optimized for use with multipoles derived from polarized molecular electron densities, to account for induction effects in molecular crystals. Parameterization is performed against a set of 186 experimentally determined, low-temperature crystal structures and 53 measured sublimation enthalpies of hydrogen-bonding organic molecules. The resulting force fields are tested on a validation set of 129 crystal structures and show improved reproduction of the structures and lattice energies of a range of organic molecular crystals compared with the original force field with atomic partial charge electrostatics. Unit-cell dimensions of the validation set are typically reproduced to within 3% with the re-parameterized force fields. Lattice energies, which were all included during parameterization, are systematically underestimated when compared with measured sublimation enthalpies, with mean absolute errors of between 7.4 and 9.0%. PMID:27484370

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

    NASA Astrophysics Data System (ADS)

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2013-09-01

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

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

    NASA Astrophysics Data System (ADS)

    Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

    2014-06-01

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

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

    PubMed Central

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

    2014-01-01

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

  15. An optimized intermolecular force field for hydrogen-bonded organic molecular crystals using atomic multipole electrostatics.

    PubMed

    Pyzer-Knapp, Edward O; Thompson, Hugh P G; Day, Graeme M

    2016-08-01

    We present a re-parameterization of a popular intermolecular force field for describing intermolecular interactions in the organic solid state. Specifically we optimize the performance of the exp-6 force field when used in conjunction with atomic multipole electrostatics. We also parameterize force fields that are optimized for use with multipoles derived from polarized molecular electron densities, to account for induction effects in molecular crystals. Parameterization is performed against a set of 186 experimentally determined, low-temperature crystal structures and 53 measured sublimation enthalpies of hydrogen-bonding organic molecules. The resulting force fields are tested on a validation set of 129 crystal structures and show improved reproduction of the structures and lattice energies of a range of organic molecular crystals compared with the original force field with atomic partial charge electrostatics. Unit-cell dimensions of the validation set are typically reproduced to within 3% with the re-parameterized force fields. Lattice energies, which were all included during parameterization, are systematically underestimated when compared with measured sublimation enthalpies, with mean absolute errors of between 7.4 and 9.0%. PMID:27484370

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

    PubMed

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

    2014-10-01

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

  17. Intra- and intermolecular forces dependent main chain conformations of esters of α,β-dehydroamino acids

    NASA Astrophysics Data System (ADS)

    Siodłak, Dawid; Bujak, Maciej; Staś, Monika

    2013-09-01

    Esters of dehydroamino acids occur in nature. To investigate their conformational properties, the low-temperature structures of Ac-ΔAla-OMe, Ac-ΔVal-OMe, Z-(Z)-ΔAbu-OMe, and Z-(Z)-ΔAbu-NHMe were studied by single-crystal X-ray diffraction. The ΔAla ester prefers the fully extended conformation C5. Both the ΔVal and (Z)-ΔAbu esters assume the conformation β, whereas the amide analogue of the latter prefers the conformation α. For the conformations found, DFT calculations using B3LYP/6-311++G(d,p) with the SCRF-PCM and M062X/6-311++G(d,p) with the SCRF-SMD method were applied to mimicking chloroform and water environment. The tendency of the ΔVal and (Z)-ΔAbu esters towards the conformation β, and their amide analogues towards the conformation α, with increase of the polarity of environment was found. The analysis of both intra- and intermolecular interactions including hydrogen bonds, carbonyl dipole attraction, and π-electron conjugation, enabled to understand and elucidate the conformational preferences of studied compounds. The studies show how the molecular structure, and in consequence, the conformation adopted by molecules is influenced by the different intra- and intermolecular forces.

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

    This research study aims to examine the effectiveness of a problem-based learning (PBL) on 9th grade students’ understanding of intermolecular forces (dipole-dipole forces, London dispersion forces and hydrogen bonding). The student’s alternate conceptions about intermolecular bonding and their beliefs about PBL were also measured. Seventy-eight 9th grade students were stratified by cognitive levels and then randomly assigned to experimental (PBL, 40 students) and control (lecture-style teaching, 38 students) groups. Following a preparatory lesson where activation and remediation of existing knowledge occur, a pre-test was given, and no significant difference was found between the two groups of students ( p > .05). After the instruction was completed, a post-test and also a questionnaire related to the quality of the problem, the teacher’s role and group functioning were administered. Results from the post-test of both groups ( p < .05) and questionnaire showed that PBL is affective on students’ achievement, remedying formation of alternate conceptions and also social skills.

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

    SciTech Connect

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

    2010-04-19

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

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

    PubMed

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

    2014-08-01

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

  1. Spatio-spectral infrared vibrational nano-imaging of intermolecular coupling

    NASA Astrophysics Data System (ADS)

    Pollard, Benjamin; Muller, Eric; Raschke, Markus

    2014-03-01

    Molecular self-assembly, the function of biomembranes, and the performance of organic solar cells rely on molecular interactions on the nanoscale. The understanding and design of such heterogeneous functional soft matter has long been impeded by a lack of spectroscopic tools with sufficient nanometer spatial resolution, attomolar sensitivity, and intermolecular spectroscopic specificity. We implement vibrational scattering-scanning near-field optical microscopy (s-SNOM) in a multi-spectral modality to investigate the structure-function relationship in PS- b-PMMA block copolymers. Using a vibrational resonance as a sensitive reporter of local structure, coupling, and dynamics, we resolve spectral Stark shifts and line broadening correlated with molecular-scale morphologies. By creating images of solvatochromic vibrational shifts we discriminate local variations in electric fields between nanoscale bulk and interface regions, with quantitative agreement to dielectric continuum models. This new nano-chemometric ability to directly resolve nanoscale morphology and associated intermolecular interactions can form a basis for the systematic control of functionality in multicomponent soft matter systems.

  2. Role of silver ions in destabilization of intermolecular adhesion forces measured by atomic force microscopy in Staphylococcus epidermidis biofilms.

    PubMed

    Chaw, K C; Manimaran, M; Tay, Francis E H

    2005-12-01

    In this paper, we report on the potential use of atomic force microscopy (AFM) as a tool to measure the intermolecular forces in biofilm structures and to study the effect of silver ions on sessile Staphylococcus epidermidis cell viability and stability. We propose a strategy of destabilizing the biofilm matrix by reducing the intermolecular forces within the extracellular polymeric substances (EPSs) using a low concentration (50 ppb) of silver ions. Our AFM studies on the intermolecular forces within the EPSs of S. epidermidis RP62A and S.epidermidis 1457 biofilms suggest that the silver ions can destabilize the biofilm matrix by binding to electron donor groups of the biological molecules. This leads to reductions in the number of binding sites for hydrogen bonds and electrostatic and hydrophobic interactions and, hence, the destabilization of the biofilm structure.

  3. Strong anisotropy of momentum-relaxation time induced by intermolecular vibrations of single-crystal organic semiconductors

    NASA Astrophysics Data System (ADS)

    Ishii, Hiroyuki; Kobayashi, Nobuhiko; Hirose, Kenji

    2013-11-01

    We present a theoretical study of the relationships between intermolecular vibrations and anisotropic transport properties of pentacene and rubrene single-crystal organic semiconductors. Using our wave-packet approach based on the Kubo formula beyond the effective-mass approximation with the assumption of an isotropic momentum-relaxation time, we find that the intermolecular vibrations induce a strong anisotropic momentum-relaxation time but moderate the anisotropy of carrier mobility much more than that of the effective mass. This clarifies the mechanism behind the deviation of the anisotropic ratio of mobility from that of effective mass observed in angle-resolved photoelectron spectroscopy experiments.

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

    PubMed

    McKenzie, S; Kang, H C

    2014-12-21

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

  5. CO2 Dimer: Four Intermolecular Modes Observed via Infrared Combination Bands

    NASA Astrophysics Data System (ADS)

    Norooz Oliaee, Jalal; Dehghany, Mehdi; Rezaei, Mojtaba; McKellar, Bob; Moazzen-Ahmadi, Nasser

    2016-06-01

    Study of the carbon dioxide dimer has a long history, but there is only one previous observation of an intermolecular vibration [1]. Here we analyze four new combination bands of (CO2)2 in the CO2 νb{3} region (˜2350 wn), observed using tunable infrared lasers and a pulsed slit-jet supersonic expansion. The previous combination band at 2382.2 wn was simple to assign [1]. A much more complicated band (˜2370 wn) turns out to involve two upper states, one at 2369.0 wn (Bu symmetry), and the other at 2370.0 wn (Au). The spectrum can be nicely fit by including the Coriolis interactions between these states. Another complicated band around 2443 wn also involves two nearby upper states which are highly perturbed in so-far unexplained ways (possibly related to tunneling shifts). With the help of new ab initio calculations [2], we assign the results as follows. The 2369.0 wn band is the combination of the forbidden Ag intramolecular fundamental (probably [1] at about 2346.76 wn) and the intermolecular geared bend (Bu). The 2370.0 wn band is the combination of the same Ag fundamental and the intermolecular torsion (Au). This gives about 22.3 and 23.2 wn for the geared bend and torsion. The previous 2382.2 wn band [1] is the allowed Bu fundamental (2350.771 wn) plus two quanta of the geared bend (Bu), giving 31.509 wn for this overtone. The highly perturbed 2442.7 wn band is the Bu fundamental plus the antigeared bend (Ag), giving about 91.9 wn for the antigeared bend. Finally, the perturbed 2442.1 wn band is due to an unknown combination of modes which gains intensity from the antigeared bend by a Fermi-type interaction. Calculated values [2] are: 20.64 (geared bend), 24.44 (torsion), 32.34 (geared bend overtone), and 92.30 wn (antigeared bend), in good agreement with experiment. \\vskip 0.2 truecm [1] M. Dehghany, A.R.W. McKellar, Mahin Afshari, and N. Moazzen-Ahmadi, Mol. Phys. 108, 2195 (2010). [2] X.-G. Wang, T. Carrington, Jr., and R. Dawes, private communication.

  6. Photoinduced intermolecular cross-linking of gas phase triacylglycerol lipid ions.

    PubMed

    Nie, Shuai; Pham, Huong T; Blanksby, Stephen J; Reid, Gavin E

    2015-01-01

    Complex mixtures of plant derived triglycerol (TG) lipids are commonly used as feedstock components for the production of industrial polymers. However, there remains a need for the development of analytical strategies to investigate the intrinsic intermolecular cross-linking reactivity of individual TG molecules within these mixtures as a function of their structures and physicochemical properties, and for the characterization of the resultant products. Here, to address this need, we describe a novel multistage tandem mass spectrometry based method for intermolecular cross-linking and subsequent structural characterization of TG lipid ions in the gas phase. Cross-linking reactions were initiated using 266 nm ultraviolet photodissociation tandem mass spectrometry (UVPD-MS/MS) of saturated or unsaturated TG dimers introduced via electrospray ionization into a linear ion trap mass spectrometer as noncovalent complexes with protonated 3,4-, 2,4- or 3,5- diiodoaniline (diIA). UVPD resulted in the initial formation of an anilinyl biradical via the sequential loss of two iodine radicals, which underwent further reaction to yield multiple cross-linked TG products along with competing noncross-linking processes. These chemistries are proposed to occur via sequential combinations of hydrogen abstraction (H-abstraction), radical addition and radical recombination. Multistage collision induced dissociation tandem mass spectrometry (CID-MS(n)) was used to obtain evidence for the structures and mechanisms of formation for these products, as a function of both the TG lipid and diIA ion structures. The efficiency of the UVPD reaction was shown to be dependent on the number of unsaturation sites present within the TG lipids. However, when unsaturation sites were present, formation of the cross-linked and noncross-linked product ions via H-abstraction and radical addition mechanisms was found to be competitive. Finally, the identity of the anilinyl biradical (e.g., 3,4- versus 2

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

    PubMed

    Ikeda, S; Nishinari, K

    2000-01-01

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

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

    PubMed

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

    2015-10-01

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

  9. Intermolecular Electronic Coupling of Organic Units for Efficient Persistent Room‐Temperature Phosphorescence

    PubMed Central

    Yang, Zhiyong; Mao, Zhu; Zhang, Xuepeng; Ou, Depei; Mu, Yingxiao; Zhao, Cunyuan; Liu, Siwei; Xu, Jiarui; Wu, Yuan‐Chun; Lu, Po‐Yen; Lien, Alan

    2016-01-01

    Abstract Although persistent room‐temperature phosphorescence (RTP) emission has been observed for a few pure crystalline organic molecules, there is no consistent mechanism and no universal design strategy for organic persistent RTP (pRTP) materials. A new mechanism for pRTP is presented, based on combining the advantages of different excited‐state configurations in coupled intermolecular units, which may be applicable to a wide range of organic molecules. By following this mechanism, we have developed a successful design strategy to obtain bright pRTP by utilizing a heavy halogen atom to further increase the intersystem crossing rate of the coupled units. RTP with a remarkably long lifetime of 0.28 s and a very high quantum efficiency of 5 % was thus obtained under ambient conditions. This strategy represents an important step in the understanding of organic pRTP emission. PMID:26836346

  10. Local modification of intermolecular interactions at a sub-molecule level.

    PubMed

    Song, Sang Yong; Jeong, Yong Chan; Kim, Youngjae; Kang, Joongoo; Seo, Jungpil

    2016-10-14

    The local modification of intermolecular interactions in nickel-phthalocyanine molecules (NiPCs) is investigated on an Au(111) substrate using scanning tunneling microscopy. When the molecules are physisorbed on the substrate, they repel each other due to induced charge dipole moments. However, when the NiPC is chemisorbed on the substrate through the dehydrogenation of one of its ligands by a bias pulse, we find that a nearby physisorbed NiPC is attracted to the dehydrogenated ligand and trapped. Using our experimental results in combination with density functional theory calculations, we show that the observed attraction can be ascribed to the local charge redistribution around the dehydrogenated ligand of the chemisorbed NiPC. Furthermore, we demonstrate that desorption of the attracted NiPC from the trapped site can be readily controlled by changing the density of NiPCs around the dehydrogenated ligand. PMID:27609354

  11. Role of long-range intermolecular forces in the formation of inorganic nanoparticle clusters.

    PubMed

    Gibbs, G V; Crawford, T D; Wallace, A F; Cox, D F; Parrish, R M; Hohenstein, E G; Sherrill, C D

    2011-11-17

    An understanding of the role played by intermolecular forces in terms of the electron density distribution is fundamental to the understanding of the self-assembly of molecules in the formation of a molecular crystal. Using ab initio methods capable of describing both short-range intramolecular interactions and long-range London dispersion interactions arising from electron correlation, analyses of inorganic dimers of As(4)S(4) and As(4)O(6) molecules cut from the structures of realgar and arsenolite, respectively, reveal that the molecules adopt a configuration that closely matches that observed for the crystal. Decomposition of the interaction energies using symmetry-adapted perturbation theory reveals that both model dimers feature significant stabilization from electrostatic forces as anticipated by a Lewis acid/Lewis base picture of the interaction. London dispersion forces also contribute significantly to the interaction, although they play a greater role in the realgar structure near equilibrium than in arsenolite.

  12. Multi-curvature liquid meniscus in a nanochannel: evidence of interplay between intermolecular and surface forces.

    PubMed

    Kim, Pilnam; Kim, Ho-Young; Kim, Jae Kwan; Reiter, Günter; Suh, Kahp Y

    2009-11-21

    We examined the formation of a multiply curved meniscus inside rectangular nanochannels, whose width ranges from 50 to 800 nm at a constant height of 200 nm. When the channel width is smaller than approximately 400 nm under partial wetting conditions, a distinct multi-curvature meniscus was observed at the advancing front with an edge disjoined from the wall. In contrast, a typical pre-wetting film was observed at the front regardless of the channel size for complete wetting conditions. Our theoretical analysis demonstrated that the multi-curvature meniscus is generated from the increased contribution of an extra pressure due to intermolecular interactions near the wall. In particular, a plug-like meniscus profile was observed at the advancing liquid front for the 50 nm wide channel owing to an overlap between convex curvatures at the channel walls. Finally, we showed that the filling velocity of liquid can be decreased by decreasing the channel size due to the reduced wettability.

  13. Brief history of intermolecular and intersurface forces in complex fluid systems.

    PubMed

    Israelachvili, Jacob; Ruths, Marina

    2013-08-01

    We review the developments of ideas, concepts, and theories of intermolecular and intersurface forces and how these were influenced (or ignored) by observations of nature and, later, systematic experimentation. The emphasis of this review is on the way things gradually changed: experimentation replaced rhetoric, measurement and quantification replaced hand waving, energy replaced force in calculations, discrete atoms replaced the (continuum) aether, thermodynamics replaced mechanistic models, randomness and probability replaced certainty, and delicate experiments on the subnanoscale revealed fascinating self-assembling structures and complex behavior of even the simplest systems. We conclude by discussing today's unresolved challenges: how complex "dynamic" multicomponent--especially living biological--systems that receive a continuous supply of energy can be far from equilibrium and not even in any steady state. Such systems, never static but evolving in both space and time, are still far from being understood both experimentally and theoretically.

  14. Inhibition of tau aggregation by a rosamine derivative that blocks tau intermolecular disulfide cross-linking.

    PubMed

    Haque, Md Mamunul; Kim, Dohee; Yu, Young Hyun; Lim, Sungsu; Kim, Dong Jin; Chang, Young-Tae; Ha, Hyung-Ho; Kim, Yun Kyung

    2014-09-01

    Abnormal tau aggregates are presumed to be neurotoxic and are an important therapeutic target for multiple neurodegenerative disorders including Alzheimer's disease. Growing evidence has shown that tau intermolecular disulfide cross-linking is critical in generating tau oligomers that serve as a building block for higher-order aggregates. Here we report that a small molecule inhibitor prevents tau aggregation by blocking the generation of disulfide cross-linked tau oligomers. Among the compounds tested, a rosamine derivative bearing mild thiol reactivity selectively labeled tau and effectively inhibited oligomerization and fibrillization processes in vitro. Our data suggest that controlling tau oxidation status could be a new therapeutic strategy for prevention of abnormal tau aggregation. PMID:24919397

  15. Intermolecular Electronic Coupling of Organic Units for Efficient Persistent Room-Temperature Phosphorescence.

    PubMed

    Yang, Zhiyong; Mao, Zhu; Zhang, Xuepeng; Ou, Depei; Mu, Yingxiao; Zhang, Yi; Zhao, Cunyuan; Liu, Siwei; Chi, Zhenguo; Xu, Jiarui; Wu, Yuan-Chun; Lu, Po-Yen; Lien, Alan; Bryce, Martin R

    2016-02-01

    Although persistent room-temperature phosphorescence (RTP) emission has been observed for a few pure crystalline organic molecules, there is no consistent mechanism and no universal design strategy for organic persistent RTP (pRTP) materials. A new mechanism for pRTP is presented, based on combining the advantages of different excited-state configurations in coupled intermolecular units, which may be applicable to a wide range of organic molecules. By following this mechanism, we have developed a successful design strategy to obtain bright pRTP by utilizing a heavy halogen atom to further increase the intersystem crossing rate of the coupled units. RTP with a remarkably long lifetime of 0.28 s and a very high quantum efficiency of 5 % was thus obtained under ambient conditions. This strategy represents an important step in the understanding of organic pRTP emission. PMID:26836346

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

    SciTech Connect

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

    2015-10-07

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

  17. Experimental evolution of complexity: in vitro emergence of intermolecular ribozyme interactions.

    PubMed Central

    Hanczyc, M M; Dorit, R L

    1998-01-01

    In the course of evolving variants of the Tetrahymena thermophila Group I ribozyme for improved DNA cleavage in vitro, we witnessed the unexpected emergence of a derived molecular species, capable of acting as a partner for the ribozyme, but no longer autocatalytic. This new RNA species exhibits a deletion in the catalytic core and participates in a productive intermolecular interaction with an active ribozyme, thus insuring its survival in the population. These novel RNA molecules have evolved a precise catalytic interaction with the Group I ribozyme and depend for their survival on the continued presence of active catalysts. This interaction hints at the complexity that may inevitably arise even in simple evolving systems. PMID:9510329

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

    PubMed

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

    2015-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    SciTech Connect

    Heßelmann, Andreas; Korona, Tatiana

    2014-09-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    SciTech Connect

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

    2015-12-15

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

  3. Projectile containing metastable intermolecular composites and spot fire method of use

    DOEpatents

    Asay, Blaine W.; Son, Steven F.; Sanders, V. Eric; Foley, Timothy; Novak, Alan M.; Busse, James R.

    2012-07-31

    A method for altering the course of a conflagration involving firing a projectile comprising a powder mixture of oxidant powder and nanosized reductant powder at velocity sufficient for a violent reaction between the oxidant powder and the nanosized reductant powder upon impact of the projectile, and causing impact of the projectile at a location chosen to draw a main fire to a spot fire at such location and thereby change the course of the conflagration, whereby the air near the chosen location is heated to a temperature sufficient to cause a spot fire at such location. The invention also includes a projectile useful for such method and said mixture preferably comprises a metastable intermolecular composite.

  4. Local modification of intermolecular interactions at a sub-molecule level

    NASA Astrophysics Data System (ADS)

    Song, Sang Yong; Jeong, Yong Chan; Kim, Youngjae; Kang, Joongoo; Seo, Jungpil

    2016-10-01

    The local modification of intermolecular interactions in nickel-phthalocyanine molecules (NiPCs) is investigated on an Au(111) substrate using scanning tunneling microscopy. When the molecules are physisorbed on the substrate, they repel each other due to induced charge dipole moments. However, when the NiPC is chemisorbed on the substrate through the dehydrogenation of one of its ligands by a bias pulse, we find that a nearby physisorbed NiPC is attracted to the dehydrogenated ligand and trapped. Using our experimental results in combination with density functional theory calculations, we show that the observed attraction can be ascribed to the local charge redistribution around the dehydrogenated ligand of the chemisorbed NiPC. Furthermore, we demonstrate that desorption of the attracted NiPC from the trapped site can be readily controlled by changing the density of NiPCs around the dehydrogenated ligand.

  5. Spectroscopic determination of intermolecular potentials of gas laser components and of major atmospheric constituents. Final report

    SciTech Connect

    Klemperer, W.

    1982-01-01

    A systematic study of the structure of weakly bound complexes of hydrogen fluoride has been accomplished. This research provides a broad account of the interaction of hydrogen fluoride with a variety of laser components and atmospheric constituents. Precision structures are now available for the species ArHF, CO/sub 2/HF, N/sub 2/OHF and SCOHF as a result of the present research program. In addition, precision structures have been obtained for ArCO2 and ArN/sub 2/0. This research provides the basic information necessary for reliable modelling of intermolecular forces between HF and Ar, CO/sub 2/, N/sub 2/0 and OCS as well as between Ar and CO/sub 2/ and N/sub 2/0.

  6. First-order exchange energy of intermolecular interactions from coupled cluster density matrices and their cumulants.

    PubMed

    Korona, Tatiana

    2008-06-14

    A new method for the calculation of the first-order intermolecular exchange energy is proposed. It is based on the partition of two-particle density matrices of monomers into the antisymmetrized product of one-particle density matrices and the remaining cumulant part. This partition is used to modify the formula for the first-order exchange energy developed by Moszynski et al. [J. Chem. Phys. 100, 5080 (1994)]. The new expression has been applied for the case of monomer density matrices derived from the expectation value expression for the coupled cluster singles and doubles wave function. In this way an accurate method of calculation of the first-order exchange energy for many-electron systems has been obtained, where both monomers are described on the coupled cluster level. Numerical results are presented for several benchmark van der Waals systems to illustrate the performance of the new approach.

  7. Intermolecular hydrogen bonded and self-assembled β-pleated sheet structures of β-sulfidocarbonyls

    NASA Astrophysics Data System (ADS)

    Hussain, Sahid; Das, Gopal; Chaudhuri, Mihir K.

    2007-06-01

    The three crystal structures of β-sulfidocarbonyls 1, 2 and 3 synthesized from the reaction of acryl amide with cystiene, 1,2-dithiol and 1,3-dithiols, respectively, in water catalyzed by borax, have been determined at 273 K. The characteristic features of the structures are self-assembly through intermolecular hydrogen bonding leading to infinite chains of molecules in one direction, in addition to the stacking of layers of such molecular chains in the perpendicular direction ultimately giving rise to β-pleated sheets of 3D molecular network involving N-H⋯O, C-H⋯O and C-H⋯S bonding in the crystal lattice.

  8. Local modification of intermolecular interactions at a sub-molecule level.

    PubMed

    Song, Sang Yong; Jeong, Yong Chan; Kim, Youngjae; Kang, Joongoo; Seo, Jungpil

    2016-10-14

    The local modification of intermolecular interactions in nickel-phthalocyanine molecules (NiPCs) is investigated on an Au(111) substrate using scanning tunneling microscopy. When the molecules are physisorbed on the substrate, they repel each other due to induced charge dipole moments. However, when the NiPC is chemisorbed on the substrate through the dehydrogenation of one of its ligands by a bias pulse, we find that a nearby physisorbed NiPC is attracted to the dehydrogenated ligand and trapped. Using our experimental results in combination with density functional theory calculations, we show that the observed attraction can be ascribed to the local charge redistribution around the dehydrogenated ligand of the chemisorbed NiPC. Furthermore, we demonstrate that desorption of the attracted NiPC from the trapped site can be readily controlled by changing the density of NiPCs around the dehydrogenated ligand.

  9. Manifestation of structure and intermolecular interactions of biologically active brassinosteroids in infrared spectra

    NASA Astrophysics Data System (ADS)

    Borisevich, N. A.; Skornyakov, I. V.; Khripach, V. A.; Tolstorozhev, G. B.; Zhabinskii, V. N.

    2007-09-01

    We have analyzed the IR spectra obtained for steroidal phytohormones 24-epibrassinolide, 24-epicastasterone, 28-homobrassinolide, and 28-homocastasterone. The characteristic frequencies of the stretching vibrations of the hydrocarbon groups CH3, CH2, and CH and also the C=O groups in the spectra of brassinolides are higher than in the spectra of castasterones, which makes it possible to identify them from the IR spectra. Study of the spectra of these brassinosteroids in different media (pressed samples in KBr, films, solutions in CHCl3 and CDCl3) allowed us to establish the presence of intermolecular interactions in which C=O and OH groups, OH-OH groups participate, and also the possible formation of intramolecular hydrogen bonds between the OH groups of the molecules.

  10. Ab initio intermolecular potential energy surface and thermophysical properties of nitrous oxide

    SciTech Connect

    Crusius, Johann-Philipp Hassel, Egon; Hellmann, Robert Bich, Eckard

    2015-06-28

    We present an analytical intermolecular potential energy surface (PES) for two rigid nitrous oxide (N{sub 2}O) molecules derived from high-level quantum-chemical ab initio calculations. Interaction energies for 2018 N{sub 2}O–N{sub 2}O configurations were computed utilizing the counterpoise-corrected supermolecular approach at the CCSD(T) level of theory using basis sets up to aug-cc-pVQZ supplemented with bond functions. A site-site potential function with seven sites per N{sub 2}O molecule was fitted to the pair interaction energies. We validated our PES by computing the second virial coefficient as well as shear viscosity and thermal conductivity in the dilute-gas limit. The values of these properties are substantiated by the best experimental data.

  11. Circular dichroism studies on intermolecular interactions of amphotericin B in ionic liquid-rich environments.

    PubMed

    Jameson, Laramie P; Dzyuba, Sergei V

    2013-07-01

    Aggregation of amphotericin B (AmB) in an ionic liquid-rich environment was investigated using circular dichroism (CD) spectroscopy. It was found that nature of the ionic liquids' anion had a strong impact not only on the aggregation of AmB, but more importantly on the nature of AmB aggregates, as observed in the asymmetry of the exciton couplet of the aggregate in CD spectra. Unique CD signals for AmB aggregates were observed in three different 1-butyl-3-methylimidazolium ionic liquid solutions: [C4 -mim]Br favored the formation of AmB aggregates that were similar to those found in water, whereas [C4 -mim]BF4 and [C4 -mim]NO3 produced AmB aggregates that were different from each other and those found in water. The obtained results suggest that the designer solvent ability of ionic liquids could be expanded to address numerous intermolecular processes.

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

    PubMed

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

    2015-07-14

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

  13. Structure and intermolecular interactions in selected binary solutions studied by X-ray methods

    NASA Astrophysics Data System (ADS)

    Drozdowski, Henryk; Romaniuk, Anna; Błaszczak, Zdzisław

    2013-12-01

    The results of X-ray structural studies of liquid chloroanisole C6H4OCH3Cl and 10% solutions of chloroanisole in 1,4-dimethylbenzene C8H10 are presented. It is the first paper on an X-ray diffraction study of the liquid solutions of chloroanisole. The X-ray measurements were made at 293 K for the scattering angle range 2Θ varying from 6° to 120°. Averaged scattered X-ray angular distributions I¯(S) were determined. The angular distributions of the intensity of X-ray scattered by 10% solutions of chloroanisole in 1,4-dimethylbenzene were compared to the angular distributions obtained for liquid ortho-, meta- and para-chloroanisole. The differential radial distribution functions of electron density 4πr∑j,knK[ρk(r)-ρ0] were numerically found using the Fourier analysis from a modified Warren, Krutter and Morningstar equation. To the maxima of DRDFs, interatomic and intermolecular distances were assigned. The use of short-wave radiation from an X-ray tube with a molybdenum anode permitted determination of the spheres of intermolecular ordering in the studied liquids and their solutions. The experimental results were used to plot models of the most highly probable mutual disposition of the molecules in liquid chloroanisole and their solutions. The benzene rings of two molecules are situated in parallel plane what results in antiparallel setting of the dipole moments of the chloroanisole molecules. X-ray structural analysis was applied to determine the packing coefficients of chloroanisole molecules. The results obtained in this paper confirm the specific structural properties of the solutions studied.

  14. Bile salt-induced intermolecular disulfide bond formation activates Vibrio cholerae virulence.

    PubMed

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

    2013-02-01

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

  15. Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization

    SciTech Connect

    Christensen, Anders S. E-mail: cui@chem.wisc.edu; Cui, Qiang E-mail: cui@chem.wisc.edu; Elstner, Marcus

    2015-08-28

    Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular interaction energies are also underestimated, especially for intermolecular interactions involving charged species. In this work, the third-order self-consistent charge density functional tight-binding method (DFTB3) is augmented with an auxiliary response density using the chemical-potential equalization (CPE) method and an empirical dispersion correction (D3). The parameters in the CPE and D3 models are fitted to high-level CCSD(T) reference interaction energies for a broad range of chemical species, as well as dipole moments calculated at the DFT level; the impact of including polarizabilities of molecules in the parameterization is also considered. Parameters for the elements H, C, N, O, and S are presented. The Root Mean Square Deviation (RMSD) interaction energy is improved from 6.07 kcal/mol to 1.49 kcal/mol for interactions with one charged species, whereas the RMSD is improved from 5.60 kcal/mol to 1.73 for a set of 9 salt bridges, compared to uncorrected DFTB3. For large water clusters and complexes that are dominated by dispersion interactions, the already satisfactory performance of the DFTB3-D3 model is retained; polarizabilities of neutral molecules are also notably improved. Overall, the CPE extension of DFTB3-D3 provides a more balanced description of different types of non-covalent interactions than Neglect of Diatomic Differential Overlap type of semi-empirical methods (e.g., PM6-D3H4) and PBE-D3 with modest basis sets.

  16. Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization

    PubMed Central

    Christensen, Anders S.; Elstner, Marcus; Cui, Qiang

    2015-01-01

    Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular interaction energies are also underestimated, especially for intermolecular interactions involving charged species. In this work, the third-order self-consistent charge density functional tight-binding method (DFTB3) is augmented with an auxiliary response density using the chemical-potential equalization (CPE) method and an empirical dispersion correction (D3). The parameters in the CPE and D3 models are fitted to high-level CCSD(T) reference interaction energies for a broad range of chemical species, as well as dipole moments calculated at the DFT level; the impact of including polarizabilities of molecules in the parameterization is also considered. Parameters for the elements H, C, N, O, and S are presented. The Root Mean Square Deviation (RMSD) interaction energy is improved from 6.07 kcal/mol to 1.49 kcal/mol for interactions with one charged species, whereas the RMSD is improved from 5.60 kcal/mol to 1.73 for a set of 9 salt bridges, compared to uncorrected DFTB3. For large water clusters and complexes that are dominated by dispersion interactions, the already satisfactory performance of the DFTB3-D3 model is retained; polarizabilities of neutral molecules are also notably improved. Overall, the CPE extension of DFTB3-D3 provides a more balanced description of different types of non-covalent interactions than Neglect of Diatomic Differential Overlap type of semi-empirical methods (e.g., PM6-D3H4) and PBE-D3 with modest basis sets. PMID:26328834

  17. Increased pathogenicity in a pseudorecombinant bipartite geminivirus correlates with intermolecular recombination.

    PubMed Central

    Hou, Y M; Gilbertson, R L

    1996-01-01

    Most whitefly-transmitted geminiviruses possess bipartite DNA genomes, and this feature may facilitate viral evolution through pseudorecombination and/or recombination. To test this hypothesis, the DNA-A and DNA-B components of the geminiviruses bean dwarf mosaic virus (BDMV) and tomato mottle virus (ToMoV) were exchanged, and the resultant pseudorecombinants were serially passaged through plants. Both pseudorecombinants were infectious in Nicotiana benthamiana but induced attenuated symptoms and had reduced DNA-B levels. Serial passage experiments revealed that the BDMV DNA-A plus ToMoV DNA-B pseudorecombinant could not be maintained beyond three passages. In contrast, the ToMoV DNA-A plus BDMV DNA-B pseudorecombinant was maintained during serial passage through N. benthamiana and Phaseolus vulgaris and, after three to five passages, became highly pathogenic. Furthermore, the increased pathogenicity of this pseudorecombinant was consistently associated with an increased level of DNA-B, which eventuated in equivalent levels of both components. Sequence analysis of the DNA-B component of the more pathogenic pseudorecombinant revealed that intermolecular recombination had taken place in which most of the BDMV DNA-B common region was replaced with the ToMoV DNA-A common region. This recombinant DNA-B component, which contained the ToMoV origin of replication, was the predominant DNA-B component associated with the more pathogenic pseudorecombinant. These results provide the first demonstration of recombination between distinct bipartite geminiviruses and establish that the bipartite genome can facilitate viral evolution through pseudorecombination and intermolecular recombination. PMID:8764054

  18. Strategic directions and mechanisms in technology transfer

    NASA Technical Reports Server (NTRS)

    Mackin, Robert

    1992-01-01

    An outline summarizing the Working Panel discussion related to strategic directions for technology transfer is presented. Specific topics addressed include measuring success, management of technology, innovation and experimentation in the tech transfer process, integration of tech transfer into R&D planning, institutionalization of tech transfer, and policy/legislative resources.

  19. The Transfer Achievement Program (TAP): Information Packet.

    ERIC Educational Resources Information Center

    Segura, Armando; Noseworthy, Victoria

    Santa Barbara City College (California) created the Transfer Achievement Program (TAP) to deliver an integrated and cohesive set of services to underrepresented students to help increase their transfer rate to four-year institutions. TAP provides students with a developmental map of transfer-related activities through the use of the Transfer Task…

  20. An integrated model of transcription factor diffusion shows the importance of intersegmental transfer and quaternary protein structure for target site finding.

    PubMed

    Schmidt, Hugo G; Sewitz, Sven; Andrews, Steven S; Lipkow, Karen

    2014-01-01

    We present a computational model of transcription factor motion that explains both the observed rapid target finding of transcription factors, and how this motion influences protein and genome structure. Using the Smoldyn software, we modelled transcription factor motion arising from a combination of unrestricted 3D diffusion in the nucleoplasm, sliding along the DNA filament, and transferring directly between filament sections by intersegmental transfer. This presents a fine-grain picture of the way in which transcription factors find their targets two orders of magnitude faster than 3D diffusion alone allows. Eukaryotic genomes contain sections of nucleosome free regions (NFRs) around the promoters; our model shows that the presence and size of these NFRs can be explained as their acting as antennas on which transcription factors slide to reach their targets. Additionally, our model shows that intersegmental transfer may have shaped the quaternary structure of transcription factors: sequence specific DNA binding proteins are unusually enriched in dimers and tetramers, perhaps because these allow intersegmental transfer, which accelerates target site finding. Finally, our model shows that a 'hopping' motion can emerge from 3D diffusion on small scales. This explains the apparently long sliding lengths that have been observed for some DNA binding proteins observed in vitro. Together, these results suggest that transcription factor diffusion dynamics help drive the evolution of protein and genome structure.