WorldWideScience

Sample records for long-range proton transfer

  1. Tyrosine oxidation in heme oxygenase: examination of long-range proton-coupled electron transfer.

    Science.gov (United States)

    Smirnov, Valeriy V; Roth, Justine P

    2014-10-01

    Heme oxygenase is responsible for the degradation of a histidine-ligated ferric protoporphyrin IX (Por) to biliverdin, CO, and the free ferrous ion. Described here are studies of tyrosyl radical formation reactions that occur after oxidizing Fe(III)(Por) to Fe(IV)=O(Por(·+)) in human heme oxygenase isoform-1 (hHO-1) and the structurally homologous protein from Corynebacterium diphtheriae (cdHO). Site-directed mutagenesis on hHO-1 probes the reduction of Fe(IV)=O(Por(·+)) by tyrosine residues within 11 Å of the prosthetic group. In hHO-1, Y58· is implicated as the most likely site of oxidation, based on the pH and pD dependent kinetics. The absence of solvent deuterium isotope effects in basic solutions of hHO-1 and cdHO contrasts with the behavior of these proteins in the acidic solution, suggesting that long-range proton-coupled electron transfer predominates over electron transfer.

  2. Long-range proton transfer in aqueous acid-base reactions

    NARCIS (Netherlands)

    Siwick, B.J.; Cox, M.J.; Bakker, H.J.

    2008-01-01

    We study the mechanism of proton transfer (PT) in the aqueous acid−base reaction between the photoacid 8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTS) and acetate by probing the vibrational resonances of HPTS, acetate, and the hydrated proton with femtosecond mid-infrared laser pulses. We find that PT

  3. Long-Range Electrostatics-Induced Two-Proton Transfer Captured by Neutron Crystallography in an Enzyme Catalytic Site.

    Science.gov (United States)

    Gerlits, Oksana; Wymore, Troy; Das, Amit; Shen, Chen-Hsiang; Parks, Jerry M; Smith, Jeremy C; Weiss, Kevin L; Keen, David A; Blakeley, Matthew P; Louis, John M; Langan, Paul; Weber, Irene T; Kovalevsky, Andrey

    2016-04-11

    Neutron crystallography was used to directly locate two protons before and after a pH-induced two-proton transfer between catalytic aspartic acid residues and the hydroxy group of the bound clinical drug darunavir, located in the catalytic site of enzyme HIV-1 protease. The two-proton transfer is triggered by electrostatic effects arising from protonation state changes of surface residues far from the active site. The mechanism and pH effect are supported by quantum mechanics/molecular mechanics (QM/MM) calculations. The low-pH proton configuration in the catalytic site is deemed critical for the catalytic action of this enzyme and may apply more generally to other aspartic proteases. Neutrons therefore represent a superb probe to obtain structural details for proton transfer reactions in biological systems at a truly atomic level.

  4. Mechanism of long-range proton translocation along biological membranes.

    Science.gov (United States)

    Medvedev, Emile S; Stuchebrukhov, Alexei A

    2013-02-14

    Recent experiments suggest that protons can travel along biological membranes up to tens of micrometers, but the mechanism of transport is unknown. To explain such a long-range proton translocation we describe a model that takes into account the coupled bulk diffusion that accompanies the migration of protons on the surface. We show that protons diffusing at or near the surface before equilibrating with the bulk desorb and re-adsorb at the surface thousands of times, giving rise to a power-law desorption kinetics. As a result, the decay of the surface protons occurs very slowly, allowing for establishing local gradient and local exchange, as was envisioned in the early local models of biological energy transduction.

  5. Long-range azimuthal correlations in proton-proton and proton-nucleus collisions from the incoherent scattering of partons

    OpenAIRE

    Guo-Liang Ma; Adam Bzdak

    2014-01-01

    We show that the incoherent elastic scattering of partons, as present in a multi-phase transport model (AMPT), with a modest parton-parton cross-section of $\\sigma=1.5 - 3$ mb, naturally explains the long-range two-particle azimuthal correlation as observed in proton-proton and proton-nucleus collisions at the Large Hadron Collider.

  6. Proton clouds to measure long-range contacts between nonexchangeable side chain protons in solid-state NMR.

    Science.gov (United States)

    Sinnige, Tessa; Daniëls, Mark; Baldus, Marc; Weingarth, Markus

    2014-03-26

    We show that selective labeling of proteins with protonated amino acids embedded in a perdeuterated matrix, dubbed 'proton clouds', provides general access to long-range contacts between nonexchangeable side chain protons in proton-detected solid-state NMR, which is important to study protein tertiary structure. Proton-cloud labeling significantly improves spectral resolution by simultaneously reducing proton line width and spectral crowding despite a high local proton density in clouds. The approach is amenable to almost all canonical amino acids. Our method is demonstrated on ubiquitin and the β-barrel membrane protein BamA.

  7. Long range energy transfer in graphene hybrid structures

    Science.gov (United States)

    Gonçalves, Hugo; Bernardo, César; Moura, Cacilda; Ferreira, R. A. S.; André, P. S.; Stauber, Tobias; Belsley, Michael; Schellenberg, Peter

    2016-08-01

    In this work we quantify the distance dependence for the extraction of energy from excited chromophores by a single layer graphene flake over a large separation range. To this end hybrid structures were prepared, consisting of a thin (2 nm) layer of a polymer matrix doped with a well chosen strongly fluorescent organic molecule, followed by an un-doped spacer layer of well-defined thicknesses made of the same polymer material and an underlying single layer of pristine, undoped graphene. The coupling strength is assessed through the variation of the fluorescence decay kinetics as a function of distance between the graphene and the excited chromophore molecules. Non-radiative energy transfer to the graphene was observed at distances of up to 60 nm a range much greater than typical energy transfer distances observed in molecular systems.

  8. Long-range excitation energy transfer in Langmuir-Blodgett multilayer systems

    Science.gov (United States)

    Draxler, Sonja; Lippitsch, Max E.; Aussenegg, Franz R.

    1989-07-01

    In Langmuir-Blodgett films containing organic dyes, efficient energy transfer over distances exceeding 100 nm is observed. This exceptionally long-range transfer is interpreted as due to special mutual orientation of the dye molecules.

  9. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane;

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...... new light on how oxidative enzymes present in plant degraders may act in concert....

  10. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane;

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...

  11. Long-range protein electron transfer observed at the single-molecule level

    DEFF Research Database (Denmark)

    Chi, Qijin; Farver, Ole; Ulstrup, Jens

    2005-01-01

    A biomimetic long-range electron transfer (ET) system consisting of the blue copper protein azurin, a tunneling barrier bridge, and a gold single-crystal electrode was designed on the basis of molecular wiring self-assembly principles. This system is sufficiently stable and sensitive in a quasi...

  12. Observation of Long-Range, Near-Side Angular Correlations in Proton-Proton Collisions at the LHC

    CERN Document Server

    Khachatryan, Vardan; Tumasyan, Armen; Adam, Wolfgang; Bergauer, Thomas; Dragicevic, Marko; Erö, Janos; Fabjan, Christian; Friedl, Markus; Fruehwirth, Rudolf; Ghete, Vasile Mihai; Hammer, Josef; Haensel, Stephan; Hartl, Christian; Hoch, Michael; Hörmann, Natascha; Hrubec, Josef; Jeitler, Manfred; Kasieczka, Gregor; Kiesenhofer, Wolfgang; Krammer, Manfred; Liko, Dietrich; Mikulec, Ivan; Pernicka, Manfred; Rohringer, Herbert; Schöfbeck, Robert; Strauss, Josef; Taurok, Anton; Teischinger, Florian; Waltenberger, Wolfgang; Walzel, Gerhard; Widl, Edmund; Wulz, Claudia-Elisabeth; Mossolov, Vladimir; Shumeiko, Nikolai; Suarez Gonzalez, Juan; Benucci, Leonardo; Ceard, Ludivine; De Wolf, Eddi A.; Janssen, Xavier; Maes, Thomas; Mucibello, Luca; Ochesanu, Silvia; Roland, Benoit; Rougny, Romain; Selvaggi, Michele; Van Haevermaet, Hans; Van Mechelen, Pierre; Van Remortel, Nick; Adler, Volker; Beauceron, Stephanie; Blyweert, Stijn; D'Hondt, Jorgen; Devroede, Olivier; Kalogeropoulos, Alexis; Maes, Joris; Maes, Michael; Tavernier, Stefaan; Van Doninck, Walter; Van Mulders, Petra; Villella, Ilaria; Chabert, Eric Christian; Charaf, Otman; Clerbaux, Barbara; De Lentdecker, Gilles; Dero, Vincent; Gay, Arnaud; Hammad, Gregory Habib; Hreus, Tomas; Marage, Pierre Edouard; Vander Velde, Catherine; Vanlaer, Pascal; Wickens, John; Costantini, Silvia; Grunewald, Martin; Klein, Benjamin; Marinov, Andrey; Ryckbosch, Dirk; Thyssen, Filip; Tytgat, Michael; Vanelderen, Lukas; Verwilligen, Piet; Walsh, Sinead; Zaganidis, Nicolas; Basegmez, Suzan; Bruno, Giacomo; Caudron, Julien; De Favereau De Jeneret, Jerome; Delaere, Christophe; Demin, Pavel; Favart, Denis; Giammanco, Andrea; Grégoire, Ghislain; Hollar, Jonathan; Lemaitre, Vincent; Militaru, Otilia; Ovyn, Severine; Pagano, Davide; Pin, Arnaud; Piotrzkowski, Krzysztof; Quertenmont, Loic; Schul, Nicolas; Beliy, Nikita; Caebergs, Thierry; Daubie, Evelyne; Alves, Gilvan; De Jesus Damiao, Dilson; Pol, Maria Elena; Henrique Gomes E Souza, Moacyr; Carvalho, Wagner; Melo Da Costa, Eliza; De Oliveira Martins, Carley; Fonseca De Souza, Sandro; Mundim, Luiz; Nogima, Helio; Oguri, Vitor; Otalora Goicochea, Juan Martin; Prado Da Silva, Wanda Lucia; Santoro, Alberto; Silva Do Amaral, Sheila Mara; Sznajder, Andre; Torres Da Silva De Araujo, Felipe; De Almeida Dias, Flavia; Ferreira Dias, Marco Andre; Tomei, Thiago; De Moraes Gregores, Eduardo; Da Cunha Marinho, Franciole; Novaes, Sergio F.; Padula, Sandra; Darmenov, Nikolay; Dimitrov, Lubomir; Genchev, Vladimir; Iaydjiev, Plamen; Piperov, Stefan; Rodozov, Mircho; Stoykova, Stefka; Sultanov, Georgi; Tcholakov, Vanio; Trayanov, Rumen; Vankov, Ivan; Dyulendarova, Milena; Hadjiiska, Roumyana; Kozhuharov, Venelin; Litov, Leander; Marinova, Evelina; Mateev, Matey; Pavlov, Borislav; Petkov, Peicho; Bian, Jian-Guo; Chen, Guo-Ming; Chen, He-Sheng; Jiang, Chun-Hua; Liang, Dong; Liang, Song; Wang, Jian; Wang, Jian; Wang, Xianyou; Wang, Zheng; Yang, Min; Zang, Jingjing; Zhang, Zhen; Ban, Yong; Guo, Shuang; Hu, Zhen; Li, Wenbo; Mao, Yajun; Qian, Si-Jin; Teng, Haiyun; Zhu, Bo; Cabrera, Andrés; Gomez Moreno, Bernardo; Ocampo Rios, Alberto Andres; Osorio Oliveros, Andres Felipe; Sanabria, Juan Carlos; Godinovic, Nikola; Lelas, Damir; Lelas, Karlo; Plestina, Roko; Polic, Dunja; Puljak, Ivica; Antunovic, Zeljko; Dzelalija, Mile; Brigljevic, Vuko; Duric, Senka; Kadija, Kreso; Morovic, Srecko; Attikis, Alexandros; Fereos, Reginos; Galanti, Mario; Mousa, Jehad; Nicolaou, Charalambos; Ptochos, Fotios; Razis, Panos A.; Rykaczewski, Hans; Assran, Yasser; Mahmoud, Mohammed; Hektor, Andi; Kadastik, Mario; Kannike, Kristjan; Müntel, Mait; Raidal, Martti; Rebane, Liis; Azzolini, Virginia; Eerola, Paula; Czellar, Sandor; Härkönen, Jaakko; Heikkinen, Mika Aatos; Karimäki, Veikko; Kinnunen, Ritva; Klem, Jukka; Kortelainen, Matti J.; Lampén, Tapio; Lassila-Perini, Kati; Lehti, Sami; Lindén, Tomas; Luukka, Panja-Riina; Mäenpää, Teppo; Tuominen, Eija; Tuominiemi, Jorma; Tuovinen, Esa; Ungaro, Donatella; Wendland, Lauri; Banzuzi, Kukka; Korpela, Arja; Tuuva, Tuure; Sillou, Daniel; Besancon, Marc; Dejardin, Marc; Denegri, Daniel; Descamps, Julien; Fabbro, Bernard; Faure, Jean-Louis; Ferri, Federico; Ganjour, Serguei; Gentit, François-Xavier; Givernaud, Alain; Gras, Philippe; Hamel de Monchenault, Gautier; Jarry, Patrick; Locci, Elizabeth; Malcles, Julie; Marionneau, Matthieu; Millischer, Laurent; Rander, John; Rosowsky, André; Rousseau, Delphine; Titov, Maksym; Verrecchia, Patrice; Baffioni, Stephanie; Bianchini, Lorenzo; Bluj, Michal; Broutin, Clementine; Busson, Philippe; Charlot, Claude; Dobrzynski, Ludwik; Granier de Cassagnac, Raphael; Haguenauer, Maurice; Miné, Philippe; Mironov, Camelia; Ochando, Christophe; Paganini, Pascal; Sabes, David; Salerno, Roberto; Sirois, Yves; Thiebaux, Christophe; Zabi, Alexandre; Agram, Jean-Laurent; Besson, Auguste; Bloch, Daniel; Bodin, David; Brom, Jean-Marie; Cardaci, Marco; Conte, Eric; Drouhin, Frédéric; Ferro, Cristina; Fontaine, Jean-Charles; Gelé, Denis; Goerlach, Ulrich; Greder, Sebastien; Juillot, Pierre; Karim, Mehdi; Le Bihan, Anne-Catherine; Mikami, Yoshinari; Van Hove, Pierre; Fassi, Farida; Mercier, Damien; Baty, Clement; Beaupere, Nicolas; Bedjidian, Marc; Bondu, Olivier; Boudoul, Gaelle; Boumediene, Djamel; Brun, Hugues; Chanon, Nicolas; Chierici, Roberto; Contardo, Didier; Depasse, Pierre; El Mamouni, Houmani; Falkiewicz, Anna; Fay, Jean; Gascon, Susan; Ille, Bernard; Kurca, Tibor; Le Grand, Thomas; Lethuillier, Morgan; Mirabito, Laurent; Perries, Stephane; Sordini, Viola; Tosi, Silvano; Tschudi, Yohann; Verdier, Patrice; Xiao, Hong; Roinishvili, Vladimir; Anagnostou, Georgios; Edelhoff, Matthias; Feld, Lutz; Heracleous, Natalie; Hindrichs, Otto; Jussen, Ruediger; Klein, Katja; Merz, Jennifer; Mohr, Niklas; Ostapchuk, Andrey; Perieanu, Adrian; Raupach, Frank; Sammet, Jan; Schael, Stefan; Sprenger, Daniel; Weber, Hendrik; Weber, Martin; Wittmer, Bruno; Ata, Metin; Bender, Walter; Erdmann, Martin; Frangenheim, Jens; Hebbeker, Thomas; Hinzmann, Andreas; Hoepfner, Kerstin; Hof, Carsten; Klimkovich, Tatsiana; Klingebiel, Dennis; Kreuzer, Peter; Lanske, Dankfried; Magass, Carsten; Masetti, Gianni; Merschmeyer, Markus; Meyer, Arnd; Papacz, Paul; Pieta, Holger; Reithler, Hans; Schmitz, Stefan Antonius; Sonnenschein, Lars; Steggemann, Jan; Teyssier, Daniel; Bontenackels, Michael; Davids, Martina; Duda, Markus; Flügge, Günter; Geenen, Heiko; Giffels, Manuel; Haj Ahmad, Wael; Heydhausen, Dirk; Kress, Thomas; Kuessel, Yvonne; Linn, Alexander; Nowack, Andreas; Perchalla, Lars; Pooth, Oliver; Rennefeld, Jörg; Sauerland, Philip; Stahl, Achim; Thomas, Maarten; Tornier, Daiske; Zoeller, Marc Henning; Aldaya Martin, Maria; Behrenhoff, Wolf; Behrens, Ulf; Bergholz, Matthias; Borras, Kerstin; Campbell, Alan; Castro, Elena; Dammann, Dirk; Eckerlin, Guenter; Flossdorf, Alexander; Flucke, Gero; Geiser, Achim; Glushkov, Ivan; Hauk, Johannes; Jung, Hannes; Kasemann, Matthias; Katkov, Igor; Katsas, Panagiotis; Kleinwort, Claus; Kluge, Hannelies; Knutsson, Albert; Krücker, Dirk; Kuznetsova, Ekaterina; Lange, Wolfgang; Lohmann, Wolfgang; Mankel, Rainer; Marienfeld, Markus; Melzer-Pellmann, Isabell-Alissandra; Meyer, Andreas Bernhard; Mnich, Joachim; Mussgiller, Andreas; Olzem, Jan; Parenti, Andrea; Raspereza, Alexei; Raval, Amita; Schmidt, Ringo; Schoerner-Sadenius, Thomas; Sen, Niladri; Stein, Matthias; Tomaszewska, Justyna; Volyanskyy, Dmytro; Walsh, Roberval; Wissing, Christoph; Autermann, Christian; Bobrovskyi, Sergei; Draeger, Jula; Eckstein, Doris; Enderle, Holger; Gebbert, Ulla; Kaschube, Kolja; Kaussen, Gordon; Klanner, Robert; Mura, Benedikt; Naumann-Emme, Sebastian; Nowak, Friederike; Pietsch, Niklas; Sander, Christian; Schettler, Hannes; Schleper, Peter; Schröder, Matthias; Schum, Torben; Schwandt, Joern; Srivastava, Ajay Kumar; Stadie, Hartmut; Steinbrück, Georg; Thomsen, Jan; Wolf, Roger; Bauer, Julia; Buege, Volker; Cakir, Altan; Chwalek, Thorsten; Daeuwel, Daniel; De Boer, Wim; Dierlamm, Alexander; Dirkes, Guido; Feindt, Michael; Gruschke, Jasmin; Hackstein, Christoph; Hartmann, Frank; Heinrich, Michael; Held, Hauke; Hoffmann, Karl-Heinz; Honc, Simon; Kuhr, Thomas; Martschei, Daniel; Mueller, Steffen; Müller, Thomas; Neuland, Maike Brigitte; Niegel, Martin; Oberst, Oliver; Oehler, Andreas; Ott, Jochen; Peiffer, Thomas; Piparo, Danilo; Quast, Gunter; Rabbertz, Klaus; Ratnikov, Fedor; Renz, Manuel; Sabellek, Andreas; Saout, Christophe; Scheurer, Armin; Schieferdecker, Philipp; Schilling, Frank-Peter; Schott, Gregory; Simonis, Hans-Jürgen; Stober, Fred-Markus Helmut; Troendle, Daniel; Wagner-Kuhr, Jeannine; Zeise, Manuel; Zhukov, Valery; Ziebarth, Eva Barbara; Daskalakis, Georgios; Geralis, Theodoros; Kesisoglou, Stilianos; Kyriakis, Aristotelis; Loukas, Demetrios; Manolakos, Ioannis; Markou, Athanasios; Markou, Christos; Mavrommatis, Charalampos; Petrakou, Eleni; Gouskos, Loukas; Mertzimekis, Theodoros; Panagiotou, Apostolos; Evangelou, Ioannis; Kokkas, Panagiotis; Manthos, Nikolaos; Papadopoulos, Ioannis; Patras, Vaios; Triantis, Frixos A.; Aranyi, Attila; Bencze, Gyorgy; Boldizsar, Laszlo; Debreczeni, Gergely; Hajdu, Csaba; Horvath, Dezso; Kapusi, Anita; Krajczar, Krisztian; Laszlo, Andras; Sikler, Ferenc; Vesztergombi, Gyorgy; Beni, Noemi; Molnar, Jozsef; Palinkas, Jozsef; Szillasi, Zoltan; Veszpremi, Viktor; Raics, Peter; Trocsanyi, Zoltan Laszlo; Ujvari, Balazs; Bansal, Sunil; Beri, Suman Bala; Bhatnagar, Vipin; Jindal, Monika; Kaur, Manjit; Kohli, Jatinder Mohan; Mehta, Manuk Zubin; Nishu, Nishu; Saini, Lovedeep Kaur; Sharma, Archana; Sharma, Richa; Singh, Anil; Singh, Jas Bir; Singh, Supreet Pal; Ahuja, Sudha; Bhattacharya, Satyaki; Chauhan, Sushil; Choudhary, Brajesh C.; Gupta, Pooja; Jain, Sandhya; Jain, Shilpi; Kumar, Ashok; Shivpuri, Ram Krishen; Choudhury, Rajani Kant; Dutta, Dipanwita; Kailas, Swaminathan; Kataria, Sushil Kumar; Mohanty, Ajit Kumar; Pant, Lalit Mohan; Shukla, Prashant; Suggisetti, Praveenkumar; Aziz, Tariq; Guchait, Monoranjan; Gurtu, Atul; Maity, Manas; Majumder, Devdatta; Majumder, Gobinda; Mazumdar, Kajari; Mohanty, Gagan Bihari; Saha, Anirban; Sudhakar, Katta; Wickramage, Nadeesha; Banerjee, Sudeshna; Dugad, Shashikant; Mondal, Naba Kumar; Arfaei, Hessamaddin; Bakhshiansohi, Hamed; Etesami, Seyed Mohsen; Fahim, Ali; Hashemi, Majid; Jafari, Abideh; Khakzad, Mohsen; Mohammadi, Abdollah; Mohammadi Najafabadi, Mojtaba; Paktinat Mehdiabadi, Saeid; Safarzadeh, Batool; Zeinali, Maryam; Abbrescia, Marcello; Barbone, Lucia; Calabria, Cesare; Colaleo, Anna; Creanza, Donato; De Filippis, Nicola; De Palma, Mauro; Dimitrov, Anton; Fedele, Francesca; Fiore, Luigi; Iaselli, Giuseppe; Lusito, Letizia; Maggi, Giorgio; Maggi, Marcello; Manna, Norman; Marangelli, Bartolomeo; My, Salvatore; Nuzzo, Salvatore; Pierro, Giuseppe Antonio; Pompili, Alexis; Pugliese, Gabriella; Romano, Francesco; Roselli, Giuseppe; Selvaggi, Giovanna; Silvestris, Lucia; Trentadue, Raffaello; Tupputi, Salvatore; Zito, Giuseppe; Abbiendi, Giovanni; Benvenuti, Alberto; Bonacorsi, Daniele; Braibant-Giacomelli, Sylvie; Capiluppi, Paolo; Castro, Andrea; Cavallo, Francesca Romana; Cuffiani, Marco; Dallavalle, Gaetano-Marco; Fabbri, Fabrizio; Fanfani, Alessandra; Fasanella, Daniele; Giacomelli, Paolo; Giunta, Marina; Grandi, Claudio; Marcellini, Stefano; Meneghelli, Marco; Montanari, Alessandro; Navarria, Francesco; Odorici, Fabrizio; Perrotta, Andrea; Rossi, Antonio; Rovelli, Tiziano; Siroli, Gianni; Travaglini, Riccardo; Albergo, Sebastiano; Cappello, Gigi; Chiorboli, Massimiliano; Costa, Salvatore; Tricomi, Alessia; Tuve, Cristina; Barbagli, Giuseppe; Broccolo, Giuseppe; Ciulli, Vitaliano; Civinini, Carlo; D'Alessandro, Raffaello; Focardi, Ettore; Frosali, Simone; Gallo, Elisabetta; Lenzi, Piergiulio; Meschini, Marco; Paoletti, Simone; Sguazzoni, Giacomo; Tropiano, Antonio; Benussi, Luigi; Bianco, Stefano; Colafranceschi, Stefano; Fabbri, Franco; Piccolo, Davide; Fabbricatore, Pasquale; Musenich, Riccardo; Benaglia, Andrea; Cerati, Giuseppe Benedetto; De Guio, Federico; Di Matteo, Leonardo; Ghezzi, Alessio; Govoni, Pietro; Malberti, Martina; Malvezzi, Sandra; Martelli, Arabella; Massironi, Andrea; Menasce, Dario; Miccio, Vincenzo; Moroni, Luigi; Paganoni, Marco; Pedrini, Daniele; Ragazzi, Stefano; Redaelli, Nicola; Sala, Silvano; Tabarelli de Fatis, Tommaso; Tancini, Valentina; Buontempo, Salvatore; Carrillo Montoya, Camilo Andres; Cimmino, Anna; De Cosa, Annapaola; De Gruttola, Michele; Fabozzi, Francesco; Iorio, Alberto Orso Maria; Lista, Luca; Noli, Pasquale; Paolucci, Pierluigi; Azzi, Patrizia; Bacchetta, Nicola; Bellan, Paolo; Bisello, Dario; Branca, Antonio; Carlin, Roberto; Checchia, Paolo; Conti, Enrico; De Mattia, Marco; Dorigo, Tommaso; Dosselli, Umberto; Fanzago, Federica; Gasparini, Fabrizio; Gasparini, Ugo; Giubilato, Piero; Gresele, Ambra; Lacaprara, Stefano; Lazzizzera, Ignazio; Margoni, Martino; Mazzucato, Mirco; Meneguzzo, Anna Teresa; Perrozzi, Luca; Pozzobon, Nicola; Ronchese, Paolo; Simonetto, Franco; Torassa, Ezio; Tosi, Mia; Vanini, Sara; Zotto, Pierluigi; Zumerle, Gianni; Baesso, Paolo; Berzano, Umberto; Riccardi, Cristina; Torre, Paola; Vitulo, Paolo; Viviani, Claudio; Biasini, Maurizio; Bilei, Gian Mario; Caponeri, Benedetta; Fanò, Livio; Lariccia, Paolo; Lucaroni, Andrea; Mantovani, Giancarlo; Menichelli, Mauro; Nappi, Aniello; Santocchia, Attilio; Servoli, Leonello; Taroni, Silvia; Valdata, Marisa; Volpe, Roberta; Azzurri, Paolo; Bagliesi, Giuseppe; Bernardini, Jacopo; Boccali, Tommaso; Castaldi, Rino; D'Agnolo, Raffaele Tito; Dell'Orso, Roberto; Fiori, Francesco; Foà, Lorenzo; Giassi, Alessandro; Kraan, Aafke; Ligabue, Franco; Lomtadze, Teimuraz; Martini, Luca; Messineo, Alberto; Palla, Fabrizio; Palmonari, Francesco; Sarkar, Subir; Segneri, Gabriele; Serban, Alin Titus; Spagnolo, Paolo; Tenchini, Roberto; Tonelli, Guido; Venturi, Andrea; Verdini, Piero Giorgio; Barone, Luciano; Cavallari, Francesca; Del Re, Daniele; Di Marco, Emanuele; Diemoz, Marcella; Franci, Daniele; Grassi, Marco; Longo, Egidio; Organtini, Giovanni; Palma, Alessandro; Pandolfi, Francesco; Paramatti, Riccardo; Rahatlou, Shahram; Amapane, Nicola; Arcidiacono, Roberta; Argiro, Stefano; Arneodo, Michele; Biino, Cristina; Botta, Cristina; Cartiglia, Nicolo; Castello, Roberto; Costa, Marco; Demaria, Natale; Graziano, Alberto; Mariotti, Chiara; Marone, Matteo; Maselli, Silvia; Migliore, Ernesto; Mila, Giorgia; Monaco, Vincenzo; Musich, Marco; Obertino, Maria Margherita; Pastrone, Nadia; Pelliccioni, Mario; Romero, Alessandra; Ruspa, Marta; Sacchi, Roberto; Sola, Valentina; Solano, Ada; Staiano, Amedeo; Trocino, Daniele; Vilela Pereira, Antonio; Ambroglini, Filippo; Belforte, Stefano; Cossutti, Fabio; Della Ricca, Giuseppe; Gobbo, Benigno; Montanino, Damiana; Penzo, Aldo; Heo, Seong Gu; Chang, Sunghyun; Chung, Jin Hyuk; Kim, Dong Hee; Kim, Gui Nyun; Kim, Ji Eun; Kong, Dae Jung; Park, Hyangkyu; Son, Dohhee; Son, Dong-Chul; Kim, Jaeho; Kim, Jae Yool; Song, Sanghyeon; Choi, Suyong; Hong, Byung-Sik; Jo, Mihee; Kim, Hyunchul; Kim, Ji Hyun; Kim, Tae Jeong; Lee, Kyong Sei; Moon, Dong Ho; Park, Sung Keun; Rhee, Han-Bum; Seo, Eunsung; Shin, Seungsu; Sim, Kwang Souk; Choi, Minkyoo; Kang, Seokon; Kim, Hyunyong; Park, Chawon; Park, Inkyu; Park, Sangnam; Ryu, Geonmo; Choi, Young-Il; Choi, Young Kyu; Goh, Junghwan; Lee, Jongseok; Lee, Sungeun; Seo, Hyunkwan; Yu, Intae; Bilinskas, Mykolas Jurgis; Grigelionis, Ignas; Janulis, Mindaugas; Martisiute, Dalia; Petrov, Pavel; Sabonis, Tomas; Castilla Valdez, Heriberto; De La Cruz Burelo, Eduard; Lopez-Fernandez, Ricardo; Sánchez Hernández, Alberto; Villasenor-Cendejas, Luis Manuel; Carrillo Moreno, Salvador; Vazquez Valencia, Fabiola; Salazar Ibarguen, Humberto Antonio; Casimiro Linares, Edgar; Morelos Pineda, Antonio; Reyes-Santos, Marco A.; Allfrey, Philip; Krofcheck, David; Tam, Jason; Butler, Philip H.; Doesburg, Robert; Silverwood, Hamish; Ahmad, Muhammad; Ahmed, Ijaz; Asghar, Muhammad Irfan; Hoorani, Hafeez R.; Khan, Wajid Ali; Khurshid, Taimoor; Qazi, Shamona; Cwiok, Mikolaj; Dominik, Wojciech; Doroba, Krzysztof; Kalinowski, Artur; Konecki, Marcin; Krolikowski, Jan; Frueboes, Tomasz; Gokieli, Ryszard; Górski, Maciej; Kazana, Malgorzata; Nawrocki, Krzysztof; Szleper, Michal; Wrochna, Grzegorz; Zalewski, Piotr; Almeida, Nuno; David Tinoco Mendes, Andre; Faccioli, Pietro; Ferreira Parracho, Pedro Guilherme; Gallinaro, Michele; Sá Martins, Pedro; Mini, Giuliano; Musella, Pasquale; Nayak, Aruna; Raposo, Luis; Ribeiro, Pedro Quinaz; Seixas, Joao; Silva, Pedro; Soares, David; Varela, Joao; Wöhri, Hermine Katharina; Belotelov, Ivan; Bunin, Pavel; Finger, Miroslav; Finger Jr., Michael; Golutvin, Igor; Kamenev, Alexey; Karjavin, Vladimir; Kozlov, Guennady; Lanev, Alexander; Moisenz, Petr; Palichik, Vladimir; Perelygin, Victor; Shmatov, Sergey; Smirnov, Vitaly; Volodko, Anton; Zarubin, Anatoli; Bondar, Nikolai; Golovtsov, Victor; Ivanov, Yury; Kim, Victor; Levchenko, Petr; Murzin, Victor; Oreshkin, Vadim; Smirnov, Igor; Sulimov, Valentin; Uvarov, Lev; Vavilov, Sergey; Vorobyev, Alexey; Andreev, Yuri; Gninenko, Sergei; Golubev, Nikolai; Kirsanov, Mikhail; Krasnikov, Nikolai; Matveev, Viktor; Pashenkov, Anatoli; Toropin, Alexander; Troitsky, Sergey; Epshteyn, Vladimir; Gavrilov, Vladimir; Kaftanov, Vitali; Kossov, Mikhail; Krokhotin, Andrey; Kuleshov, Sergey; Lychkovskaya, Natalia; Oulianov, Alexei; Safronov, Grigory; Semenov, Sergey; Shreyber, Irina; Stolin, Viatcheslav; Vlasov, Evgueni; Zhokin, Alexander; Boos, Edouard; Dubinin, Mikhail; Dudko, Lev; Ershov, Alexander; Gribushin, Andrey; Kodolova, Olga; Lokhtin, Igor; Obraztsov, Stepan; Petrushanko, Sergey; Sarycheva, Ludmila; Savrin, Viktor; Snigirev, Alexander; Andreev, Vladimir; Azarkin, Maksim; Dremin, Igor; Kirakosyan, Martin; Rusakov, Sergey V.; Vinogradov, Alexey; Azhgirey, Igor; Bitioukov, Sergei; Grishin, Viatcheslav; Kachanov, Vassili; Konstantinov, Dmitri; Krychkine, Victor; Petrov, Vladimir; Ryutin, Roman; Slabospitsky, Sergey; Sobol, Andrei; Tourtchanovitch, Leonid; Troshin, Sergey; Tyurin, Nikolay; Uzunian, Andrey; Volkov, Alexey; Adzic, Petar; Djordjevic, Milos; Krpic, Dragomir; Maletic, Dimitrije; Milosevic, Jovan; Puzovic, Jovan; Aguilar-Benitez, Manuel; Alcaraz Maestre, Juan; Arce, Pedro; Battilana, Carlo; Calvo, Enrique; Cepeda, Maria; Cerrada, Marcos; Colino, Nicanor; De La Cruz, Begona; Diez Pardos, Carmen; Fernandez Bedoya, Cristina; Fernández Ramos, Juan Pablo; Ferrando, Antonio; Flix, Jose; Fouz, Maria Cruz; Garcia-Abia, Pablo; Gonzalez Lopez, Oscar; Goy Lopez, Silvia; Hernandez, Jose M.; Josa, Maria Isabel; Merino, Gonzalo; Puerta Pelayo, Jesus; Redondo, Ignacio; Romero, Luciano; Santaolalla, Javier; Willmott, Carlos; Albajar, Carmen; Codispoti, Giuseppe; de Trocóniz, Jorge F; Cuevas, Javier; Fernandez Menendez, Javier; Folgueras, Santiago; Gonzalez Caballero, Isidro; Lloret Iglesias, Lara; Vizan Garcia, Jesus Manuel; Cabrillo, Iban Jose; Calderon, Alicia; Chamizo Llatas, Maria; Chuang, Shan-Huei; Diaz Merino, Irma; Diez Gonzalez, Carlos; Duarte Campderros, Jordi; Felcini, Marta; Fernandez, Marcos; Gomez, Gervasio; Gonzalez Sanchez, Javier; Gonzalez Suarez, Rebeca; Jorda, Clara; Lobelle Pardo, Patricia; Lopez Virto, Amparo; Marco, Jesus; Marco, Rafael; Martinez Rivero, Celso; Matorras, Francisco; Piedra Gomez, Jonatan; Rodrigo, Teresa; Ruiz Jimeno, Alberto; Scodellaro, Luca; Sobron Sanudo, Mar; Vila, Ivan; Vilar Cortabitarte, Rocio; Abbaneo, Duccio; Auffray, Etiennette; Baillon, Paul; Ball, Austin; Barney, David; Beaudette, Florian; Bell, Alan James; Benedetti, Daniele; Bernet, Colin; Bhattacharyya, Anirban Krishna; Bialas, Wojciech; Bloch, Philippe; Bocci, Andrea; Bolognesi, Sara; Breuker, Horst; Brona, Grzegorz; Bunkowski, Karol; Camporesi, Tiziano; Cano, Eric; Cattai, Ariella; Cerminara, Gianluca; Christiansen, Tim; Coarasa Perez, Jose Antonio; Covarelli, Roberto; Curé, Benoît; D'Enterria, David; Dahms, Torsten; De Roeck, Albert; Elliott-Peisert, Anna; Funk, Wolfgang; Gaddi, Andrea; Gennai, Simone; Georgiou, Georgios; Gerwig, Hubert; Gigi, Dominique; Gill, Karl; Giordano, Domenico; Glege, Frank; Gomez-Reino Garrido, Robert; Gouzevitch, Maxime; Gowdy, Stephen; Guiducci, Luigi; Hansen, Magnus; Harvey, John; Hegeman, Jeroen; Hegner, Benedikt; Henderson, Conor; Hoffmann, Hans Falk; Honma, Alan; Innocente, Vincenzo; Janot, Patrick; Karavakis, Edward; Lecoq, Paul; Leonidopoulos, Christos; Lourenco, Carlos; Macpherson, Alick; Maki, Tuula; Malgeri, Luca; Mannelli, Marcello; Masetti, Lorenzo; Meijers, Frans; Mersi, Stefano; Meschi, Emilio; Moser, Roland; Mozer, Matthias Ulrich; Mulders, Martijn; Nesvold, Erik; Orsini, Luciano; Perez, Emmanuelle; Petrilli, Achille; Pfeiffer, Andreas; Pierini, Maurizio; Pimiä, Martti; Polese, Giovanni; Racz, Attila; Rolandi, Gigi; Rovelli, Chiara; Rovere, Marco; Sakulin, Hannes; Schäfer, Christoph; Schwick, Christoph; Segoni, Ilaria; Sharma, Archana; Siegrist, Patrice; Simon, Michal; Sphicas, Paraskevas; Spiga, Daniele; Spiropulu, Maria; Stöckli, Fabian; Stoye, Markus; Tropea, Paola; Tsirou, Andromachi; Veres, Gabor Istvan; Vichoudis, Paschalis; Voutilainen, Mikko; Zeuner, Wolfram Dietrich; Bertl, Willi; Deiters, Konrad; Erdmann, Wolfram; Gabathuler, Kurt; Horisberger, Roland; Ingram, Quentin; Kaestli, Hans-Christian; König, Stefan; Kotlinski, Danek; Langenegger, Urs; Meier, Frank; Renker, Dieter; Rohe, Tilman; Sibille, Jennifer; Starodumov, Andrei; Caminada, Lea; Chen, Zhiling; Cittolin, Sergio; Dissertori, Günther; Dittmar, Michael; Eugster, Jürg; Freudenreich, Klaus; Grab, Christoph; Hervé, Alain; Hintz, Wieland; Lecomte, Pierre; Lustermann, Werner; Marchica, Carmelo; Martinez Ruiz del Arbol, Pablo; Meridiani, Paolo; Milenovic, Predrag; Moortgat, Filip; Nardulli, Alessandro; Nef, Pascal; Nessi-Tedaldi, Francesca; Pape, Luc; Pauss, Felicitas; Punz, Thomas; Rizzi, Andrea; Ronga, Frederic Jean; Sala, Leonardo; Sanchez, Ann - Karin; Sawley, Marie-Christine; Stieger, Benjamin; Tauscher, Ludwig; Thea, Alessandro; Theofilatos, Konstantinos; Treille, Daniel; Urscheler, Christina; Wallny, Rainer; Weber, Matthias; Wehrli, Lukas; Weng, Joanna; Aguiló, Ernest; Amsler, Claude; Chiochia, Vincenzo; De Visscher, Simon; Favaro, Carlotta; Ivova Rikova, Mirena; Jaeger, Andreas; Millan Mejias, Barbara; Regenfus, Christian; Robmann, Peter; Rommerskirchen, Tanja; Schmidt, Alexander; Snoek, Hella; Wilke, Lotte; Chang, Yuan-Hann; Chen, Kuan-Hsin; Chen, Wan-Ting; Dutta, Suchandra; Go, Apollo; Kuo, Chia-Ming; Li, Syue-Wei; Lin, Willis; Liu, Ming-Hsiung; Liu, Zong-kai; Lu, Yun-Ju; Wu, Jing-Han; Yu, Shin-Shan; Bartalini, Paolo; Chang, Paoti; Chang, You-Hao; Chang, Yu-Wei; Chao, Yuan; Chen, Kai-Feng; Hou, George Wei-Shu; Hsiung, Yee; Kao, Kai-Yi; Lei, Yeong-Jyi; Lu, Rong-Shyang; Shiu, Jing-Ge; Tzeng, Yeng-Ming; Wang, Minzu; Wei, Jui-Te; Adiguzel, Aytul; Bakirci, Mustafa Numan; Cerci, Salim; Demir, Zahide; Dozen, Candan; Dumanoglu, Isa; Eskut, Eda; Girgis, Semiray; Gökbulut, Gül; Güler, Yalcin; Gurpinar, Emine; Hos, Ilknur; Kangal, Evrim Ersin; Karaman, Turker; Kayis Topaksu, Aysel; Nart, Alisah; Önengüt, Gülsen; Ozdemir, Kadri; Ozturk, Sertac; Polatöz, Ayse; Sogut, Kenan; Tali, Bayram; Topakli, Huseyin; Uzun, Dilber; Vergili, Latife Nukhet; Vergili, Mehmet; Zorbilmez, Caglar; Akin, Ilina Vasileva; Aliev, Takhmasib; Bilmis, Selcuk; Deniz, Muhammed; Gamsizkan, Halil; Guler, Ali Murat; Ocalan, Kadir; Ozpineci, Altug; Serin, Meltem; Sever, Ramazan; Surat, Ugur Emrah; Yildirim, Eda; Zeyrek, Mehmet; Deliomeroglu, Mehmet; Demir, Durmus; Gülmez, Erhan; Halu, Arda; Isildak, Bora; Kaya, Mithat; Kaya, Ozlem; Özbek, Melih; Ozkorucuklu, Suat; Sonmez, Nasuf; Levchuk, Leonid; Bell, Peter; Bostock, Francis; Brooke, James John; Cheng, Teh Lee; Cussans, David; Frazier, Robert; Goldstein, Joel; Grimes, Mark; Hansen, Maria; Heath, Greg P.; Heath, Helen F.; Hill, Christopher; Huckvale, Benedickt; Jackson, James; Kreczko, Lukasz; Metson, Simon; Newbold, Dave M.; Nirunpong, Kachanon; Poll, Anthony; Smith, Vincent J.; Ward, Simon; Basso, Lorenzo; Bell, Ken W.; Belyaev, Alexander; Brew, Christopher; Brown, Robert M.; Camanzi, Barbara; Cockerill, David J.A.; Coughlan, John A.; Harder, Kristian; Harper, Sam; Kennedy, Bruce W.; Olaiya, Emmanuel; Petyt, David; Radburn-Smith, Benjamin Charles; Shepherd-Themistocleous, Claire; Tomalin, Ian R.; Womersley, William John; Worm, Steven; Bainbridge, Robert; Ball, Gordon; Ballin, Jamie; Beuselinck, Raymond; Buchmuller, Oliver; Colling, David; Cripps, Nicholas; Cutajar, Michael; Davies, Gavin; Della Negra, Michel; Foudas, Costas; Fulcher, Jonathan; Futyan, David; Guneratne Bryer, Arlo; Hall, Geoffrey; Hatherell, Zoe; Hays, Jonathan; Iles, Gregory; Karapostoli, Georgia; Lyons, Louis; Magnan, Anne-Marie; Marrouche, Jad; Nandi, Robin; Nash, Jordan; Nikitenko, Alexander; Papageorgiou, Anastasios; Pesaresi, Mark; Petridis, Konstantinos; Pioppi, Michele; Raymond, David Mark; Rompotis, Nikolaos; Rose, Andrew; Ryan, Matthew John; Seez, Christopher; Sharp, Peter; Sparrow, Alex; Tapper, Alexander; Tourneur, Stephane; Vazquez Acosta, Monica; Virdee, Tejinder; Wakefield, Stuart; Wardrope, David; Whyntie, Tom; Barrett, Matthew; Chadwick, Matthew; Cole, Joanne; Hobson, Peter R.; Khan, Akram; Kyberd, Paul; Leslie, Dawn; Martin, William; Reid, Ivan; Teodorescu, Liliana; Hatakeyama, Kenichi; Bose, Tulika; Carrera Jarrin, Edgar; Clough, Andrew; Fantasia, Cory; Heister, Arno; St. John, Jason; Lawson, Philip; Lazic, Dragoslav; Rohlf, James; Sulak, Lawrence; Andrea, Jeremy; Avetisyan, Aram; Bhattacharya, Saptaparna; Chou, John Paul; Cutts, David; Esen, Selda; Ferapontov, Alexey; Heintz, Ulrich; Jabeen, Shabnam; Kukartsev, Gennadiy; Landsberg, Greg; Narain, Meenakshi; Nguyen, Duong; Segala, Michael; Speer, Thomas; Tsang, Ka Vang; Borgia, Maria Assunta; Breedon, Richard; Calderon De La Barca Sanchez, Manuel; Cebra, Daniel; Chertok, Maxwell; Conway, John; Cox, Peter Timothy; Dolen, James; Erbacher, Robin; Friis, Evan; Ko, Winston; Kopecky, Alexandra; Lander, Richard; Liu, Haidong; Maruyama, Sho; Miceli, Tia; Nikolic, Milan; Pellett, Dave; Robles, Jorge; Schwarz, Thomas; Searle, Matthew; Smith, John; Squires, Michael; Tripathi, Mani; Vasquez Sierra, Ricardo; Veelken, Christian; Andreev, Valeri; Arisaka, Katsushi; Cline, David; Cousins, Robert; Deisher, Amanda; Duris, Joseph; Erhan, Samim; Farrell, Chris; Hauser, Jay; Ignatenko, Mikhail; Jarvis, Chad; Plager, Charles; Rakness, Gregory; Schlein, Peter; Tucker, Jordan; Valuev, Vyacheslav; Babb, John; Clare, Robert; Ellison, John Anthony; Gary, J William; Giordano, Ferdinando; Hanson, Gail; Jeng, Geng-Yuan; Kao, Shih-Chuan; Liu, Feng; Liu, Hongliang; Luthra, Arun; Nguyen, Harold; Pasztor, Gabriella; Satpathy, Asish; Shen, Benjamin C.; Stringer, Robert; Sturdy, Jared; Sumowidagdo, Suharyo; Wilken, Rachel; Wimpenny, Stephen; Andrews, Warren; Branson, James G.; Dusinberre, Elizabeth; Evans, David; Golf, Frank; Holzner, André; Kelley, Ryan; Lebourgeois, Matthew; Letts, James; Mangano, Boris; Muelmenstaedt, Johannes; Padhi, Sanjay; Palmer, Christopher; Petrucciani, Giovanni; Pi, Haifeng; Pieri, Marco; Ranieri, Riccardo; Sani, Matteo; Sharma, Vivek; Simon, Sean; Tu, Yanjun; Vartak, Adish; Würthwein, Frank; Yagil, Avraham; Barge, Derek; Bellan, Riccardo; Campagnari, Claudio; D'Alfonso, Mariarosaria; Danielson, Thomas; Geffert, Paul; Incandela, Joe; Justus, Christopher; Kalavase, Puneeth; Koay, Sue Ann; Kovalskyi, Dmytro; Krutelyov, Vyacheslav; Lowette, Steven; Mccoll, Nickolas; Pavlunin, Viktor; Rebassoo, Finn; Ribnik, Jacob; Richman, Jeffrey; Rossin, Roberto; Stuart, David; To, Wing; Vlimant, Jean-Roch; Witherell, Michael; Bornheim, Adolf; Bunn, Julian; Chen, Yi; Gataullin, Marat; Kcira, Dorian; Litvine, Vladimir; Ma, Yousi; Mott, Alexander; Newman, Harvey B.; Rogan, Christopher; Shin, Kyoungha; Timciuc, Vladlen; Traczyk, Piotr; Veverka, Jan; Wilkinson, Richard; Yang, Yong; Zhu, Ren-Yuan; Akgun, Bora; Calamba, Aristotle; Carroll, Ryan; Ferguson, Thomas; Iiyama, Yutaro; Jang, Dong Wook; Jun, Soon Yung; Liu, Yueh-Feng; Paulini, Manfred; Russ, James; Terentyev, Nikolay; Vogel, Helmut; Vorobiev, Igor; Cumalat, John Perry; Dinardo, Mauro Emanuele; Drell, Brian Robert; Edelmaier, Christopher; Ford, William T.; Heyburn, Bernadette; Luiggi Lopez, Eduardo; Nauenberg, Uriel; Smith, James; Stenson, Kevin; Ulmer, Keith; Wagner, Stephen Robert; Zang, Shi-Lei; Agostino, Lorenzo; Alexander, James; Blekman, Freya; Chatterjee, Avishek; Das, Souvik; Eggert, Nicholas; Fields, Laura Johanna; Gibbons, Lawrence Kent; Heltsley, Brian; Henriksson, Kristofer; Hopkins, Walter; Khukhunaishvili, Aleko; Kreis, Benjamin; Kuznetsov, Valentin; Liu, Yao; Nicolas Kaufman, Gala; Patterson, Juliet Ritchie; Puigh, Darren; Riley, Daniel; Ryd, Anders; Saelim, Michael; Shi, Xin; Sun, Werner; Teo, Wee Don; Thom, Julia; Thompson, Joshua; Vaughan, Jennifer; Weng, Yao; Wittich, Peter; Biselli, Angela; Cirino, Guy; Winn, Dave; Abdullin, Salavat; Albrow, Michael; Anderson, Jacob; Apollinari, Giorgio; Atac, Muzaffer; Bakken, Jon Alan; Banerjee, Sunanda; Bauerdick, Lothar A.T.; Beretvas, Andrew; Berryhill, Jeffrey; Bhat, Pushpalatha C.; Bloch, Ingo; Borcherding, Frederick; Burkett, Kevin; Butler, Joel Nathan; Chetluru, Vasundhara; Cheung, Harry; Chlebana, Frank; Cihangir, Selcuk; Demarteau, Marcel; Eartly, David P.; Elvira, Victor Daniel; Fisk, Ian; Freeman, Jim; Gao, Yanyan; Gottschalk, Erik; Green, Dan; Gunthoti, Kranti; Gutsche, Oliver; Hahn, Alan; Hanlon, Jim; Harris, Robert M.; Hirschauer, James; James, Eric; Jensen, Hans; Johnson, Marvin; Joshi, Umesh; Khatiwada, Rakshya; Kilminster, Benjamin; Klima, Boaz; Kousouris, Konstantinos; Kunori, Shuichi; Kwan, Simon; Limon, Peter; Lipton, Ron; Lykken, Joseph; Maeshima, Kaori; Marraffino, John Michael; Mason, David; McBride, Patricia; McCauley, Thomas; Miao, Ting; Mishra, Kalanand; Mrenna, Stephen; Musienko, Yuri; Newman-Holmes, Catherine; O'Dell, Vivian; Popescu, Sorina; Pordes, Ruth; Prokofyev, Oleg; Saoulidou, Niki; Sexton-Kennedy, Elizabeth; Sharma, Seema; Soha, Aron; Spalding, William J.; Spiegel, Leonard; Tan, Ping; Taylor, Lucas; Tkaczyk, Slawek; Uplegger, Lorenzo; Vaandering, Eric Wayne; Vidal, Richard; Whitmore, Juliana; Wu, Weimin; Yang, Fan; Yumiceva, Francisco; Yun, Jae Chul; Acosta, Darin; Avery, Paul; Bourilkov, Dimitri; Chen, Mingshui; Di Giovanni, Gian Piero; Dobur, Didar; Drozdetskiy, Alexey; Field, Richard D.; Fisher, Matthew; Fu, Yu; Furic, Ivan-Kresimir; Gartner, Joseph; Goldberg, Sean; Kim, Bockjoo; Klimenko, Sergey; Konigsberg, Jacobo; Korytov, Andrey; Kotov, Khristian; Kropivnitskaya, Anna; Kypreos, Theodore; Matchev, Konstantin; Mitselmakher, Guenakh; Muniz, Lana; Pakhotin, Yuriy; Petterson, Maureen; Prescott, Craig; Remington, Ronald; Schmitt, Michael Houston; Scurlock, Bobby; Sellers, Paul; Snowball, Matthew; Wang, Dayong; Yelton, John; Zakaria, Mohammed; Ceron, Cristobal; Gaultney, Vanessa; Kramer, Laird; Lebolo, Luis Miguel; Linn, Stephan; Markowitz, Pete; Martinez, German; Mesa, Dalgis; Rodriguez, Jorge Luis; Adams, Todd; Askew, Andrew; Bochenek, Joseph; Chen, Jie; Diamond, Brendan; Gleyzer, Sergei V; Haas, Jeff; Hagopian, Sharon; Hagopian, Vasken; Jenkins, Merrill; Johnson, Kurtis F.; Prosper, Harrison; Sekmen, Sezen; Veeraraghavan, Venkatesh; Baarmand, Marc M.; Dorney, Brian; Guragain, Samir; Hohlmann, Marcus; Kalakhety, Himali; Ralich, Robert; Vodopiyanov, Igor; Adams, Mark Raymond; Anghel, Ioana Maria; Apanasevich, Leonard; Bai, Yuting; Bazterra, Victor Eduardo; Betts, Russell Richard; Callner, Jeremy; Cavanaugh, Richard; Dragoiu, Cosmin; Garcia-Solis, Edmundo Javier; Gerber, Cecilia Elena; Hofman, David Jonathan; Khalatyan, Samvel; Lacroix, Florent; O'Brien, Christine; Shabalina, Elizaveta; Silvestre, Catherine; Smoron, Agata; Strom, Derek; Varelas, Nikos; Akgun, Ugur; Albayrak, Elif Asli; Bilki, Burak; Cankocak, Kerem; Clarida, Warren; Duru, Firdevs; Lae, Chung Khim; McCliment, Edward; Merlo, Jean-Pierre; Mermerkaya, Hamit; Mestvirishvili, Alexi; Moeller, Anthony; Nachtman, Jane; Newsom, Charles Ray; Norbeck, Edwin; Olson, Jonathan; Onel, Yasar; Ozok, Ferhat; Sen, Sercan; Wetzel, James; Yetkin, Taylan; Yi, Kai; Barnett, Bruce Arnold; Blumenfeld, Barry; Bonato, Alessio; Eskew, Christopher; Fehling, David; Giurgiu, Gavril; Gritsan, Andrei; Guo, Zijin; Hu, Guofan; Maksimovic, Petar; Rappoccio, Salvatore; Swartz, Morris; Tran, Nhan Viet; Whitbeck, Andrew; Baringer, Philip; Bean, Alice; Benelli, Gabriele; Grachov, Oleg; Murray, Michael; Noonan, Daniel; Radicci, Valeria; Sanders, Stephen; Wood, Jeffrey Scott; Zhukova, Victoria; Bandurin, Dmitry; Bolton, Tim; Chakaberia, Irakli; Ivanov, Andrew; Makouski, Mikhail; Maravin, Yurii; Shrestha, Shruti; Svintradze, Irakli; Wan, Zongru; Gronberg, Jeffrey; Lange, David; Wright, Douglas; Baden, Drew; Boutemeur, Madjid; Eno, Sarah Catherine; Ferencek, Dinko; Gomez, Jaime; Hadley, Nicholas John; Kellogg, Richard G.; Kirn, Malina; Lu, Ying; Mignerey, Alice; Rossato, Kenneth; Rumerio, Paolo; Santanastasio, Francesco; Skuja, Andris; Temple, Jeffrey; Tonjes, Marguerite; Tonwar, Suresh C.; Twedt, Elizabeth; Alver, Burak; Bauer, Gerry; Bendavid, Joshua; Busza, Wit; Butz, Erik; Cali, Ivan Amos; Chan, Matthew; Dutta, Valentina; Everaerts, Pieter; Gomez Ceballos, Guillelmo; Goncharov, Maxim; Hahn, Kristan Allan; Harris, Philip; Kim, Yongsun; Klute, Markus; Lee, Yen-Jie; Li, Wei; Loizides, Constantinos; Luckey, Paul David; Ma, Teng; Nahn, Steve; Paus, Christoph; Roland, Christof; Roland, Gunther; Rudolph, Matthew; Stephans, George; Sumorok, Konstanty; Sung, Kevin; Wenger, Edward Allen; Wyslouch, Bolek; Xie, Si; Yang, Mingming; Yilmaz, Yetkin; Yoon, Sungho; Zanetti, Marco; Cole, Perrie; Cooper, Seth; Cushman, Priscilla; Dahmes, Bryan; De Benedetti, Abraham; Dudero, Phillip Russell; Franzoni, Giovanni; Haupt, Jason; Klapoetke, Kevin; Kubota, Yuichi; Mans, Jeremy; Rekovic, Vladimir; Rusack, Roger; Sasseville, Michael; Singovsky, Alexander; Cremaldi, Lucien Marcus; Godang, Romulus; Kroeger, Rob; Perera, Lalith; Rahmat, Rahmat; Sanders, David A; Summers, Don; Bloom, Kenneth; Bose, Suvadeep; Butt, Jamila; Claes, Daniel R.; Dominguez, Aaron; Eads, Michael; Keller, Jason; Kelly, Tony; Kravchenko, Ilya; Lazo-Flores, Jose; Lundstedt, Carl; Malbouisson, Helena; Malik, Sudhir; Snow, Gregory R.; Baur, Ulrich; Godshalk, Andrew; Iashvili, Ia; Kharchilava, Avto; Kumar, Ashish; Smith, Kenneth; Zennamo, Joseph; Alverson, George; Barberis, Emanuela; Baumgartel, Darin; Boeriu, Oana; Chasco, Matthew; Kaadze, Ketino; Reucroft, Steve; Swain, John; Wood, Darien; Zhang, Jinzhong; Anastassov, Anton; Kubik, Andrew; Odell, Nathaniel; Ofierzynski, Radoslaw Adrian; Pollack, Brian; Pozdnyakov, Andrey; Schmitt, Michael Henry; Stoynev, Stoyan; Velasco, Mayda; Won, Steven; Antonelli, Louis; Berry, Douglas; Hildreth, Michael; Jessop, Colin; Karmgard, Daniel John; Kolb, Jeff; Kolberg, Ted; Lannon, Kevin; Luo, Wuming; Lynch, Sean; Marinelli, Nancy; Morse, David Michael; Pearson, Tessa; Ruchti, Randy; Slaunwhite, Jason; Valls, Nil; Warchol, Jadwiga; Wayne, Mitchell; Ziegler, Jill; Bylsma, Ben; Durkin, Lloyd Stanley; Gu, Jianhui; Killewald, Phillip; Ling, Ta-Yung; Rodenburg, Marissa; Williams, Grayson; Adam, Nadia; Berry, Edmund; Elmer, Peter; Gerbaudo, Davide; Halyo, Valerie; Hebda, Philip; Hunt, Adam; Jones, John; Laird, Edward; Lopes Pegna, David; Marlow, Daniel; Medvedeva, Tatiana; Mooney, Michael; Olsen, James; Piroué, Pierre; Saka, Halil; Stickland, David; Tully, Christopher; Werner, Jeremy Scott; Zuranski, Andrzej; Acosta, Jhon Gabriel; Huang, Xing Tao; Lopez, Angel; Mendez, Hector; Oliveros, Sandra; Ramirez Vargas, Juan Eduardo; Zatserklyaniy, Andriy; Alagoz, Enver; Barnes, Virgil E.; Bolla, Gino; Borrello, Laura; Bortoletto, Daniela; Everett, Adam; Garfinkel, Arthur F.; Gecse, Zoltan; Gutay, Laszlo; Jones, Matthew; Koybasi, Ozhan; Laasanen, Alvin T.; Leonardo, Nuno; Liu, Chang; Maroussov, Vassili; Meier, Michael; Merkel, Petra; Miller, David Harry; Neumeister, Norbert; Potamianos, Karolos; Shipsey, Ian; Silvers, David; Svyatkovskiy, Alexey; Yoo, Hwi Dong; Zablocki, Jakub; Zheng, Yu; Jindal, Pratima; Parashar, Neeti; Boulahouache, Chaouki; Cuplov, Vesna; Ecklund, Karl Matthew; Geurts, Frank J.M.; Liu, Jinghua H.; Morales, Jafet; Padley, Brian Paul; Redjimi, Radia; Roberts, Jay; Zabel, James; Betchart, Burton; Bodek, Arie; Chung, Yeon Sei; de Barbaro, Pawel; Demina, Regina; Eshaq, Yossof; Flacher, Henning; Garcia-Bellido, Aran; Goldenzweig, Pablo; Gotra, Yury; Han, Jiyeon; Harel, Amnon; Miner, Daniel Carl; Orbaker, Douglas; Petrillo, Gianluca; Vishnevskiy, Dmitry; Zielinski, Marek; Bhatti, Anwar; Demortier, Luc; Goulianos, Konstantin; Lungu, Gheorghe; Mesropian, Christina; Yan, Ming; Atramentov, Oleksiy; Barker, Anthony; Duggan, Daniel; Gershtein, Yuri; Gray, Richard; Halkiadakis, Eva; Hidas, Dean; Hits, Dmitry; Lath, Amitabh; Panwalkar, Shruti; Patel, Rishi; Richards, Alan; Rose, Keith; Schnetzer, Steve; Somalwar, Sunil; Stone, Robert; Thomas, Scott; Cerizza, Giordano; Hollingsworth, Matthew; Spanier, Stefan; Yang, Zong-Chang; York, Andrew; Asaadi, Jonathan; Eusebi, Ricardo; Gilmore, Jason; Gurrola, Alfredo; Kamon, Teruki; Khotilovich, Vadim; Montalvo, Roy; Nguyen, Chi Nhan; Pivarski, James; Safonov, Alexei; Sengupta, Sinjini; Tatarinov, Aysen; Toback, David; Weinberger, Michael; Akchurin, Nural; Bardak, Cemile; Damgov, Jordan; Jeong, Chiyoung; Kovitanggoon, Kittikul; Lee, Sung Won; Mane, Poonam; Roh, Youn; Sill, Alan; Volobouev, Igor; Wigmans, Richard; Yazgan, Efe; Appelt, Eric; Brownson, Eric; Engh, Daniel; Florez, Carlos; Gabella, William; Johns, Willard; Kurt, Pelin; Maguire, Charles; Melo, Andrew; Sheldon, Paul; Velkovska, Julia; Arenton, Michael Wayne; Balazs, Michael; Boutle, Sarah; Buehler, Marc; Conetti, Sergio; Cox, Bradley; Francis, Brian; Hirosky, Robert; Ledovskoy, Alexander; Lin, Chuanzhe; Neu, Christopher; Patel, Tushita; Yohay, Rachel; Gollapinni, Sowjanya; Harr, Robert; Karchin, Paul Edmund; Loggins, Vera; Mattson, Mark; Milstène, Caroline; Sakharov, Alexandre; Anderson, Michael; Bachtis, Michail; Bellinger, James Nugent; Carlsmith, Duncan; Dasu, Sridhara; Efron, Jonathan; Gray, Lindsey; Grogg, Kira Suzanne; Grothe, Monika; Hall-Wilton, Richard; Herndon, Matthew; Klabbers, Pamela; Klukas, Jeffrey; Lanaro, Armando; Lazaridis, Christos; Leonard, Jessica; Liu, Jie; Lomidze, David; Loveless, Richard; Mohapatra, Ajit; Parker, William; Reeder, Don; Ross, Ian; Savin, Alexander; Smith, Wesley H.; Swanson, Joshua; Weinberg, Marc

    2010-01-01

    Results on two-particle angular correlations for charged particles emitted in proton-proton collisions at center-of-mass energies of 0.9, 2.36, and 7 TeV are presented, using data collected with the CMS detector over a broad range of pseudorapidity (eta) and azimuthal angle ($\\phi$). Short-range correlations in $\\Delta\\eta$, which are studied in minimum bias events, are characterized using a simple "independent cluster" parametrization in order to quantify their strength (cluster size) and their extent in $\\eta$ (cluster decay width). Long-range azimuthal correlations are studied differentially as a function of charged particle multiplicity and particle transverse momentum using a 980 inverse nb data set at 7 TeV. In high multiplicity events, a pronounced structure emerges in the two-dimensional correlation function for particle pairs with intermediate transverse momentum of 1-3 GeV/c, 2.0 < |$\\Delta\\eta$| < 4.8 and $\\Delta\\phi \\approx 0$. This is the first observation of such a long-range, near-side fe...

  13. Observation of Long-Range, Near-Side Angular Correlations in Proton-Proton Collisions at the LHC

    CERN Document Server

    Khachatryan, Vardan; Tumasyan, Armen; Adam, Wolfgang; Bergauer, Thomas; Dragicevic, Marko; Erö, Janos; Fabjan, Christian; Friedl, Markus; Fruehwirth, Rudolf; Ghete, Vasile Mihai; Hammer, Josef; Haensel, Stephan; Hartl, Christian; Hoch, Michael; Hörmann, Natascha; Hrubec, Josef; Jeitler, Manfred; Kasieczka, Gregor; Kiesenhofer, Wolfgang; Krammer, Manfred; Liko, Dietrich; Mikulec, Ivan; Pernicka, Manfred; Rohringer, Herbert; Schöfbeck, Robert; Strauss, Josef; Taurok, Anton; Teischinger, Florian; Waltenberger, Wolfgang; Walzel, Gerhard; Widl, Edmund; Wulz, Claudia-Elisabeth; Mossolov, Vladimir; Shumeiko, Nikolai; Suarez Gonzalez, Juan; Benucci, Leonardo; Ceard, Ludivine; De Wolf, Eddi A.; Janssen, Xavier; Maes, Thomas; Mucibello, Luca; Ochesanu, Silvia; Roland, Benoit; Rougny, Romain; Selvaggi, Michele; Van Haevermaet, Hans; Van Mechelen, Pierre; Van Remortel, Nick; Adler, Volker; Beauceron, Stephanie; Blyweert, Stijn; D'Hondt, Jorgen; Devroede, Olivier; Kalogeropoulos, Alexis; Maes, Joris; Maes, Michael; Tavernier, Stefaan; Van Doninck, Walter; Van Mulders, Petra; Villella, Ilaria; Chabert, Eric Christian; Charaf, Otman; Clerbaux, Barbara; De Lentdecker, Gilles; Dero, Vincent; Gay, Arnaud; Hammad, Gregory Habib; Hreus, Tomas; Marage, Pierre Edouard; Vander Velde, Catherine; Vanlaer, Pascal; Wickens, John; Costantini, Silvia; Grunewald, Martin; Klein, Benjamin; Marinov, Andrey; Ryckbosch, Dirk; Thyssen, Filip; Tytgat, Michael; Vanelderen, Lukas; Verwilligen, Piet; Walsh, Sinead; Zaganidis, Nicolas; Basegmez, Suzan; Bruno, Giacomo; Caudron, Julien; De Favereau De Jeneret, Jerome; Delaere, Christophe; Demin, Pavel; Favart, Denis; Giammanco, Andrea; Grégoire, Ghislain; Hollar, Jonathan; Lemaitre, Vincent; Militaru, Otilia; Ovyn, Severine; Pagano, Davide; Pin, Arnaud; Piotrzkowski, Krzysztof; Quertenmont, Loic; Schul, Nicolas; Beliy, Nikita; Caebergs, Thierry; Daubie, Evelyne; Alves, Gilvan; De Jesus Damiao, Dilson; Pol, Maria Elena; Henrique Gomes E Souza, Moacyr; Carvalho, Wagner; Da Costa, Eliza Melo; De Oliveira Martins, Carley; Fonseca De Souza, Sandro; Mundim, Luiz; Nogima, Helio; Oguri, Vitor; Otalora Goicochea, Juan Martin; Prado Da Silva, Wanda Lucia; Santoro, Alberto; Silva Do Amaral, Sheila Mara; Sznajder, Andre; Torres Da Silva De Araujo, Felipe; De Almeida Dias, Flavia; Ferreira Dias, Marco Andre; Tomei, Thiago; De Moraes Gregores, Eduardo; Da Cunha Marinho, Franciole; Novaes, Sergio F.; Padula, Sandra; Darmenov, Nikolay; Dimitrov, Lubomir; Genchev, Vladimir; Iaydjiev, Plamen; Piperov, Stefan; Rodozov, Mircho; Stoykova, Stefka; Sultanov, Georgi; Tcholakov, Vanio; Trayanov, Rumen; Vankov, Ivan; Dyulendarova, Milena; Hadjiiska, Roumyana; Kozhuharov, Venelin; Litov, Leander; Marinova, Evelina; Mateev, Matey; Pavlov, Borislav; Petkov, Peicho; Bian, Jian-Guo; Chen, Guo-Ming; Chen, He-Sheng; Jiang, Chun-Hua; Liang, Dong; Liang, Song; Wang, Jian; Wang, Jian; Wang, Xianyou; Wang, Zheng; Yang, Min; Zang, Jingjing; Zhang, Zhen; Ban, Yong; Guo, Shuang; Hu, Zhen; Li, Wenbo; Mao, Yajun; Qian, Si-Jin; Teng, Haiyun; Zhu, Bo; Cabrera, Andrés; Gomez Moreno, Bernardo; Ocampo Rios, Alberto Andres; Osorio Oliveros, Andres Felipe; Sanabria, Juan Carlos; Godinovic, Nikola; Lelas, Damir; Lelas, Karlo; Plestina, Roko; Polic, Dunja; Puljak, Ivica; Antunovic, Zeljko; Dzelalija, Mile; Brigljevic, Vuko; Duric, Senka; Kadija, Kreso; Morovic, Srecko; Attikis, Alexandros; Fereos, Reginos; Galanti, Mario; Mousa, Jehad; Nicolaou, Charalambos; Ptochos, Fotios; Razis, Panos A.; Rykaczewski, Hans; Assran, Yasser; Mahmoud, Mohammed; Hektor, Andi; Kadastik, Mario; Kannike, Kristjan; Müntel, Mait; Raidal, Martti; Rebane, Liis; Azzolini, Virginia; Eerola, Paula; Czellar, Sandor; Härkönen, Jaakko; Heikkinen, Mika Aatos; Karimäki, Veikko; Kinnunen, Ritva; Klem, Jukka; Kortelainen, Matti J.; Lampén, Tapio; Lassila-Perini, Kati; Lehti, Sami; Lindén, Tomas; Luukka, Panja-Riina; Mäenpää, Teppo; Tuominen, Eija; Tuominiemi, Jorma; Tuovinen, Esa; Ungaro, Donatella; Wendland, Lauri; Banzuzi, Kukka; Korpela, Arja; Tuuva, Tuure; Sillou, Daniel; Besancon, Marc; Dejardin, Marc; Denegri, Daniel; Descamps, Julien; Fabbro, Bernard; Faure, Jean-Louis; Ferri, Federico; Ganjour, Serguei; Gentit, François-Xavier; Givernaud, Alain; Gras, Philippe; Hamel de Monchenault, Gautier; Jarry, Patrick; Locci, Elizabeth; Malcles, Julie; Marionneau, Matthieu; Millischer, Laurent; Rander, John; Rosowsky, André; Rousseau, Delphine; Titov, Maksym; Verrecchia, Patrice; Baffioni, Stephanie; Bianchini, Lorenzo; Bluj, Michal; Broutin, Clementine; Busson, Philippe

    2010-01-01

    Results on two-particle angular correlations for charged particles emitted in proton-proton collisions at center-of-mass energies of 0.9, 2.36, and 7 TeV are presented, using data collected with the CMS detector over a broad range of pseudorapidity (eta) and azimuthal angle ($\\phi$). Short-range correlations in $\\Delta\\eta$, which are studied in minimum bias events, are characterized using a simple "independent cluster" parametrization in order to quantify their strength (cluster size) and their extent in $\\eta$ (cluster decay width). Long-range azimuthal correlations are studied differentially as a function of charged particle multiplicity and particle transverse momentum using a 980 inverse nb data set at 7 TeV. In high multiplicity events, a pronounced structure emerges in the two-dimensional correlation function for particle pairs with intermediate transverse momentum of 1-3 GeV/c, 2.0 < |$\\Delta\\eta$| < 4.8 and $\\Delta\\phi \\approx 0$. This is the first observation of such a long-range, near-side fe...

  14. Long-Range Plasmon Assisted Energy Transfer Between Two Fluorescent Emitters

    CERN Document Server

    Bouchet, D; Carminati, R; De Wilde, Y; Krachmalnicoff, V

    2016-01-01

    We demonstrate plasmon assisted energy transfer between two fluorophores located at distances up to $7\\; \\mu$m on the top of a thin silver film. Thanks to the strong confinement and large propagation length of surface plasmon polaritons, the range of the energy transfer is almost two orders of magnitude larger than the values reported in the literature so far. The parameters driving the energy transfer range are thoroughly characterized and are in very good agreement with theoretically expected values. This work shows the potential of plasmonic structures for efficient long-range energy transfer and opens rich perspectives for the study of collective emission phenomena.

  15. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer.

    Science.gov (United States)

    Westereng, Bjørge; Cannella, David; Wittrup Agger, Jane; Jørgensen, Henning; Larsen Andersen, Mogens; Eijsink, Vincent G H; Felby, Claus

    2015-12-21

    Enzymatic oxidation of cell wall polysaccharides by lytic polysaccharide monooxygenases (LPMOs) plays a pivotal role in the degradation of plant biomass. While experiments have shown that LPMOs are copper dependent enzymes requiring an electron donor, the mechanism and origin of the electron supply in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds new light on how oxidative enzymes present in plant degraders may act in concert.

  16. [Long-range electron transfer in globular proteins by polaron excitation].

    Science.gov (United States)

    Lakhno, V L; Chuev, G N

    1997-01-01

    Considering polaron model, we have calculated an electron state localized in the protein heme. Using these calculations: the electron density and electron energy, we estimated the self-exchange rate constant for cyt c (horse heart), its reorganization energy, matrix element, and dependence of this rate on the distance between hemes. The results are compared with the experimental data and other theoretical estimations. We discuss the role of polaron excitations in the long-range electron transfer in globular proteins.

  17. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane

    2015-01-01

    Enzymatic oxidation of cell wall polysaccharides by lytic polysaccharide monooxygenases (LPMOs) plays a pivotal role in the degradation of plant biomass. While experiments have shown that LPMOs are copper dependent enzymes requiring an electron donor, the mechanism and origin of the electron supply...... in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant...... new light on how oxidative enzymes present in plant degraders may act in concert....

  18. Long-range azimuthal correlations in proton–proton and proton–nucleus collisions from the incoherent scattering of partons

    Directory of Open Access Journals (Sweden)

    Guo-Liang Ma

    2014-12-01

    Full Text Available We show that the incoherent elastic scattering of partons, as present in a multi-phase transport model (AMPT, with a modest parton–parton cross-section of σ=1.5–3 mb, naturally explains the long-range two-particle azimuthal correlation as observed in proton–proton and proton–nucleus collisions at the Large Hadron Collider.

  19. Determination of long-range scalar 1H-1H coupling constants responsible for polarization transfer in SABRE

    Science.gov (United States)

    Eshuis, Nan; Aspers, Ruud L. E. G.; van Weerdenburg, Bram J. A.; Feiters, Martin C.; Rutjes, Floris P. J. T.; Wijmenga, Sybren S.; Tessari, Marco

    2016-04-01

    SABRE (Signal Amplification By Reversible Exchange) nuclear spin hyperpolarization method can provide strongly enhanced NMR signals as a result of the reversible association of small molecules with para-hydrogen (p-H2) at an iridium metal complex. The conversion of p-H2 singlet order to enhanced substrate proton magnetization within such complex is driven by the scalar coupling interactions between the p-H2 derived hydrides and substrate nuclear spins. In the present study these long-range homonuclear couplings are experimentally determined for several SABRE substrates using an NMR pulse sequence for coherent hyperpolarization transfer at high magnetic field. Pyridine and pyrazine derivatives appear to have a similar ∼1.2 Hz 4J coupling to p-H2 derived hydrides for their ortho protons, and a much lower 5J coupling for their meta protons. Interestingly, the 4J hydride-substrate coupling for five-membered N-heterocyclic substrates is well below 1 Hz.

  20. Long-range energy transfer in self-assembled quantum dot-DNA cascades

    Science.gov (United States)

    Goodman, Samuel M.; Siu, Albert; Singh, Vivek; Nagpal, Prashant

    2015-11-01

    The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient transport of energy across QD-DNA thin films.The size-dependent energy bandgaps of semiconductor nanocrystals or quantum dots (QDs) can be utilized in converting broadband incident radiation efficiently into electric current by cascade energy transfer (ET) between layers of different sized quantum dots, followed by charge dissociation and transport in the bottom layer. Self-assembling such cascade structures with angstrom-scale spatial precision is important for building realistic devices, and DNA-based QD self-assembly can provide an important alternative. Here we show long-range Dexter energy transfer in QD-DNA self-assembled single constructs and ensemble devices. Using photoluminescence, scanning tunneling spectroscopy, current-sensing AFM measurements in single QD-DNA cascade constructs, and temperature-dependent ensemble devices using TiO2 nanotubes, we show that Dexter energy transfer, likely mediated by the exciton-shelves formed in these QD-DNA self-assembled structures, can be used for efficient

  1. Cobamide-mediated enzymatic reductive dehalogenation via long-range electron transfer.

    Science.gov (United States)

    Kunze, Cindy; Bommer, Martin; Hagen, Wilfred R; Uksa, Marie; Dobbek, Holger; Schubert, Torsten; Diekert, Gabriele

    2017-07-03

    The capacity of metal-containing porphyrinoids to mediate reductive dehalogenation is implemented in cobamide-containing reductive dehalogenases (RDases), which serve as terminal reductases in organohalide-respiring microbes. RDases allow for the exploitation of halogenated compounds as electron acceptors. Their reaction mechanism is under debate. Here we report on substrate-enzyme interactions in a tetrachloroethene RDase (PceA) that also converts aryl halides. The shape of PceA's highly apolar active site directs binding of bromophenols at some distance from the cobalt and with the hydroxyl substituent towards the metal. A close cobalt-substrate interaction is not observed by electron paramagnetic resonance spectroscopy. Nonetheless, a halogen substituent para to the hydroxyl group is reductively eliminated and the path of the leaving halide is traced in the structure. Based on these findings, an enzymatic mechanism relying on a long-range electron transfer is concluded, which is without parallel in vitamin B12-dependent biochemistry and represents an effective mode of RDase catalysis.

  2. Proton conduction and long-range ferrimagnetic ordering in two isostructural Copper(II) mesoxalate metal-organic frameworks.

    Science.gov (United States)

    Gil-Hernández, Beatriz; Savvin, Stanislav; Makhloufi, Gamall; Núñez, Pedro; Janiak, Christoph; Sanchiz, Joaquín

    2015-02-16

    Two compounds of formula {(H3O)[Cu7(Hmesox)5(H2O)7]·9H2O}n (1a) and {(NH4)0.6(H3O)0.4[Cu7(Hmesox)5(H2O)7]·11H2O}n (1b) were prepared and structurally characterized by single-crystal X-ray diffraction (H4mesox = mesoxalic acid, 2-dihydroxymalonic acid). The compounds are crystalline functional metal-organic frameworks exhibiting proton conduction and magnetic ordering. Variable-temperature magnetic susceptibility measurements reveal that the copper(II) ions are strongly ferro- and antiferromagnetically coupled by the alkoxide and carboxylate bridges of the mesoxalate linker to yield long-range magnetic ordering with a Tc of 17.6 K, which is reached by a rare mechanism known as topologic ferrimagnetism. Electric conductivity, measured by impedance methods, shows values as high as 6.5 × 10(-5) S cm(-1) and occurs by proton exchange among the hydronium/ammonium and water molecules of crystallization, which fill the voids left by the three-dimensional copper(II) mesoxalate anionic network.

  3. Gold nanoparticle assisted assembly of a heme protein for enhancement of long-range interfacial electron transfer

    DEFF Research Database (Denmark)

    Jensen, Palle Skovhus; Chi, Qijin; Grumsen, Flemming Bjerg

    2007-01-01

    of bioelectronics. A key challenge in molecular bioelectronics is to improve the efficiency of long-range charge transfer. The present work shows that this can be achieved by nanoparticle (NP) assisted assembly of cytochrome c (cyt c) on macroscopic single-crystalline electrode surfaces. We present the synthesis...... and characterization of water-soluble gold nanoparticles (AuNPs) with core diameter 3-4 nm and their application for the enhancement of long-range interfacial ET of a heme protein. Gold nanoparticles were electrostatically conjugated with cyt c to form nanoparticle-protein hybrid ET systems with well......-defined stoichiometry. The systems were investigated in homogeneous solution and at liquid/solid interface. Conjugation of cyt c results in a small but consistent broadening of the nanoparticle plasmon band. This phenomenon can be explained in terms of long-range electronic interactions between the gold nanoparticle...

  4. Solvent-mediated electron hopping: long-range charge transfer in IBr-(CO2) photodissociation.

    Science.gov (United States)

    Sheps, Leonid; Miller, Elisa M; Horvath, Samantha; Thompson, Matthew A; Parson, Robert; McCoy, Anne B; Lineberger, W Carl

    2010-04-09

    Chemical bond breaking involves coupled electronic and nuclear dynamics that can take place on multiple electronic surfaces. Here we report a time-resolved experimental and theoretical investigation of nonadiabatic dynamics during photodissociation of a complex of iodine monobromide anion with carbon dioxide [IBr-(CO2)] on the second excited (A') electronic state. Previous experimental work showed that the dissociation of bare IBr- yields only I- + Br products. However, in IBr-(CO2), time-resolved photoelectron spectroscopy reveals that a subset of the dissociating molecules undergoes an electron transfer from iodine to bromine 350 femtoseconds after the initial excitation. Ab initio calculations and molecular dynamics simulations elucidate the mechanism for this charge hop and highlight the crucial role of the carbon dioxide molecule. The charge transfer between two recoiling atoms, assisted by a single solvent-like molecule, provides a notable limiting case of solvent-driven electron transfer over a distance of 7 angstroms.

  5. Mesoscopic order and the dimensionality of long-range resonance energy transfer in supramolecular semiconductors

    Science.gov (United States)

    Daniel, Clément; Makereel, François; Herz, Laura M.; Hoeben, Freek J. M.; Jonkheijm, Pascal; Schenning, Albertus P. H. J.; Meijer, E. W.; Silva, Carlos

    2008-09-01

    We present time-resolved photoluminescence measurements on two series of oligo-p-phenylenevinylene materials that self-assemble into supramolecular nanostructures with thermotropic reversibility in dodecane. One set of derivatives form chiral helical stacks, while the second set form less organized "frustrated" stacks. Here we study the effects of supramolecular organization on the resonance energy transfer rates. We measure these rates in nanoassemblies formed with mixed blends of oligomers and compare them with the rates predicted by Förster theory. Our results and analysis show that control of supramolecular order in the nanometer length scale has a dominant effect on the efficiency and dimensionality of resonance energy transfer.

  6. Long-range electron transfer in engineered azurins exhibits marcus inverted region behavior

    DEFF Research Database (Denmark)

    Farver, Ole; Hosseinzadeh, Parisa; Marshall, Nicholas M.

    2015-01-01

    The Marcus theory of electron transfer (ET) predicts that while the ET rate constants increase with rising driving force until it equals a reaction’s reorganization energy, at higher driving force the ET rate decreases, having reached the Marcus inverted region. While experimental evidence...

  7. Role of ligand substitution on long-range electron transfer in azurins

    DEFF Research Database (Denmark)

    Farver, O; Jeuken, L J; Canters, G W

    2000-01-01

    Azurin contains two potential redox sites, a copper centre and, at the opposite end of the molecule, a cystine disulfide (RSSR). Intramolecular electron transfer between a pulse radiolytically produced RSSR- radical anion and the blue Cu(II) ion was studied in a series of azurins in which single-...

  8. Long Range Transport of Air Pollution Into Norway - A Transfer Function Approach

    Directory of Open Access Journals (Sweden)

    Eivind Damsleth

    1984-07-01

    Full Text Available The daily and monthly concentration of sulphate in the air at Birkcnes in the southern part of Norway is analysed within an intervention analysis and transfer function framework. As input to the model we use the prevailing wind direction. It is shown that when the wind comes mainly from the South, that is from Central Europe and England, this gives a significant increase in the sulphate concentration, while a northern wind leads to a decrease.

  9. Long-range intramolecular electron transfer in aromatic radical anions and binuclear transition metal complexes

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    1981-01-01

    Intramolecular electron transfer (ET) over distances up to about 10 Å between states in which the electron is localized on donor and acceptor groups by interaction with molecular or external solvent nuclear motion occurs, in particular, in two classes of systems. The excess electron in anionic...... in the intermediate states. We have furthermore provided criteria for the distinction between direct ET, ET through high-energy (superexchange), and low-energy (''radical'' intermediate mechanism) intermediate states on the basis of experimental rate data and illustrated this with data for organic radical anions...

  10. Long-Range Reduced Predictive Information Transfers of Autistic Youths in EEG Sensor-Space During Face Processing.

    Science.gov (United States)

    Khadem, Ali; Hossein-Zadeh, Gholam-Ali; Khorrami, Anahita

    2016-03-01

    The majority of previous functional/effective connectivity studies conducted on the autistic patients converged to the underconnectivity theory of ASD: "long-range underconnectivity and sometimes short-rang overconnectivity". However, to the best of our knowledge the total (linear and nonlinear) predictive information transfers (PITs) of autistic patients have not been investigated yet. Also, EEG data have rarely been used for exploring the information processing deficits in autistic subjects. This study is aimed at comparing the total (linear and nonlinear) PITs of autistic and typically developing healthy youths during human face processing by using EEG data. The ERPs of 12 autistic youths and 19 age-matched healthy control (HC) subjects were recorded while they were watching upright and inverted human face images. The PITs among EEG channels were quantified using two measures separately: transfer entropy with self-prediction optimality (TESPO), and modified transfer entropy with self-prediction optimality (MTESPO). Afterwards, the directed differential connectivity graphs (dDCGs) were constructed to characterize the significant changes in the estimated PITs of autistic subjects compared with HC ones. By using both TESPO and MTESPO, long-range reduction of PITs of ASD group during face processing was revealed (particularly from frontal channels to right temporal channels). Also, it seemed the orientation of face images (upright or upside down) did not modulate the binary pattern of PIT-based dDCGs, significantly. Moreover, compared with TESPO, the results of MTESPO were more compatible with the underconnectivity theory of ASD in the sense that MTESPO showed no long-range increase in PIT. It is also noteworthy that to the best of our knowledge it is the first time that a version of MTE is applied for patients (here ASD) and it is also its first use for EEG data analysis.

  11. Ab initio study of long-range electron transfer between biphenyl anion radical and naphthalene

    Institute of Scientific and Technical Information of China (English)

    李象远; 肖顺清; 何福城

    1999-01-01

    After the separation of the donor, the aeceptor, and the σ-type bridge from the π-σ-π system, the geometries of biphenyl, biphenyl anion radical, naphthalene, and naphthalene anion radical are optimized, and then the reorganization energy for the intermolecular electron transfer (ET) at the levels of HF/4-31G and HF/DZP is calculated. The ET matrix elements of the self-exchange reactions of the π-σ-π systems have been calculated by means of both the direct calculation based on the variational principle, and the transition energy between the molecular orbitals at the linear coordinate R=0.5. For the cross reactions, the ET matrix element and the geometry of the transition state are determined by searching the minimum energy splitting △min along the reaction coordinate. In the evaluation of the solvent reorganization energy of the ET in solution, the Marcus’ two-sphere model has been invoked. A few of ET rate constants for the intramolecular ET reactions for the π-σ-π systems, which contain

  12. Long-Range Energy Transfer and Singlet-Exciton Migration in Working Organic Light-Emitting Diodes

    Science.gov (United States)

    Ingram, Grayson L.; Nguyen, Carmen; Lu, Zheng-Hong

    2016-06-01

    Rapid industrialization of organic light-emitting devices for flat-panel displays and solid-state lighting makes a deep understanding of device physics more desirable than ever. Developing reliable experimental techniques to measure fundamental physical properties such as exciton diffusion lengths is a vital part of developing device physics. In this paper, we present a study of exciton diffusion and long-range energy transfer in working organic light-emitting devices, and a study of the interplay between these two tangled processes through both experimental probes and simulations. With the inclusion of multiple factors including long-range energy transfer, exciton boundary conditions, and the finite width of the exciton generation zone, we quantify exciton migration based on emission characteristics from rubrene sensing layers placed in working organic light-emitting devices. This comprehensive analysis is found to be essential to accurately measuring exciton diffusion length, and in the present case the measured singlet-exciton diffusion length in the archetype material 4' -bis(carbazol-9-yl)biphenyl is 4.3 ±0.3 nm with a corresponding diffusivity of (2.6 ±0.3 )×10-4 cm2/s .

  13. 8.4% efficient fullerene-free organic solar cells exploiting long-range exciton energy transfer.

    Science.gov (United States)

    Cnops, Kjell; Rand, Barry P; Cheyns, David; Verreet, Bregt; Empl, Max A; Heremans, Paul

    2014-03-07

    In order to increase the power conversion efficiency of organic solar cells, their absorption spectrum should be broadened while maintaining efficient exciton harvesting. This requires the use of multiple complementary absorbers, usually incorporated in tandem cells or in cascaded exciton-dissociating heterojunctions. Here we present a simple three-layer architecture comprising two non-fullerene acceptors and a donor, in which an energy-relay cascade enables an efficient two-step exciton dissociation process. Excitons generated in the remote wide-bandgap acceptor are transferred by long-range Förster energy transfer to the smaller-bandgap acceptor, and subsequently dissociate at the donor interface. The photocurrent originates from all three complementary absorbing materials, resulting in a quantum efficiency above 75% between 400 and 720 nm. With an open-circuit voltage close to 1 V, this leads to a remarkable power conversion efficiency of 8.4%. These results confirm that multilayer cascade structures are a promising alternative to conventional donor-fullerene organic solar cells.

  14. Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

    Science.gov (United States)

    Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

    2012-11-05

    In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

  15. Measurements of long-range near-side angular correlations in $\\sqrt{s_{\\text{NN}}}=5$TeV proton-lead collisions in the forward region

    CERN Document Server

    Aaij, Roel; Adeva, Bernardo; Adinolfi, Marco; Affolder, Anthony; Ajaltouni, Ziad; Akar, Simon; Albrecht, Johannes; Alessio, Federico; Alexander, Michael; Ali, Suvayu; Alkhazov, Georgy; Alvarez Cartelle, Paula; Alves Jr, Antonio Augusto; Amato, Sandra; Amerio, Silvia; Amhis, Yasmine; An, Liupan; Anderlini, Lucio; Anderson, Jonathan; Andreassi, Guido; Andreotti, Mirco; Andrews, Jason; Appleby, Robert; Aquines Gutierrez, Osvaldo; Archilli, Flavio; d'Argent, Philippe; Artamonov, Alexander; Artuso, Marina; Aslanides, Elie; Auriemma, Giulio; Baalouch, Marouen; Bachmann, Sebastian; Back, John; Badalov, Alexey; Baesso, Clarissa; Baldini, Wander; Barlow, Roger; Barschel, Colin; Barsuk, Sergey; Barter, William; Batozskaya, Varvara; Battista, Vincenzo; Bay, Aurelio; Beaucourt, Leo; Beddow, John; Bedeschi, Franco; Bediaga, Ignacio; Bel, Lennaert; Bellee, Violaine; Belloli, Nicoletta; Belyaev, Ivan; Ben-Haim, Eli; Bencivenni, Giovanni; Benson, Sean; Benton, Jack; Berezhnoy, Alexander; Bernet, Roland; Bertolin, Alessandro; Bettler, Marc-Olivier; van Beuzekom, Martinus; Bien, Alexander; Bifani, Simone; Billoir, Pierre; Bird, Thomas; Birnkraut, Alex; Bizzeti, Andrea; Blake, Thomas; Blanc, Frédéric; Blouw, Johan; Blusk, Steven; Bocci, Valerio; Bondar, Alexander; Bondar, Nikolay; Bonivento, Walter; Borghi, Silvia; Borsato, Martino; Bowcock, Themistocles; Bowen, Espen Eie; Bozzi, Concezio; Braun, Svende; Britsch, Markward; Britton, Thomas; Brodzicka, Jolanta; Brook, Nicholas; Buchanan, Emma; Burr, Christopher; Bursche, Albert; Buytaert, Jan; Cadeddu, Sandro; Calabrese, Roberto; Calvi, Marta; Calvo Gomez, Miriam; Campana, Pierluigi; Campora Perez, Daniel; Capriotti, Lorenzo; Carbone, Angelo; Carboni, Giovanni; Cardinale, Roberta; Cardini, Alessandro; Carniti, Paolo; Carson, Laurence; Carvalho Akiba, Kazuyoshi; Casse, Gianluigi; Cassina, Lorenzo; Castillo Garcia, Lucia; Cattaneo, Marco; Cauet, Christophe; Cavallero, Giovanni; Cenci, Riccardo; Charles, Matthew; Charpentier, Philippe; Chefdeville, Maximilien; Chen, Shanzhen; Cheung, Shu-Faye; Chiapolini, Nicola; Chrzaszcz, Marcin; Cid Vidal, Xabier; Ciezarek, Gregory; Clarke, Peter; Clemencic, Marco; Cliff, Harry; Closier, Joel; Coco, Victor; Cogan, Julien; Cogneras, Eric; Cogoni, Violetta; Cojocariu, Lucian; Collazuol, Gianmaria; Collins, Paula; Comerma-Montells, Albert; Contu, Andrea; Cook, Andrew; Coombes, Matthew; Coquereau, Samuel; Corti, Gloria; Corvo, Marco; Couturier, Benjamin; Cowan, Greig; Craik, Daniel Charles; Crocombe, Andrew; Cruz Torres, Melissa Maria; Cunliffe, Samuel; Currie, Robert; D'Ambrosio, Carmelo; Dall'Occo, Elena; Dalseno, Jeremy; David, Pieter; Davis, Adam; De Aguiar Francisco, Oscar; De Bruyn, Kristof; De Capua, Stefano; De Cian, Michel; De Miranda, Jussara; De Paula, Leandro; De Simone, Patrizia; Dean, Cameron Thomas; Decamp, Daniel; Deckenhoff, Mirko; Del Buono, Luigi; Déléage, Nicolas; Demmer, Moritz; Derkach, Denis; Deschamps, Olivier; Dettori, Francesco; Dey, Biplab; Di Canto, Angelo; Di Ruscio, Francesco; Dijkstra, Hans; Donleavy, Stephanie; Dordei, Francesca; Dorigo, Mirco; Dosil Suárez, Alvaro; Dossett, David; Dovbnya, Anatoliy; Dreimanis, Karlis; Dufour, Laurent; Dujany, Giulio; Dupertuis, Frederic; Durante, Paolo; Dzhelyadin, Rustem; Dziurda, Agnieszka; Dzyuba, Alexey; Easo, Sajan; Egede, Ulrik; Egorychev, Victor; Eidelman, Semen; Eisenhardt, Stephan; Eitschberger, Ulrich; Ekelhof, Robert; Eklund, Lars; El Rifai, Ibrahim; Elsasser, Christian; Ely, Scott; Esen, Sevda; Evans, Hannah Mary; Evans, Timothy; Falabella, Antonio; Färber, Christian; Farley, Nathanael; Farry, Stephen; Fay, Robert; Ferguson, Dianne; Fernandez Albor, Victor; Ferrari, Fabio; Ferreira Rodrigues, Fernando; Ferro-Luzzi, Massimiliano; Filippov, Sergey; Fiore, Marco; Fiorini, Massimiliano; Firlej, Miroslaw; Fitzpatrick, Conor; Fiutowski, Tomasz; Fohl, Klaus; Fol, Philip; Fontana, Marianna; Fontanelli, Flavio; Forshaw, Dean Charles; Forty, Roger; Frank, Markus; Frei, Christoph; Frosini, Maddalena; Fu, Jinlin; Furfaro, Emiliano; Gallas Torreira, Abraham; Galli, Domenico; Gallorini, Stefano; Gambetta, Silvia; Gandelman, Miriam; Gandini, Paolo; Gao, Yuanning; García Pardiñas, Julián; Garra Tico, Jordi; Garrido, Lluis; Gascon, David; Gaspar, Clara; Gauld, Rhorry; Gavardi, Laura; Gazzoni, Giulio; Gerick, David; Gersabeck, Evelina; Gersabeck, Marco; Gershon, Timothy; Ghez, Philippe; Gianì, Sebastiana; Gibson, Valerie; Girard, Olivier Göran; Giubega, Lavinia-Helena; Gligorov, V.V.; Göbel, Carla; Golubkov, Dmitry; Golutvin, Andrey; Gomes, Alvaro; Gotti, Claudio; Grabalosa Gándara, Marc; Graciani Diaz, Ricardo; Granado Cardoso, Luis Alberto; Graugés, Eugeni; Graverini, Elena; Graziani, Giacomo; Grecu, Alexandru; Greening, Edward; Gregson, Sam; Griffith, Peter; Grillo, Lucia; Grünberg, Oliver; Gui, Bin; Gushchin, Evgeny; Guz, Yury; Gys, Thierry; Hadavizadeh, Thomas; Hadjivasiliou, Christos; Haefeli, Guido; Haen, Christophe; Haines, Susan; Hall, Samuel; Hamilton, Brian; Han, Xiaoxue; Hansmann-Menzemer, Stephanie; Harnew, Neville; Harnew, Samuel; Harrison, Jonathan; He, Jibo; Head, Timothy; Heijne, Veerle; Heister, Arno; Hennessy, Karol; Henrard, Pierre; Henry, Louis; Hernando Morata, Jose Angel; van Herwijnen, Eric; Heß, Miriam; Hicheur, Adlène; Hill, Donal; Hoballah, Mostafa; Hombach, Christoph; Hulsbergen, Wouter; Humair, Thibaud; Hussain, Nazim; Hutchcroft, David; Hynds, Daniel; Idzik, Marek; Ilten, Philip; Jacobsson, Richard; Jaeger, Andreas; Jalocha, Pawel; Jans, Eddy; Jawahery, Abolhassan; Jing, Fanfan; John, Malcolm; Johnson, Daniel; Jones, Christopher; Joram, Christian; Jost, Beat; Jurik, Nathan; Kandybei, Sergii; Kanso, Walaa; Karacson, Matthias; Karbach, Moritz; Karodia, Sarah; Kecke, Matthieu; Kelsey, Matthew; Kenyon, Ian; Kenzie, Matthew; Ketel, Tjeerd; Khairullin, Egor; Khanji, Basem; Khurewathanakul, Chitsanu; Kirn, Thomas; Klaver, Suzanne; Klimaszewski, Konrad; Kochebina, Olga; Kolpin, Michael; Komarov, Ilya; Koopman, Rose; Koppenburg, Patrick; Kozeiha, Mohamad; Kravchuk, Leonid; Kreplin, Katharina; Kreps, Michal; Krocker, Georg; Krokovny, Pavel; Kruse, Florian; Krzemien, Wojciech; Kucewicz, Wojciech; Kucharczyk, Marcin; Kudryavtsev, Vasily; Kuonen, Axel Kevin; Kurek, Krzysztof; Kvaratskheliya, Tengiz; Lacarrere, Daniel; Lafferty, George; Lai, Adriano; Lambert, Dean; Lanfranchi, Gaia; Langenbruch, Christoph; Langhans, Benedikt; Latham, Thomas; Lazzeroni, Cristina; Le Gac, Renaud; van Leerdam, Jeroen; Lees, Jean-Pierre; Lefèvre, Regis; Leflat, Alexander; Lefrançois, Jacques; Lemos Cid, Edgar; Leroy, Olivier; Lesiak, Tadeusz; Leverington, Blake; Li, Yiming; Likhomanenko, Tatiana; Liles, Myfanwy; Lindner, Rolf; Linn, Christian; Lionetto, Federica; Liu, Bo; Liu, Xuesong; Loh, David; Longstaff, Iain; Lopes, Jose; Lucchesi, Donatella; Lucio Martinez, Miriam; Luo, Haofei; Lupato, Anna; Luppi, Eleonora; Lupton, Oliver; Lusiani, Alberto; Machefert, Frederic; Maciuc, Florin; Maev, Oleg; Maguire, Kevin; Malde, Sneha; Malinin, Alexander; Manca, Giulia; Mancinelli, Giampiero; Manning, Peter Michael; Mapelli, Alessandro; Maratas, Jan; Marchand, Jean François; Marconi, Umberto; Marin Benito, Carla; Marino, Pietro; Marks, Jörg; Martellotti, Giuseppe; Martin, Morgan; Martinelli, Maurizio; Martinez Santos, Diego; Martinez Vidal, Fernando; Martins Tostes, Danielle; Massafferri, André; Matev, Rosen; Mathad, Abhijit; Mathe, Zoltan; Matteuzzi, Clara; Mauri, Andrea; Maurin, Brice; Mazurov, Alexander; McCann, Michael; McCarthy, James; McNab, Andrew; McNulty, Ronan; Meadows, Brian; Meier, Frank; Meissner, Marco; Melnychuk, Dmytro; Merk, Marcel; Michielin, Emanuele; Milanes, Diego Alejandro; Minard, Marie-Noelle; Mitzel, Dominik Stefan; Molina Rodriguez, Josue; Monroy, Ignacio Alberto; Monteil, Stephane; Morandin, Mauro; Morawski, Piotr; Mordà, Alessandro; Morello, Michael Joseph; Moron, Jakub; Morris, Adam Benjamin; Mountain, Raymond; Muheim, Franz; Müller, Dominik; Müller, Janine; Müller, Katharina; Müller, Vanessa; Mussini, Manuel; Muster, Bastien; Naik, Paras; Nakada, Tatsuya; Nandakumar, Raja; Nandi, Anita; Nasteva, Irina; Needham, Matthew; Neri, Nicola; Neubert, Sebastian; Neufeld, Niko; Neuner, Max; Nguyen, Anh Duc; Nguyen, Thi-Dung; Nguyen-Mau, Chung; Niess, Valentin; Niet, Ramon; Nikitin, Nikolay; Nikodem, Thomas; Novoselov, Alexey; O'Hanlon, Daniel Patrick; Oblakowska-Mucha, Agnieszka; Obraztsov, Vladimir; Ogilvy, Stephen; Okhrimenko, Oleksandr; Oldeman, Rudolf; Onderwater, Gerco; Osorio Rodrigues, Bruno; Otalora Goicochea, Juan Martin; Otto, Adam; Owen, Patrick; Oyanguren, Maria Aranzazu; Palano, Antimo; Palombo, Fernando; Palutan, Matteo; Panman, Jacob; Papanestis, Antonios; Pappagallo, Marco; Pappalardo, Luciano; Pappenheimer, Cheryl; Parker, William; Parkes, Christopher; Passaleva, Giovanni; Patel, Girish; Patel, Mitesh; Patrignani, Claudia; Pearce, Alex; Pellegrino, Antonio; Penso, Gianni; Pepe Altarelli, Monica; Perazzini, Stefano; Perret, Pascal; Pescatore, Luca; Petridis, Konstantinos; Petrolini, Alessandro; Petruzzo, Marco; Picatoste Olloqui, Eduardo; Pietrzyk, Boleslaw; Pilař, Tomas; Pinci, Davide; Pistone, Alessandro; Piucci, Alessio; Playfer, Stephen; Plo Casasus, Maximo; Poikela, Tuomas; Polci, Francesco; Poluektov, Anton; Polyakov, Ivan; Polycarpo, Erica; Popov, Alexander; Popov, Dmitry; Popovici, Bogdan; Potterat, Cédric; Price, Eugenia; Price, Joseph David; Prisciandaro, Jessica; Pritchard, Adrian; Prouve, Claire; Pugatch, Valery; Puig Navarro, Albert; Punzi, Giovanni; Qian, Wenbin; Quagliani, Renato; Rachwal, Bartolomiej; Rademacker, Jonas; Rama, Matteo; Rangel, Murilo; Raniuk, Iurii; Rauschmayr, Nathalie; Raven, Gerhard; Redi, Federico; Reichert, Stefanie; Reid, Matthew; dos Reis, Alberto; Ricciardi, Stefania; Richards, Sophie; Rihl, Mariana; Rinnert, Kurt; Rives Molina, Vincente; Robbe, Patrick; Rodrigues, Ana Barbara; Rodrigues, Eduardo; Rodriguez Lopez, Jairo Alexis; Rodriguez Perez, Pablo; Roiser, Stefan; Romanovsky, Vladimir; Romero Vidal, Antonio; Ronayne, John William; Rotondo, Marcello; Rouvinet, Julien; Ruf, Thomas; Ruiz Valls, Pablo; Saborido Silva, Juan Jose; Sagidova, Naylya; Sail, Paul; Saitta, Biagio; Salustino Guimaraes, Valdir; Sanchez Mayordomo, Carlos; Sanmartin Sedes, Brais; Santacesaria, Roberta; Santamarina Rios, Cibran; Santimaria, Marco; Santovetti, Emanuele; Sarti, Alessio; Satriano, Celestina; Satta, Alessia; Saunders, Daniel Martin; Savrina, Darya; Schael, Stefan; Schiller, Manuel; Schindler, Heinrich; Schlupp, Maximilian; Schmelling, Michael; Schmelzer, Timon; Schmidt, Burkhard; Schneider, Olivier; Schopper, Andreas; Schubiger, Maxime; Schune, Marie Helene; Schwemmer, Rainer; Sciascia, Barbara; Sciubba, Adalberto; Semennikov, Alexander; Sergi, Antonino; Serra, Nicola; Serrano, Justine; Sestini, Lorenzo; Seyfert, Paul; Shapkin, Mikhail; Shapoval, Illya; Shcheglov, Yury; Shears, Tara; Shekhtman, Lev; Shevchenko, Vladimir; Shires, Alexander; Siddi, Benedetto Gianluca; Silva Coutinho, Rafael; Silva de Oliveira, Luiz Gustavo; Simi, Gabriele; Sirendi, Marek; Skidmore, Nicola; Skwarnicki, Tomasz; Smith, Edmund; Smith, Eluned; Smith, Iwan Thomas; Smith, Jackson; Smith, Mark; Snoek, Hella; Sokoloff, Michael; Soler, Paul; Soomro, Fatima; Souza, Daniel; Souza De Paula, Bruno; Spaan, Bernhard; Spradlin, Patrick; Sridharan, Srikanth; Stagni, Federico; Stahl, Marian; Stahl, Sascha; Stefkova, Slavomira; Steinkamp, Olaf; Stenyakin, Oleg; Stevenson, Scott; Stoica, Sabin; Stone, Sheldon; Storaci, Barbara; Stracka, Simone; Straticiuc, Mihai; Straumann, Ulrich; Sun, Liang; Sutcliffe, William; Swientek, Krzysztof; Swientek, Stefan; Syropoulos, Vasileios; Szczekowski, Marek; Szumlak, Tomasz; T'Jampens, Stephane; Tayduganov, Andrey; Tekampe, Tobias; Teklishyn, Maksym; Tellarini, Giulia; Teubert, Frederic; Thomas, Christopher; Thomas, Eric; van Tilburg, Jeroen; Tisserand, Vincent; Tobin, Mark; Todd, Jacob; Tolk, Siim; Tomassetti, Luca; Tonelli, Diego; Topp-Joergensen, Stig; Torr, Nicholas; Tournefier, Edwige; Tourneur, Stephane; Trabelsi, Karim; Tran, Minh Tâm; Tresch, Marco; Trisovic, Ana; Tsaregorodtsev, Andrei; Tsopelas, Panagiotis; Tuning, Niels; Ukleja, Artur; Ustyuzhanin, Andrey; Uwer, Ulrich; Vacca, Claudia; Vagnoni, Vincenzo; Valenti, Giovanni; Vallier, Alexis; Vazquez Gomez, Ricardo; Vazquez Regueiro, Pablo; Vázquez Sierra, Carlos; Vecchi, Stefania; van Veghel, Maarten; Velthuis, Jaap; Veltri, Michele; Veneziano, Giovanni; Vesterinen, Mika; Viaud, Benoit; Vieira, Daniel; Vieites Diaz, Maria; Vilasis-Cardona, Xavier; Volkov, Vladimir; Vollhardt, Achim; Volyanskyy, Dmytro; Voong, David; Vorobyev, Alexey; Vorobyev, Vitaly; Voß, Christian; de Vries, Jacco; Waldi, Roland; Wallace, Charlotte; Wallace, Ronan; Walsh, John; Wandernoth, Sebastian; Wang, Jianchun; Ward, David; Watson, Nigel; Websdale, David; Weiden, Andreas; Whitehead, Mark; Wilkinson, Guy; Wilkinson, Michael; Williams, Mark Richard James; Williams, Matthew; Williams, Mike; Williams, Timothy; Wilson, Fergus; Wimberley, Jack; Wishahi, Julian; Wislicki, Wojciech; Witek, Mariusz; Wormser, Guy; Wotton, Stephen; Wright, Simon; Wyllie, Kenneth; Xie, Yuehong; Xu, Zhirui; Yang, Zhenwei; Yu, Jiesheng; Yuan, Xuhao; Yushchenko, Oleg; Zangoli, Maria; Zavertyaev, Mikhail; Zhang, Liming; Zhang, Yanxi; Zhelezov, Alexey; Zhokhov, Anatoly; Zhong, Liang; Zhukov, Valery; Zucchelli, Stefano

    2016-01-01

    Two-particle angular correlations are studied in proton-lead collisions at a nucleon-nucleon centre-of-mass energy of $\\sqrt{s_{\\text{NN}}}=5$TeV, collected with the LHCb detector at the LHC. The analysis is based on data recorded in two beam configurations, in which either the direction of the proton or that of the lead ion is analysed. The correlations are measured as a function of relative pseudorapidity, $\\Delta\\eta$, and relative azimuthal angle, $\\Delta\\phi$, for events in different classes of event activity and for different bins of particle transverse momentum. In high-activity events a long-range correlation on the near side, $\\Delta\\phi \\approx 0$, is observed in the pseudorapidity range $2.0<\\eta<4.9$. This measurement of long-range correlations on the near side in proton-lead collisions extends previous observations into the forward region up to $\\eta=4.9$. The correlation increases with growing event activity and is found to be more pronounced in the direction of the lead beam. However, the...

  16. LHCb - First measurements of long-range near-side angular correlations in $\\sqrt {^SNN} = 5$ TeV proton-lead collisions in the forward region

    CERN Multimedia

    Yang, Zhenwei

    2015-01-01

    Two-particle angular correlations are studied in proton-lead collisions at a nucleon-nucleon centre-of-mass energy of $\\sqrt {^SNN} = 5$ TeV, collected with the LHCb detector at the LHC. The analysis is based on data recorded in two opposing beam configurations, in which either the direction of the proton or that of the lead remnant is analysed. The correlations are measured as a function of relative pseudorapidity, $\\Delta \\eta$, and relative azimuthal angle, $\\Delta \\phi$, for events in different classes of event activity and for different bins of particle transverse momentum. In high-activity events a long-range correlation on the near side is observed in the pseudorapidity range $2.0 < \\eta < 4.9$. This is the first measurement of a long-range correlation on the near side in proton-lead collisions in the forward region and extends previous observations in the central region. The correlation increases with growing event activity and is found to be more pronounced in the direction of the lead beam. Wh...

  17. First measurements of long-range near-side angular correlations in $\\sqrt{s_{NN}}=5 TeV$ proton-lead collisions in the forward region

    CERN Document Server

    AUTHOR|(SzGeCERN)685390; The LHCb Collaboration

    2015-01-01

    Two-particle angular correlations are studied in proton-lead collisions at a nucleon-nucleon centre-of-mass energy of $\\sqrt{s_{NN}}=5 TeV$, collected with the \\lhcb detector at the \\lhc. The analysis is based on data recorded in two opposing beam configurations, in which either the direction of the proton or that of the lead remnant is analysed. The correlations are measured as a function of relative pseudorapidity, $\\Delta\\eta$, and relative azimuthal angle, $\\Delta\\phi$, for events in different classes of event activity and for different bins of particle transverse momentum. In high-activity events a long-range correlation on the near side is observed in the pseudorapidity range $2.0<\\eta<4.9$. This is the first measurement of a long-range correlation on the near side in proton-lead collisions in the forward region and extends previous observations in the central region. The correlation increases with growing event activity and is found to be more pronounced in the direction of the lead beam. When c...

  18. Acceleration of Long-Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs.

    Science.gov (United States)

    Bätzner, Effi; Liang, Yu; Schweigert, Caroline; Unterreiner, Andreas-Neil; Wagenknecht, Hans-Achim

    2015-06-08

    The C-nucleoside based on the hydroxyquinoline ligand (Hq) is complementary to itself and forms stable Hq-Hq pairs in double-stranded DNA. These artificial Hq-Hq pairs may serve as artificial electron carriers for long-range photoinduced electron transfer in DNA, as elucidated by a combination of gel electrophoretic analysis of irradiated samples and time-resolved transient absorption spectroscopy. For this study, the Hq-Hq pair was combined with a DNA-based donor-acceptor system consisting of 6-N,N-dimethylaminopyrene conjugated to 2'-deoxyuridine as photoinducible electron donor, and methyl viologen attached to the 2'-position of uridine as electron acceptor. The Hq radical anion was identified in the time-resolved measurements and strand cleavage products support its role as an intermediate charge carrier. Hence, the Hq-Hq pair significantly enhances the electron hopping capability of DNA compared to natural DNA bases over long distances while keeping the self-assembly properties as the most attractive feature of DNA as a supramolecular architecture. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. An Approach to Long-Range Electron Transfer Mechanisms in Metalloproteins: In situ Scanning Tunneling Microscopy with Submolecular Resolution

    Science.gov (United States)

    Friis, Esben P.; Andersen, Jens E. T.; Kharkats, Yu. I.; Kuznetsov, A. M.; Nichols, R. J.; Zhang, J.-D.; Ulstrup, Jens

    1999-02-01

    In situ scanning tunneling microscopy (STM) of redox molecules, in aqueous solution, shows interesting analogies and differences compared with interfacial electrochemical electron transfer (ET) and ET in homogeneous solution. This is because the redox level represents a deep indentation in the tunnel barrier, with possible temporary electronic population. Particular perspectives are that both the bias voltage and the overvoltage relative to a reference electrode can be controlled, reflected in spectroscopic features when the potential variation brings the redox level to cross the Fermi levels of the substrate and tip. The blue copper protein azurin adsorbs on gold(111) via a surface disulfide group. Well resolved in situ STM images show arrays of molecules on the triangular gold(111) terraces. This points to the feasibility of in situ STM of redox metalloproteins directly in their natural aqueous medium. Each structure also shows a central brighter contrast in the constant current mode, indicative of 2- to 4-fold current enhancement compared with the peripheral parts. This supports the notion of tunneling via the redox level of the copper atom and of in situ STM as a new approach to long-range electron tunneling in metalloproteins.

  20. Effects of Magnetic Field Cycle on the Polarization Transfer from Parahydrogen to Heteronuclei through Long-Range J-Couplings.

    Science.gov (United States)

    Cavallari, Eleonora; Carrera, Carla; Boi, Tommaso; Aime, Silvio; Reineri, Francesca

    2015-08-06

    Hyperpolarization of (13)C carboxylate signals of metabolically relevant molecules, such as acetate and pyruvate, was recently obtained by means of ParaHydrogen Induced Polarization by Side Arm Hydrogenation (PHIP-SAH). This method relies on functionalization of the carboxylic acid with an unsaturated alcohol (side arm), hydrogenation of the unsaturated alcohol using parahydrogen, and polarization transfer to the target (13)C signal. In this case, parahydrogen protons are added three to four bonds away from the target (13)C nucleus, while biologically relevant molecules had been hyperpolarized, using parahydrogen, through hydrogenation of an unsaturated bond adjacent to the target (13)C signal. The herein reported results show that the same polarization level can be obtained on the (13)C carboxylate signal of an ester by means of addition of parahydrogen to the acidic or to the alcoholic moiety and successive application of magnetic field cycle (MFC). Experimental results are supported by calculations that allow one to predict that, upon accurate control of magnetic field strength and speed of the passages, more than 20% polarization can be achieved on the (13)C-carboxylate resonance of the esters by means of side arm hydrogenation and MFC.

  1. A dual-isotope rubidium comagnetometer to search for anomalous long-range spin-mass (spin-gravity) couplings of the proton

    CERN Document Server

    Kimball, D F Jackson; Valdez, J; Swiatlowski, J; Rios, C; Peregrina-Ramirez, R; Montcrieffe, C; Kremer, J; Dudley, J; Sanchez, C

    2013-01-01

    The experimental concept of a search for a long-range coupling between rubidium (Rb) nuclear spins and the mass of the Earth is described. The experiment is based on simultaneous measurement of the spin precession frequencies for overlapping ensembles of Rb-85 and Rb-87 atoms contained within an evacuated, antirelaxation-coated vapor cell. Rubidium atoms are spin-polarized in the presence of an applied magnetic field by synchronous optical pumping with circularly polarized laser light. Spin precession is probed by measuring optical rotation of far-off-resonant, linearly polarized laser light. Simultaneous measurement of Rb-85 and Rb-87 spin precession frequencies enables suppression of magnetic-field-related systematic effects. The nuclear structure of the Rb isotopes makes the experiment particularly sensitive to anomalous spin-dependent interactions of the proton. Experimental sensitivity and a variety of systematic effects are discussed, and initial data are presented.

  2. Overpotential-induced lability of the electronic overlap factor in long-range electrochemical electron transfer: charge and distance dependence

    DEFF Research Database (Denmark)

    Kornyshev, A. A.; Kuznetsov, A. M.; Nielsen, Jens Ulrik;

    2000-01-01

    Long-distance electrochemical electron transfer exhibits approximately exponential dependence on the electron transfer distance. On the basis of a jellium model of the metal surface we show that the slope of the logarithm of the current vs. the transfer distance also depends strongly...

  3. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  4. A dual-isotope rubidium comagnetometer to search for anomalous long-range spin-mass (spin-gravity) couplings of the proton

    Energy Technology Data Exchange (ETDEWEB)

    Kimball, Derek F.J.; Lacey, Ian; Valdez, Julian; Swiatlowski, Jerlyn; Rios, Cesar; Peregrina-Ramirez, Rodrigo; Montcrieffe, Caitlin; Kremer, Jackie; Dudley, Jordan; Sanchez, C. [Department of Physics, California State University - East Bay, Hayward, California, 94542-3084 (United States)

    2013-07-15

    The experimental concept of a search for a long-range coupling between rubidium (Rb) nuclear spins and the mass of the Earth is described. The experiment is based on simultaneous measurement of the spin precession frequencies for overlapping ensembles of {sup 85}Rb and {sup 87}Rb atoms contained within an evacuated, antirelaxation-coated vapor cell. Rubidium atoms are spin-polarized in the presence of an applied magnetic field by synchronous optical pumping with circularly polarized laser light. Spin precession is probed by measuring optical rotation of far-off-resonant, linearly polarized laser light. Simultaneous measurement of {sup 85}Rb and {sup 87}Rb spin precession frequencies enables suppression of magnetic-field-related systematic effects. The nuclear structure of the Rb isotopes makes the experiment particularly sensitive to anomalous spin-dependent interactions of the proton. Experimental sensitivity and a variety of systematic effects are discussed, and initial data are presented. (copyright 2013 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Assessment of Charge-Transfer Excitations in Organic Dyes obtained from TD-srDFT Based on Long-Range MP2 and MCSCF Wave Functions

    CERN Document Server

    Hedegård, Erik D; Knecht, Stefan; Fromager, Emmanuel; Jensen, Hans Jørgen Aa

    2013-01-01

    Charge transfer excitations can be described within TD-DFT, not only by means of long-range corrected exchange functionals but also with a combination of wave function theory and TD-DFT based on range separation. The latter approach enables a rigorous formulation of multi-determinantal TD-DFT schemes where excitation classes, which are absent in conventional TD-DFT spectra (like for example double excitations), can be addressed. This paper investigates the combination of both the long-range MCSCF and SOPPA ans\\"atze with a short-range DFT (srDFT) description. We find that the combinations of SOPPA or MCSCF with TD-DFT yield better results than could be expected from the pure wave function schemes. For the Time-Dependent MCSCF short-range DFT ansatz (TD-MC-srDFT) excitation energies calculated over a larger benchmark set of molecules with predominantly single reference character yield good agreement with their reference values, and are in general comparable to the long-range corrected functional CAM-B3LYP. The...

  6. Long-range protein electron transfer observed at the single-molecule level: In situ mapping of redox-gated tunneling resonance

    DEFF Research Database (Denmark)

    Chi, Qijin; Farver, O; Ulstrup, Jens

    2005-01-01

    A biomimetic long-range electron transfer (ET) system consisting of the blue copper protein azurin, a tunneling barrier bridge, and a gold single-crystal electrode was designed on the basis of molecular wiring self-assembly principles. This system is sufficiently stable and sensitive in a quasi...... constants display tunneling features with distance-decay factors of 0.83 and 0.91 angstrom(-1) in H2O and D2O, respectively. Redox-gated tunneling resonance is observed in situ at the single-molecule level by using electrochemical scanning tunneling microscopy, exhibiting an asymmetric dependence...

  7. "Long-range" metal-ligand cooperation in H2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex.

    Science.gov (United States)

    Gunanathan, Chidambaram; Gnanaprakasam, Boopathy; Iron, Mark A; Shimon, Linda J W; Milstein, David

    2010-10-27

    The acridine-based pincer complex 1 exhibits an unprecedented mode of metal-ligand cooperation involving a "long-range" interaction between the distal acridine C9 position and the metal center. Reaction of 1 with H(2)/KOH results in H(2) splitting between the Ru center and C9 with concomitant dearomatization of the acridine moiety. DFT calculations show that this process involves the formation of a Ru dihydride intermediate bearing a bent acridine ligand in which C9 is in close proximity to a hydride ligand followed by through-space hydride transfer. Ammonia induces transfer of a hydride from the Ru center of 1 to C9 of the flexible acridine pincer ligand, forming an unusual dearomatized fac-acridine PNP complex.

  8. Vibrational Förster transfer to hydrated protons.

    Science.gov (United States)

    Timmer, R L A; Tielrooij, K J; Bakker, H J

    2010-05-21

    We have studied the influence of excess protons on the vibrational energy relaxation of the O-H and O-D stretching modes in water using femtosecond pump-probe spectroscopy. Without excess protons, we observe exponential decays with time constants of 1.7 and 4.3 ps for the bulk and anion bound O-D stretch vibrations. The addition of protons introduces a new energy relaxation pathway, which leads to an increasingly nonexponential decay of the O-D stretch vibration. This new pathway is attributed to a distance-dependent long range dipole-dipole (Forster) interaction between the O-D stretching vibration and modes associated with dissolved protons. The high efficiency of hydrated protons as receptors of vibrational energy follows from the very large absorption cross section and broad bandwidth of protons in water. For a proton concentration of 1M we find that Forster energy transfer occurs over an average distance of 4.5 A, which corresponds to a separation of about two water molecules.

  9. Challenging Adiabatic Time-dependent Density Functional Theory with a Hubbard Dimer: The Case of Time-Resolved Long-Range Charge Transfer

    CERN Document Server

    Fuks, Johanna I

    2014-01-01

    We explore an asymmetric two-fermion Hubbard dimer to test the accuracy of the adiabatic approximation of time-dependent density functional theory in modelling time-resolved charge transfer. We show that the model shares essential features of a ground state long-range molecule in real-space, and by applying a resonant field we show that the model also reproduces essential traits of the CT dynamics. The simplicity of the model allows us to propagate with an "adiabatically-exact" approximation, i.e. one that uses the exact ground-state exchange-correlation functional, and compare with the exact propagation. This allows us to study the impact of the time-dependent charge-transfer step feature in the exact correlation potential of real molecules on the resulting dynamics. Tuning the parameters of the dimer allows a study both of charge-transfer between open-shell fragments and between closed-shell fragments. We find that the adiabatically-exact functional is unable to properly transfer charge, even in situations ...

  10. Hydrogen Bonds in Excited State Proton Transfer

    Science.gov (United States)

    Horke, D. A.; Watts, H. M.; Smith, A. D.; Jager, E.; Springate, E.; Alexander, O.; Cacho, C.; Chapman, R. T.; Minns, R. S.

    2016-10-01

    Hydrogen bonding interactions between biological chromophores and their surrounding protein and solvent environment significantly affect the photochemical pathways of the chromophore and its biological function. A common first step in the dynamics of these systems is excited state proton transfer between the noncovalently bound molecules, which stabilizes the system against dissociation and principally alters relaxation pathways. Despite such fundamental importance, studying excited state proton transfer across a hydrogen bond has proven difficult, leaving uncertainties about the mechanism. Through time-resolved photoelectron imaging measurements, we demonstrate how the addition of a single hydrogen bond and the opening of an excited state proton transfer channel dramatically changes the outcome of a photochemical reaction, from rapid dissociation in the isolated chromophore to efficient stabilization and ground state recovery in the hydrogen bonded case, and uncover the mechanism of excited state proton transfer at a hydrogen bond, which follows sequential hydrogen and charge transfer processes.

  11. Excited state Intramolecular Proton Transfer in Anthralin

    DEFF Research Database (Denmark)

    Møller, Søren; Andersen, Kristine B.; Spanget-Larsen, Jens

    1998-01-01

    Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results in an unus......Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results......, associated with an excited-state intramolecular proton transfer process....

  12. Solvent control of intramolecular proton transfer

    DEFF Research Database (Denmark)

    Manolova, Y.; Marciniak, Heinz; Tschierlei, S.

    2017-01-01

    The solvent dependent excited state dynamics of 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (compound 2), a candidate for a molecular switch based on intramolecular proton transfer, was investigated by ultrafast spectroscopy and quantum-chemical calculations. In acetonitrile a mixture...... of molecules in the enol and zwitterionic proton transfer (PT) form exists in the ground state. However, the zwitterion is the energetically favored one in the electronically excited state. Optical excitation of the enol form results in intramolecular proton transfer and formation of the PT form within 1.4 ps....... In addition we observe the appearance of a long living species with a rate of 1/(330 ps) which returns to the original ground state on time scales beyond 2 ns and which is attributed to the triplet state. In toluene the enol form is the only observed ground state tautomer, but no light induced proton transfer...

  13. Assessment of a simple correction for the long-range charge-transfer problem in time-dependent density-functional theory

    Science.gov (United States)

    Neugebauer, Johannes; Gritsenko, Oleg; Baerends, Evert Jan

    2006-06-01

    The failure of the time-dependent density-functional theory to describe long-range charge-transfer (CT) excitations correctly is a serious problem for calculations of electronic transitions in large systems, especially if they are composed of several weakly interacting units. The problem is particularly severe for molecules in solution, either modeled by periodic boundary calculations with large box sizes or by cluster calculations employing extended solvent shells. In the present study we describe the implementation and assessment of a simple physically motivated correction to the exchange-correlation kernel suggested in a previous study [O. Gritsenko and E. J. Baerends J. Chem. Phys. 121, 655 (2004)]. It introduces the required divergence in the kernel when the transition density goes to zero due to a large spatial distance between the "electron" (in the virtual orbital) and the "hole" (in the occupied orbital). A major benefit arises for solvated molecules, for which many CT excitations occur from solvent to solute or vice versa. In these cases, the correction of the exchange-correlation kernel can be used to automatically "clean up" the spectrum and significantly reduce the computational effort to determine low-lying transitions of the solute. This correction uses a phenomenological parameter, which is needed to identify a CT excitation in terms of the orbital density overlap of the occupied and virtual orbitals involved. Another quantity needed in this approach is the magnitude of the correction in the asymptotic limit. Although this can, in principle, be calculated rigorously for a given CT transition, we assess a simple approximation to it that can automatically be applied to a number of low-energy CT excitations without additional computational effort. We show that the method is robust and correctly shifts long-range CT excitations, while other excitations remain unaffected. We discuss problems arising from a strong delocalization of orbitals, which leads

  14. Assessment of a simple correction for the long-range charge-transfer problem in time-dependent density-functional theory.

    Science.gov (United States)

    Neugebauer, Johannes; Gritsenko, Oleg; Baerends, Evert Jan

    2006-06-07

    The failure of the time-dependent density-functional theory to describe long-range charge-transfer (CT) excitations correctly is a serious problem for calculations of electronic transitions in large systems, especially if they are composed of several weakly interacting units. The problem is particularly severe for molecules in solution, either modeled by periodic boundary calculations with large box sizes or by cluster calculations employing extended solvent shells. In the present study we describe the implementation and assessment of a simple physically motivated correction to the exchange-correlation kernel suggested in a previous study [O. Gritsenko and E. J. Baerends J. Chem. Phys. 121, 655 (2004)]. It introduces the required divergence in the kernel when the transition density goes to zero due to a large spatial distance between the "electron" (in the virtual orbital) and the "hole" (in the occupied orbital). A major benefit arises for solvated molecules, for which many CT excitations occur from solvent to solute or vice versa. In these cases, the correction of the exchange-correlation kernel can be used to automatically "clean up" the spectrum and significantly reduce the computational effort to determine low-lying transitions of the solute. This correction uses a phenomenological parameter, which is needed to identify a CT excitation in terms of the orbital density overlap of the occupied and virtual orbitals involved. Another quantity needed in this approach is the magnitude of the correction in the asymptotic limit. Although this can, in principle, be calculated rigorously for a given CT transition, we assess a simple approximation to it that can automatically be applied to a number of low-energy CT excitations without additional computational effort. We show that the method is robust and correctly shifts long-range CT excitations, while other excitations remain unaffected. We discuss problems arising from a strong delocalization of orbitals, which leads

  15. LONG RANGE HEALTH PLANNING

    Directory of Open Access Journals (Sweden)

    ST. Motameni

    1974-03-01

    Full Text Available In the past, health planning in Iran has been carried out in the context of short-range economic plans. Although this mechanism has helped a great deal in the achievement of certain health plans however, the said scheme has been short in meeting the health objectives on a comprehensive basis. Most often, the heath programs have lost their values to the priority and cost effectiveness of economic plans. A brief review of heath planning in the past shows that the second development plan has been devoted to the establishment of new hospitals on a scattered pattern. The development of a coordinated hospital and health center system has been accepted and partly implemented during the third plan period. In the fourth plan the whole direction has changed towards the de­velopment of private hospitals on profit making basis, and now the fifth plan calls for the regionalized hospital system. Thus, one can say that the past twenty years have been spent to the experimentation of different schemes with­out a real long-range goal. In the past decade the World Health Organization has ventured in the development of health planning principles, but most of the efforts have been devoted to the short-range planning. The long-range health planning is not only a new look to the prin­ciples of planning, but a thorough examination of the time factor in health planning.

  16. Insights into Proton-Coupled Electron Transfer from Computation

    Science.gov (United States)

    Provorse, Makenzie R.

    Proton-coupled electron transfer (PCET) is utilized throughout Nature to facilitate essential biological processes, such as photosynthesis, cellular respiration, and DNA replication and repair. The general approach to studying PCET processes is based on a two-dimensional More O'Ferrall-Jencks diagram in which electron transfer (ET) and proton transfer (PT) occur in a sequential or concerted fashion. Experimentally, it is difficult to discern the contributing factors of concerted PCET mechanisms. Several theoretical approaches have arisen to qualitatively and quantitatively investigate these reactions. Here, we present a multistate density functional theory (MSDFT) method to efficiently and accurately model PCET mechanisms. The MSDFT method is validated against experimental and computational data previously reported on an isoelectronic series of small molecule self-exchange hydrogen atom transfer reactions and a model complex specifically designed to study long-range ET through a hydrogen-bonded salt-bridge interface. Further application of this method to the hydrogen atom abstraction of ascorbate by a nitroxyl radical demonstrates the sensitivity of the thermodynamic and kinetic properties to solvent effects. In particular, the origin of the unusual kinetic isotope effect is investigated. Lastly, the MSDFT is employed in a combined quantum mechanical/molecular mechanical (QM/MM) approach to explicitly model PCET in condensed phases.

  17. Polarization Transfer in Proton Compton Scattering at High Momentum Transfer

    CERN Document Server

    Hamilton, D J; Aniol, K A; Annand, J R M; Bertin, P Y; Bimbot, L; Bosted, P; Calarco, J R; Camsonne, A; Chang, G C; Chang, T H; Chen, J P; Seonho Choi; Chudakov, E; Danagulyan, A S; Degtyarenko, P; De Jager, C W; Deur, A; Dutta, D; Egiyan, K; Gao, H; Garibaldi, F; Gayou, O; Gilman, R; Glamazdin, A; Glashausser, C; Gómez, J; Hansen, J O; Hayes, D; Higinbotham, D W; Hinton, W; Horn, T; Howell, C; Hunyady, T; Hyde-Wright, C E; Jiang, X; Jones, M K; Khandaker, M; Ketikyan, A; Koubarovski, V; Krämer, K; Kumbartzki, G; Laveissière, G; Le Rose, J J; Lindgren, R A; Margaziotis, D J; Markowitz, P; McCormick, K; Meziani, Z E; Michaels, R; Moussiegt, P; Nanda, S; Nathan, A M; Nikolenko, D M; Nelyubin, V V; Norum, B E; Paschke, K; Pentchev, L; Perdrisat, C F; Piasetzky, E; Pomatsalyuk, R I; Punjabi, V A; Rachek, Igor A; Radyushkin, A V; Reitz, B; Roché, R; Roedelbronn, M; Ron, G; Sabatie, F; Saha, A; Savvinov, N; Shahinyan, A; Shestakov, Yu V; Sirca, S; Slifer, K J; Solvignon, P; Stoler, P; Tajima, S; Sulkosky, V; Todor, L; Vlahovic, B; Weinstein, L B; Wang, K; Wojtsekhowski, B; Voskanyan, H; Xiang, H; Zheng, X; Zhu, L

    2004-01-01

    Compton scattering from the proton was investigated at s=6.9 (GeV/c)**2 and \\t=-4.0 (GeV/c)**2 via polarization transfer from circularly polarized incident photons. The longitudinal and transverse components of the recoil proton polarization were measured. The results are in excellent agreement with a prediction based on a reaction mechanism in which the photon interacts with a single quark carrying the spin of the proton and in disagreement with a prediction of pQCD based on a two-gluon exchange mechanism.

  18. Proton transfer pathways in Photosystem II

    Science.gov (United States)

    Ishikita, Hiroshi

    2014-03-01

    Using quantum mechanics/molecular mechanics calculations and the 1.9-Å crystal structure of Photosystem II (Umena, Y., Kawakami, K., Shen, J.-R., and Kamiya, N. (2011) Nature 473, 55-60), we investigated the H-bonding environment of the redox active tyrosine, TyrD and obtained insights that help explain its slow redox kinetics and the stability of TyrD radical. The water molecule distal to TyrD, 4 Å away from the phenolic O of TyrD (OTyrD) , corresponds to the presence of the tyrosyl radical state. The water molecule proximal to TyrD, in H-bonding distance to OTyrD, corresponds to the presence of the unoxidised tyrosine. The H+ released upon oxidation of TyrD is transferred to the proximal water, which shifts to the distal position, triggering a concerted proton transfer pathway involving D2-Arg180 and a series of waters, through which the proton reaches the aqueous phase at D2-His61. The water movement linked to the ejection of the proton from the hydrophobic environment near TyrD makes oxidation slow and quasi-irreversible, explaining the great stability of the TyrD radical. A symmetry-related proton pathway associated with TyrZ is pointed out and this is associated with one of the Cl- sites. This may represent a proton pathway functional in the water oxidation cycle.

  19. Hydrogen-bonded proton transfer in the protonated guanine-cytosine (GC+H)+ base pair.

    Science.gov (United States)

    Lin, Yuexia; Wang, Hongyan; Gao, Simin; Schaefer, Henry F

    2011-10-13

    The single proton transfer at the different sites of the Watson-Crick (WC) guanine-cytosine (GC) DNA base pair are studied here using density functional methods. The conventional protonated structures, transition state (TS) and proton-transferred product (PT) structures of every relevant species are optimized. Each transition state and proton-transferred product structure has been compared with the corresponding conventional protonated structure to demonstrate the process of proton transfer and the change of geometrical structures. The relative energies of the protonated tautomers and the proton-transfer energy profiles in gas and solvent are analyzed. The proton-transferred product structure G(+H(+))-H(+)C(N3)(-H(+))(PT) has the lowest relative energy for which only two hydrogen bonds exist. Almost all 14 isomers of the protonated GC base pair involve hydrogen-bonded proton transfer following the three pathways, with the exception of structure G-H(+)C(O2). When the positive charge is primarily "located" on the guanine moiety (H(+)G-C, G-H(+)C(C4), and G-H(+)C(C6)), the H(1) proton transfers from the N(1) site of guanine to the N(3) site of cytosine. The structures G-H(+)C(C5) and G-H(+)C(C4) involve H(4a) proton transfer from the N(4) of cytosine to the O(6) site of guanine. H(2a) proton transfer from the N(2) site of guanine to the O(2) site of cytosine is found only for the structure G-H(+)C(C4). The structures to which a proton is added on the six-centered sites adjoining the hydrogen bonds are more prone to proton transfer in the gas phase, whereas a proton added on the minor groove and the sites adjoining the hydrogen bonds is favorable to the proton transfer in energy in the aqueous phase.

  20. Proton transfer studies in CGC+ assembly

    Science.gov (United States)

    Żabicki, Michał; Gudowska-Nowak, Ewa; Fischer, Sighart F.

    2009-12-01

    We have designed and analyzed a molecular model of a generic triple helix DNA base structure - the cytosine-guanine-cytosine (CGC+) assembly. The complex has been investigated for the ability of a concerted proton transfer from cytosine to guanine. Ab initio calculations have been preformed using Unrestricted Hartree-Fock (UHF) method with 6-31G ∗+ basis set. In order to determine possible reaction paths, the potential map has been constructed pointing the most stable configuration for the process to occur. Based on this observation, we have estimated a transmission coefficient for the transfer and found no support for a concerted motion. The effect of fluctuations of the barrier height on the kinetics is also discussed.

  1. Heteronuclear Long-Range Correlation

    DEFF Research Database (Denmark)

    Sørensen, Ole W.

    The lecture will cover heteronuclear long-range correlation techniques like HMBC, H2BC, and HAT HMBC with the emphasis on determining the number of covalent bonds between two spins being correlated. H2BC and HMBC spectra are quite complementary as a peak can be strong in one of the two spectra...

  2. Proton Transfer in Nucleobases is Mediated by Water

    Energy Technology Data Exchange (ETDEWEB)

    Khistyaev, Kirill; Golan, Amir; Bravaya, Ksenia B.; Orms, Natalie; Krylov, Anna I.; Ahmed, Musahid

    2013-08-08

    Water plays a central role in chemistry and biology by mediating the interactions between molecules, altering energy levels of solvated species, modifying potential energy proles along reaction coordinates, and facilitating ecient proton transport through ion channels and interfaces. This study investigates proton transfer in a model system comprising dry and microhydrated clusters of nucleobases. With mass spectrometry and tunable vacuum ultraviolet synchrotron radiation, we show that water shuts down ionization-induced proton transfer between nucleobases, which is very ecient in dry clusters. Instead, a new pathway opens up in which protonated nucleo bases are generated by proton transfer from the ionized water molecule and elimination of a hydroxyl radical. Electronic structure calculations reveal that the shape of the potential energy prole along the proton transfer coordinate depends strongly on the character of the molecular orbital from which the electron is removed, i.e., the proton transfer from water to nucleobases is barrierless when an ionized state localized on water is accessed. The computed energetics of proton transfer is in excellent agreement with the experimental appearance energies. Possible adiabatic passage on the ground electronic state of the ionized system, while energetically accessible at lower energies, is not ecient. Thus, proton transfer is controlled electronically, by the character of the ionized state, rather than statistically, by simple energy considerations.

  3. Theory of interrelated electron and proton transfer processes

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2003-01-01

    A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic and nonadiaba......A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic...

  4. Parallel proton transfer pathways in aqueous acid-base reactions

    NARCIS (Netherlands)

    Cox, M.J.; Bakker, H.J.

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using femtose

  5. Long-Range Collisions in Magnetized Plasmas

    Science.gov (United States)

    Dubin, D.

    2015-12-01

    Astrophysical (and earthbound) plasmas in strong magnetic fields exhibit collisional effects that are not described by classical collision theory nor by the standard collision operators, such as the Landau or Balescu-Lenard operators. These theories implicitly neglect "long-range" collisions, i.e. collisions with impact parameters large compared to the cyclotron radius. This presentation will review several important physical effects such collisions have on various phenomena, including cross-magnetic field diffusion, heat conduction, and collisional slowing parallel to the magnetic field. Long-range collisions are analyzed as guiding-centers moving in one-dimension along the magnetic field, with parallel energy and momentum transferred to particles on separate field lines through the screened Coulomb interaction. This causes cross-field heat transport that is independent of magnetic field strength B (as opposed to the classical 1/B2 scaling), and enhances the rate of collisional slowing parallel to B. The Coulomb interaction between guiding centers on different field lines also produces random ExB drifts that enhance cross-magnetic field diffusion compared to the classical theory. The theory of long-range guiding center collisions must also include the novel effect of "collisional caging": plasma noise causes two colliding guiding centers to diffuse in relative parallel velocity, reversing their motion along B and colliding several times before becoming uncorrelated. This further enhances cross-field diffusion from long-range collisions by a factor of three, and enhances parallel slowing by a factor of approximately 1.5.

  6. Parallel proton transfer pathways in aqueous acid-base reactions

    OpenAIRE

    Cox, M. J.; Bakker, H.J.

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using femtosecond midinfrared spectroscopy, we probe the vibrational responses of HPTS, its conjugate photobase, the hydrated proton/deuteron, and chloroacetate. The measurement of these four resonances allows ...

  7. Long-Range Facilities - Plan

    Science.gov (United States)

    1981-07-31

    time for reviewing instructions, searching existing data sources , gathering and maintaining the data needed, and completing and reviewing the...sternwheeler “Mark Twain” for Disneyland and fabrication of eight 52 foot submarines for the Disneyland “Navy.” This was followed by fabrication of the masts...reconstruction. This long-range plan provides a baseline against which the funds required for reconstruction can be balanced against a definite structure

  8. Linear energy relationships in ground state proton transfer and excited state proton-coupled electron transfer.

    Science.gov (United States)

    Gamiz-Hernandez, Ana P; Magomedov, Artiom; Hummer, Gerhard; Kaila, Ville R I

    2015-02-12

    Proton-coupled electron transfer (PCET) processes are elementary chemical reactions involved in a broad range of radical and redox reactions. Elucidating fundamental PCET reaction mechanisms are thus of central importance for chemical and biochemical research. Here we use quantum chemical density functional theory (DFT), time-dependent density functional theory (TDDFT), and the algebraic diagrammatic-construction through second-order (ADC(2)) to study the mechanism, thermodynamic driving force effects, and reaction barriers of both ground state proton transfer (pT) and photoinduced proton-coupled electron transfer (PCET) between nitrosylated phenyl-phenol compounds and hydrogen-bonded t-butylamine as an external base. We show that the obtained reaction barriers for the ground state pT reactions depend linearly on the thermodynamic driving force, with a Brønsted slope of 1 or 0. Photoexcitation leads to a PCET reaction, for which we find that the excited state reaction barrier depends on the thermodynamic driving force with a Brønsted slope of 1/2. To support the mechanistic picture arising from the static potential energy surfaces, we perform additional molecular dynamics simulations on the excited state energy surface, in which we observe a spontaneous PCET between the donor and the acceptor groups. Our findings suggest that a Brønsted analysis may distinguish the ground state pT and excited state PCET processes.

  9. Long-Range Electron Transfer Across Cytochrome-Hematite (a-Fe2O3) Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Wigginton, Nicholas S. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Swiss Federal Institute of Technology in Lausanne (Switzerland); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stack, Andrew G. [Georgia Inst. of Technology, Atlanta, GA (United States); Hochella, Michael F. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

    2009-01-06

    Electrochemical scanning tunneling microscopy (EC-STM) was used to assess the distance dependence of electron tunneling facilitated by a bacterial multiheme cytochrome to a single crystal iron oxide surface. We measured tunneling current-distance (I-s) profiles across the nanoscale space between insulated Au STM tips and the basal (001) surface of a hematite (α-Fe2O3) crystal, and compared them to the case in which an intervening small tetraheme cytochrome (STC) from Shewanella oneidensis covalently linked to the Au tip surface. Tunneling profiles were collected at constant surface potentials in solutions having a range of ionic strengths. At short tip-sample separation, the distance dependece of the tunneling current shows a quasi-linear behavior. At longer distances it shows an exponential decay. The different regions are discussed in terms of ordering of interfacial water and ion layers in the electrical double layer associated with the hematite surface. The effective tunneling range and its rate of decay are substantially increased when STC is present in the tunneling junction, suggesting that cytochrome molecules provide enhanced tunneling pathways and stronger electronic coupling to the hematite surface. Based on these results, cytochrome-mediated electron transfer during bacterial metal reduction may be possible at distances further than originally thought. Also, as multiheme cytochromes and other similar molecules gain attention for their promising role in fuel cells and molecular electronics, we show that the solution conditions and surface properties of the substrate must be carefully considered.

  10. Asymptotic correction of the exchange-correlation kernel of time-dependent density functional theory for long-range charge-transfer excitations.

    Science.gov (United States)

    Gritsenko, Oleg; Baerends, Evert Jan

    2004-07-08

    Time-dependent density functional theory (TDDFT) calculations of charge-transfer excitation energies omegaCT are significantly in error when the adiabatic local density approximation (ALDA) is employed for the exchange-correlation kernel fxc. We relate the error to the physical meaning of the orbital energy of the Kohn-Sham lowest unoccupied molecular orbital (LUMO). The LUMO orbital energy in Kohn-Sham DFT--in contrast to the Hartree-Fock model--approximates an excited electron, which is correct for excitations in compact molecules. In CT transitions the energy of the LUMO of the acceptor molecule should instead describe an added electron, i.e., approximate the electron affinity. To obtain a contribution that compensates for the difference, a specific divergence of fxc is required in rigorous TDDFT, and a suitable asymptotically correct form of the kernel fxc(asymp) is proposed. The importance of the asymptotic correction of fxc is demonstrated with the calculation of omegaCT(R) for the prototype diatomic system HeBe at various separations R(He-Be). The TDDFT-ALDA curve omegaCT(R) roughly resembles the benchmark ab initio curve omegaCT CISD(R) of a configuration interaction calculation with single and double excitations in the region R=1-1.5 A, where a sizable He-Be interaction exists, but exhibits the wrong behavior omegaCT(R)

  11. Excited-state intermolecular proton transfer of firefly luciferin III. Proton transfer to a mild base.

    Science.gov (United States)

    Presiado, Itay; Erez, Yuval; Huppert, Dan

    2010-12-30

    Steady-state and time-resolved techniques were employed to study the excited-state proton transfer (ESPT) from d-luciferin, the natural substrate of the firefly luciferase, to the mild acetate base in aqueous solutions. We found that in 1 M aqueous solutions of acetate or higher, a proton transfer (PT) process to the acetate takes place within 30 ps in both H(2)O and D(2)O solutions. The time-resolved emission signal is composed of three components. We found that the short-time component decay time is 300 and 600 fs in H(2)O and D(2)O, respectively. This component is attributed either to a PT process via the shortest water bridged complex available, ROH··H(2)O··Ac(-), or to PT taking place within a contact ion pair. The second time component of 2000 and 3000 fs for H(2)O and D(2)O, respectively, is attributed to ROH* acetate complex, whose proton wire is longer by one water molecule. The decay rate of the third, long-time component is proportional to the acetate concentration. We attribute it to the diffusion-assisted reaction as well as to PT process to the solvent.

  12. Heteronuclear Long-Range Correlation

    DEFF Research Database (Denmark)

    Sørensen, Ole W.

    and absent in the other. Editing according to the number of protons attached to the 13C spin is an additional useful feature simplifying and purging this type of spectra. Combining spectra with evolution under the coupling in the conventional and opposite sense, respectively, helps improve the editing...

  13. Density functional theory study of proton transfer in carbonic anhydrase

    Institute of Scientific and Technical Information of China (English)

    ZHANG Lidong; XIE Daiqian

    2005-01-01

    Proton transfer in carbonic anhydrase II has been studied at the B3LYP/6-31G(D) level. The active site model consists of the zinc ion, four histidine residues, two threonine residues, and three water molecules. Our calculations showed that the proton of the zinc-bound water molecule could be transferred to the nearest water molecule and an intermediate containing H3O+ is then formed. The intermediate is only 1.3 kJ·mol-1 above the reactant complex, whereas the barrier height for the proton transfer is about 8.1 kJ·mol-1.

  14. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    B Saritha; M Durga Prasad

    2012-01-01

    Recently, we had suggested that the motion along the promoter mode in the first part of the IRC of proton transfer reaction enhances the delocalization of electrons on the acceptor atom into the * orbital of the donor-hydrogen covalent bond, and as a consequence weakens it. This leads to a reduction of the barrier to the proton transfer as well as the stretching frequency of donor-hydrogen bond. An extension of this to the concerted multiple proton transfer reactions implies that the kinetic isotope effect in such reaction depends exponentially on the number of protons that are being transferred. Computational evidence on three systems, (HF)3, formic acid dimer, and (H2O) clusters is provided to support this assertion.

  15. Modelling proton transfer in water molecule chains

    CERN Document Server

    Korzhimanov, Artem; Shutova, Tatiana; Samuelsson, Goran

    2011-01-01

    The process of protons transport in molecular water chains is of fundamental interest for many biological systems. Although many features of such systems can be analyzed using large-scale computational modeling, other features are better understood in terms of simplified model problems. Here we have tested, analytically and numerically, a model describing the classical proton hopping process in molecular water chains. In order to capture the main features of the proton hopping process in such molecular chains, we use a simplified model for our analysis. In particular, our discrete model describes a 1D chain of water molecules situated in an external protein channel structure, and each water molecule is allowed to oscillate around its equilibrium point in this system, while the protons are allowed to move along the line of neighboring oxygen atoms. The occurrence and properties of nonlinear solitary transport structures, allowing for much faster proton transport, are discussed, and the possible implications of...

  16. Ultrafast excited-state intramolecular proton transfer of aloesaponarin I.

    Science.gov (United States)

    Nagaoka, Shin-ichi; Uno, Hidemitsu; Huppert, Dan

    2013-04-25

    Time-resolved emission of aloesaponarin I was studied with the fluorescence up-conversion and time-correlated single-photon-counting techniques. The rates of the excited-state intramolecular proton transfer, of the solvent and molecular rearrangements, and of the decay from the excited proton-transferred species were determined and interpreted in the light of time-dependent density functional calculations. These results were discussed in conjunction with UV protection and singlet-oxygen quenching activity of aloe.

  17. Excited-state intermolecular proton transfer of firefly luciferin V. Direct proton transfer to fluoride and other mild bases.

    Science.gov (United States)

    Presiado, Itay; Gepshtein, Rinat; Erez, Yuval; Huppert, Dan

    2011-07-07

    We studied the direct proton transfer (PT) from electronically excited D-luciferin to several mild bases. The fluorescence up-conversion technique is used to measure the rise and decay of the fluorescence signals of the protonated and deprotonated species of D-luciferin. From a base concentration of 0.25 M or higher the proton transfer rates to the fluoride, dihdyrogen phosphate or acetate bases are fast and comparable. The fluorescence signals are nonexponential and complex. We suggest that the fastest decay component arises from a direct proton transfer process from the hydroxyl group of D-luciferin to the mild base. The proton donor and acceptor molecules form an ion pair prior to photoexcitation. Upon photoexcitation solvent rearrangement occurs on a 1 ps time-scale. The PT reaction time constant is ∼2 ps for all three bases. A second decay component of about 10 ps is attributed to the proton transfer in a contact pair bridged by one water molecule. The longest decay component is due to both the excited-state proton transfer (ESPT) to the solvent and the diffusion-assisted PT process between a photoacid and a base pair positioned remotely from each other prior to photoexcitation.

  18. Measurement of the long--range pseudorapidity correlations between muons and charged-particles in $\\sqrt{s_{\\mathrm{NN}}}$=8.16~TeV proton-lead collisions with the ATLAS detector

    CERN Document Server

    The ATLAS collaboration

    2017-01-01

    Measurements of correlations between inclusive charged-particle pairs and between inclusive charged-particle and muon pairs in relative azimuthal angle ($\\Delta\\phi$) and pseudorapidity ($\\Delta\\eta$) are presented for $p$+Pb collisions at $\\sqrt{s_{\\mathrm{NN}}}$=8.16~TeV using muons and charged particles with $|\\eta|<2.5$. The correlations involving the muons are interesting as the muons primarily come from heavy-flavor decays and studying these correlations gives an understanding of the long-range correlations involving heavy-flavor quarks. The measurements show the presence of long-range correlations between muons and inclusive charged-particles extending to $|\\Delta\\eta|=5$. A template fitting method is used to remove the contribution from dijets to the correlations, and obtain the second-order Fourier coefficient, $v_{2,2}$, corresponding to the genuine long-range correlations. The $v_{2,2}$ is factorized to obtain the single-particle anisotropy coefficient, $v_2$, of the muons. The dependence of the...

  19. Specific Heat Properties of Proton Transfer in Hydrogen Bonded Systems

    Institute of Scientific and Technical Information of China (English)

    庞小峰; 封原平

    2003-01-01

    The thermodynamic properties of proton transport along hydrogen-bonded systems at finite temperatures have been studied by our model. We first derive the dynamic equations of the proton transport and find the solutions and the free energy of the systems. Finally, we obtain the specific heats of the hydrogen bonded systems, resulting from the motion of the soliton, by using transfer integral way. The theoretical value is basically consistent with the experimental data.

  20. The nature of tryptophan radicals involved in the long-range electron transfer of lignin peroxidase and lignin peroxidase-like systems: Insights from quantum mechanical/molecular mechanics simulations.

    Science.gov (United States)

    Bernini, Caterina; Pogni, Rebecca; Basosi, Riccardo; Sinicropi, Adalgisa

    2012-05-01

    A catalytically active tryptophan radical has been demonstrated to be involved in the long-range electron transfer to the heme cofactor of lignin peroxidase (LiP) from Phanerochaete chrysosporium although no direct detection by EPR spectroscopy of the tryptophan radical intermediate has been reported to date. An engineering-based approach has been used to manipulate the microenvironment of the redox-active tryptophan site in LiP and Coprinus cinereus Peroxidase (CiP), allowing the direct evidence of the tryptophan radical species. In light of the newly available EPR experimental data, we performed a quantum mechanical/molecular mechanics computational study to characterize the tryptophan radicals in the above protein matrices as well as in pristine LiP. The nature of the tryptophan radicals is discussed together with the analysis of their environment with the aim of understanding the different behavior of pristine LiP in comparison with that of LiP and CiP variants.

  1. Long-range correlations in high multiplicity and collisions

    Indian Academy of Sciences (India)

    Gunther Roland

    2015-05-01

    This review summarizes recent discoveries in high-energy proton+proton and proton+nucleus collisions, with particular attention on the observation of long-range azimuthal correlations in high multiplicity collisions. These correlations, which resemble those seen in ultrarelativistic nucleus–nucleus collisions, provide a unique window into the physics of the very early collision stage in high energy nuclear interactions. Here we present a compilation of the most important experimental results and briefly discuss successes and challenges for a selection of theoretical approaches.

  2. Proton position near QB and coupling of electron and proton transfer in photosynthesis

    Science.gov (United States)

    Belousov, R. V.; Poltev, S. V.; Kukushkin, A. K.

    2003-05-01

    We have calculated the energy levels and wavefunctions of a proton in a histidine (His)-plastoquinone (PQ) system in the reaction centre (RC) of photosystem 2 of higher plants and the RC of purple bacteria for different redox states of PQ QB. For oxidized QB, the proton is located near His. For once-reduced PQ, it is positioned in the middle between the nitrogen of His and the oxygen of PQ. For twofold-reduced PQ, the proton is localized near the oxygen of PQ. Using the values of total energy of the system in these states, we have also estimated the frequency of proton oscillations. On the basis of these results we propose a hypothesis about the coupling of electron-proton transfer.

  3. Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer

    Science.gov (United States)

    Sotiriou, Georgios A.; Blattmann, Christoph O.; Deligiannakis, Yiannis

    2015-12-01

    Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol-1 and therefore facilitates PCET. The nanoparticle-driven plasmon-enhancement of PCET brings together the so far unrelated research domains of nanoplasmonics and electron/proton translocation with significant impact on applications based on interfacial electron/proton transfer.Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol-1 and therefore facilitates PCET. The nanoparticle-driven plasmon

  4. Observation of Associated Near-side and Away-side Long-range Correlations in $\\sqrt{s_{NN}}$=5.02 TeV Proton-lead Collisions with the ATLAS Detector

    CERN Document Server

    Aad, Georges; Abbott, Brad; Abdallah, Jalal; Abdel Khalek, Samah; Abdelalim, Ahmed Ali; Abdinov, Ovsat; Aben, Rosemarie; Abi, Babak; Abolins, Maris; AbouZeid, Ossama; Abramowicz, Halina; Abreu, Henso; Acharya, Bobby Samir; Adamczyk, Leszek; Adams, David; Addy, Tetteh; Adelman, Jahred; Adomeit, Stefanie; Adragna, Paolo; Adye, Tim; Aefsky, Scott; Aguilar-Saavedra, Juan Antonio; Agustoni, Marco; Ahlen, Steven; Ahles, Florian; Ahmad, Ashfaq; Ahsan, Mahsana; Aielli, Giulio; Åkesson, Torsten Paul Ake; Akimoto, Ginga; Akimov, Andrei; Alam, Muhammad Aftab; Albert, Justin; Albrand, Solveig; Aleksa, Martin; Aleksandrov, Igor; Alessandria, Franco; Alexa, Calin; Alexander, Gideon; Alexandre, Gauthier; Alexopoulos, Theodoros; Alhroob, Muhammad; Aliev, Malik; Alimonti, Gianluca; Alison, John; Allbrooke, Benedict; Allison, Lee John; Allport, Phillip; Allwood-Spiers, Sarah; Almond, John; Aloisio, Alberto; Alon, Raz; Alonso, Alejandro; Alonso, Francisco; Altheimer, Andrew David; Alvarez Gonzalez, Barbara; Alviggi, Mariagrazia; Amako, Katsuya; Amelung, Christoph; Ammosov, Vladimir; Amor Dos Santos, Susana Patricia; Amorim, Antonio; Amoroso, Simone; Amram, Nir; Anastopoulos, Christos; Ancu, Lucian Stefan; Andari, Nansi; Andeen, Timothy; Anders, Christoph Falk; Anders, Gabriel; Anderson, Kelby; Andreazza, Attilio; Andrei, George Victor; Anduaga, Xabier; Angelidakis, Stylianos; Anger, Philipp; Angerami, Aaron; Anghinolfi, Francis; Anisenkov, Alexey; Anjos, Nuno; Annovi, Alberto; Antonaki, Ariadni; Antonelli, Mario; Antonov, Alexey; Antos, Jaroslav; Anulli, Fabio; Aoki, Masato; Aperio Bella, Ludovica; Apolle, Rudi; Arabidze, Giorgi; Aracena, Ignacio; Arai, Yasuo; Arce, Ayana; Arfaoui, Samir; Arguin, Jean-Francois; Argyropoulos, Spyridon; Arik, Engin; Arik, Metin; Armbruster, Aaron James; Arnaez, Olivier; Arnal, Vanessa; Artamonov, Andrei; Artoni, Giacomo; Arutinov, David; Asai, Shoji; Ask, Stefan; Åsman, Barbro; Asquith, Lily; Assamagan, Ketevi; Astalos, Robert; Astbury, Alan; Atkinson, Markus; Auerbach, Benjamin; Auge, Etienne; Augsten, Kamil; Aurousseau, Mathieu; Avolio, Giuseppe; Axen, David; Azuelos, Georges; Azuma, Yuya; Baak, Max; Baccaglioni, Giuseppe; Bacci, Cesare; Bach, Andre; Bachacou, Henri; Bachas, Konstantinos; Backes, Moritz; Backhaus, Malte; Backus Mayes, John; Badescu, Elisabeta; Bagnaia, Paolo; Bai, Yu; Bailey, David; Bain, Travis; Baines, John; Baker, Oliver Keith; Baker, Sarah; Balek, Petr; Balli, Fabrice; Banas, Elzbieta; Banerjee, Piyali; Banerjee, Swagato; Banfi, Danilo; Bangert, Andrea Michelle; Bansal, Vikas; Bansil, Hardeep Singh; Barak, Liron; Baranov, Sergei; Barber, Tom; Barberio, Elisabetta Luigia; Barberis, Dario; Barbero, Marlon; Bardin, Dmitri; Barillari, Teresa; Barisonzi, Marcello; Barklow, Timothy; Barlow, Nick; Barnett, Bruce; Barnett, Michael; Baroncelli, Antonio; Barone, Gaetano; Barr, Alan; Barreiro, Fernando; Barreiro Guimarães da Costa, João; Bartoldus, Rainer; Barton, Adam Edward; Bartsch, Valeria; Basye, Austin; Bates, Richard; Batkova, Lucia; Batley, Richard; Battaglia, Andreas; Battistin, Michele; Bauer, Florian; Bawa, Harinder Singh; Beale, Steven; Beau, Tristan; Beauchemin, Pierre-Hugues; Beccherle, Roberto; Bechtle, Philip; Beck, Hans Peter; Becker, Anne Kathrin; Becker, Sebastian; Beckingham, Matthew; Becks, Karl-Heinz; Beddall, Andrew; Beddall, Ayda; Bedikian, Sourpouhi; Bednyakov, Vadim; Bee, Christopher; Beemster, Lars; Beermann, Thomas; Begel, Michael; Behar Harpaz, Silvia; Belanger-Champagne, Camille; Bell, Paul; Bell, William; Bella, Gideon; Bellagamba, Lorenzo; Bellomo, Massimiliano; Belloni, Alberto; Beloborodova, Olga; Belotskiy, Konstantin; Beltramello, Olga; Benary, Odette; Benchekroun, Driss; Bendtz, Katarina; Benekos, Nektarios; Benhammou, Yan; Benhar Noccioli, Eleonora; Benitez Garcia, Jorge-Armando; Benjamin, Douglas; Benoit, Mathieu; Bensinger, James; Benslama, Kamal; Bentvelsen, Stan; Berge, David; Bergeaas Kuutmann, Elin; Berger, Nicolas; Berghaus, Frank; Berglund, Elina; Beringer, Jürg; Bernat, Pauline; Bernhard, Ralf; Bernius, Catrin; Bernlochner, Florian Urs; Berry, Tracey; Bertella, Claudia; Bertin, Antonio; Bertolucci, Federico; Besana, Maria Ilaria; Besjes, Geert-Jan; Besson, Nathalie; Bethke, Siegfried; Bhimji, Wahid; Bianchi, Riccardo-Maria; Bianchini, Louis; Bianco, Michele; Biebel, Otmar; Bieniek, Stephen Paul; Bierwagen, Katharina; Biesiada, Jed; Biglietti, Michela; Bilokon, Halina; Bindi, Marcello; Binet, Sebastien; Bingul, Ahmet; Bini, Cesare; Biscarat, Catherine; Bittner, Bernhard; Black, Curtis; Black, James; Black, Kevin; Blair, Robert

    2013-01-01

    Two-particle correlations in relative azimuthal angle ($\\Delta-\\phi$) and pseudorapidity ($\\Delta-\\eta$) are measured in $\\sqrt{s_{NN}}$ = 5.02 TeV p+Pb collisions using the ATLAS detector at the LHC. The measurements are performed using approximately 1 $\\mu b^{-1}$ of data as a function of $p_T$ and the transverse energy ($\\sum E_T^{Pb}$) summed over 3.1 < $\\eta$ < 4.9 in the direction of the Pb beam. The correlation function, constructed from charged particles, exhibits a long-range (2<|$\\Delta-\\eta$|<5) near-side ($\\Delta-\\phi$ ~ 0) correlation that grows rapidly with increasing $\\sum E_T^{Pb}$. A long-range away-side ($\\Delta-\\phi$ ~ pi) correlation, obtained by subtracting the expected contributions from recoiling dijets and other sources estimated using events with small $\\sum E_T^{Pb}$, is found to match the near-side correlation in magnitude, shape (in $\\Delta-\\eta$ and $\\Delta-\\phi$) and $\\sum E_T^{Pb}$ dependence. The resultant $\\Delta-\\phi$ correlation is approximately symmetric about $...

  5. Observation of associated near-side and away-side long-range correlations in sqrt[s(NN)]=5.02 TeV proton-lead collisions with the ATLAS detector.

    Science.gov (United States)

    Aad, G; Abajyan, T; Abbott, B; Abdallah, J; Abdel Khalek, S; Abdelalim, A A; Abdinov, O; Aben, R; Abi, B; Abolins, M; Abouzeid, O S; Abramowicz, H; Abreu, H; Acharya, B S; Adamczyk, L; Adams, D L; Addy, T N; Adelman, J; Adomeit, S; Adragna, P; Adye, T; Aefsky, S; Aguilar-Saavedra, J A; Agustoni, M; Ahlen, S P; Ahles, F; Ahmad, A; Ahsan, M; Aielli, G; Akesson, T P A; Akimoto, G; Akimov, A V; Alam, M A; Albert, J; Albrand, S; Aleksa, M; Aleksandrov, I N; Alessandria, F; Alexa, C; Alexander, G; Alexandre, G; Alexopoulos, T; Alhroob, M; Aliev, M; Alimonti, G; Alison, J; Allbrooke, B M M; Allison, L J; Allport, P P; Allwood-Spiers, S E; Almond, J; Aloisio, A; Alon, R; Alonso, A; Alonso, F; Altheimer, A; Alvarez Gonzalez, B; Alviggi, M G; Amako, K; Amelung, C; Ammosov, V V; Amor Dos Santos, S P; Amorim, A; Amoroso, S; Amram, N; Anastopoulos, C; Ancu, L S; Andari, N; Andeen, T; Anders, C F; Anders, G; Anderson, K J; Andreazza, A; Andrei, V; Anduaga, X S; Angelidakis, S; Anger, P; Angerami, A; Anghinolfi, F; Anisenkov, A; Anjos, N; Annovi, A; Antonaki, A; Antonelli, M; Antonov, A; Antos, J; Anulli, F; Aoki, M; Aperio Bella, L; Apolle, R; Arabidze, G; Aracena, I; Arai, Y; Arce, A T H; Arfaoui, S; Arguin, J-F; Argyropoulos, S; Arik, E; Arik, M; Armbruster, A J; Arnaez, O; Arnal, V; Artamonov, A; Artoni, G; Arutinov, D; Asai, S; Ask, S; Asman, B; Asquith, L; Assamagan, K; Astalos, R; Astbury, A; Atkinson, M; Auerbach, B; Auge, E; Augsten, K; Aurousseau, M; Avolio, G; Axen, D; Azuelos, G; Azuma, Y; Baak, M A; Baccaglioni, G; Bacci, C; Bach, A M; Bachacou, H; Bachas, K; Backes, M; Backhaus, M; Backus Mayes, J; Badescu, E; Bagnaia, P; Bai, Y; Bailey, D C; Bain, T; Baines, J T; Baker, O K; Baker, S; Balek, P; Balli, F; Banas, E; Banerjee, P; Banerjee, Sw; Banfi, D; Bangert, A; Bansal, V; Bansil, H S; Barak, L; Baranov, S P; Barber, T; Barberio, E L; Barberis, D; Barbero, M; Bardin, D Y; Barillari, T; Barisonzi, M; Barklow, T; Barlow, N; Barnett, B M; Barnett, R M; Baroncelli, A; Barone, G; Barr, A J; Barreiro, F; Barreiro Guimarães da Costa, J; Bartoldus, R; Barton, A E; Bartsch, V; Basye, A; Bates, R L; Batkova, L; Batley, J R; Battaglia, A; Battistin, M; Bauer, F; Bawa, H S; Beale, S; Beau, T; Beauchemin, P H; Beccherle, R; Bechtle, P; Beck, H P; Becker, K; Becker, S; Beckingham, M; Becks, K H; Beddall, A J; Beddall, A; Bedikian, S; Bednyakov, V A; Bee, C P; Beemster, L J; Beermann, T A; Begel, M; Behar Harpaz, S; Belanger-Champagne, C; Bell, P J; Bell, W H; Bella, G; Bellagamba, L; Bellomo, M; Belloni, A; Beloborodova, O; Belotskiy, K; Beltramello, O; Benary, O; Benchekroun, D; Bendtz, K; Benekos, N; Benhammou, Y; Benhar Noccioli, E; Benitez Garcia, J A; Benjamin, D P; Benoit, M; Bensinger, J R; Benslama, K; Bentvelsen, S; Berge, D; Bergeaas Kuutmann, E; Berger, N; Berghaus, F; Berglund, E; Beringer, J; Bernat, P; Bernhard, R; Bernius, C; Bernlochner, F U; Berry, T; Bertella, C; Bertin, A; Bertolucci, F; Besana, M I; Besjes, G J; Besson, N; Bethke, S; Bhimji, W; Bianchi, R M; Bianchini, L; Bianco, M; Biebel, O; Bieniek, S P; Bierwagen, K; Biesiada, J; Biglietti, M; Bilokon, H; Bindi, M; Binet, S; Bingul, A; Bini, C; Biscarat, C; Bittner, B; Black, C W; Black, J E; Black, K M; Blair, R E; Blanchard, J-B; Blazek, T; Bloch, I; Blocker, C; Blocki, J; Blum, W; Blumenschein, U; Bobbink, G J; Bobrovnikov, V S; Bocchetta, S S; Bocci, A; Boddy, C R; Boehler, M; Boek, J; Boek, T T; Boelaert, N; Bogaerts, J A; Bogdanchikov, A; Bogouch, A; Bohm, C; Bohm, J; Boisvert, V; Bold, T; Boldea, V; Bolnet, N M; Bomben, M; Bona, M; Boonekamp, M; Bordoni, S; Borer, C; Borisov, A; Borissov, G; Borjanovic, I; Borri, M; Borroni, S; Bortfeldt, J; Bortolotto, V; Bos, K; Boscherini, D; Bosman, M; Boterenbrood, H; Bouchami, J; Boudreau, J; Bouhova-Thacker, E V; Boumediene, D; Bourdarios, C; Bousson, N; Boutouil, S; Boveia, A; Boyd, J; Boyko, I R; Bozovic-Jelisavcic, I; Bracinik, J; Branchini, P; Brandt, A; Brandt, G; Brandt, O; Bratzler, U; Brau, B; Brau, J E; Braun, H M; Brazzale, S F; Brelier, B; Bremer, J; Brendlinger, K; Brenner, R; Bressler, S; Bristow, T M; Britton, D; Brochu, F M; Brock, I; Brock, R; Broggi, F; Bromberg, C; Bronner, J; Brooijmans, G; Brooks, T; Brooks, W K; Brown, G; Bruckman de Renstrom, P A; Bruncko, D; Bruneliere, R; Brunet, S; Bruni, A; Bruni, G; Bruschi, M; Bryngemark, L; Buanes, T; Buat, Q; Bucci, F; Buchanan, J; Buchholz, P; Buckingham, R M; Buckley, A G; Buda, S I; Budagov, I A; Budick, B; Bugge, L; Bulekov, O; Bundock, A C; Bunse, M; Buran, T; Burckhart, H; Burdin, S; Burgess, T; Burke, S; Busato, E; Büscher, V; Bussey, P; Buszello, C P; Butler, B; Butler, J M; Buttar, C M; Butterworth, J M; Buttinger, W; Byszewski, M; Cabrera Urbán, S; Caforio, D; Cakir, O; Calafiura, P; Calderini, G; Calfayan, P; Calkins, R; Caloba, L P; Caloi, R; Calvet, D; Calvet, S; Camacho Toro, R; Camarri, P; Cameron, D; Caminada, L M; Caminal Armadans, R; Campana, S; Campanelli, M; Canale, V; Canelli, F; Canepa, A; Cantero, J; Cantrill, R; Cao, T; Capeans Garrido, M D M; Caprini, I; Caprini, M; Capriotti, D; Capua, M; Caputo, R; Cardarelli, R; Carli, T; Carlino, G; Carminati, L; Caron, S; Carquin, E; Carrillo-Montoya, G D; Carter, A A; Carter, J R; Carvalho, J; Casadei, D; Casado, M P; Cascella, M; Caso, C; Castaneda-Miranda, E; Castillo Gimenez, V; Castro, N F; Cataldi, G; Catastini, P; Catinaccio, A; Catmore, J R; Cattai, A; Cattani, G; Caughron, S; Cavaliere, V; Cavalleri, P; Cavalli, D; Cavalli-Sforza, M; Cavasinni, V; Ceradini, F; Cerqueira, A S; Cerri, A; Cerrito, L; Cerutti, F; Cetin, S A; Chafaq, A; Chakraborty, D; Chalupkova, I; Chan, K; Chang, P; Chapleau, B; Chapman, J D; Chapman, J W; Charlton, D G; Chavda, V; Chavez Barajas, C A; Cheatham, S; Chekanov, S; Chekulaev, S V; Chelkov, G A; Chelstowska, M A; Chen, C; Chen, H; Chen, S; Chen, X; Chen, Y; Cheng, Y; Cheplakov, A; Cherkaoui El Moursli, R; Chernyatin, V; Cheu, E; Cheung, S L; Chevalier, L; Chiefari, G; Chikovani, L; Childers, J T; Chilingarov, A; Chiodini, G; Chisholm, A S; Chislett, R T; Chitan, A; Chizhov, M V; Choudalakis, G; Chouridou, S; Chow, B K B; Christidi, I A; Christov, A; Chromek-Burckhart, D; Chu, M L; Chudoba, J; Ciapetti, G; Ciftci, A K; Ciftci, R; Cinca, D; Cindro, V; Ciocio, A; Cirilli, M; Cirkovic, P; Citron, Z H; Citterio, M; Ciubancan, M; Clark, A; Clark, P J; Clarke, R N; Cleland, W; Clemens, J C; Clement, B; Clement, C; Coadou, Y; Cobal, M; Coccaro, A; Cochran, J; Coffey, L; Cogan, J G; Coggeshall, J; Colas, J; Cole, B; Cole, S; Colijn, A P; Collins, N J; Collins-Tooth, C; Collot, J; Colombo, T; Colon, G; Compostella, G; Conde Muiño, P; Coniavitis, E; Conidi, M C; Consonni, S M; Consorti, V; Constantinescu, S; Conta, C; Conti, G; Conventi, F; Cooke, M; Cooper, B D; Cooper-Sarkar, A M; Copic, K; Cornelissen, T; Corradi, M; Corriveau, F; Cortes-Gonzalez, A; Cortiana, G; Costa, G; Costa, M J; Costanzo, D; Côté, D; Cottin, G; Courneyea, L; Cowan, G; Cox, B E; Cranmer, K; Crépé-Renaudin, S; Crescioli, F; Cristinziani, M; Crosetti, G; Cuciuc, C-M; Cuenca Almenar, C; Cuhadar Donszelmann, T; Cummings, J; Curatolo, M; Curtis, C J; Cuthbert, C; Cwetanski, P; Czirr, H; Czodrowski, P; Czyczula, Z; D'Auria, S; D'Onofrio, M; D'Orazio, A; Da Cunha Sargedas De Sousa, M J; Da Via, C; Dabrowski, W; Dafinca, A; Dai, T; Dallaire, F; Dallapiccola, C; Dam, M; Damiani, D S; Danielsson, H O; Dao, V; Darbo, G; Darlea, G L; Dassoulas, J A; Davey, W; Davidek, T; Davidson, N; Davidson, R; Davies, E; Davies, M; Davignon, O; Davison, A R; Davygora, Y; Dawe, E; Dawson, I; Daya-Ishmukhametova, R K; De, K; de Asmundis, R; De Castro, S; De Cecco, S; de Graat, J; De Groot, N; de Jong, P; De La Taille, C; De la Torre, H; De Lorenzi, F; De Nooij, L; De Pedis, D; De Salvo, A; De Sanctis, U; De Santo, A; De Vivie De Regie, J B; De Zorzi, G; Dearnaley, W J; Debbe, R; Debenedetti, C; Dechenaux, B; Dedovich, D V; Degenhardt, J; Del Peso, J; Del Prete, T; Delemontex, T; Deliyergiyev, M; Dell'acqua, A; Dell'asta, L; Della Pietra, M; Della Volpe, D; Delmastro, M; Delsart, P A; Deluca, C; Demers, S; Demichev, M; Demirkoz, B; Denisov, S P; Derendarz, D; Derkaoui, J E; Derue, F; Dervan, P; Desch, K; Deviveiros, P O; Dewhurst, A; Dewilde, B; Dhaliwal, S; Dhullipudi, R; Di Ciaccio, A; Di Ciaccio, L; Di Donato, C; Di Girolamo, A; Di Girolamo, B; Di Luise, S; Di Mattia, A; Di Micco, B; Di Nardo, R; Di Simone, A; Di Sipio, R; Diaz, M A; Diehl, E B; Dietrich, J; Dietzsch, T A; Diglio, S; Dindar Yagci, K; Dingfelder, J; Dinut, F; Dionisi, C; Dita, P; Dita, S; Dittus, F; Djama, F; Djobava, T; do Vale, M A B; Do Valle Wemans, A; Doan, T K O; Dobbs, M; Dobos, D; Dobson, E; Dodd, J; Doglioni, C; Doherty, T; Dohmae, T; Doi, Y; Dolejsi, J; Dolezal, Z; Dolgoshein, B A; Donadelli, M; Donini, J; Dopke, J; Doria, A; Dos Anjos, A; Dotti, A; Dova, M T; Doyle, A T; Dressnandt, N; Dris, M; Dubbert, J; Dube, S; Dubreuil, E; Duchovni, E; Duckeck, G; Duda, D; Dudarev, A; Dudziak, F; Duerdoth, I P; Duflot, L; Dufour, M-A; Duguid, L; Dührssen, M; Dunford, M; Duran Yildiz, H; Düren, M; Duxfield, R; Dwuznik, M; Ebenstein, W L; Ebke, J; Eckweiler, S; Edson, W; Edwards, C A; Edwards, N C; Ehrenfeld, W; Eifert, T; Eigen, G; Einsweiler, K; Eisenhandler, E; Ekelof, T; El Kacimi, M; Ellert, M; Elles, S; Ellinghaus, F; Ellis, K; Ellis, N; Elmsheuser, J; Elsing, M; Emeliyanov, D; Engelmann, R; Engl, A; Epp, B; Erdmann, J; Ereditato, A; Eriksson, D; Ernst, J; Ernst, M; Ernwein, J; Errede, D; Errede, S; Ertel, E; Escalier, M; Esch, H; Escobar, C; Espinal Curull, X; Esposito, B; Etienne, F; Etienvre, A I; Etzion, E; Evangelakou, D; Evans, H; Fabbri, L; Fabre, C; Facini, G J; Fakhrutdinov, R M; Falciano, S; Fang, Y; Fanti, M; Farbin, A; Farilla, A; Farley, J; Farooque, T; Farrell, S; Farrington, S M; Farthouat, P; Fassi, F; Fassnacht, P; Fassouliotis, D; Fatholahzadeh, B; Favareto, A; Fayard, L; Federic, P; Fedin, O L; Fedorko, W; Fehling-Kaschek, M; Feligioni, L; Feng, C; Feng, E J; Fenyuk, A B; Ferencei, J; Fernando, W; Ferrag, S; Ferrando, J; Ferrara, V; Ferrari, A; Ferrari, P; Ferrari, R; Ferreira de Lima, D E; Ferrer, A; Ferrere, D; Ferretti, C; Ferretto Parodi, A; Fiascaris, M; Fiedler, F; Filipčič, A; Filthaut, F; Fincke-Keeler, M; Fiolhais, M C N; Fiorini, L; Firan, A; Fischer, J; Fisher, M J; Fitzgerald, E A; Flechl, M; Fleck, I; Fleischmann, P; Fleischmann, S; Fletcher, G T; Fletcher, G; Flick, T; Floderus, A; Flores Castillo, L R; Florez Bustos, A C; Flowerdew, M J; Fonseca Martin, T; Formica, A; Forti, A; Fortin, D; Fournier, D; Fowler, A J; Fox, H; Francavilla, P; Franchini, M; Franchino, S; Francis, D; Frank, T; Franklin, M; Franz, S; Fraternali, M; Fratina, S; French, S T; Friedrich, C; Friedrich, F; Froidevaux, D; Frost, J A; Fukunaga, C; Fullana Torregrosa, E; Fulsom, B G; Fuster, J; Gabaldon, C; Gabizon, O; Gadatsch, S; Gadfort, T; Gadomski, S; Gagliardi, G; Gagnon, P; Galea, C; Galhardo, B; Gallas, E J; Gallo, V; Gallop, B J; Gallus, P; Gan, K K; Gandrajula, R P; Gao, Y S; Gaponenko, A; Garay Walls, F M; Garberson, F; García, C; García Navarro, J E; Garcia-Sciveres, M; Gardner, R W; Garelli, N; Garonne, V; Gatti, C; Gaudio, G; Gaur, B; Gauthier, L; Gauzzi, P; Gavrilenko, I L; Gay, C; Gaycken, G; Gazis, E N; Ge, P; Gecse, Z; Gee, C N P; Geerts, D A A; Geich-Gimbel, Ch; Gellerstedt, K; Gemme, C; Gemmell, A; Genest, M H; Gentile, S; George, M; George, S; Gerbaudo, D; Gerlach, P; Gershon, A; Geweniger, C; Ghazlane, H; Ghodbane, N; Giacobbe, B; Giagu, S; Giangiobbe, V; Gianotti, F; Gibbard, B; Gibson, A; Gibson, S M; Gilchriese, M; Gillam, T P S; Gillberg, D; Gillman, A R; Gingrich, D M; Ginzburg, J; Giokaris, N; Giordani, M P; Giordano, R; Giorgi, F M; Giovannini, P; Giraud, P F; Giugni, D; Giunta, M; Gjelsten, B K; Gladilin, L K; Glasman, C; Glatzer, J; Glazov, A; Glonti, G L; Goddard, J R; Godfrey, J; Godlewski, J; Goebel, M; Goeringer, C; Goldfarb, S; Golling, T; Golubkov, D; Gomes, A; Gomez Fajardo, L S; Gonçalo, R; Goncalves Pinto Firmino Da Costa, J; Gonella, L; González de la Hoz, S; Gonzalez Parra, G; Gonzalez Silva, M L; Gonzalez-Sevilla, S; Goodson, J J; Goossens, L; Göpfert, T; Gorbounov, P A; Gordon, H A; Gorelov, I; Gorfine, G; Gorini, B; Gorini, E; Gorišek, A; Gornicki, E; Goshaw, A T; Gössling, C; Gostkin, M I; Gough Eschrich, I; Gouighri, M; Goujdami, D; Goulette, M P; Goussiou, A G; Goy, C; Gozpinar, S; Grabowska-Bold, I; Grafström, P; Grahn, K-J; Gramstad, E; Grancagnolo, F; Grancagnolo, S; Grassi, V; Gratchev, V; Gray, H M; Gray, J A; Graziani, E; Grebenyuk, O G; Greenshaw, T; Greenwood, Z D; Gregersen, K; Gregor, I M; Grenier, P; Griffiths, J; Grigalashvili, N; Grillo, A A; Grimm, K; Grinstein, S; Gris, Ph; Grishkevich, Y V; Grivaz, J-F; Grohs, J P; Grohsjean, A; Gross, E; Grosse-Knetter, J; Groth-Jensen, J; Grybel, K; Guest, D; Gueta, O; Guicheney, C; Guido, E; Guillemin, T; Guindon, S; Gul, U; Gunther, J; Guo, B; Guo, J; Gutierrez, P; Guttman, N; Gutzwiller, O; Guyot, C; Gwenlan, C; Gwilliam, C B; Haas, A; Haas, S; Haber, C; Hadavand, H K; Hadley, D R; Haefner, P; Hajduk, Z; Hakobyan, H; Hall, D; Halladjian, G; Hamacher, K; Hamal, P; Hamano, K; Hamer, M; Hamilton, A; Hamilton, S; Han, L; Hanagaki, K; Hanawa, K; Hance, M; Handel, C; Hanke, P; Hansen, J R; Hansen, J B; Hansen, J D; Hansen, P H; Hansson, P; Hara, K; Harenberg, T; Harkusha, S; Harper, D; Harrington, R D; Harris, O M; Hartert, J; Hartjes, F; Haruyama, T; Harvey, A; Hasegawa, S; Hasegawa, Y; Hassani, S; Haug, S; Hauschild, M; Hauser, R; Havranek, M; Hawkes, C M; Hawkings, R J; Hawkins, A D; Hayakawa, T; Hayashi, T; Hayden, D; Hays, C P; Hayward, H S; Haywood, S J; Head, S J; Heck, T; Hedberg, V; Heelan, L; Heim, S; Heinemann, B; Heisterkamp, S; Helary, L; Heller, C; Heller, M; Hellman, S; Hellmich, D; Helsens, C; Henderson, R C W; Henke, M; Henrichs, A; Henriques Correia, A M; Henrot-Versille, S; Hensel, C; Hernandez, C M; Hernández Jiménez, Y; Herrberg, R; Herten, G; Hertenberger, R; Hervas, L; Hesketh, G G; Hessey, N P; Hickling, R; Higón-Rodriguez, E; Hill, J C; Hiller, K H; Hillert, S; Hillier, S J; Hinchliffe, I; Hines, E; Hirose, M; Hirsch, F; Hirschbuehl, D; Hobbs, J; Hod, N; Hodgkinson, M C; Hodgson, P; Hoecker, A; Hoeferkamp, M R; Hoffman, J; Hoffmann, D; Hohlfeld, M; Holmgren, S O; Holy, T; Holzbauer, J L; Hong, T M; Hooft van Huysduynen, L; Hostachy, J-Y; Hou, S; Hoummada, A; Howard, J; Howarth, J; Hrabovsky, M; Hristova, I; Hrivnac, J; Hryn'ova, T; Hsu, P J; Hsu, S-C; Hu, D; Hubacek, Z; Hubaut, F; Huegging, F; Huettmann, A; Huffman, T B; Hughes, E W; Hughes, G; Huhtinen, M; Hülsing, T A; Hurwitz, M; Huseynov, N; Huston, J; Huth, J; Iacobucci, G; Iakovidis, G; Ibbotson, M; Ibragimov, I; Iconomidou-Fayard, L; Idarraga, J; Iengo, P; Igonkina, O; Ikegami, Y; Ikematsu, K; Ikeno, M; Iliadis, D; Ilic, N; Ince, T; Ioannou, P; Iodice, M; Iordanidou, K; Ippolito, V; Irles Quiles, A; Isaksson, C; Ishino, M; Ishitsuka, M; Ishmukhametov, R; Issever, C; Istin, S; Ivashin, A V; Iwanski, W; Iwasaki, H; Izen, J M; Izzo, V; Jackson, B; Jackson, J N; Jackson, P; Jaekel, M R; Jain, V; Jakobs, K; Jakobsen, S; Jakoubek, T; Jakubek, J; Jamin, D O; Jana, D K; Jansen, E; Jansen, H; Janssen, J; Jantsch, A; Janus, M; Jared, R C; Jarlskog, G; Jeanty, L; Jeng, G-Y; Jen-La Plante, I; Jennens, D; Jenni, P; Jež, P; Jézéquel, S; Jha, M K; Ji, H; Ji, W; Jia, J; Jiang, Y; Jimenez Belenguer, M; Jin, S; Jinnouchi, O; Joergensen, M D; Joffe, D; Johansen, M; Johansson, K E; Johansson, P; Johnert, S; Johns, K A; Jon-And, K; Jones, G; Jones, R W L; Jones, T J; Joram, C; Jorge, P M; Joshi, K D; Jovicevic, J; Jovin, T; Ju, X; Jung, C A; Jungst, R M; Juranek, V; Jussel, P; Juste Rozas, A; Kabana, S; Kaci, M; Kaczmarska, A; Kadlecik, P; Kado, M; Kagan, H; Kagan, M; Kajomovitz, E; Kalinin, S; Kama, S; Kanaya, N; Kaneda, M; Kaneti, S; Kanno, T; Kantserov, V A; Kanzaki, J; Kaplan, B; Kapliy, A; Kar, D; Karagounis, M; Karakostas, K; Karnevskiy, M; Kartvelishvili, V; Karyukhin, A N; Kashif, L; Kasieczka, G; Kass, R D; Kastanas, A; Kataoka, Y; Katzy, J; Kaushik, V; Kawagoe, K; Kawamoto, T; Kawamura, G; Kazama, S; Kazanin, V F; Kazarinov, M Y; Keeler, R; Keener, P T; Kehoe, R; Keil, M; Keller, J S; Kenyon, M; Keoshkerian, H; Kepka, O; Kerschen, N; Kerševan, B P; Kersten, S; Kessoku, K; Keung, J; Khalil-Zada, F; Khandanyan, H; Khanov, A; Kharchenko, D; Khodinov, A; Khomich, A; Khoo, T J; Khoriauli, G; Khoroshilov, A; Khovanskiy, V; Khramov, E; Khubua, J; Kim, H; Kim, S H; Kimura, N; Kind, O; King, B T; King, M; King, R S B; Kirk, J; Kiryunin, A E; Kishimoto, T; Kisielewska, D; Kitamura, T; Kittelmann, T; Kiuchi, K; Kladiva, E; Klein, M; Klein, U; Kleinknecht, K; Klemetti, M; Klier, A; Klimek, P; Klimentov, A; Klingenberg, R; Klinger, J A; Klinkby, E B; Klioutchnikova, T; Klok, P F; Klous, S; Kluge, E-E; Kluge, T; Kluit, P; Kluth, S; Kneringer, E; Knoops, E B F G; Knue, A; Ko, B R; Kobayashi, T; Kobel, M; Kocian, M; Kodys, P; Koenig, S; Koetsveld, F; Koevesarki, P; Koffas, T; Koffeman, E; Kogan, L A; Kohlmann, S; Kohn, F; Kohout, Z; Kohriki, T; Koi, T; Kolanoski, H; Kolesnikov, V; Koletsou, I; Koll, J; Komar, A A; Komori, Y; Kondo, T; Köneke, K; König, A C; Kono, T; Kononov, A I; Konoplich, R; Konstantinidis, N; Kopeliansky, R; Koperny, S; Köpke, L; Kopp, A K; Korcyl, K; Kordas, K; Korn, A; Korol, A; Korolkov, I; Korolkova, E V; Korotkov, V A; Kortner, O; Kortner, S; Kostyukhin, V V; Kotov, S; Kotov, V M; Kotwal, A; Kourkoumelis, C; Kouskoura, V; Koutsman, A; Kowalewski, R; Kowalski, T Z; Kozanecki, W; Kozhin, A S; Kral, V; Kramarenko, V A; Kramberger, G; Krasny, M W; Krasznahorkay, A; Kraus, J K; Kravchenko, A; Kreiss, S; Krejci, F; Kretzschmar, J; Kreutzfeldt, K; Krieger, N; Krieger, P; Kroeninger, K; Kroha, H; Kroll, J; Kroseberg, J; Krstic, J; Kruchonak, U; Krüger, H; Kruker, T; Krumnack, N; Krumshteyn, Z V; Kruse, M K; Kubota, T; Kuday, S; Kuehn, S; Kugel, A; Kuhl, T; Kukhtin, V; Kulchitsky, Y; Kuleshov, S; Kuna, M; Kunkle, J; Kupco, A; Kurashige, H; Kurata, M; Kurochkin, Y A; Kus, V; Kuwertz, E S; Kuze, M; Kvita, J; Kwee, R; La Rosa, A; La Rotonda, L; Labarga, L; Lablak, S; Lacasta, C; Lacava, F; Lacey, J; Lacker, H; Lacour, D; Lacuesta, V R; Ladygin, E; Lafaye, R; Laforge, B; Lagouri, T; Lai, S; Laisne, E; Lambourne, L; Lampen, C L; Lampl, W; Lancon, E; Landgraf, U; Landon, M P J; Lang, V S; Lange, C; Lankford, A J; Lanni, F; Lantzsch, K; Lanza, A; Laplace, S; Lapoire, C; Laporte, J F; Lari, T; Larner, A; Lassnig, M; Laurelli, P; Lavorini, V; Lavrijsen, W; Laycock, P; Le Dortz, O; Le Guirriec, E; Le Menedeu, E; Lecompte, T; Ledroit-Guillon, F; Lee, H; Lee, J S H; Lee, S C; Lee, L; Lefebvre, M; Legendre, M; Legger, F; Leggett, C; Lehmacher, M; Lehmann Miotto, G; Leister, A G; Leite, M A L; Leitner, R; Lellouch, D; Lemmer, B; Lendermann, V; Leney, K J C; Lenz, T; Lenzen, G; Lenzi, B; Leonhardt, K; Leontsinis, S; Lepold, F; Leroy, C; Lessard, J-R; Lester, C G; Lester, C M; Levêque, J; Levin, D; Levinson, L J; Lewis, A; Lewis, G H; Leyko, A M; Leyton, M; Li, B; Li, B; Li, H; Li, H L; Li, S; Li, X; Liang, Z; Liao, H; Liberti, B; Lichard, P; Lie, K; Liebal, J; Liebig, W; Limbach, C; Limosani, A; Limper, M; Lin, S C; Linde, F; Linnemann, J T; Lipeles, E; Lipniacka, A; Lisovyi, M; Liss, T M; Lissauer, D; Lister, A; Litke, A M; Liu, D; Liu, J B; Liu, L; Liu, M; Liu, Y; Livan, M; Livermore, S S A; Lleres, A; Llorente Merino, J; Lloyd, S L; Lo Sterzo, F; Lobodzinska, E; Loch, P; Lockman, W S; Loddenkoetter, T; Loebinger, F K; Loevschall-Jensen, A E; Loginov, A; Loh, C W; Lohse, T; Lohwasser, K; Lokajicek, M; Lombardo, V P; Long, R E; Lopes, L; Lopez Mateos, D; Lorenz, J; Lorenzo Martinez, N; Losada, M; Loscutoff, P; Losty, M J; Lou, X; Lounis, A; Loureiro, K F; Love, J; Love, P A; Lowe, A J; Lu, F; Lubatti, H J; Luci, C; Lucotte, A; Ludwig, D; Ludwig, I; Ludwig, J; Luehring, F; Lukas, W; Luminari, L; Lund, E; Lundberg, B; Lundberg, J; Lundberg, O; Lund-Jensen, B; Lundquist, J; Lungwitz, M; Lynn, D; Lysak, R; Lytken, E; Ma, H; Ma, L L; Maccarrone, G; Macchiolo, A; Maček, B; Machado Miguens, J; Macina, D; Mackeprang, R; Madar, R; Madaras, R J; Maddocks, H J; Mader, W F; Madsen, A; Maeno, M; Maeno, T; Magnoni, L; Magradze, E; Mahboubi, K; Mahlstedt, J; Mahmoud, S; Mahout, G; Maiani, C; Maidantchik, C; Maio, A; Majewski, S; Makida, Y; Makovec, N; Mal, P; Malaescu, B; Malecki, Pa; Malecki, P; Maleev, V P; Malek, F; Mallik, U; Malon, D; Malone, C; Maltezos, S; Malyshev, V; Malyukov, S; Mamuzic, J; Manabe, A; Mandelli, L; Mandić, I; Mandrysch, R; Maneira, J; Manfredini, A; Manhaes de Andrade Filho, L; Manjarres Ramos, J A; Mann, A; Manning, P M; Manousakis-Katsikakis, A; Mansoulie, B; Mantifel, R; Mapelli, A; Mapelli, L; March, L; Marchand, J F; Marchese, F; Marchiori, G; Marcisovsky, M; Marino, C P; Marroquim, F; Marshall, Z; Marti, L F; Marti-Garcia, S; Martin, B; Martin, B; Martin, J P; Martin, T A; Martin, V J; Martin Dit Latour, B; Martinez, H; Martinez, M; Martinez Outschoorn, V; Martin-Haugh, S; Martyniuk, A C; Marx, M; Marzano, F; Marzin, A; Masetti, L; Mashimo, T; Mashinistov, R; Masik, J; Maslennikov, A L; Massa, I; Massol, N; Mastrandrea, P; Mastroberardino, A; Masubuchi, T; Matsunaga, H; Matsushita, T; Mättig, P; Mättig, S; Mattravers, C; Maurer, J; Maxfield, S J; Maximov, D A; Mazini, R; Mazur, M; Mazzaferro, L; Mazzanti, M; Mc Donald, J; Mc Kee, S P; McCarn, A; McCarthy, R L; McCarthy, T G; McCubbin, N A; McFarlane, K W; McFayden, J A; McHedlidze, G; McLaughlan, T; McMahon, S J; McPherson, R A; Meade, A; Mechnich, J; Mechtel, M; Medinnis, M; Meehan, S; Meera-Lebbai, R; Meguro, T; Mehlhase, S; Mehta, A; Meier, K; Meineck, C; Meirose, B; Melachrinos, C; Mellado Garcia, B R; Meloni, F; Mendoza Navas, L; Meng, Z; Mengarelli, A; Menke, S; Meoni, E; Mercurio, K M; Meric, N; Mermod, P; Merola, L; Meroni, C; Merritt, F S; Merritt, H; Messina, A; Metcalfe, J; Mete, A S; Meyer, C; Meyer, C; Meyer, J-P; Meyer, J; Meyer, J; Michal, S; Micu, L; Middleton, R P; Migas, S; Mijović, L; Mikenberg, G; Mikestikova, M; Mikuž, M; Miller, D W; Miller, R J; Mills, W J; Mills, C; Milov, A; Milstead, D A; Milstein, D; Milutinovic-Dumbelovic, G; Minaenko, A A; Miñano Moya, M; Minashvili, I A; Mincer, A I; Mindur, B; Mineev, M; Ming, Y; Mir, L M; Mirabelli, G; Mitrevski, J; Mitsou, V A; Mitsui, S; Miyagawa, P S; Mjörnmark, J U; Moa, T; Moeller, V; Mohapatra, S; Mohr, W; Moles-Valls, R; Molfetas, A; Mönig, K; Monk, J; Monnier, E; Montejo Berlingen, J; Monticelli, F; Monzani, S; Moore, R W; Mora Herrera, C; Moraes, A; Morange, N; Morel, J; Moreno, D; Moreno Llácer, M; Morettini, P; Morgenstern, M; Morii, M; Morley, A K; Mornacchi, G; Morris, J D; Morvaj, L; Möser, N; Moser, H G; Mosidze, M; Moss, J; Mount, R; Mountricha, E; Mouraviev, S V; Moyse, E J W; Mueller, F; Mueller, J; Mueller, K; Mueller, T; Muenstermann, D; Müller, T A; Munwes, Y; Murray, W J; Mussche, I; Musto, E; Myagkov, A G; Myska, M; Nackenhorst, O; Nadal, J; Nagai, K; Nagai, R; Nagai, Y; Nagano, K; Nagarkar, A; Nagasaka, Y; Nagel, M; Nairz, A M; Nakahama, Y; Nakamura, K; Nakamura, T; Nakano, I; Namasivayam, H; Nanava, G; Napier, A; Narayan, R; Nash, M; Nattermann, T; Naumann, T; Navarro, G; Neal, H A; Nechaeva, P Yu; Neep, T J; Negri, A; Negri, G; Negrini, M; Nektarijevic, S; Nelson, A; Nelson, T K; Nemecek, S; Nemethy, P; Nepomuceno, A A; Nessi, M; Neubauer, M S; Neumann, M; Neusiedl, A; Neves, R M; Nevski, P; Newcomer, F M; Newman, P R; Nguyen, D H; Nguyen Thi Hong, V; Nickerson, R B; Nicolaidou, R; Nicquevert, B; Niedercorn, F; Nielsen, J; Nikiforou, N; Nikiforov, A; Nikolaenko, V; Nikolic-Audit, I; Nikolics, K; Nikolopoulos, K; Nilsen, H; Nilsson, P; Ninomiya, Y; Nisati, A; Nisius, R; Nobe, T; Nodulman, L; Nomachi, M; Nomidis, I; Norberg, S; Nordberg, M; Novakova, J; Nozaki, M; Nozka, L; Nuncio-Quiroz, A-E; Nunes Hanninger, G; Nunnemann, T; Nurse, E; O'Brien, B J; O'Neil, D C; O'Shea, V; Oakes, L B; Oakham, F G; Oberlack, H; Ocariz, J; Ochi, A; Ochoa, M I; Oda, S; Odaka, S; Odier, J; Ogren, H; Oh, A; Oh, S H; Ohm, C C; Ohshima, T; Okamura, W; Okawa, H; Okumura, Y; Okuyama, T; Olariu, A; Olchevski, A G; Olivares Pino, S A; Oliveira, M; Oliveira Damazio, D; Oliver Garcia, E; Olivito, D; Olszewski, A; Olszowska, J; Onofre, A; Onyisi, P U E; Oram, C J; Oreglia, M J; Oren, Y; Orestano, D; Orlando, N; Oropeza Barrera, C; Orr, R S; Osculati, B; Ospanov, R; Osuna, C; Otero Y Garzon, G; Ottersbach, J P; Ouchrif, M; Ouellette, E A; Ould-Saada, F; Ouraou, A; Ouyang, Q; Ovcharova, A; Owen, M; Owen, S; Ozcan, V E; Ozturk, N; Pacheco Pages, A; Padilla Aranda, C; Pagan Griso, S; Paganis, E; Pahl, C; Paige, F; Pais, P; Pajchel, K; Palacino, G; Paleari, C P; Palestini, S; Pallin, D; Palma, A; Palmer, J D; Pan, Y B; Panagiotopoulou, E; Panduro Vazquez, J G; Pani, P; Panikashvili, N; Panitkin, S; Pantea, D; Papadelis, A; Papadopoulou, Th D; Paramonov, A; Paredes Hernandez, D; Park, W; Parker, M A; Parodi, F; Parsons, J A; Parzefall, U; Pashapour, S; Pasqualucci, E; Passaggio, S; Passeri, A; Pastore, F; Pastore, Fr; Pásztor, G; Pataraia, S; Patel, N D; Pater, J R; Patricelli, S; Pauly, T; Pearce, J; Pedersen, M; Pedraza Lopez, S; Pedraza Morales, M I; Peleganchuk, S V; Pelikan, D; Peng, H; Penning, B; Penson, A; Penwell, J; Perepelitsa, D V; Perez Cavalcanti, T; Perez Codina, E; Pérez García-Estañ, M T; Perez Reale, V; Perini, L; Pernegger, H; Perrino, R; Perrodo, P; Peshekhonov, V D; Peters, K; Peters, R F Y; Petersen, B A; Petersen, J; Petersen, T C; Petit, E; Petridis, A; Petridou, C; Petrolo, E; Petrucci, F; Petschull, D; Petteni, M; Pezoa, R; Phan, A; Phillips, P W; Piacquadio, G; Picazio, A; Piccaro, E; Piccinini, M; Piec, S M; Piegaia, R; Pignotti, D T; Pilcher, J E; Pilkington, A D; Pina, J; Pinamonti, M; Pinder, A; Pinfold, J L; Pingel, A; Pinto, B; Pizio, C; Pleier, M-A; Pleskot, V; Plotnikova, E; Plucinski, P; Poblaguev, A; Poddar, S; Podlyski, F; Poettgen, R; Poggioli, L; Pohl, D; Pohl, M; Polesello, G; Policicchio, A; Polifka, R; Polini, A; Poll, J; Polychronakos, V; Pomeroy, D; Pommès, K; Pontecorvo, L; Pope, B G; Popeneciu, G A; Popovic, D S; Poppleton, A; Portell Bueso, X; Pospelov, G E; Pospisil, S; Potrap, I N; Potter, C J; Potter, C T; Poulard, G; Poveda, J; Pozdnyakov, V; Prabhu, R; Pralavorio, P; Pranko, A; Prasad, S; Pravahan, R; Prell, S; Pretzl, K; Price, D; Price, J; Price, L E; Prieur, D; Primavera, M; Proissl, M; Prokofiev, K; Prokoshin, F; Protopapadaki, E; Protopopescu, S; Proudfoot, J; Prudent, X; Przybycien, M; Przysiezniak, H; Psoroulas, S; Ptacek, E; Pueschel, E; Puldon, D; Purohit, M; Puzo, P; Pylypchenko, Y; Qian, J; Quadt, A; Quarrie, D R; Quayle, W B; Raas, M; Radeka, V; Radescu, V; Radloff, P; Ragusa, F; Rahal, G; Rahimi, A M; Rajagopalan, S; Rammensee, M; Rammes, M; Randle-Conde, A S; Randrianarivony, K; Rangel-Smith, C; Rao, K; Rauscher, F; Rave, T C; Ravenscroft, T; Raymond, M; Read, A L; Rebuzzi, D M; Redelbach, A; Redlinger, G; Reece, R; Reeves, K; Reinsch, A; Reisinger, I; Relich, M; Rembser, C; Ren, Z L; Renaud, A; Rescigno, M; Resconi, S; Resende, B; Reznicek, P; Rezvani, R; Richter, R; Richter-Was, E; Ridel, M; Rieck, P; Rijssenbeek, M; Rimoldi, A; Rinaldi, L; Rios, R R; Ritsch, E; Riu, I; Rivoltella, G; Rizatdinova, F; Rizvi, E; Robertson, S H; Robichaud-Veronneau, A; Robinson, D; Robinson, J E M; Robson, A; Rocha de Lima, J G; Roda, C; Roda Dos Santos, D; Roe, A; Roe, S; Røhne, O; Rolli, S; Romaniouk, A; Romano, M; Romeo, G; Romero Adam, E; Rompotis, N; Roos, L; Ros, E; Rosati, S; Rosbach, K; Rose, A; Rose, M; Rosenbaum, G A; Rosendahl, P L; Rosenthal, O; Rosselet, L; Rossetti, V; Rossi, E; Rossi, L P; Rotaru, M; Roth, I; Rothberg, J; Rousseau, D; Royon, C R; Rozanov, A; Rozen, Y; Ruan, X; Rubbo, F; Rubinskiy, I; Ruckstuhl, N; Rud, V I; Rudolph, C; Rudolph, M S; Rühr, F; Ruiz-Martinez, A; Rumyantsev, L; Rurikova, Z; Rusakovich, N A; Ruschke, A; Rutherfoord, J P; Ruthmann, N; Ruzicka, P; Ryabov, Y F; Rybar, M; Rybkin, G; Ryder, N C; Saavedra, A F; Sadeh, I; Sadrozinski, H F-W; Sadykov, R; Safai Tehrani, F; Sakamoto, H; Salamanna, G; Salamon, A; Saleem, M; Salek, D; Salihagic, D; Salnikov, A; Salt, J; Salvachua Ferrando, B M; Salvatore, D; Salvatore, F; Salvucci, A; Salzburger, A; Sampsonidis, D; Sanchez, A; Sánchez, J; Sanchez Martinez, V; Sandaker, H; Sander, H G; Sanders, M P; Sandhoff, M; Sandoval, T; Sandoval, C; Sandstroem, R; Sankey, D P C; Sansoni, A; Santamarina Rios, C; Santoni, C; Santonico, R; Santos, H; Santoyo Castillo, I; Sapp, K; Saraiva, J G; Sarangi, T; Sarkisyan-Grinbaum, E; Sarrazin, B; Sarri, F; Sartisohn, G; Sasaki, O; Sasaki, Y; Sasao, N; Satsounkevitch, I; Sauvage, G; Sauvan, E; Sauvan, J B; Savard, P; Savinov, V; Savu, D O; Sawyer, L; Saxon, D H; Saxon, J; Sbarra, C; Sbrizzi, A; Scannicchio, D A; Scarcella, M; Schaarschmidt, J; Schacht, P; Schaefer, D; Schaelicke, A; Schaepe, S; Schaetzel, S; Schäfer, U; Schaffer, A C; Schaile, D; Schamberger, R D; Scharf, V; Schegelsky, V A; Scheirich, D; Schernau, M; Scherzer, M I; Schiavi, C; Schieck, J; Schillo, C; Schioppa, M; Schlenker, S; Schmidt, E; Schmieden, K; Schmitt, C; Schmitt, C; Schmitt, S; Schneider, B; Schnellbach, Y J; Schnoor, U; Schoeffel, L; Schoening, A; Schorlemmer, A L S; Schott, M; Schouten, D; Schovancova, J; Schram, M; Schroeder, C; Schroer, N; Schultens, M J; Schultes, J; Schultz-Coulon, H-C; Schulz, H; Schumacher, M; Schumm, B A; Schune, Ph; Schwartzman, A; Schwegler, Ph; Schwemling, Ph; Schwienhorst, R; Schwindling, J; Schwindt, T; Schwoerer, M; Sciacca, F G; Scifo, E; Sciolla, G; Scott, W G; Searcy, J; Sedov, G; Sedykh, E; Seidel, S C; Seiden, A; Seifert, F; Seixas, J M; Sekhniaidze, G; Sekula, S J; Selbach, K E; Seliverstov, D M; Sellden, B; Sellers, G; Seman, M; Semprini-Cesari, N; Serfon, C; Serin, L; Serkin, L; Serre, T; Seuster, R; Severini, H; Sfyrla, A; Shabalina, E; Shamim, M; Shan, L Y; Shank, J T; Shao, Q T; Shapiro, M; Shatalov, P B; Shaw, K; Sherwood, P; Shimizu, S; Shimojima, M; Shin, T; Shiyakova, M; Shmeleva, A; Shochet, M J; Short, D; Shrestha, S; Shulga, E; Shupe, M A; Sicho, P; Sidoti, A; Siegert, F; Sijacki, Dj; Silbert, O; Silva, J; Silver, Y; Silverstein, D; Silverstein, S B; Simak, V; Simard, O; Simic, Lj; Simion, S; Simioni, E; Simmons, B; Simoniello, R; Simonyan, M; Sinervo, P; Sinev, N B; Sipica, V; Siragusa, G; Sircar, A; Sisakyan, A N; Sivoklokov, S Yu; Sjölin, J; Sjursen, T B; Skinnari, L A; Skottowe, H P; Skovpen, K; Skubic, P; Slater, M; Slavicek, T; Sliwa, K; Smakhtin, V; Smart, B H; Smestad, L; Smirnov, S Yu; Smirnov, Y; Smirnova, L N; Smirnova, O; Smith, B C; Smith, K M; Smizanska, M; Smolek, K; Snesarev, A A; Snidero, G; Snow, S W; Snow, J; Snyder, S; Sobie, R; Sodomka, J; Soffer, A; Soh, D A; Solans, C A; Solar, M; Solc, J; Soldatov, E Yu; Soldevila, U; Solfaroli Camillocci, E; Solodkov, A A; Solovyanov, O V; Solovyev, V; Soni, N; Sood, A; Sopko, V; Sopko, B; Sosebee, M; Soualah, R; Soueid, P; Soukharev, A; South, D; Spagnolo, S; Spanò, F; Spighi, R; Spigo, G; Spiwoks, R; Spousta, M; Spreitzer, T; Spurlock, B; St Denis, R D; Stahlman, J; Stamen, R; Stanecka, E; Stanek, R W; Stanescu, C; Stanescu-Bellu, M; Stanitzki, M M; Stapnes, S; Starchenko, E A; Stark, J; Staroba, P; Starovoitov, P; Staszewski, R; Staude, A; Stavina, P; Steele, G; Steinbach, P; Steinberg, P; Stekl, I; Stelzer, B; Stelzer, H J; Stelzer-Chilton, O; Stenzel, H; Stern, S; Stewart, G A; Stillings, J A; Stockton, M C; Stoebe, M; Stoerig, K; Stoicea, G; Stonjek, S; Strachota, P; Stradling, A R; Straessner, A; Strandberg, J; Strandberg, S; Strandlie, A; Strang, M; Strauss, E; Strauss, M; Strizenec, P; Ströhmer, R; Strom, D M; Strong, J A; Stroynowski, R; Stugu, B; Stumer, I; Stupak, J; Sturm, P; Styles, N A; Su, D; Subramania, Hs; Subramaniam, R; Succurro, A; Sugaya, Y; Suhr, C; Suk, M; Sulin, V V; Sultansoy, S; Sumida, T; Sun, X; Sundermann, J E; Suruliz, K; Susinno, G; Sutton, M R; Suzuki, Y; Suzuki, Y; Svatos, M; Swedish, S; Swiatlowski, M; Sykora, I; Sykora, T; Ta, D; Tackmann, K; Taffard, A; Tafirout, R; Taiblum, N; Takahashi, Y; Takai, H; Takashima, R; Takeda, H; Takeshita, T; Takubo, Y; Talby, M; Talyshev, A; Tam, J Y C; Tamsett, M C; Tan, K G; Tanaka, J; Tanaka, R; Tanaka, S; Tanaka, S; Tanasijczuk, A J; Tani, K; Tannoury, N; Tapprogge, S; Tardif, D; Tarem, S; Tarrade, F; Tartarelli, G F; Tas, P; Tasevsky, M; Tassi, E; Tayalati, Y; Taylor, C; Taylor, F E; Taylor, G N; Taylor, W; Teinturier, M; Teischinger, F A; Teixeira Dias Castanheira, M; Teixeira-Dias, P; Temming, K K; Ten Kate, H; Teng, P K; Terada, S; Terashi, K; Terron, J; Testa, M; Teuscher, R J; Therhaag, J; Theveneaux-Pelzer, T; Thoma, S; Thomas, J P; Thompson, E N; Thompson, P D; Thompson, P D; Thompson, A S; Thomsen, L A; Thomson, E; Thomson, M; Thong, W M; Thun, R P; Tian, F; Tibbetts, M J; Tic, T; Tikhomirov, V O; Tikhonov, Y A; Timoshenko, S; Tiouchichine, E; Tipton, P; Tisserant, S; Todorov, T; Todorova-Nova, S; Toggerson, B; Tojo, J; Tokár, S; Tokushuku, K; Tollefson, K; Tomlinson, L; Tomoto, M; Tompkins, L; Toms, K; Tonoyan, A; Topfel, C; Topilin, N D; Torrence, E; Torres, H; Torró Pastor, E; Toth, J; Touchard, F; Tovey, D R; Tran, H L; Trefzger, T; Tremblet, L; Tricoli, A; Trigger, I M; Trincaz-Duvoid, S; Tripiana, M F; Triplett, N; Trischuk, W; Trocmé, B; Troncon, C; Trottier-McDonald, M; Trovatelli, M; True, P; Trzebinski, M; Trzupek, A; Tsarouchas, C; Tseng, J C-L; Tsiakiris, M; Tsiareshka, P V; Tsionou, D; Tsipolitis, G; Tsiskaridze, S; Tsiskaridze, V; Tskhadadze, E G; Tsukerman, I I; Tsulaia, V; Tsung, J-W; Tsuno, S; Tsybychev, D; Tua, A; Tudorache, A; Tudorache, V; Tuggle, J M; Turala, M; Turecek, D; Turk Cakir, I; Turra, R; Tuts, P M; Tykhonov, A; Tylmad, M; Tyndel, M; Tzanakos, G; Uchida, K; Ueda, I; Ueno, R; Ughetto, M; Ugland, M; Uhlenbrock, M; Ukegawa, F; Unal, G; Undrus, A; Unel, G; Ungaro, F C; Unno, Y; Urbaniec, D; Urquijo, P; Usai, G; Vacavant, L; Vacek, V; Vachon, B; Vahsen, S; Valencic, N; Valentinetti, S; Valero, A; Valery, L; Valkar, S; Valladolid Gallego, E; Vallecorsa, S; Valls Ferrer, J A; Van Berg, R; Van Der Deijl, P C; van der Geer, R; van der Graaf, H; Van Der Leeuw, R; van der Poel, E; van der Ster, D; van Eldik, N; van Gemmeren, P; Van Nieuwkoop, J; van Vulpen, I; Vanadia, M; Vandelli, W; Vaniachine, A; Vankov, P; Vannucci, F; Vari, R; Varnes, E W; Varol, T; Varouchas, D; Vartapetian, A; Varvell, K E; Vassilakopoulos, V I; Vazeille, F; Vazquez Schroeder, T; Veloso, F; Veneziano, S; Ventura, A; Ventura, D; Venturi, M; Venturi, N; Vercesi, V; Verducci, M; Verkerke, W; Vermeulen, J C; Vest, A; Vetterli, M C; Vichou, I; Vickey, T; Vickey Boeriu, O E; Viehhauser, G H A; Viel, S; Villa, M; Villaplana Perez, M; Vilucchi, E; Vincter, M G; Vinek, E; Vinogradov, V B; Virzi, J; Vitells, O; Viti, M; Vivarelli, I; Vives Vaque, F; Vlachos, S; Vladoiu, D; Vlasak, M; Vogel, A; Vokac, P; Volpi, G; Volpi, M; Volpini, G; von der Schmitt, H; von Radziewski, H; von Toerne, E; Vorobel, V; Vorwerk, V; Vos, M; Voss, R; Vossebeld, J H; Vranjes, N; Vranjes Milosavljevic, M; Vrba, V; Vreeswijk, M; Vu Anh, T; Vuillermet, R; Vukotic, I; Vykydal, Z; Wagner, W; Wagner, P; Wahlen, H; Wahrmund, S; Wakabayashi, J; Walch, S; Walder, J; Walker, R; Walkowiak, W; Wall, R; Waller, P; Walsh, B; Wang, C; Wang, H; Wang, H; Wang, J; Wang, J; Wang, K; Wang, R; Wang, S M; Wang, T; Wang, X; Warburton, A; Ward, C P; Wardrope, D R; Warsinsky, M; Washbrook, A; Wasicki, C; Watanabe, I; Watkins, P M; Watson, A T; Watson, I J; Watson, M F; Watts, G; Watts, S; Waugh, A T; Waugh, B M; Weber, M S; Webster, J S; Weidberg, A R; Weigell, P; Weingarten, J; Weiser, C; Wells, P S; Wenaus, T; Wendland, D; Weng, Z; Wengler, T; Wenig, S; Wermes, N; Werner, M; Werner, P; Werth, M; Wessels, M; Wetter, J; Weydert, C; Whalen, K; White, A; White, M J; White, S; Whitehead, S R; Whiteson, D; Whittington, D; Wicke, D; Wickens, F J; Wiedenmann, W; Wielers, M; Wienemann, P; Wiglesworth, C; Wiik-Fuchs, L A M; Wijeratne, P A; Wildauer, A; Wildt, M A; Wilhelm, I; Wilkens, H G; Will, J Z; Williams, E; Williams, H H; Williams, S; Willis, W; Willocq, S; Wilson, J A; Wilson, M G; Wilson, A; Wingerter-Seez, I; Winkelmann, S; Winklmeier, F; Wittgen, M; Wittig, T; Wittkowski, J; Wollstadt, S J; Wolter, M W; Wolters, H; Wong, W C; Wooden, G; Wosiek, B K; Wotschack, J; Woudstra, M J; Wozniak, K W; Wraight, K; Wright, M; Wrona, B; Wu, S L; Wu, X; Wu, Y; Wulf, E; Wynne, B M; Xella, S; Xiao, M; Xie, S; Xu, C; Xu, D; Xu, L; Yabsley, B; Yacoob, S; Yamada, M; Yamaguchi, H; Yamamoto, A; Yamamoto, K; Yamamoto, S; Yamamura, T; Yamanaka, T; Yamauchi, K; Yamazaki, T; Yamazaki, Y; Yan, Z; Yang, H; Yang, H; Yang, U K; Yang, Y; Yang, Z; Yanush, S; Yao, L; Yasu, Y; Yatsenko, E; Ye, J; Ye, S; Yen, A L; Yilmaz, M; Yoosoofmiya, R; Yorita, K; Yoshida, R; Yoshihara, K; Young, C; Young, C J; Youssef, S; Yu, D; Yu, D R; Yu, J; Yu, J; Yuan, L; Yurkewicz, A; Zabinski, B; Zaidan, R; Zaitsev, A M; Zambito, S; Zanello, L; Zanzi, D; Zaytsev, A; Zeitnitz, C; Zeman, M; Zemla, A; Zenin, O; Zeniš, T; Zerwas, D; Zevi Della Porta, G; Zhang, D; Zhang, H; Zhang, J; Zhang, L; Zhang, X; Zhang, Z; Zhao, L; Zhao, Z; Zhemchugov, A; Zhong, J; Zhou, B; Zhou, N; Zhou, Y; Zhu, C G; Zhu, H; Zhu, J; Zhu, Y; Zhuang, X; Zhuravlov, V; Zibell, A; Zieminska, D; Zimin, N I; Zimmermann, R; Zimmermann, S; Zimmermann, S; Zinonos, Z; Ziolkowski, M; Zitoun, R; Zivković, L; Zmouchko, V V; Zobernig, G; Zoccoli, A; Zur Nedden, M; Zutshi, V; Zwalinski, L

    2013-05-01

    Two-particle correlations in relative azimuthal angle (Δø) and pseudorapidity (Δη) are measured in sqrt[s(NN)] = 5.02 TeV p+Pb collisions using the ATLAS detector at the LHC. The measurements are performed using approximately 1 μb(-1) of data as a function of transverse momentum (p(T)) and the transverse energy (ΣE(T)(Pb)) summed over 3.1 < η < 4.9 in the direction of the Pb beam. The correlation function, constructed from charged particles, exhibits a long-range (2 < |Δ η | < 5) "near-side" (Δø ~ 0) correlation that grows rapidly with increasing ΣE(T)(Pb). A long-range "away-side" (Δø ~ π) correlation, obtained by subtracting the expected contributions from recoiling dijets and other sources estimated using events with small ΣE(T)(Pb), is found to match the near-side correlation in magnitude, shape (in Δη and Δø) and ΣE(T)(Pb) dependence. The resultant Δø correlation is approximately symmetric about π/2, and is consistent with a dominant cos2Δø modulation for all ΣE(T)(Pb) ranges and particle p(T).

  6. Alternating electron and proton transfer steps in photosynthetic water oxidation.

    Science.gov (United States)

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-02

    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

  7. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

    Science.gov (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

    2016-10-24

    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order.

  8. Water-assisted proton transfer in ferredoxin I.

    Science.gov (United States)

    Lutz, Stephan; Tubert-Brohman, Ivan; Yang, Yonggang; Meuwly, Markus

    2011-07-08

    The role of water molecules in assisting proton transfer (PT) is investigated for the proton-pumping protein ferredoxin I (FdI) from Azotobacter vinelandii. It was shown previously that individual water molecules can stabilize between Asp(15) and the buried [3Fe-4S](0) cluster and thus can potentially act as a proton relay in transferring H(+) from the protein to the μ(2) sulfur atom. Here, we generalize molecular mechanics with proton transfer to studying proton transfer reactions in the condensed phase. Both umbrella sampling simulations and electronic structure calculations suggest that the PT Asp(15)-COOH + H(2)O + [3Fe-4S](0) → Asp(15)-COO(-) + H(2)O + [3Fe-4S](0) H(+) is concerted, and no stable intermediate hydronium ion (H(3)O(+)) is expected. The free energy difference of 11.7 kcal/mol for the forward reaction is in good agreement with the experimental value (13.3 kcal/mol). For the reverse reaction (Asp(15)-COO(-) + H(2)O + [3Fe-4S](0)H(+) → Asp(15)-COOH + H(2)O + [3Fe-4S](0)), a larger barrier than for the forward reaction is correctly predicted, but it is quantitatively overestimated (23.1 kcal/mol from simulations versus 14.1 from experiment). Possible reasons for this discrepancy are discussed. Compared with the water-assisted process (ΔE ≈ 10 kcal/mol), water-unassisted proton transfer yields a considerably higher barrier of ΔE ≈ 35 kcal/mol.

  9. Lateral proton transfer between the membrane and a membrane protein.

    Science.gov (United States)

    Ojemyr, Linda; Sandén, Tor; Widengren, Jerker; Brzezinski, Peter

    2009-03-17

    Proton transport across biological membranes is a key step of the energy conservation machinery in living organisms, and it has been proposed that the membrane itself plays an important role in this process. In the present study we have investigated the effect of incorporation of a proton transporter, cytochrome c oxidase, into a membrane on the protonation kinetics of a fluorescent pH-sensitive probe attached at the surface of the protein. The results show that proton transfer to the probe was slightly accelerated upon attachment at the protein surface (approximately 7 x 1010 s(-1) M(-1), compared to the expected value of (1-2) x 10(10) s(-1) M(-1)), which is presumably due to the presence of acidic/His groups in the vicinity. Upon incorporation of the protein into small unilamellar phospholipid vesicles the rate increased by more than a factor of 400 to approximately 3 x 10(13) s(-1) M(-1), which indicates that the protein-attached probe is in rapid protonic contact with the membrane surface. The results indicate that the membrane acts to accelerate proton uptake by the membrane-bound proton transporter.

  10. A new smoothing function to introduce long-range electrostatic effects in QM/MM calculations

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Dong [Department of Chemistry, Wayne State University, Detroit, Michigan 48202 (United States); Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706 (United States); Duke, Robert E.; Andrés Cisneros, G., E-mail: andres@chem.wayne.edu [Department of Chemistry, Wayne State University, Detroit, Michigan 48202 (United States)

    2015-07-28

    A new method to account for long range electrostatic contributions is proposed and implemented for quantum mechanics/molecular mechanics long range electrostatic correction (QM/MM-LREC) calculations. This method involves the use of the minimum image convention under periodic boundary conditions and a new smoothing function for energies and forces at the cutoff boundary for the Coulomb interactions. Compared to conventional QM/MM calculations without long-range electrostatic corrections, the new method effectively includes effects on the MM environment in the primary image from its replicas in the neighborhood. QM/MM-LREC offers three useful features including the avoidance of calculations in reciprocal space (k-space), with the concomitant avoidance of having to reproduce (analytically or approximately) the QM charge density in k-space, and the straightforward availability of analytical Hessians. The new method is tested and compared with results from smooth particle mesh Ewald (PME) for three systems including a box of neat water, a double proton transfer reaction, and the geometry optimization of the critical point structures for the rate limiting step of the DNA dealkylase AlkB. As with other smoothing or shifting functions, relatively large cutoffs are necessary to achieve comparable accuracy with PME. For the double-proton transfer reaction, the use of a 22 Å cutoff shows a close reaction energy profile and geometries of stationary structures with QM/MM-LREC compared to conventional QM/MM with no truncation. Geometry optimization of stationary structures for the hydrogen abstraction step by AlkB shows some differences between QM/MM-LREC and the conventional QM/MM. These differences underscore the necessity of the inclusion of the long-range electrostatic contribution.

  11. The Membrane Modulates Internal Proton Transfer in Cytochrome c Oxidase

    DEFF Research Database (Denmark)

    Öjemyr, Linda Nasvik; Ballmoos, Christoph von; Faxén, Kristina

    2012-01-01

    The functionality of membrane proteins is often modulated by the surrounding membrane. Here, we investigated the effect of membrane reconstitution of purified cytochrome c oxidase (CytcO) on the kinetics and thermodynamics of internal electron and proton-transfer reactions during O-2 reduction...

  12. Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer.

    Science.gov (United States)

    Sotiriou, Georgios A; Blattmann, Christoph O; Deligiannakis, Yiannis

    2016-01-14

    Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol(-1) and therefore facilitates PCET. The nanoparticle-driven plasmon-enhancement of PCET brings together the so far unrelated research domains of nanoplasmonics and electron/proton translocation with significant impact on applications based on interfacial electron/proton transfer.

  13. Distance dependence of bidirectional concerted proton-electron transfer in phenol-Ru(2,2'-bipyridine)3(2+) dyads.

    Science.gov (United States)

    Chen, Jing; Kuss-Petermann, Martin; Wenger, Oliver S

    2014-04-01

    Proton-coupled electron transfer (PCET) was investigated in three covalent donor-bridge-acceptor molecules with different bridge lengths. Upon photoexcitation of their Ru(bpy)3(2+) (bpy=2,2'-bipyridine) photosensitizer in acetonitrile, intramolecular long-range electron transfer from a phenolic unit to Ru(bpy)3(2+) occurs in concert with release of the phenolic proton to pyrrolidine base. The kinetics of this bidirectional concerted proton-electron transfer (CPET) reaction were studied as a function of phenol-Ru(bpy)3(2+) distance by increasing the number of bridging p-xylene units. A distance decay constant (β) of 0.67±0.23 Å(-1) was determined. The distance dependence of the rates for CPET is thus not significantly steeper than that for ordinary (i.e., not proton coupled) electron transfer across the same bridges, despite the concerted motion of oppositely charged particles into different directions. Long-range bidirectional CPET is an important reaction in many proteins and plays a key role in photosynthesis; our results are relevant in the context of photoinduced separation of protons and electrons as a means of light-to-chemical energy conversion. This is the first determination of β for a bidirectional CPET reaction.

  14. Nonradiative charge transfer in collisions of protons with rubidium atoms

    Institute of Scientific and Technical Information of China (English)

    Yan Ling-Ling; Qu Yi-Zhi; Liu Chun-Hua; Zhang Yu; Wang Jian-Guo; Buenker Robert J

    2012-01-01

    The nonradiative charge-transfer cross sections for protons colliding with Rb(5s) atoms are calculated by using the quantum-mechanical molecularorbital close-coupling method in an energy range of 10-3 keV 10 keV.The total and state-selective charge-transfer cross sections are in good agreement with the experimental data in the relatively low energy region.The importance of rotational coupling for chargetransfer process is stressed.Compared with the radiative charge-transfer process,nonradiative charge transfer is a dominant mechanism at energies above 15 eV.The resonance structures of state-selective charge-transfer cross sections arising from the competition among channels are analysed in detail.The radiative and nonradiative charge-transfer rate coefficients from low to high temperature are presented.

  15. Measurement of long-range pseudorapidity correlations and azimuthal harmonics in $\\sqrt{s_{\\mathrm{NN}}}$=5.02 TeV proton-lead collisions with the ATLAS detector

    CERN Document Server

    Aad, Georges; Abdallah, Jalal; Abdel Khalek, Samah; Abdinov, Ovsat; Aben, Rosemarie; Abi, Babak; Abolins, Maris; AbouZeid, Ossama; Abramowicz, Halina; Abreu, Henso; Abreu, Ricardo; Abulaiti, Yiming; Acharya, Bobby Samir; Adamczyk, Leszek; Adams, David; Adelman, Jahred; Adomeit, Stefanie; Adye, Tim; Agatonovic-Jovin, Tatjana; Aguilar-Saavedra, Juan Antonio; Agustoni, Marco; Ahlen, Steven; Ahmadov, Faig; Aielli, Giulio; Akerstedt, Henrik; Åkesson, Torsten Paul Ake; Akimoto, Ginga; Akimov, Andrei; Alberghi, Gian Luigi; Albert, Justin; Albrand, Solveig; Alconada Verzini, Maria Josefina; Aleksa, Martin; Aleksandrov, Igor; Alexa, Calin; Alexander, Gideon; Alexandre, Gauthier; Alexopoulos, Theodoros; Alhroob, Muhammad; Alimonti, Gianluca; Alio, Lion; Alison, John; Allbrooke, Benedict; Allison, Lee John; Allport, Phillip; Almond, John; Aloisio, Alberto; Alonso, Alejandro; Alonso, Francisco; Alpigiani, Cristiano; Altheimer, Andrew David; Alvarez Gonzalez, Barbara; Alviggi, Mariagrazia; Amako, Katsuya; Amaral Coutinho, Yara; Amelung, Christoph; Amidei, Dante; Amor Dos Santos, Susana Patricia; Amorim, Antonio; Amoroso, Simone; Amram, Nir; Amundsen, Glenn; Anastopoulos, Christos; Ancu, Lucian Stefan; Andari, Nansi; Andeen, Timothy; Anders, Christoph Falk; Anders, Gabriel; Anderson, Kelby; Andreazza, Attilio; Andrei, George Victor; Anduaga, Xabier; Angelidakis, Stylianos; Angelozzi, Ivan; Anger, Philipp; Angerami, Aaron; Anghinolfi, Francis; Anisenkov, Alexey; Anjos, Nuno; Annovi, Alberto; Antonaki, Ariadni; Antonelli, Mario; Antonov, Alexey; Antos, Jaroslav; Anulli, Fabio; Aoki, Masato; Aperio Bella, Ludovica; Apolle, Rudi; Arabidze, Giorgi; Aracena, Ignacio; Arai, Yasuo; Araque, Juan Pedro; Arce, Ayana; Arguin, Jean-Francois; Argyropoulos, Spyridon; Arik, Metin; Armbruster, Aaron James; Arnaez, Olivier; Arnal, Vanessa; Arnold, Hannah; Arratia, Miguel; Arslan, Ozan; Artamonov, Andrei; Artoni, Giacomo; Asai, Shoji; Asbah, Nedaa; Ashkenazi, Adi; Åsman, Barbro; Asquith, Lily; Assamagan, Ketevi; Astalos, Robert; Atkinson, Markus; Atlay, Naim Bora; Auerbach, Benjamin; Augsten, Kamil; Aurousseau, Mathieu; Avolio, Giuseppe; Azuelos, Georges; Azuma, Yuya; Baak, Max; Baas, Alessandra; Bacci, Cesare; Bachacou, Henri; Bachas, Konstantinos; Backes, Moritz; Backhaus, Malte; Backus Mayes, John; Badescu, Elisabeta; Bagiacchi, Paolo; Bagnaia, Paolo; Bai, Yu; Bain, Travis; Baines, John; Baker, Oliver Keith; Balek, Petr; Balli, Fabrice; Banas, Elzbieta; Banerjee, Swagato; Bannoura, Arwa A E; Bansal, Vikas; Bansil, Hardeep Singh; Barak, Liron; Baranov, Sergei; Barberio, Elisabetta Luigia; Barberis, Dario; Barbero, Marlon; Barillari, Teresa; Barisonzi, Marcello; Barklow, Timothy; Barlow, Nick; Barnett, Bruce; Barnett, Michael; Barnovska, Zuzana; Baroncelli, Antonio; Barone, Gaetano; Barr, Alan; Barreiro, Fernando; Barreiro Guimarães da Costa, João; Bartoldus, Rainer; Barton, Adam Edward; Bartos, Pavol; Bartsch, Valeria; Bassalat, Ahmed; Basye, Austin; Bates, Richard; Batley, Richard; Battaglia, Marco; Battistin, Michele; Bauer, Florian; Bawa, Harinder Singh; Beattie, Michael David; Beau, Tristan; Beauchemin, Pierre-Hugues; Beccherle, Roberto; Bechtle, Philip; Beck, Hans Peter; Becker, Anne Kathrin; Becker, Sebastian; Beckingham, Matthew; Becot, Cyril; Beddall, Andrew; Beddall, Ayda; Bedikian, Sourpouhi; Bednyakov, Vadim; Bee, Christopher; Beemster, Lars; Beermann, Thomas; Begel, Michael; Behr, Katharina; Belanger-Champagne, Camille; Bell, Paul; Bell, William; Bella, Gideon; Bellagamba, Lorenzo; Bellerive, Alain; Bellomo, Massimiliano; Belotskiy, Konstantin; Beltramello, Olga; Benary, Odette; Benchekroun, Driss; Bendtz, Katarina; Benekos, Nektarios; Benhammou, Yan; Benhar Noccioli, Eleonora; Benitez Garcia, Jorge-Armando; Benjamin, Douglas; Bensinger, James; Benslama, Kamal; Bentvelsen, Stan; Berge, David; Bergeaas Kuutmann, Elin; Berger, Nicolas; Berghaus, Frank; Beringer, Jürg; Bernard, Clare; Bernat, Pauline; Bernius, Catrin; Bernlochner, Florian Urs; Berry, Tracey; Berta, Peter; Bertella, Claudia; Bertoli, Gabriele; Bertolucci, Federico; Bertsche, Carolyn; Bertsche, David; Besana, Maria Ilaria; Besjes, Geert-Jan; Bessidskaia, Olga; Bessner, Martin Florian; Besson, Nathalie; Betancourt, Christopher; Bethke, Siegfried; Bhimji, Wahid; Bianchi, Riccardo-Maria; Bianchini, Louis; Bianco, Michele; Biebel, Otmar; Bieniek, Stephen Paul; Bierwagen, Katharina; Biesiada, Jed; Biglietti, Michela; Bilbao De Mendizabal, Javier; Bilokon, Halina; Bindi, Marcello; Binet, Sebastien; Bingul, Ahmet; Bini, Cesare; Black, Curtis; Black, James

    2014-01-01

    Measurements of two-particle correlation functions and the first five azimuthal harmonics, $v_1$ to $v_5$, are presented, using 28 $\\mathrm{nb}^{-1}$ of $p$+Pb collisions at a nucleon-nucleon center-of-mass energy of $\\sqrt{s_{\\mathrm{NN}}}=5.02$ TeV measured with the ATLAS detector at the LHC. Significant long-range "ridge-like" correlations are observed for pairs with small relative azimuthal angle ($|\\Delta\\phi|2\\pi/3$) over the transverse momentum range $0.44$ GeV. The $v_2(p_{\\rm T})$, $v_3(p_{\\rm T})$ and $v_4(p_{\\rm T})$ are compared to the $v_n$ coefficients in Pb+Pb collisions at $\\sqrt{s_{\\mathrm{NN}}} =2.76$ TeV with similar event multiplicities. Reasonable agreement is observed after accounting for the difference in the average $p_{\\rm T}$ of particles produced in the two collision systems.

  16. Long-Range WindScanner System

    DEFF Research Database (Denmark)

    Vasiljevic, Nikola; Lea, Guillaume; Courtney, Michael

    2016-01-01

    The technical aspects of a multi-Doppler LiDAR instrument, the long-range WindScanner system, are presented accompanied by an overview of the results from several field campaigns. The long-range WindScanner system consists of three spatially-separated, scanning coherent Doppler LiDARs and a remot...

  17. An Approach to Extract the Spin Transfer to in Polarized Proton-Proton Collision

    Institute of Scientific and Technical Information of China (English)

    HAN Ran; YE Hong-Xue; LIANG Yu-Tie; MAO Ya-Jun

    2008-01-01

    We introduce an approach to extract the spin transfer to (A) in polarized proton-proton collision, based on the relation between single spin asymmetry and the polarization of (A) production. With 4 × 106 (A) events simulated for a PHENIX detector system, DLL = 0.1598 ± 0.0343 is retrieved by the approach and it agrees very well with the input value of 0.1429. The approach is further tested and confirmed with 'bunch shuffling' method for the simulated events as well as experimental events collected at PHENIX in 2003. It is concluded that one can correctly extract the spin transfer without detailed understanding of acceptance correction even if the correction is significantly large in PHENIX experiment by using the approach described here. The method can be generally used for spin transfer study.

  18. Hydrated alizarin complexes: hydrogen bonding and proton transfer.

    Science.gov (United States)

    Huh, Hyun; Cho, Sung Haeng; Heo, Jiyoung; Kim, Nam Joon; Kim, Seong Keun

    2012-07-07

    We investigated the hydrogen bonding structures and proton transfer for the hydration complexes of alizarin (Az) produced in a supersonic jet using fluorescence excitation (FE), dispersed laser induced fluorescence (LIF), visible-visible hole burning (HB), and fluorescence detected infrared (FDIR) spectroscopy. The FDIR spectrum of bare Az with two O-H groups exhibits two vibrational bands at 3092 and 3579 cm(-1), which, respectively, correspond to the stretching vibration of O1-H1 that forms a strong intramolecular hydrogen bond with the C9=O9 carbonyl group and the stretching vibration of O2-H2 that is weakly hydrogen-bonded to O1-H1. For the 1:1 hydration complex Az(H(2)O)(1), we identified three conformers. In the most stable conformer, the water molecule forms hydrogen bonds with the O1-H1 and O2-H2 groups of Az as a proton donor and proton acceptor, respectively. In the other conformers, the water binds to the C10=O10 group in two nearly isoenergetic configurations. In contrast to the sharp vibronic peaks in the FE spectra of Az and Az(H(2)O)(1), only broad, structureless absorption was observed for Az(H(2)O)(n) (n≥ 2), indicating a facile decay process, possibly due to proton transfer in the electronic excited state. The FDIR spectrum with the wavelength of the probe laser fixed at the broad band exhibited a broad vibrational band near the O2-H2 stretching vibration frequency of the most stable conformer of Az(H(2)O)(1). With the help of theoretical calculations, we suggest that the broad vibrational band may represent the occurrence of proton transfer by tunnelling in the electronic ground state of Az(H(2)O)(n) (n≥ 2) upon excitation of the O2-H2 vibration.

  19. Proton Transfer Time-of-Flight Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Watson, Thomas B [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2016-03-01

    The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H3O+), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-charge ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.

  20. Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Miller, David C; Choi, Gilbert J; Orbe, Hudson S; Knowles, Robert R

    2015-10-28

    Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

  1. Measurement of Long-Range Angular Correlation and Quadrupole Anisotropy of Pions and (Anti)Protons in Central d+Au Collisions at sqrt[s_{NN}]=200 GeV.

    Science.gov (United States)

    Adare, A; Aidala, C; Ajitanand, N N; Akiba, Y; Akimoto, R; Al-Bataineh, H; Al-Ta'ani, H; Alexander, J; Andrews, K R; Angerami, A; Aoki, K; Apadula, N; Appelt, E; Aramaki, Y; Armendariz, R; Aschenauer, E C; Atomssa, E T; Averbeck, R; Awes, T C; Azmoun, B; Babintsev, V; Bai, M; Baksay, G; Baksay, L; Bannier, B; Barish, K N; Bassalleck, B; Basye, A T; Bathe, S; Baublis, V; Baumann, C; Bazilevsky, A; Belikov, S; Belmont, R; Ben-Benjamin, J; Bennett, R; Bhom, J H; Blau, D S; Bok, J S; Boyle, K; Brooks, M L; Broxmeyer, D; Buesching, H; Bumazhnov, V; Bunce, G; Butsyk, S; Campbell, S; Caringi, A; Castera, P; Chen, C-H; Chi, C Y; Chiu, M; Choi, I J; Choi, J B; Choudhury, R K; Christiansen, P; Chujo, T; Chung, P; Chvala, O; Cianciolo, V; Citron, Z; Cole, B A; Conesa Del Valle, Z; Connors, M; Csanád, M; Csörgő, T; Dahms, T; Dairaku, S; Danchev, I; Das, K; Datta, A; David, G; Dayananda, M K; Denisov, A; Deshpande, A; Desmond, E J; Dharmawardane, K V; Dietzsch, O; Dion, A; Donadelli, M; Drapier, O; Drees, A; Drees, K A; Durham, J M; Durum, A; Dutta, D; D'Orazio, L; Edwards, S; Efremenko, Y V; Ellinghaus, F; Engelmore, T; Enokizono, A; En'yo, H; Esumi, S; Fadem, B; Fields, D E; Finger, M; Finger, M; Fleuret, F; Fokin, S L; Fraenkel, Z; Frantz, J E; Franz, A; Frawley, A D; Fujiwara, K; Fukao, Y; Fusayasu, T; Gal, C; Garishvili, I; Glenn, A; Gong, H; Gong, X; Gonin, M; Goto, Y; Granier de Cassagnac, R; Grau, N; Greene, S V; Grim, G; Grosse Perdekamp, M; Gunji, T; Guo, L; Gustafsson, H-Å; Haggerty, J S; Hahn, K I; Hamagaki, H; Hamblen, J; Han, R; Hanks, J; Harper, C; Hashimoto, K; Haslum, E; Hayano, R; He, X; Heffner, M; Hemmick, T K; Hester, T; Hill, J C; Hohlmann, M; Hollis, R S; Holzmann, W; Homma, K; Hong, B; Horaguchi, T; Hori, Y; Hornback, D; Huang, S; Ichihara, T; Ichimiya, R; Iinuma, H; Ikeda, Y; Imai, K; Inaba, M; Iordanova, A; Isenhower, D; Ishihara, M; Issah, M; Ivanischev, D; Iwanaga, Y; Jacak, B V; Jia, J; Jiang, X; Jin, J; John, D; Johnson, B M; Jones, T; Joo, K S; Jouan, D; Jumper, D S; Kajihara, F; Kamin, J; Kaneti, S; Kang, B H; Kang, J H; Kang, J S; Kapustinsky, J; Karatsu, K; Kasai, M; Kawall, D; Kawashima, M; Kazantsev, A V; Kempel, T; Khanzadeev, A; Kijima, K M; Kikuchi, J; Kim, A; Kim, B I; Kim, D J; Kim, E-J; Kim, Y-J; Kim, Y K; Kinney, E; Kiss, Á; Kistenev, E; Kleinjan, D; Kline, P; Kochenda, L; Komkov, B; Konno, M; Koster, J; Kotov, D; Král, A; Kravitz, A; Kunde, G J; Kurita, K; Kurosawa, M; Kwon, Y; Kyle, G S; Lacey, R; Lai, Y S; Lajoie, J G; Lebedev, A; Lee, D M; Lee, J; Lee, K B; Lee, K S; Lee, S H; Lee, S R; Leitch, M J; Leite, M A L; Li, X; Lichtenwalner, P; Liebing, P; Lim, S H; Linden Levy, L A; Liška, T; Liu, H; Liu, M X; Love, B; Lynch, D; Maguire, C F; Makdisi, Y I; Malik, M D; Manion, A; Manko, V I; Mannel, E; Mao, Y; Masui, H; Matathias, F; McCumber, M; McGaughey, P L; McGlinchey, D; McKinney, C; Means, N; Mendoza, M; Meredith, B; Miake, Y; Mibe, T; Mignerey, A C; Miki, K; Milov, A; Mitchell, J T; Miyachi, Y; Mohanty, A K; Moon, H J; Morino, Y; Morreale, A; Morrison, D P; Motschwiller, S; Moukhanova, T V; Murakami, T; Murata, J; Nagamiya, S; Nagle, J L; Naglis, M; Nagy, M I; Nakagawa, I; Nakamiya, Y; Nakamura, K R; Nakamura, T; Nakano, K; Nam, S; Newby, J; Nguyen, M; Nihashi, M; Nouicer, R; Nyanin, A S; Oakley, C; O'Brien, E; Oda, S X; Ogilvie, C A; Oka, M; Okada, K; Onuki, Y; Oskarsson, A; Ouchida, M; Ozawa, K; Pak, R; Pantuev, V; Papavassiliou, V; Park, B H; Park, I H; Park, S K; Park, W J; Pate, S F; Patel, L; Pei, H; Peng, J-C; Pereira, H; Peressounko, D Yu; Petti, R; Pinkenburg, C; Pisani, R P; Proissl, M; Purschke, M L; Qu, H; Rak, J; Ravinovich, I; Read, K F; Rembeczki, S; Reygers, K; Riabov, V; Riabov, Y; Richardson, E; Roach, D; Roche, G; Rolnick, S D; Rosati, M; Rosen, C A; Rosendahl, S S E; Ružička, P; Sahlmueller, B; Saito, N; Sakaguchi, T; Sakashita, K; Samsonov, V; Sano, S; Sarsour, M; Sato, T; Savastio, M; Sawada, S; Sedgwick, K; Seele, J; Seidl, R; Seto, R; Sharma, D; Shein, I; Shibata, T-A; Shigaki, K; Shim, H H; Shimomura, M; Shoji, K; Shukla, P; Sickles, A; Silva, C L; Silvermyr, D; Silvestre, C; Sim, K S; Singh, B K; Singh, C P; Singh, V; Slunečka, M; Sodre, T; Soltz, R A; Sondheim, W E; Sorensen, S P; Sourikova, I V; Stankus, P W; Stenlund, E; Stoll, S P; Sugitate, T; Sukhanov, A; Sun, J; Sziklai, J; Takagui, E M; Takahara, A; Taketani, A; Tanabe, R; Tanaka, Y; Taneja, S; Tanida, K; Tannenbaum, M J; Tarafdar, S; Taranenko, A; Tennant, E; Themann, H; Thomas, D; Thomas, T L; Togawa, M; Toia, A; Tomášek, L; Tomášek, M; Torii, H; Towell, R S; Tserruya, I; Tsuchimoto, Y; Utsunomiya, K; Vale, C; Valle, H; van Hecke, H W; Vazquez-Zambrano, E; Veicht, A; Velkovska, J; Vértesi, R; Virius, M; Vossen, A; Vrba, V; Vznuzdaev, E; Wang, X R; Watanabe, D; Watanabe, K; Watanabe, Y; Watanabe, Y S; Wei, F; Wei, R; Wessels, J; White, S N; Winter, D; Woody, C L; Wright, R M; Wysocki, M

    2015-05-15

    We present azimuthal angular correlations between charged hadrons and energy deposited in calorimeter towers in central d+Au and minimum bias p+p collisions at sqrt[s_{NN}]=200 GeV. The charged hadron is measured at midrapidity |η|2.75 is observed in d+Au collisions. Using the event plane method applied to the Au-going energy distribution, we extract the anisotropy strength v_{2} for inclusive charged hadrons at midrapidity up to p_{T}=4.5 GeV/c. We also present the measurement of v_{2} for identified π^{±} and (anti)protons in central d+Au collisions, and observe a mass-ordering pattern similar to that seen in heavy-ion collisions. These results are compared with viscous hydrodynamic calculations and measurements from p+Pb at sqrt[s_{NN}]=5.02 TeV. The magnitude of the mass ordering in d+Au is found to be smaller than that in p+Pb collisions, which may indicate smaller radial flow in lower energy d+Au collisions.

  2. Measurement of long-range angular correlation and quadrupole anisotropy of pions and (anti)protons in central $d$$+$Au collisions at $\\sqrt{s_{_{NN}}}$=200 GeV

    CERN Document Server

    Adare, A; Ajitanand, N N; Akiba, Y; Akimoto, R; Al-Bataineh, H; Al-Ta'ani, H; Alexander, J; Andrews, K R; Angerami, A; Aoki, K; Apadula, N; Appelt, E; Aramaki, Y; Armendariz, R; Aschenauer, E C; Atomssa, E T; Averbeck, R; Awes, T C; Azmoun, B; Babintsev, V; Bai, M; Baksay, G; Baksay, L; Bannier, B; Barish, K N; Bassalleck, B; Basye, A T; Bathe, S; Baublis, V; Baumann, C; Bazilevsky, A; Belikov, S; Belmont, R; Ben-Benjamin, J; Bennett, R; Bhom, J H; Blau, D S; Bok, J S; Boyle, K; Brooks, M L; Broxmeyer, D; Buesching, H; Bumazhnov, V; Bunce, G; Butsyk, S; Campbell, S; Caringi, A; Castera, P; Chen, C -H; Chi, C Y; Chiu, M; Choi, I J; Choi, J B; Choudhury, R K; Christiansen, P; Chujo, T; Chung, P; Chvala, O; Cianciolo, V; Citron, Z; Cole, B A; del Valle, Z Conesa; Connors, M; Csanád, M; Csörgő, T; Dahms, T; Dairaku, S; Danchev, I; Das, K; Datta, A; David, G; Dayananda, M K; Denisov, A; Deshpande, A; Desmond, E J; Dharmawardane, K V; Dietzsch, O; Dion, A; Donadelli, M; Drapier, O; Drees, A; Drees, K A; Durham, J M; Durum, A; Dutta, D; D'Orazio, L; Edwards, S; Efremenko, Y V; Ellinghaus, F; Engelmore, T; Enokizono, A; En'yo, H; Esumi, S; Fadem, B; Fields, D E; Finger, M; Jr., \\,; Fleuret, F; Fokin, S L; Fraenkel, Z; Frantz, J E; Franz, A; Frawley, A D; Fujiwara, K; Fukao, Y; Fusayasu, T; Gal, C; Garishvili, I; Glenn, A; Gong, H; Gong, X; Gonin, M; Goto, Y; de Cassagnac, R Granier; Grau, N; Greene, S V; Grim, G; Perdekamp, M Grosse; Gunji, T; Guo, L; Gustafsson, H -Å; Haggerty, J S; Hahn, K I; Hamagaki, H; Hamblen, J; Han, R; Hanks, J; Harper, C; Hashimoto, K; Haslum, E; Hayano, R; He, X; Heffner, M; Hemmick, T K; Hester, T; Hill, J C; Hohlmann, M; Hollis, R S; Holzmann, W; Homma, K; Hong, B; Horaguchi, T; Hori, Y; Hornback, D; Huang, S; Ichihara, T; Ichimiya, R; Iinuma, H; Ikeda, Y; Imai, K; Inaba, M; Iordanova, A; Isenhower, D; Ishihara, M; Issah, M; Ivanischev, D; Iwanaga, Y; Jacak, B V; Jia, J; Jiang, X; Jin, J; John, D; Johnson, B M; Jones, T; Joo, K S; Jouan, D; Jumper, D S; Kajihara, F; Kamin, J; Kaneti, S; Kang, B H; Kang, J H; Kang, J S; Kapustinsky, J; Karatsu, K; Kasai, M; Kawall, D; Kawashima, M; Kazantsev, A V; Kempel, T; Khanzadeev, A; Kijima, K M; Kikuchi, J; Kim, A; Kim, B I; Kim, D J; Kim, E -J; Kim, Y -J; Kim, Y K; Kinney, E; Kiss, Á; Kistenev, E; Kleinjan, D; Kline, P; Kochenda, L; Komkov, B; Konno, M; Koster, J; Kotov, D; Král, A; Kravitz, A; Kunde, G J; Kurita, K; Kurosawa, M; Kwon, Y; Kyle, G S; Lacey, R; Lai, Y S; Lajoie, J G; Lebedev, A; Lee, D M; Lee, J; Lee, K B; Lee, K S; Lee, S H; Lee, S R; Leitch, M J; Leite, M A L; Li, X; Lichtenwalner, P; Liebing, P; Lim, S H; Levy, L A Linden; Liška, T; Liu, H; Liu, M X; Love, B; Lynch, D; Maguire, C F; Makdisi, Y I; Malik, M D; Manion, A; Manko, V I; Mannel, E; Mao, Y; Masui, H; Matathias, F; McCumber, M; McGaughey, P L; McGlinchey, D; McKinney, C; Means, N; Mendoza, M; Meredith, B; Miake, Y; Mibe, T; Mignerey, A C; Miki, K; Milov, A; Mitchell, J T; Miyachi, Y; Mohanty, A K; Moon, H J; Morino, Y; Morreale, A; Morrison, D P; Motschwiller, S; Moukhanova, T V; Murakami, T; Murata, J; Nagamiya, S; Nagle, J L; Naglis, M; Nagy, M I; Nakagawa, I; Nakamiya, Y; Nakamura, K R; Nakamura, T; Nakano, K; Nam, S; Newby, J; Nguyen, M; Nihashi, M; Nouicer, R; Nyanin, A S; Oakley, C; O'Brien, E; Oda, S X; Ogilvie, C A; Oka, M; Okada, K; Onuki, Y; Oskarsson, A; Ouchida, M; Ozawa, K; Pak, R; Pantuev, V; Papavassiliou, V; Park, B H; Park, I H; Park, S K; Park, W J; Pate, S F; Patel, L; Pei, H; Peng, J -C; Pereira, H; Peressounko, D Yu; Petti, R; Pinkenburg, C; Pisani, R P; Proissl, M; Purschke, M L; Qu, H; Rak, J; Ravinovich, I; Read, K F; Rembeczki, S; Reygers, K; Riabov, V; Riabov, Y; Richardson, E; Roach, D; Roche, G; Rolnick, S D; Rosati, M; Rosen, C A; Rosendahl, S S E; Ružička, P; Sahlmueller, B; Saito, N; Sakaguchi, T; Sakashita, K; Samsonov, V; Sano, S; Sarsour, M; Sato, T; Savastio, M; Sawada, S; Sedgwick, K; Seele, J; Seidl, R; Seto, R; Sharma, D; Shein, I; Shibata, T -A; Shigaki, K; Shim, H H; Shimomura, M; Shoji, K; Shukla, P; Sickles, A; Silva, C L; Silvermyr, D; Silvestre, C; Sim, K S; Singh, B K; Singh, C P; Singh, V; Slunečka, M; Sodre, T; Soltz, R A; Sondheim, W E; Sorensen, S P; Sourikova, I V; Stankus, P W; Stenlund, E; Stoll, S P; Sugitate, T; Sukhanov, A; Sun, J; Sziklai, J; Takagui, E M; Takahara, A; Taketani, A; Tanabe, R; Tanaka, Y; Taneja, S; Tanida, K; Tannenbaum, M J; Tarafdar, S; Taranenko, A; Tennant, E; Themann, H; Thomas, D; Thomas, T L; Togawa, M; Toia, A; Tomášek, L; Tomášek, M; Torii, H; Towell, R S; Tserruya, I; Tsuchimoto, Y; Utsunomiya, K; Vale, C; Valle, H; van Hecke, H W; Vazquez-Zambrano, E; Veicht, A; Velkovska, J; Vértesi, R; Virius, M; Vossen, A; Vrba, V; Vznuzdaev, E; Wang, X R; Watanabe, D; Watanabe, K; Watanabe, Y; Watanabe, Y S; Wei, F; Wei, R; Wessels, J; White, S N; Winter, D; Woody, C L; Wright, R M; Wysocki, M

    2014-01-01

    We present azimuthal angular correlations between charged hadrons and energy deposited in calorimeter towers in central $d$$+$Au and minimum bias $p$$+$$p$ collisions at \\sqsn=200 GeV. The charged hadron is measured at midrapidity $|\\eta|$ 2.75 is observed in $d$$+$Au collisions. Using the event plane method applied to the Au-going energy distribution, we extract the anisotropy strength $v_2$ for inclusive charged hadrons at midrapidity up to $p_T=$ 4.5 GeV/$c$. We also present the measurement of $v_2$ for identified $\\pi^{\\pm}$ and (anti)protons in central $d$$+$Au collisions, and observe a mass-ordering pattern similar to that seen in heavy ion collisions. These results are compared with viscous hydrodynamic calculations and measurements from $p$$+$Pb at \\sqsn=5.02 TeV. The magnitude of the mass-ordering in $d$$+$Au is found to be smaller than that in $p$$+$Pb collisions, which may indicate smaller radial flow in lower energy $d$$+$Au collisions.

  3. Reaction dynamics and proton coupled electron transfer: studies of tyrosine-based charge transfer in natural and biomimetic systems.

    Science.gov (United States)

    Barry, Bridgette A

    2015-01-01

    In bioenergetic reactions, electrons are transferred long distances via a hopping mechanism. In photosynthesis and DNA synthesis, the aromatic amino acid residue, tyrosine, functions as an intermediate that is transiently oxidized and reduced during long distance electron transfer. At physiological pH values, oxidation of tyrosine is associated with a deprotonation of the phenolic oxygen, giving rise to a proton coupled electron transfer (PCET) reaction. Tyrosine-based PCET reactions are important in photosystem II, which carries out the light-induced oxidation of water, and in ribonucleotide reductase, which reduces ribonucleotides to form deoxynucleotides. Photosystem II contains two redox-active tyrosines, YD (Y160 in the D2 polypeptide) and YZ (Y161 in the D1 polypeptide). YD forms a light-induced stable radical, while YZ functions as an essential charge relay, oxidizing the catalytic Mn₄CaO₅ cluster on each of four photo-oxidation reactions. In Escherichia coli class 1a RNR, the β2 subunit contains the radical initiator, Y122O•, which is reversibly reduced and oxidized in long range electron transfer with the α2 subunit. In the isolated E. coli β2 subunit, Y122O• is a stable radical, but Y122O• is activated for rapid PCET in an α2β2 substrate/effector complex. Recent results concerning the structure and function of YD, YZ, and Y122 are reviewed here. Comparison is made to recent results derived from bioengineered proteins and biomimetic compounds, in which tyrosine-based charge transfer mechanisms have been investigated. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Remarks on long range interactions in simulations

    Energy Technology Data Exchange (ETDEWEB)

    Pollock, E L

    1999-08-11

    Long range interactions in periodic systems should be treated using the Ewald potential. For systems larger than a few hundred particles this is best calculated using the particle-particle, particle-mesh (P3M) method.

  5. Remarks on long range interactions in simulations

    Energy Technology Data Exchange (ETDEWEB)

    Pollock, E L

    1999-08-11

    Long range interactions in periodic systems should be treated using the Ewald potential. For systems larger than a few hundred particles this is best calculated using the particle-particle, particle-mesh (P3M) method.

  6. Long-Range Nondestructive Testing System Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This proposal is for the development of a long range, multi-point non-destructive system for the detection of subsurface flaws in metallic and composite materials of...

  7. Proton transfer in liquid water confined inside graphene slabs.

    Science.gov (United States)

    Tahat, Amani; Martí, Jordi

    2015-09-01

    The microscopic structure and dynamics of an excess proton in water constrained in narrow graphene slabs between 0.7 and 3.1 nm wide has been studied by means of a series of molecular dynamics simulations. Interaction of water and carbon with the proton species was modeled using a multistate empirical valence bond Hamiltonian model. The analysis of the effects of confinement on proton solvation structure and on its dynamical properties has been considered for varying densities. The system is organized in one interfacial and a bulk-like region, both of variable size. In the widest interplate separations, the lone proton shows a marked tendency to place itself in the bulk phase of the system, due to the repulsive interaction with the carbon atoms. However, as the system is compressed and the proton is forced to move to the vicinity of graphene walls it moves closer to the interface, producing a neat enhancement of the local structure. We found a marked slowdown of proton transfer when the separation of the two graphene plates is reduced. In the case of lowest distances between graphene plates (0.7 and 0.9 nm), only one or two water layers persist and the two-dimensional character of water structure becomes evident. By means of spectroscopical analysis, we observed the persistence of Zundel and Eigen structures in all cases, although at low interplate separations a signature frequency band around 2500 cm^{-1} suffers a blue shift and moves to characteristic values of asymmetric hydronium ion vibrations, indicating some unstability of the typical Zundel-Eigen moieties and their eventual conversion to a single hydronium species solvated by water.

  8. Proton Linear Energy Transfer measurement using Emulsion Cloud Chamber

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Jae-ik [Proton Therapy Center, National Cancer Center (Korea, Republic of); Division of Heavy Ion Clinical Research, Korea Institute of Radiological & Medical Sciences (KIRAMS), Seoul (Korea, Republic of); Park, Seyjoon [Department of Radiation Oncology, Samsung Medical Center, Sungkyunkwan University, School of Medicine, Seoul (Korea, Republic of); Kim, Haksoo; Kim, Meyoung [Proton Therapy Center, National Cancer Center (Korea, Republic of); Jeong, Chiyoung [Department of Radiation Oncology, Asan Medical Center, University of Ulsan College of Medicine, Seoul (Korea, Republic of); Cho, Sungkoo [Department of Radiation Oncology, Samsung Medical Center, Sungkyunkwan University, School of Medicine, Seoul (Korea, Republic of); Lim, Young Kyung; Shin, Dongho [Proton Therapy Center, National Cancer Center (Korea, Republic of); Lee, Se Byeong, E-mail: sblee@ncc.re.kr [Proton Therapy Center, National Cancer Center (Korea, Republic of); Morishima, Kunihiro; Naganawa, Naotaka; Sato, Osamu [Department of Physics, Nagoya University, Nagoya (Japan); Kwak, Jungwon [Department of Radiation Oncology, Asan Medical Center, University of Ulsan College of Medicine, Seoul (Korea, Republic of); Kim, Sung Hyun [Center for Underground Physics, Institute for Basic Science (IBS), Daejeon (Korea, Republic of); Cho, Jung Sook [Department of refinement education, Dongseo University, Busan (Korea, Republic of); Ahn, Jung Keun [Department of Physics, Korea University, Seoul (Korea, Republic of); Kim, Ji Hyun; Yoon, Chun Sil [Gyeongsang National University, Jinju (Korea, Republic of); Incerti, Sebastien [CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Université Bordeaux 1, CENBG, UMR 5797, F-33170 Gradignan (France)

    2015-04-15

    This study proposes to determine the correlation between the Volume Pulse Height (VPH) measured by nuclear emulsion and Linear Energy Transfer (LET) calculated by Monte Carlo simulation based on Geant4. The nuclear emulsion was irradiated at the National Cancer Center (NCC) with a therapeutic proton beam and was installed at 5.2 m distance from the beam nozzle structure with various thicknesses of water-equivalent material (PMMA) blocks to position with specific positions along the Bragg curve. After the beam exposure and development of the emulsion films, the films were scanned by S-UTS developed in Nagoya University. The proton tracks in the scanned films were reconstructed using the ‘NETSCAN’ method. Through this procedure, the VPH can be derived from each reconstructed proton track at each position along the Bragg curve. The VPH value indicates the magnitude of energy loss in proton track. By comparison with the simulation results obtained using Geant4, we found the correlation between the LET calculated by Monte Carlo simulation and the VPH measured by the nuclear emulsion.

  9. Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube.

    Science.gov (United States)

    Duster, Adam W; Lin, Hai

    2017-09-14

    Recently, a collective variable "proton indicator" was purposed for tracking an excess proton solvated in bulk water in molecular dynamics simulations. In this work, we demonstrate the feasibility of utilizing the position of this proton indicator as a reaction coordinate to model an excess proton migrating through a hydrophobic carbon nanotube in combined quantum-mechanics/molecular-mechanics simulations. Our results indicate that applying a harmonic restraint to the proton indicator in the bulk solvent near the nanotube pore entrance leads to the recruitment of water molecules into the pore. This is consistent with an earlier study that employed a multistate empirical valence bond potential and a different representation (center of excess charge) of the proton. We attribute this water recruitment to the delocalized nature of the solvated proton, which prefers to be in high-dielectric bulk solvent. While water recruitment into the pore is considered an artifact in the present simulations (because of the artificially imposed restraint on the proton), if the proton were naturally restrained, it could assist in building water wires prior to proton transfer through the pore. The potential of mean force for a proton translocation through the water-filled pore was computed by umbrella sampling, where the bias potentials were applied to the proton indicator. The free energy curve and barrier heights agree reasonably with those in the literature. The results suggest that the proton indicator can be used as a reaction coordinate in simulations of proton transport in confined environments.

  10. Dual Fluorescence in GFP Chromophore Analogues: Chemical Modulation of Charge Transfer and Proton Transfer Bands.

    Science.gov (United States)

    Chatterjee, Tanmay; Mandal, Mrinal; Das, Ananya; Bhattacharyya, Kalishankar; Datta, Ayan; Mandal, Prasun K

    2016-04-14

    Dual fluorescence of GFP chromophore analogues has been observed for the first time. OHIM (o-hydroxy imidazolidinone) shows only a charge transfer (CT) band, CHBDI (p-cyclicamino o-hydroxy benzimidazolidinone) shows a comparable intensity CT and PT (proton transfer) band, and MHBDI (p-methoxy o-hydroxy benzimidazolidinone) shows a higher intensity PT band. It could be shown that the differential optical behavior is not due to conformational variation in the solid or solution phase. Rather, control of the excited state electronic energy level and excited state acidity constant by functional group modification could be shown to be responsible for the differential optical behavior. Chemical modification-induced electronic control over the relative intensity of the charge transfer and proton transfer bands could thus be evidenced. Support from single-crystal X-ray structure, NMR, femtosecond to nanosecond fluorescence decay analysis, and TDDFT-based calculation provided important information and thus helped us understand the photophysics better.

  11. Photon assisted long-range tunneling

    Energy Technology Data Exchange (ETDEWEB)

    Gallego-Marcos, Fernando; Sánchez, Rafael; Platero, Gloria [Instituto de Ciencia de Materiales, CSIC, Cantoblanco, 28049 Madrid (Spain)

    2015-03-21

    We analyze long-range transport through an ac driven triple quantum dot with a single electron. Resonant transitions between separated and detuned dots are mediated by the exchange of n photons with the time-dependent field. An effective model is proposed in terms of second order (cotunneling) processes which dominate the long-range transport between the edge quantum dots. The ac field renormalizes the inter dot hopping, modifying the level hybridization. It results in a non-trivial behavior of the current with the frequency and amplitude of the external ac field.

  12. Umbrella sampling of proton transfer in a creatine-water system

    Science.gov (United States)

    Ivchenko, Olga; Bachert, Peter; Imhof, Petra

    2014-04-01

    Proton transfer reactions are among the most common processes in chemistry and biology. Proton transfer between creatine and surrounding solvent water is underlying the chemical exchange saturation transfer used as a contrast in magnetic resonance imaging. The free energy barrier, determined by first-principles umbrella sampling simulations (EaDFT 3 kcal/mol) is in the same order of magnitude as the experimentally obtained activation energy. The underlying mechanism is a first proton transfer from the guanidinium group to the water pool, followed by a second transition where a proton is "transferred back" from the nearest water molecule to the deprotonated nitrogen atom of creatine.

  13. Resources and Long-Range Forecasts

    Science.gov (United States)

    Smith, Waldo E.

    1973-01-01

    The author argues that forecasts of quick depletion of resources in the environment as a result of overpopulation and increased usage may not be free from error. Ignorance still exists in understanding the recovery mechanisms of nature. Long-range forecasts are likely to be wrong in such situations. (PS)

  14. Resources and Long-Range Forecasts

    Science.gov (United States)

    Smith, Waldo E.

    1973-01-01

    The author argues that forecasts of quick depletion of resources in the environment as a result of overpopulation and increased usage may not be free from error. Ignorance still exists in understanding the recovery mechanisms of nature. Long-range forecasts are likely to be wrong in such situations. (PS)

  15. Long-range coherent energy transport in Photosystem II

    CERN Document Server

    Roden, Jan J J; Whaley, K Birgitta

    2015-01-01

    We simulate the long-range inter-complex electronic energy transfer in Photosystem II -- from the antenna complex, via a core complex, to the reaction center -- using a non-Markovian (ZOFE) quantum master equation description that allows us to quantify the electronic coherence involved in the energy transfer. We identify the pathways of the energy transfer in the network of coupled chromophores, using a description based on excitation probability currents. We investigate how the energy transfer depends on the initial excitation -- localized, coherent initial excitation versus delocalized, incoherent initial excitation -- and find that the energy transfer is remarkably robust with respect to such strong variations of the initial condition. To explore the importance of vibrationally enhanced transfer and to address the question of optimization in the system parameters, we vary the strength of the coupling between the electronic and the vibrational degrees of freedom. We find that the original parameters lie in ...

  16. Proton transfer pathways in an aspartate-water cluster sampled by a network of discrete states

    Science.gov (United States)

    Reidelbach, Marco; Betz, Fridtjof; Mäusle, Raquel Maya; Imhof, Petra

    2016-08-01

    Proton transfer reactions are complex transitions due to the size and flexibility of the hydrogen-bonded networks along which the protons may ;hop;. The combination of molecular dynamics based sampling of water positions and orientations with direct sampling of proton positions is an efficient way to capture the interplay of these degrees of freedom in a transition network. The energetically most favourable pathway in the proton transfer network computed for an aspartate-water cluster shows the pre-orientation of water molecules and aspartate side chains to be a pre-requisite for the subsequent concerted proton transfer to the product state.

  17. High Energy Proton-Proton Elastic Scattering for Large Momentum Transfers and Van der Waals Type Model

    Science.gov (United States)

    Aleem, F.

    1980-03-01

    The most recent measurements of the angular distribution in proton-proton elastic scattering at sqrt{s}=27.4, 45 and 62GeV with squared four momentum transfer, -t, extending up to 14(GeV/c)2, have been explained using Van der Waals type model.

  18. Assessment of charge-transfer excitations with time-dependent, range-separated density functional theory based on long-range MP2 and multiconfigurational self- consistent field wave functions

    DEFF Research Database (Denmark)

    Hedegård, Erik D.; Jensen, Hans Jørgen Aagaard; Knecht, Stefan;

    2013-01-01

    formulation of multi-determinantal TD-DFT schemes where excitation classes, which are absent in conventional TD-DFT spectra (like for example double excitations), can be addressed. This paper investigates the combination of both the long-range Multi-Configuration Self-Consistent Field (MCSCF) and Second Order...... TD-MC-srDFT and performs slightly better against the reference data for this small subset. Beyond the proof-of-principle calculations comprising the first part of this contribution, we additionally studied the low-lying singlet excited states (S1 and S2) of the retinal chromophore. The chromophore...... displays multireference character in the ground state and both excited states exhibit considerable double excitation character, which in turn cannot be described within standard TD-DFT, due to the adiabatic approximation. However, a TD-MC-srDFT approach can account for the multireference character...

  19. Long-Range Order in β Brass

    DEFF Research Database (Denmark)

    Norvell, J.C.; Als-Nielsen, Jens Aage

    1970-01-01

    The long-range order parameter M of β brass has been determined from measurements of the intensity of superlattice reflections of Bragg-scattered neutrons. Over the whole temperature range T=300 °K to T=Tc=736 °K, the data are in remarkable agreement with the prediction for the compressible Ising...... bcc lattice with only nearest-neighbor interactions. © 1970 The American Physical Society......The long-range order parameter M of β brass has been determined from measurements of the intensity of superlattice reflections of Bragg-scattered neutrons. Over the whole temperature range T=300 °K to T=Tc=736 °K, the data are in remarkable agreement with the prediction for the compressible Ising...

  20. Analytical calculation of proton linear energy transfer in voxelized geometries including secondary protons.

    Science.gov (United States)

    Sanchez-Parcerisa, D; Cortés-Giraldo, M A; Dolney, D; Kondrla, M; Fager, M; Carabe, A

    2016-02-21

    In order to integrate radiobiological modelling with clinical treatment planning for proton radiotherapy, we extended our in-house treatment planning system FoCa with a 3D analytical algorithm to calculate linear energy transfer (LET) in voxelized patient geometries. Both active scanning and passive scattering delivery modalities are supported. The analytical calculation is much faster than the Monte-Carlo (MC) method and it can be implemented in the inverse treatment planning optimization suite, allowing us to create LET-based objectives in inverse planning. The LET was calculated by combining a 1D analytical approach including a novel correction for secondary protons with pencil-beam type LET-kernels. Then, these LET kernels were inserted into the proton-convolution-superposition algorithm in FoCa. The analytical LET distributions were benchmarked against MC simulations carried out in Geant4. A cohort of simple phantom and patient plans representing a wide variety of sites (prostate, lung, brain, head and neck) was selected. The calculation algorithm was able to reproduce the MC LET to within 6% (1 standard deviation) for low-LET areas (under 1.7 keV μm(-1)) and within 22% for the high-LET areas above that threshold. The dose and LET distributions can be further extended, using radiobiological models, to include radiobiological effectiveness (RBE) calculations in the treatment planning system. This implementation also allows for radiobiological optimization of treatments by including RBE-weighted dose constraints in the inverse treatment planning process.

  1. Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ailin; Yan, Tianying; Shen, Panwen [Department of Material Chemistry, Institute of New Energy Material Chemistry, Nankai University, Tianjin, 300071 (China)

    2011-02-01

    Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer. (author)

  2. Long-Range Connections in Transportation Networks

    CERN Document Server

    Viana, Matheus P

    2010-01-01

    Since its recent introduction, the small-world effect has been identified in several important real-world systems. Frequently, it is a consequence of the existence of a few long-range connections, which dominate the original regular structure of the systems and implies each node to become accessible from other nodes after a small number of steps, typically of order $\\ell \\propto \\log N$. However, this effect has been observed in pure-topological networks, where the nodes have no spatial coordinates. In this paper, we present an alalogue of small-world effect observed in real-world transportation networks, where the nodes are embeded in a hree-dimensional space. Using the multidimensional scaling method, we demonstrate how the addition of a few long-range connections can suubstantially reduce the travel time in transportation systems. Also, we investigated the importance of long-range connections when the systems are under an attack process. Our findings are illustrated for two real-world systems, namely the L...

  3. Long-range hybrid wedge plasmonic waveguide.

    Science.gov (United States)

    Zhang, Zhonglai; Wang, Jian

    2014-11-03

    We design a novel long-range hybrid wedge plasmonic (LRHWP) waveguide composed of two identical dielectric nanowires symmetrically placed on two opposed wedges of a diamond shaped metal wire. With strong coupling between the dielectric nanowire mode and long-range surface plasmon polariton (SPP) mode, both deep subwavelength mode confinement and low propagation loss are achieved. On one hand, when compared to the previous long-range hybrid SPP waveguide, LRHWP waveguide can achieve smaller mode size with similar propagation length; on the other hand, when compared to the previous hybrid wedge SPP waveguide, LRHWP waveguide can provide an order of magnitude longer propagation length with similar level of mode confinement. The designed LRHWP waveguide also features an overall advantage of one-order improvement of Figure of Merit. We further evaluate in detail the impacts of possible practical fabrication imperfections on the mode properties. The obtained results of mode properties show that the proposed LRHWP waveguide with an optimized wedge tip angle of 140 degree is fairly tolerant to practical fabrication errors in geometry parameters such as misalignment in the horizontal direction, asymmetry in the vertical direction, variation of wedge tip angle, tilt or rotation of metal wire, and variation of wedge tip curvature radius.

  4. Reconfigurable long-range phonon dynamics in optomechanical arrays

    CERN Document Server

    Xuereb, André; Pupillo, Guido; Paternostro, Mauro; Dantan, Aurélien

    2013-01-01

    We investigate periodic optomechanical arrays as reconfigurable platforms for engineering the coupling between multiple mechanical and electromagnetic modes and for exploring many-body phonon dynamics. Exploiting structural resonances in the coupling between light fields and collective motional modes of the array, we show that tunable effective long-range interactions between mechanical modes can be achieved. This paves the way towards the implementation of controlled phononic walks and heat transfer on densely-connected graphs as well as the coherent transfer of excitations between distant elements of optomechanical arrays.

  5. Real-time simulations of photoinduced coherent charge transfer and proton-coupled electron transfer.

    Science.gov (United States)

    Eisenmayer, Thomas J; Buda, Francesco

    2014-10-20

    Photoinduced electron transfer (ET) and proton-coupled electron transfer (PCET) are fundamental processes in natural phenomena, most noticeably in photosynthesis. Time-resolved spectroscopic evidence of coherent oscillatory behavior associated with these processes has been reported both in complex biological environments, as well as in biomimetic models for artificial photosynthesis. Here, we consider a few biomimetic models to investigate these processes in real-time simulations based on ab initio molecular dynamics and Ehrenfest dynamics. This allows for a detailed analysis on how photon-to-charge conversion is promoted by a coupling of the electronic excitation with specific vibrational modes and with proton displacements. The ET process shows a characteristic coherence that is linked to the nuclear motion at the interface between donor and acceptor. We also show real-time evidence of PCET in a benzimidazole-phenol redox relay. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Single mutations that redirect internal proton transfer in the ba3 oxidase from Thermus thermophilus.

    Science.gov (United States)

    Smirnova, Irina; Chang, Hsin-Yang; von Ballmoos, Christoph; Ädelroth, Pia; Gennis, Robert B; Brzezinski, Peter

    2013-10-08

    The ba3-type cytochrome c oxidase from Thermus thermophilus is a membrane-bound proton pump. Results from earlier studies have shown that with the aa3-type oxidases proton uptake to the catalytic site and "pump site" occurs simultaneously. However, with ba3 oxidase the pump site is loaded before proton transfer to the catalytic site because the proton transfer to the latter is slower than that with the aa3 oxidases. In addition, the timing of formation and decay of catalytic intermediates is different in the two types of oxidases. In the present study, we have investigated two mutant ba3 CytcOs in which residues of the proton pathway leading to the catalytic site as well as the pump site were exchanged, Thr312Val and Tyr244Phe. Even though ba3 CytcO uses only a single proton pathway for transfer of the substrate and "pumped" protons, the amino-acid residue substitutions had distinctly different effects on the kinetics of proton transfer to the catalytic site and the pump site. The results indicate that the rates of these reactions can be modified independently by replacement of single residues within the proton pathway. Furthermore, the data suggest that the Thr312Val and Tyr244Phe mutations interfere with a structural rearrangement in the proton pathway that is rate limiting for proton transfer to the catalytic site.

  7. Proton Transfers at the Air-Water Interface

    Science.gov (United States)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the

  8. Ultrafast proton coupled electron transfer (PCET dynamics in 9-anthranol-aliphatic amine system

    Directory of Open Access Journals (Sweden)

    Nibbering Erik T. J.

    2013-03-01

    Full Text Available Femtosecond infrared absorption studies strongly suggest that photoexcited 9-anthranol takes part in an ultrafast electron transfer (ET reaction in electron-donating triethylamine solvent, but that ultrafast proton coupled electron transfer (PCET occurs in diethylamine solvent.

  9. Multichannel long-range Rydberg molecules

    CERN Document Server

    Eiles, Matthew T

    2015-01-01

    A generalized class of ultra-long-range Rydberg molecules is proposed which consist of a multichannel Rydberg atom whose outermost electron creates a chemical bond with a distant ground state atom. Such multichannel Rydberg molecules exhibit favorable properties for laser excitation, because states exist where the quantum defect varies strongly with the principal quantum number. The resulting occurrence of near degeneracies with states of high orbital angular momentum promotes the admixture of low $l$ into the high $l$ deeply bound `trilobite' molecule states, thereby circumventing the usual difficulty posed by electric dipole selection rules. Such states also can exhibit multi-scale binding possibilities that could present novel options for quantum manipulation.

  10. Long-range laser-illuminated imaging

    Science.gov (United States)

    Dayton, David C.; Browne, Stephen L.; Sandven, Steven C.; Gonglewski, John D.; Gallegos, Joe; Shilko, Michael L., Sr.

    2000-11-01

    We demonstrate the utility of laser illuminated imaging for clandestine night time surveillance from a simulated airborne platform at standoff ranges in excess 20 km. In order to reduce the necessary laser per pulse energy required for illumination at such long ranges, and to mitigate atmospheric turbulence effects on image resolution, we have investigated a unique multi-frame post-processing technique. It is shown that in the presence of atmospheric turbulence and coherent speckle effects, this approach can produce superior results to conventional scene flood illumination.

  11. Long range predictability of atmospheric flows

    Directory of Open Access Journals (Sweden)

    R. Robert

    2001-01-01

    Full Text Available In the light of recent advances in 2D turbulence, we investigate the long range predictability problem of atmospheric flows. Using 2D Euler equations, we show that the full nonlinearity acting on a large number of degrees of freedom can, paradoxically, improve the predictability of the large scale motion, giving a picture opposite to the one largely popularized by Lorenz: a small local perturbation of the atmosphere will progressively gain larger and larger scales by nonlinear interaction and will finally cause large scale change in the atmospheric flow.

  12. New Oxime Ligand with Potential for Proton-Coupled Electron-Transfer Reactions

    DEFF Research Database (Denmark)

    Deville, Claire; Sundberg, Jonas; McKenzie, Christine Joy

    Proton-coupled electron-transfer (PCET) is found in a range of oxidation-reduction reactions in biology.1 This mechanism is of interest for applications in energy conversion processes. The PCET reaction has been shown to be facilitated when the proton is transferred to an intramolecular basic sit...

  13. Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis

    Science.gov (United States)

    2016-07-08

    Seesaw: How Increased Hydrogen Bonding Hinders Excited State Proton Transfer, R. Welsch , E. Driscoll, J. Dawlaty, T. Miller III, (submitted) 9. Coherent...7, 2093 (2016) 8.A Molecular Seesaw: How Increased Hydrogen Bonding Hinders Excited State Proton Transfer, R. Welsch , E. Driscoll, J. Dawlaty, T

  14. Proton transfer in ba(3) cytochrome c oxidase from Thermus thermophilus.

    Science.gov (United States)

    von Ballmoos, Christoph; Adelroth, Pia; Gennis, Robert B; Brzezinski, Peter

    2012-04-01

    The respiratory heme-copper oxidases catalyze reduction of O(2) to H(2)O, linking this process to transmembrane proton pumping. These oxidases have been classified according to the architecture, location and number of proton pathways. Most structural and functional studies to date have been performed on the A-class oxidases, which includes those that are found in the inner mitochondrial membrane and bacteria such as Rhodobacter sphaeroides and Paracoccus denitrificans (aa(3)-type oxidases in these bacteria). These oxidases pump protons with a stoichiometry of one proton per electron transferred to the catalytic site. The bacterial A-class oxidases use two proton pathways (denoted by letters D and K, respectively), for the transfer of protons to the catalytic site, and protons that are pumped across the membrane. The B-type oxidases such as, for example, the ba(3) oxidase from Thermus thermophilus, pump protons with a lower stoichiometry of 0.5 H(+)/electron and use only one proton pathway for the transfer of all protons. This pathway overlaps in space with the K pathway in the A class oxidases without showing any sequence homology though. Here, we review the functional properties of the A- and the B-class ba(3) oxidases with a focus on mechanisms of proton transfer and pumping. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Synthetic Applications of Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Gentry, Emily C; Knowles, Robert R

    2016-08-16

    Redox events in which an electron and proton are exchanged in a concerted elementary step are commonly referred to as proton-coupled electron transfers (PCETs). PCETs are known to operate in numerous important biological redox processes, as well as recent inorganic technologies for small molecule activation. These studies suggest that PCET catalysis might also function as a general mode of substrate activation in organic synthesis. Over the past three years, our group has worked to advance this hypothesis and to demonstrate the synthetic utility of PCET through the development of novel catalytic radical chemistries. The central aim of these efforts has been to demonstrate the ability of PCET to homolytically activate a wide variety of common organic functional groups that are energetically inaccessible using known molecular H atom transfer catalysts. To do so, we made use of a simple formalism first introduced by Mayer and co-workers that allowed us to predict the thermodynamic capacity of any oxidant/base or reductant/acid pair to formally add or remove H· from a given substrate. With this insight, we were able to rationally select catalyst combinations thermodynamically competent to homolyze the extraordinarily strong E-H σ-bonds found in many common protic functional groups (BDFEs > 100 kcal/mol) or to form unusually weak bonds to hydrogen via the reductive action of common organic π-systems (BDFEs < 35 kcal/mol). These ideas were reduced to practice through the development of new catalyst systems for reductive PCET activations of ketones and oxidative PCET activation of amide N-H bonds to directly furnish reactive ketyl and amidyl radicals, respectively. In both systems, the reaction outcomes were found to be successfully predicted using the effective bond strength formalism, suggesting that these simple thermochemical considerations can provide useful and actionable insights into PCET reaction design. The ability of PCET catalysis to control

  16. Long Range Surface Plasmons in Multilayer Structures

    CERN Document Server

    Delfan, Aida

    2013-01-01

    We present a new strategy, based on a Fresnel coefficient pole analysis, for designing an asymmetric multilayer structure that supports long range surface plasmons (LRSP). We find that the electric field intensity in the metal layer of a multilayer LRSP structure can be even slightly smaller than in the metal layer of the corresponding symmetric LRSP structure, minimizing absorption losses and resulting in LRSP propagation lengths up to 2mm. With a view towards biosensing applications, we also present semi-analytic expressions for a standard surface sensing parameter in arbitrary planar resonant structures, and in particular show that for an asymmetric structure consisting of a gold film deposited on a multilayer of SiO2 and TiO2 a surface sensing parameter G = 1.28(1/nm) can be achieved.

  17. Long range correlations in DNA sequences

    CERN Document Server

    Mohanty, A K

    2002-01-01

    The so called long range correlation properties of DNA sequences are studied using the variance analyses of the density distribution of a single or a group of nucleotides in a model independent way. This new method which was suggested earlier has been applied to extract slope parameters that characterize the correlation properties for several intron containing and intron less DNA sequences. An important aspect of all the DNA sequences is the properties of complimentarity by virtue of which any two complimentary distributions (like GA is complimentary to TC or G is complimentary to ATC) have identical fluctuations at all scales although their distribution functions need not be identical. Due to this complimentarity, the famous DNA walk representation whose statistical interpretation is still unresolved is shown to be a special case of the present formalism with a density distribution corresponding to a purine or a pyrimidine group. Another interesting aspect of most of the DNA sequences is that the factorial m...

  18. Long-range interaction of anisotropic systems

    KAUST Repository

    Zhang, Junyi

    2015-02-01

    The first-order electrostatic interaction energy between two far-apart anisotropic atoms depends not only on the distance between them but also on their relative orientation, according to Rayleigh-Schrödinger perturbation theory. Using the first-order interaction energy and the continuum model, we study the long-range interaction between a pair of parallel pristine graphene sheets at zero temperature. The asymptotic form of the obtained potential density, &epsi:(D) &prop: ?D ?3 ?O(D?4), is consistent with the random phase approximation and Lifshitz theory. Accordingly, neglectance of the anisotropy, especially the nonzero first-order interaction energy, is the reason why the widely used Lennard-Jones potential approach and dispersion corrections in density functional theory give a wrong asymptotic form ε(D) &prop: ?D?4. © EPLA, 2015.

  19. Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S.

    2016-07-01

    electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

  20. Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S

    2016-07-21

    electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

  1. Proton transfer and photoluminescence intermittency of single emitters in dyed crystals.

    Science.gov (United States)

    Riley, Erin A; Hess, Chelsea M; Pioquinto, Jan Rey L; Kaminsky, Werner; Kahr, Bart; Reid, Philip J

    2013-04-25

    The role of proton transfer in the photoluminescence intermittency (PI) of single molecules of violamine R (VR) overgrown in potassium acid phthalate (KAP) crystals is evaluated in comparisons of protonated (KAP) and deuterated (DKAP) mixed crystals between 23 and 60 °C. The PI is analyzed by the construction of cumulative distribution functions that are statistically compared. We find that the on- and off-interval duration distributions change with isotopic substitution consistent with proton transfer contributing to the PI of VR. The on- and off-interval duration distributions have distinct temperature dependencies consistent with different mechanisms for dark state production and decay. Additional evidence for proton-transfer is provided by distributions of single molecule emission-energy maxima that reflect emission from protonated and deprotonated VR. A mechanism for the PI of KAP is presented, where the dark state is assigned to formation of the colorless, leuco form of VR, formed by proton transfer from VR to the KAP lattice, and decay of the dark state involves ring-opening promoted by proton transfer from KAP to VR. The distributed kinetics for dark-state production and decay are modeled using a log-normal distribution for the PI data in preference to a power-law previously assumed. A discussion of the log-normal distribution with regards to PI and proton transfer is presented.

  2. Pathways of proton transfer in the light-driven pump bacteriorhodopsin

    Science.gov (United States)

    Lanyi, J. K.

    1993-01-01

    The mechanism of proton transport in the light-driven pump bacteriorhodopsin is beginning to be understood. Light causes the all-trans to 13-cis isomerization of the retinal chromophore. This sets off a sequential and directed series of transient decreases in the pKa's of a) the retinal Schiff base, b) an extracellular proton release complex which includes asp-85, and c) a cytoplasmic proton uptake complex which includes asp-96. The timing of these pKa changes during the photoreaction cycle causes sequential proton transfers which result in the net movement of a proton across the protein, from the cytoplasmic to the extracellular surface.

  3. Stochastic processes and long range dependence

    CERN Document Server

    Samorodnitsky, Gennady

    2016-01-01

    This monograph is a gateway for researchers and graduate students to explore the profound, yet subtle, world of long-range dependence (also known as long memory). The text is organized around the probabilistic properties of stationary processes that are important for determining the presence or absence of long memory. The first few chapters serve as an overview of the general theory of stochastic processes which gives the reader sufficient background, language, and models for the subsequent discussion of long memory. The later chapters devoted to long memory begin with an introduction to the subject along with a brief history of its development, followed by a presentation of what is currently the best known approach, applicable to stationary processes with a finite second moment. The book concludes with a chapter devoted to the author’s own, less standard, point of view of long memory as a phase transition, and even includes some novel results. Most of the material in the book has not previously been publis...

  4. Long-range forecasting of intermittent streamflow

    Directory of Open Access Journals (Sweden)

    F. F. van Ogtrop

    2011-01-01

    Full Text Available Long-range forecasting of intermittent streamflow in semi-arid Australia poses a number of major challenges. One of the challenges relates to modelling zero, skewed, non-stationary, and non-linear data. To address this, a probabilistic statistical model to forecast streamflow 12 months ahead is applied to five semi-arid catchments in South Western Queensland. The model uses logistic regression through Generalised Additive Models for Location, Scale and Shape (GAMLSS to determine the probability of flow occurring in any of the systems. We then use the same regression framework in combination with a right-skewed distribution, the Box-Cox t distribution, to model the intensity (depth of the non-zero streamflows. Time, seasonality and climate indices, describing the Pacific and Indian Ocean sea surface temperatures, are tested as covariates in the GAMLSS model to make probabilistic 12-month forecasts of the occurrence and intensity of streamflow. The output reveals that in the study region the occurrence and variability of flow is driven by sea surface temperatures and therefore forecasts can be made with some skill.

  5. Long range position and Orientation Tracking System

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, G.A.; Jansen, J.F.; Burks, B.L. [and others

    1996-02-01

    The long range Position and Orientation Tracking System is an active triangulation-based system that is being developed to track a target to a resolution of 6.35 mm (0.25 in.) and 0.009{degrees}(32.4 arcseconds) over a range of 13.72 m (45 ft.). The system update rate is currently set at 20 Hz but can be increased to 100 Hz or more. The tracking is accomplished by sweeping two pairs of orthogonal line lasers over infrared (IR) sensors spaced with known geometry with respect to one another on the target (the target being a rigid body attached to either a remote vehicle or a remote manipulator arm). The synchronization and data acquisition electronics correlates the time that an IR sensor has been hit by one of the four lasers and the angle of the respective mirror at the time of the hit. This information is combined with the known geometry of the IR sensors on the target to determine position and orientation of the target. This method has the advantage of allowing the target to be momentarily lost due to occlusions and then reacquired without having to return the target to a known reference point. The system also contains a camera with operator controlled lighting in each pod that allows the target to be continuously viewed from either pod, assuming their are no occlusions.

  6. Proton-Coupled Electron Transfer: Moving Together and Charging Forward

    Energy Technology Data Exchange (ETDEWEB)

    Hammes-Schiffer, Sharon

    2015-07-22

    Proton-coupled electron transfer (PCET) is ubiquitous throughout chemistry and biology. This Perspective discusses recent advances and current challenges in the field of PCET, with an emphasis on the role of theory and computation. The fundamental theoretical concepts are summarized, and expressions for rate constants and kinetic isotope effects are provided. Computational methods for calculating reduction potentials and pKa’s for molecular electrocatalysts, as well as methods for simulating the nonadiabatic dynamics of photoinduced processes, are also described. Representative applications to PCET in solution, proteins, electrochemistry, and photoinduced processes are presented, highlighting the interplay between theoretical and experimental studies. The current challenges and suggested future directions are outlined for each type of application, concluding with an overall view to the future. The work described herein was supported by National Science Foundation Grant CHE-13-61293 (theory development), National Institutes of Health Grant GM056207 (soybean lipoxygenase), Center for Chemical Innovation of the National Science Foundation Solar Fuels Grant CHE-1305124 (cobalt catalysts), Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (nickel catalysts), and Air Force Office of Scientific Research Award No. FA9550-14-1-0295 (photoinduced PCET).

  7. Theoretical Study of the Proton Transfer in Enaminones

    Directory of Open Access Journals (Sweden)

    Rita S. Elias

    2012-01-01

    Full Text Available Problem statement: Hydrogen bonding has a vital rule to unrevealed the nature of many different interactions both in gas phase and condensed media thus it is one of the most important concepts in chemistry. Enaminoes with their ability to form intrahydrogen bonded cheated rings represent one of the suitable compounds to study such concept. Approach: The three possible tautomers of eneminones were fully optimized at several theoretical levels including B3LYP with the 6-31+G(d,p, 6-311++G(d,p and aug-cc-pVDZ basis sets as well as MP2/6-311++G(d,p level of theory. Then a search for the possible transition state between the two most stable tautomers; the ketamine and the enolimine was done at the B3LYP/6-311++G(d,p level of theory. Results: The ketamine is the most stable while the diketo is the less stable within the tautomeric mixture and the proton transfer occurs through a transition state that is energetically resemble the enolimine tautomer. Conclusion: The interconversion of the tautomers is preferable in the enolimine ketamine direction.

  8. Laser control of double proton transfer in porphycenes. Towards an ultrafast switch for photonic molecular wires

    CERN Document Server

    Abdel-Latif, Mahmoud K

    2010-01-01

    Electronic excitation energy transfer along a molecular wire depends on the relative orientation of the electronic transition dipole moments of neighboring chromophores. In porphycenes this orientation is changed upon double proton transfer in the electronic ground state. We explore the possibility to trigger such a double proton transfer reaction by means of an infrared pump-dump laser control scheme. To this end a quantum chemical characterization of an asymmetrically substituted porphycene is performed using density functional theory. Ground state geometries, the topology of the potential energy surface for double proton transfer, and S0->S1 transition energies are compared with the parent compound porphycene and a symmetric derivative. Employing a simple two-dimensional model for the double proton transfer, which incorporates sequential and concerted motions, quantum dynamics simulations of the laser driven dynamics are performed which demonstrate tautomerization control. Based on the orientation of the t...

  9. Concerted proton-coupled electron transfer from a metal-hydride complex.

    Science.gov (United States)

    Bourrez, Marc; Steinmetz, Romain; Ott, Sascha; Gloaguen, Frederic; Hammarström, Leif

    2014-02-01

    Metal hydrides are key intermediates in the catalytic reduction of protons and CO2 as well as in the oxidation of H2. In these reactions, electrons and protons are transferred to or from separate acceptors or donors in bidirectional protoncoupled electron transfer (PCET) steps. The mechanistic interpretation of PCET reactions of metal hydrides has focused on the stepwise transfer of electrons and protons. A concerted transfer may, however, occur with a lower reaction barrier and therefore proceed at higher catalytic rates. Here we investigate the feasibility of such a reaction by studying the oxidation–deprotonation reactions of a tungsten hydride complex. The rate dependence on the driving force for both electron transfer and proton transfer—employing different combinations of oxidants and bases—was used to establish experimentally the concerted, bidirectional PCET of a metal-hydride species. Consideration of the findings presented here in future catalyst designs may lead to more-efficient catalysts.

  10. Free-Energy Landscape and Proton Transfer Pathways in Oxidative Deamination by Methylamine Dehydrogenase.

    Science.gov (United States)

    Zelleke, Theodros; Marx, Dominik

    2017-01-18

    The rate-determining step in the reductive half-reaction of the bacterial enzyme methylamine dehydrogenase, which is proton abstraction from the native substrate methylamine, is investigated using accelerated QM/MM molecular dynamics simulations at room temperature. Generation of the multidimensional thermal free-energy landscape without restriction of the degrees of freedom beyond a multidimensional reaction subspace maps two rather similar pathways for the underlying proton transfer to one of two aspartate carboxyl oxygen atoms, termed OD1 and OD2, which hydrogen bond with Thr122 and Trp108, respectively. Despite significant large-amplitude motion perpendicular to the one-dimensional proton transfer coordinate, due to fluctuations of the donor-acceptor distance of about 3 Å, it is found that the one-dimensional proton transfer free-energy profiles are essentially identical to the minimum free-energy pathways on the multidimensional free-energy landscapes for both proton transfer channels. Proton transfer to one of the acceptor oxygen atoms-the OD2 site-is slightly favored in methylamine dehydrogenase by approximately 2 kcal mol(-1) , both kinetically and thermodynamically. Mechanistic analyses reveal that the hydrogen bond between Thr122β and OD1 is always present in the transition state independently of the proton transfer channel. Population analysis confirms that the electronic charge gained upon oxidation of the substrate is delocalized within the ring systems of the tryptophan tryptophylquinone cofactor.

  11. Theoretical Studies on the Hydrogen Bond Transfer and Proton Transfer between Anamorphoses of the Dihydrated Glycine Complex

    Institute of Scientific and Technical Information of China (English)

    WANG Ke-Cheng; MENG Xiang-Jun; SHI Jin; LI Bing-Huan

    2007-01-01

    The conversion between anamorphoses of the dihydrated glycine complex was studied by means of B3LYP/6-31++G**. It was found that proton transfer was accompanied by hydrogen bond transfer in the process of conversion between different kinds of anamorphoses. With proton transfer, the electrostatic action was notably increased and the hydrogen-bonding action was evidently strengthened when the dihydrated neutral glycine complex converts into dihydrated zwitterionic glycine complex. The activation energy required for hydrogen bond transfer between dihydrated neutral glycine complexes is very low (6.32 kJ·mol-1); however, the hydrogen bond transfer between dihydrated zwitterionic glycine complexes is rather difficult with the required activation energy of 13.52 kJ·mol-1 due to the relatively strong electrostatic action. The activation energy required by proton transfer is at least 27.33 kJ·mol-1, higher than that needed for hydrogen bond transfer. The activation energy for either hydrogen bond transfer or proton transfer is in the bond-energy scope of medium-strong hydrogen bond, so the four kinds of anamorphoses of the dihydrated glycine complex could convert mutually.

  12. The Phenomena of Proton Transfer from Catalytic Oxides.

    Science.gov (United States)

    Schwarz

    1999-10-01

    Chemical processes that occur at the particle aqueous interface are properly termed colloidal when the particle is a material where one or more of its three dimensions lies within the range of 1-1000 nm. Nanoparticles which include porous materials and nanostructures that meet this requirement have been the subject of investigation from researchers from a variety of disciplines and their studies have been reported in the Journal of Colloid and Interface Science as well as other archival journals for many years. The chemical process of charge development on colloidal particles is, in general, determined by a plethora of complex physico-chemical properties of the particles' surfaces exposed to the surrounding aqueous environment. The existence of surface charge plays an essential role in the dispersity, flocculation properties, ion exchange capacity, dissolution, and deposition of cations and anions of synthetic and natural materials. In particular, recent advances in catalytic science have demonstrated that the "black art" of catalyst preparation does have a scientific basis. The objective of this article is to demonstrate that surface charge development (a consequence of proton transfer) as a function of pH, the so-called master variable, can identify specific domains of charge maxima. It is found that the number and strength of charged sites can be correlated with the catalytic properties of the studied materials, even though the reaction conditions are significantly different from those under which the surface charge was measured. Such findings are essential for the establishment of design and construction protocols and prediction of the performance of catalysts. Copyright 1999 Academic Press.

  13. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    Science.gov (United States)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

  14. Using computational chemistry to understand proton transfer in Green Fluorescent Protein

    Science.gov (United States)

    Hoskin, Christa; Champion, Paul; Sage, Timothy; Benabbas, Abdelkrim; Demidov, Alexander; Salna, Bridget

    2012-02-01

    Green Fluorescent Protein has been studied experimentally by the scientific community for years yet frustratingly little is known about the underlying proton transfer process that produces the green fluorescence. We are trying to elucidate more about this process using Density Functional Theory to prepare and run various calculations on GFP that we compare with kinetics data, Raman and vibrational coherence spectra. I am building a model of wild type GFP that is realistically sized for our computational power, yet still contains key residues that might affect the proton transport process. I will compare my results to those of the E222D GFP mutant. This comparison will allow us to see any differences in energy and normal modes that give insights regarding the proton transfer process. For example, how does it depend on a variety of factors such as temperature, buffer, pH, mutations, etc.? We also plan to examine if the proton transfer propagates through the three donor-acceptor pairs of the ``proton wire'' consecutively versus the three protons on the wire transferring simultaneously. Finally, we will consider how quantum tunneling may be involved in the proton transfer.

  15. Theoretical studies on proton transfer reaction of 3(5)-substituted pyrazoles

    Indian Academy of Sciences (India)

    Alireza Najafi Chermahini; Abbas Teimouri

    2014-01-01

    The inter and intra molecular proton transfer reactions of a series of pyrazole derivatives have been studied by using density functional theory (DFT) andMP2 methods implementing 6-311++G(d,p) atomic basis set. The substituents have been selected to cover a wide range of electronic effects. Proton transfer process was studied for mechanisms including single proton transfer, double proton transfer and proton transfer assisted by a water or ammonia molecule. The results showed single proton transfer reactions for interconversion pyrazole derivatives need highest activation energies in the range of 45.7−51.59 and 49.4−53.96 kcal/mol at B3LYP and MP2 levels, respectively. It was found that for the 3-substituted pyrazoles, electron withdrawing groups form stronger dimers but in the 5-substituted tautomers electron donating groups form stronger hydrogen bond. The double proton transfer reactions between dimers were studied and transition states calculated. The ranges of activation energies were found to be 17.51−19.36 and 17.02−17.80 kcal/mol for the C → E and D → D reactions respectively. In addition, the activation energies for the proton transfer reaction assisted by water or ammonia molecules were found to be in the range of 26.62−31.78 and 17.25−22.46 kcal/mol, respectively, calculated at MP2/6-311++G(d,p) level of theory.

  16. Excited-state proton transfer from pyranine to acetate in methanol

    Indian Academy of Sciences (India)

    Sudip Kumar Mondal; Subhadip Ghosh; Kalyanasis Sahu; Pratik Sen; Kankan Bhattacharyya

    2007-03-01

    Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulphonate, HPTS) to acetate in methanol has been studied by steady-state and time-resolved fluorescence spectroscopy. The rate constant of direct proton transfer from pyranine to acetate (1) is calculated to be ∼ 1 × 109 M-1 s-1. This is slower by about two orders of magnitude than that in bulk water (8 × 1010 M-1 s-1) at 4 M acetate.

  17. Long-range intramolecular electron transfer in azurins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1989-01-01

    The Cu(II) sites of azurins, the blue single copper proteins, isolated from Pseudomonas aeruginosa and Alcaligenes spp. (Iwasaki) are reduced by CO2- radicals, produced by pulse radiolysis, in two distinct reaction steps: (i) a fast bimolecular phase, at the rates (5.0 +/- 0.8) x 10(8) M-1.s-1 (P....... aeruginosa) and (6.0 +/- 1.0) x 10(8) M-1.s-1 (Alcaligenes); (ii) a slow unimolecular phase with specific rates of 44 +/- 7 s-1 in the former and 8.5 +/- 1.5 s-1 for the latter (all at 298 K, 0.1 M ionic strength). Concomitant with the fast reduction of Cu(II), the single disulfide bridge linking cysteine-3...

  18. An S-N2-model for proton transfer in hydrogen-bonded systems

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism of proton transfer in donor-acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce...... a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use...... of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution....

  19. Proton-coupled electron transfer dynamics in the catalytic mechanism of a [NiFe]-hydrogenase.

    Science.gov (United States)

    Greene, Brandon L; Wu, Chang-Hao; McTernan, Patrick M; Adams, Michael W W; Dyer, R Brian

    2015-04-08

    The movement of protons and electrons is common to the synthesis of all chemical fuels such as H2. Hydrogenases, which catalyze the reversible reduction of protons, necessitate transport and reactivity between protons and electrons, but a detailed mechanism has thus far been elusive. Here, we use a phototriggered chemical potential jump method to rapidly initiate the proton reduction activity of a [NiFe] hydrogenase. Coupling the photochemical initiation approach to nanosecond transient infrared and visible absorbance spectroscopy afforded direct observation of interfacial electron transfer and active site chemistry. Tuning of intramolecular proton transport by pH and isotopic substitution revealed distinct concerted and stepwise proton-coupled electron transfer mechanisms in catalysis. The observed heterogeneity in the two sequential proton-associated reduction processes suggests a highly engineered protein environment modulating catalysis and implicates three new reaction intermediates; Nia-I, Nia-D, and Nia-SR(-). The results establish an elementary mechanistic understanding of catalysis in a [NiFe] hydrogenase with implications in enzymatic proton-coupled electron transfer and biomimetic catalyst design.

  20. Size-restricted proton transfer within toluene-methanol cluster ions.

    Science.gov (United States)

    Chiang, Chi-Tung; Shores, Kevin S; Freindorf, Marek; Furlani, Thomas; DeLeon, Robert L; Garvey, James F

    2008-11-20

    To understand the interaction between toluene and methanol, the chemical reactivity of [(C6H5CH3)(CH3OH) n=1-7](+) cluster ions has been investigated via tandem quadrupole mass spectrometry and through calculations. Collision Induced Dissociation (CID) experiments show that the dissociated intracluster proton transfer reaction from the toluene cation to methanol clusters, forming protonated methanol clusters, only occurs for n = 2-4. For n = 5-7, CID spectra reveal that these larger clusters have to sequentially lose methanol monomers until they reach n = 4 to initiate the deprotonation of the toluene cation. Metastable decay data indicate that for n = 3 and n = 4 (CH3OH)3H(+) is the preferred fragment ion. The calculational results reveal that both the gross proton affinity of the methanol subcluster and the structure of the cluster itself play an important role in driving this proton transfer reaction. When n = 3, the cooperative effect of the methanols in the subcluster provides the most important contribution to allow the intracluster proton transfer reaction to occur with little or no energy barrier. As n >or= 4, the methanol subcluster is able to form ring structures to stabilize the cluster structures so that direct proton transfer is not a favored process. The preferred reaction product, the (CH3OH)3H(+) cluster ion, indicates that this size-restricted reaction is driven by both the proton affinity and the enhanced stability of the resulting product.

  1. Proton-transfer reactions of acridine in water-containing ionic-liquid-rich mixtures.

    Science.gov (United States)

    Kumar, Vinod; Pandey, Ashish; Pandey, Siddharth

    2013-12-02

    To assess the potential of ionic liquids (ILs) as a solubilizing media that facilitates proton-transfer reactions, acridine prototropism is investigated using UV/Vis molecular absorbance as well as steady-state and time-resolved fluorescence with different ILs in the presence of a small amount of dilute acid or base. It is found that protonation and deprotonation of acridine, when dissolved in different ILs, can be triggered by the addition of a small amount of dilute aqueous HCl and NaOH, respectively, in both the ground and excited states, irrespective of the identity of the IL. However, the amount of dilute acid/base needed to protonate/deprotonate acridine dissolved in different ILs is found to vary from one IL to another. Steady-state fluorescence measurements also imply the presence of interactions between the acidic proton(s) of IL cation and excited acridine. The interconversion of neutral and protonated acridine, as well as the presence of a weakly fluorescent complex between excited acridine and the acidic proton(s) of the IL cation, is further corroborated by the parameters recovered from the fitting of the excited-state intensity-decay data. It is established that ILs as solubilizing media readily support facile proton transfer in both ground and excited states.

  2. Polarization Transfer in Wide-Angle Compton Scattering and Single-Pion Photoproduction from the Proton

    CERN Document Server

    Fanelli, C; Hamilton, D J; Salme, G; Wojtsekhowski, B; Ahmidouch, A; Annand, J R M; Baghdasaryan, H; Beaufait, J; Bosted, P; Brash, E J; Butuceanu, C; Carter, P; Christy, E; Chudakov, E; Danagoulian, S; Day, D; Degtyarenko, P; Ent, R; Fenker, H; Fowler, M; Frlez, E; Gaskell, D; Gilman, R; Horn, T; Huber, G M; de Jager, C W; Jensen, E; Jones, M K; Kelleher, A; Keppel, C; Khandaker, M; Kohl, M; Kumbartzki, G; Lassiter, S; Li, Y; Lindgren, R; Lovelace, H; Luo, W; Mack, D; Mamyan, V; Margaziotis, D J; Markowitz, P; Maxwell, J; Mbianda, G; Meekins, D; Meziane, M; Miller, J; Mkrtchyan, A; Mkrtchyan, H; Mulholland, J; Nelyubin, V; Pentchev, L; Perdrisat, C F; Piasetzky, E; Prok, Y; Puckett, A J R; Punjabi, V; Shabestari, M; Shahinyan, A; Slifer, K; Smith, G; Solvignon, P; Subedi, R; Wesselmann, F R; Wood, S; Ye, Z; Zheng, X

    2015-01-01

    Wide-angle exclusive Compton scattering and single-pion photoproduction from the proton have been investigated via measurement of the polarization transfer from a circularly polarized photon beam to the recoil proton. The WACS polarization transfer was analyzed at an incident photon energy of 3.7 GeV at a proton scattering angle of \\cma$= 70^\\circ$. The longitudinal transfer \\KLL, measured to be $0.645 \\pm 0.059 \\pm 0.048$, where the first error is statistical and the second is systematic, has the same sign as predicted for the reaction mechanism in which the photon interacts with a single quark carrying the spin of the proton. However, the observed value is $\\sim$3 times larger than predicted by the GPD-based calculations, which indicates a significant unknown contribution to the scattering amplitude.

  3. Spin transfer to $\\Lambda_{c}^{+}$ hyperons in polarized proton collisions at RHIC

    CERN Document Server

    Rykov, V L

    2004-01-01

    The analysis\\cite{ohkuma:1} of helicity transfer to $\\Lambda_{c}^{+}$ in polarized proton collisions is extended to the proton helicity correlations with the $\\Lambda_{c}^{+}$ transverse polarization in the production plane (parameter $D_{LS}$). The available spin transfer observables for the collisions of {\\em two} longitudinally polarized protons are evaluated. It is shown that, in the central region at $\\Lambda_{c}^{+}$ transverse momenta of a few GeV/c, $D_{LS}$ parameters are of about the same size as the helicity-to-helicity correlations. The methodical issue of using spin transfers for cross-checks of systematic errors in cross-section $A_{LL}$ measurements at polarized proton colliders is also briefly discussed.

  4. Photochemistry between a ruthenium(II) pyridylimidazole complex and benzoquinone: simple electron transfer versus proton-coupled electron transfer.

    Science.gov (United States)

    Hönes, Roland; Kuss-Petermann, Martin; Wenger, Oliver S

    2013-02-01

    A ruthenium(II) complex with two 4,4'-bis(trifluoromethyl)-2,2'-bipyridine chelates and a 2-(2'-pyridyl)imidazole ligand was synthesized and characterized by electrochemical and optical spectroscopic means. The respective complex has the potential to act as a combined electron-proton donor when promoted to its long-lived (3)MLCT excited state with visible light. The possibility of proton-coupled electron transfer (PCET) between the ruthenium(II) complex and 1,4-benzoquinone as an electron/proton acceptor was explored by steady-state and time-resolved luminescence spectroscopy, as well as by transient absorption spectroscopy in the nanosecond time regime. Excited-state deactivation is found to occur predominantly via simple oxidative quenching involving no proton motion, but a minor fraction of the photoexcited complex appears to react via PCET since there is spectral evidence for semiquinone as a photoproduct. Presumably, PCET is not kinetically competitive with simple electron transfer because the latter process is sufficiently exergonic and because there is little thermodynamic benefit from coupling proton transfer to the photoinduced electron transfer.

  5. Magnetization Transfer and Amide Proton Transfer MRI of Neonatal Brain Development

    Directory of Open Access Journals (Sweden)

    Yang Zheng

    2016-01-01

    Full Text Available Purpose. This study aims to evaluate the process of brain development in neonates using combined amide proton transfer (APT imaging and conventional magnetization transfer (MT imaging. Materials and Methods. Case data were reviewed for all patients hospitalized in our institution’s neonatal ward. Patients underwent APT and MT imaging (a single protocol immediately following the routine MR examination. Single-slice APT/MT axial imaging was performed at the level of the basal ganglia. APT and MT ratio (MTR measurements were performed in multiple brain regions of interest (ROIs. Data was statistically analyzed in order to assess for significant differences between the different regions of the brain or correlation with patient gestational age. Results. A total of 38 neonates were included in the study, with ages ranging from 27 to 41 weeks’ corrected gestational age. There were statistically significant differences in both APT and MTR measurements between the frontal lobes, basal ganglia, and occipital lobes (APT: frontal lobe versus occipital lobe P=0.031 and other groups P=0.00; MTR: frontal lobe versus occipital lobe P=0.034 and other groups P=0.00. Furthermore, APT and MTR in above brain regions exhibited positive linear correlations with patient gestational age. Conclusions. APT/MT imaging can provide valuable information about the process of the neonatal brain development at the molecular level.

  6. Proton-transfer mediated quenching of pyrene/indole charge-transfer states in isooctane solutions.

    Science.gov (United States)

    Altamirano, Marcela S; Bohorquez, María del Valle; Previtali, Carlos M; Chesta, Carlos A

    2008-01-31

    The fluorescence quenching of pyrene (Py) by a series of N-methyl and N-H substituted indoles was studied in isooctane at 298 K. The fluorescence quenching rate constants were evaluated by mean of steady-state and time-resolved measurements. In all cases, the quenching process involves a charge-transfer (CT) mechanism. The I(o)/I and tau(o)/tau Stern-Volmer plots obtained for the N-H indoles show a very unusual upward deviation with increasing concentration of the quenchers. This behavior is attributed to the self-quenching of the CT intermediates by the free indoles in solution. The efficiency of quenching of the polyaromatic by the N-H indoles increases abruptly in the presence of small amount of added pyridine (or propanol). A detailed analysis of the experimental data obtained in the presence of pyridine provides unambiguous evidence that the self-quenching process involves proton transfer from the CT states to indoles.

  7. Amide Proton Transfer (APT) MR imaging and Magnetization Transfer (MT) MR imaging of pediatric brain development

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hong; Kang, Huiying; Peng, Yun [Beijing Children' s Hospital, Capital Medical University, Imaging Center, Department of Radiology, Beijing (China); Zhao, Xuna [Philips Healthcare, Beijing (China); Jiang, Shanshan; Zhang, Yi; Zhou, Jinyuan [Johns Hopkins University, Division of MR Research, Department of Radiology, Baltimore, MD (United States)

    2016-10-15

    To quantify the brain maturation process during childhood using combined amide proton transfer (APT) and conventional magnetization transfer (MT) imaging at 3 Tesla. Eighty-two neurodevelopmentally normal children (44 males and 38 females; age range, 2-190 months) were imaged using an APT/MT imaging protocol with multiple saturation frequency offsets. The APT-weighted (APTW) and MT ratio (MTR) signals were quantitatively analyzed in multiple brain areas. Age-related changes in MTR and APTW were evaluated with a non-linear regression analysis. The APTW signals followed a decreasing exponential curve with age in all brain regions measured (R{sup 2} = 0.7-0.8 for the corpus callosum, frontal and occipital white matter, and centrum semiovale). The most significant changes appeared within the first year. At maturation, larger decreases in APTW and lower APTW values were found in the white matter. On the contrary, the MTR signals followed an increasing exponential curve with age in the same brain regions measured, with the most significant changes appearing within the initial 2 years. There was an inverse correlation between the MTR and APTW signal intensities during brain maturation. Together with MT imaging, protein-based APT imaging can provide additional information in assessing brain myelination in the paediatric population. (orig.)

  8. Long-range correlation and market segmentation in bond market

    Science.gov (United States)

    Wang, Zhongxing; Yan, Yan; Chen, Xiaosong

    2017-09-01

    This paper investigates the long-range auto-correlations and cross-correlations in bond market. Based on Detrended Moving Average (DMA) method, empirical results present a clear evidence of long-range persistence that exists in one year scale. The degree of long-range correlation related to maturities has an upward tendency with a peak in short term. These findings confirm the expectations of fractal market hypothesis (FMH). Furthermore, we have developed a method based on a complex network to study the long-range cross-correlation structure and applied it to our data, and found a clear pattern of market segmentation in the long run. We also detected the nature of long-range correlation in the sub-period 2007-2012 and 2011-2016. The result from our research shows that long-range auto-correlations are decreasing in the recent years while long-range cross-correlations are strengthening.

  9. Proton impact charge transfer on hydantoin - Prebiotic implications

    Science.gov (United States)

    Bacchus-Montabonel, Marie-Christine

    2016-11-01

    Formation and destruction of prebiotic compounds in astrophysical environments is a major issue in reactions concerning the origin of life. Detection of hydantoin in laboratory irradiation of interstellar ice analogues has confirmed evidence of this prebiotic compound and its stability to UV radiation or collisions may be crucial. Considering the different astrophysical environments, we have investigated theoretically proton-induced collisions with hydantoin in a wide energy range, from eV in the interstellar medium, up to keV for processes involving solar wind or supernovae shock-waves protons. Results are compared to previous investigations and qualitative trends on damage under spatial radiations are suggested.

  10. The JLab polarization transfer measurements of proton elastic form factor

    Indian Academy of Sciences (India)

    C F Perdrisat; V Punjabi

    2003-11-01

    The ratio of the electric and magnetic proton form factors, /, has been obtained in two Hall A experiments, from measurements of the longitudinal and transverse polarizations of the recoil proton, ℓ and , in the elastic scattering of polarized electrons, $\\overrightarrow{e}p→ e\\overrightarrow{p}$. Together these experiments cover the 2 range of 0.5 to 5.6 GeV2. A new experiment is currently being prepared, to extend the 2 range to 9 GeV2 in Hall C.

  11. Ionic liquid matrix-enhanced secondary ion mass spectrometry: the role of proton transfer.

    Science.gov (United States)

    Dertinger, Jennifer J; Walker, Amy V

    2013-03-01

    Room temperature ionic liquids (ILs) are effective matrices in secondary ion mass spectrometry (SIMS) and matrix assisted laser desorption ionization (MALDI). In this paper, we examine the role of proton transfer in the mechanism of secondary ion enhancement using IL matrices in SIMS. We employ hydrogenated and deuterated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as analytes to investigate the origin of proton transfer. The data indicate that protons from the IL anion transfer to the analyte in solution leading to an increase in the secondary ion intensity of the protonated molecular ion. The chemical identity of the matrix cation also affects analyte signal intensities. Using deuterated DPPC we observe that protons (deuterium) from the DPPC tail group react with the cation of the IL liquid leading to an increase in (cation + D)(+) ion intensities. Further, the data suggest that the transfer kinetics of deuterium (hydrogen) is correlated with the secondary ion enhancements observed. The highest secondary ion enhancements are observed for the least sterically hindered cation. Neither the proton affinity nor the pKa of the IL cation have a large effect on the analyte ion intensities, suggesting that steric factors are important in determining the efficacy of IL matrices for a given analyte.

  12. Proton transfer reactions in carbon nanotubes endohedrally functionalized with selected polar amino acid sidechains

    Energy Technology Data Exchange (ETDEWEB)

    Abi, T.G. [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India); Taraphder, Srabani, E-mail: srabani@chem.iitkgp.ernet.in [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India)

    2012-09-11

    Graphical abstract: Free Energies of activation and reaction for intramolecular proton transfer between polar amino acid sidechains and hydroxyl groups inside the core of endohedrally functionalized single walled carbon nanotubes. Highlights: Black-Right-Pointing-Pointer EVB based free energy simulation of proton transfer in hydrophobic confinement. Black-Right-Pointing-Pointer Aminoacid sidechain and OH group suspended within carbon nanotube act as reactants. Black-Right-Pointing-Pointer Donors like His and Glu are efficient in confinement aided by local hydrogen bonds. -- Abstract: We use the empirical-valence-bond (EVB) theory to investigate intramolecular proton transfer reactions between a selected set of polar amino acid sidechains and hydroxyl groups suspended inside carbon nanotubes to model the effect of hydrophobic confinement on the energetics of proton transfer involving (i) translocation of an excess protonic charge (with protonated histidine sidechain as donor) and (ii) transformation of a neutral reactant state to a charge-separated product state (with sidechains of Asp, Glu, Ser and Thr as donor). In both the cases, confinement in hydrophobic medium is found to change the associated free energies compared to their respective values in the bulk solution phase. Presence of stable hydrogen bonding within the pore is found to have a significant effect on both free energies of reaction and activation and thus governs the thermodynamic and kinetic feasibilities of these intramolecular reactions in hydrophobic confinement.

  13. Photochemistry and photoinduced proton-transfer by pharaonis phoborhodopsin.

    Science.gov (United States)

    Kamo, N; Shimono, K; Iwamoto, M; Sudo, Y

    2001-11-01

    Phoborhodopsin (pR or sensory rhodopsin II, sRII) is a photoreceptor of the negative phototaxis of Halobacterium salinarum, and pharaonis phoborhodopsin (ppR or pharaonis sensory rhodopsin II, psRII) is a corresponding protein of Natronobacterium pharaonis. The photocycle of ppR is essentially as follows: ppR(498) --> ppRK(approximately 540) --> ppRKL(512) --> ppRL(488) --> ppRM(390) --> ppRO(560) --> ppR (numbers in parenthesis denote the maximum absorbance). The photocycle is very similar to that of bacteriorhodopsin, but the rate of initial pigment recovery is about two-orders of magnitude slower. By low-temperature spectroscopy, two K-intermediates were found but the L intermediate was not detected. The lack of L indicates extraordinary stability of K at low temperature. ppRM is photoactive similar to M of bR. The ground state ppR contains only all-trans retinal whereas ppRM and ppRO contain 13-cis and all-trans, respectively. ppR has the ability of light-induced proton transport from the inside to the outside. Proton uptake occurs at the formation of ppRO and the release at its decay. ppR associates with its transducer and this complex transmits a signal to the cytoplasm. The proton transport ability is lost when the complex forms, but the proton uptake and release still occur, suggesting that the proton movement is non-electrogenic (release and uptake occur from the same side). The stoichiometry of the complex between ppR and the transducer is 1 : 1. ppR or pR has absorption maximum at approximately 500 nm, which is blue-shifted from those of other archaeal rhodopsins. The molecular mechanism of this color regulation is not yet solved.

  14. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

    Science.gov (United States)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

    2017-09-01

    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  15. Roles of multiple-proton transfer pathways and proton-coupled electron transfer in the reactivity of the bis-FeIV state of MauG.

    Science.gov (United States)

    Ma, Zhongxin; Williamson, Heather R; Davidson, Victor L

    2015-09-01

    The high-valent state of the diheme enzyme MauG exhibits charge-resonance (CR) stabilization in which the major species is a bis-Fe(IV) state with one heme present as Fe(IV)=O and the other as Fe(IV) with axial heme ligands provided by His and Tyr side chains. In the absence of its substrate, the high-valent state is relatively stable and returns to the diferric state over several minutes. It is shown that this process occurs in two phases. The first phase is redistribution of the resonance species that support the CR. The second phase is the loss of CR and reduction to the diferric state. Thermodynamic analysis revealed that the rates of the two phases exhibited different temperature dependencies and activation energies of 8.9 and 19.6 kcal/mol. The two phases exhibited kinetic solvent isotope effects of 2.5 and 2.3. Proton inventory plots of each reaction phase exhibited extreme curvature that could not be fit to models for one- or multiple-proton transfers in the transition state. Each did fit well to a model for two alternative pathways for proton transfer, each involving multiple protons. In each case the experimentally determined fractionation factors were consistent with one of the pathways involving tunneling. The percent of the reaction that involved the tunneling pathway differed for the two reaction phases. Using the crystal structure of MauG it was possible to propose proton-transfer pathways consistent with the experimental data using water molecules and amino acid side chains in the distal pocket of the high-spin heme.

  16. Proton transfer and energy coupling in the bacteriorhodopsin photocycle

    Science.gov (United States)

    Lanyi, J. K.

    1992-01-01

    A description of the rate constants and the energetics of the elementary reaction steps of the photocycle of bacteriorhodopsin has been helpful in understanding the mechanism of proton transport in this light-driven pump. The evidence suggests a single unbranched reaction sequence, BR-hv----K in equilibrium with L in equilibrium with M1----M2 in equilibrium with N in equilibrium with O----BR, where coupling to the proton-motive force is at the energetically and mechanistically important M1----M2 step. The consequences of site-specific mutations expressed homologously in Halobacterium halobium have revealed characteristics of the Schiff base deprotonation in the L----M1 reaction, the reorientation of the Schiff base from the extracellular to the cytoplasmic side in the M1----M2 reaction, and the reprotonation of the Schiff base in the M2----N reaction.

  17. Membrane effects on proton transfer in cytochrome c oxidase

    OpenAIRE

    Näsvik Öjemyr, Linda

    2012-01-01

    The biological membrane is composed of lipids and proteins that make up dynamic barriers around cells and organelles. Membrane-spanning proteins are involved in many key processes in the cell such as energy conversion, nerve conduction and signal transduction. These proteins interact closely with lipids as well as with other proteins in the membrane, which modulates and affects their structure and function. In the energy-conversion process, membrane-bound proton-transport proteins maintain an...

  18. Photoinduced proton transfer promoted by peripheral subunits for some Hantzsch esters.

    Science.gov (United States)

    Azizi, Sébastien; Ulrich, Gilles; Guglielmino, Maud; le Calvé, Stéphane; Hagon, Jerry P; Harriman, Anthony; Ziessel, Raymond

    2015-01-08

    It is noted that, for a small series of 3,5-diacetyl-1,4-dihydrolutidine (DDL) derivatives and the corresponding Hantzsch esters, the presence of methyl groups at the 2,6-positions serves to extinguish fluorescence in solution but not in the solid state. Emission is weakly activated and affected by changes in solvent polarity. The latter situation arises because the optical transition involves intramolecular charge transfer. Calculations, both semiempirical and DFT, indicate that, in all cases, rotation of the carbonyl function is facile and that the dihydropyridine ring is planar. These calculations also indicate that the 2,6-methyl groups do not affect the generic structure of the molecule. It is proposed that illumination increases the molecular dipole moment and pushes electron density toward the carbonyl oxygen atom. Proton transfer can now occur from one of the methyl groups, leading to formation of a relatively low-energy, neutral intermediate, followed by a second proton transfer step that forms the enol. Reaction profiles computed for the ground-state species indicate that this route is highly favored relative to hydrogen transfer from the 4-position. The barriers for light-induced proton transfer are greatly reduced relative to the ground-state process but such large-scale structural transformations are hindered in the solid state. A rigid analogue that cannot form an enol is highly emissive in solution, supporting the conclusion that proton transfer is in competition to fluorescence in solution.

  19. A relation between long-range correlation and dielectric anomaly

    Institute of Scientific and Technical Information of China (English)

    张磊; 钟维烈; 王春雷; 彭毅萍

    1999-01-01

    A double-well potential model is established to explain the dielectric anomaly of ferroelectrics. The dielectric constant consists of two parts. One part is independent of the long-range correlation, following 1/T law. The other part originates from the long-range correlation, and can be described by the correlation length well. The deviation from Curie-Weiss law in a small size sample originates from the decrease of the long-range correlation.

  20. Can We Trust Long-Range Weather Forecasts ?

    Science.gov (United States)

    Mailier, Pascal

    2010-05-01

    Long-range weather forecasts are widely used in key sectors of the economy, but too often their properties and limitations are not understood well enough. This poster reviews the characteristics, methods and reliability of long-range weather forecasts, making recommendations regarding their use and quality assessment. Despite their limited skill, long-range weather forecasts can still be a valuable tool for managing weather risk provided the necessary caution is exercised.

  1. Proton-transfer polymerization (HTP): converting methacrylates to polyesters by an N-heterocyclic carbene.

    Science.gov (United States)

    Hong, Miao; Chen, Eugene Y-X

    2014-10-27

    A new polymerization termed proton (H)-transfer polymerization (HTP) has been developed to convert dimethacrylates to unsaturated polyesters. HTP is catalyzed by a selective N-heterocyclic carbene capable of promoting intermolecular Umpolung condensation through proton transfer and proceeds through the step-growth propagation cycles via enamine intermediates. The role of the added suitable phenol, which is critical for achieving an effective HTP, is twofold: shutting down the radically induced chain-growth addition polymerization under HTP conditions (typically at 80-120 °C) and facilitating proton transfer after each monomer enchainment. The resulting unsaturated polyesters have a high thermal stability and can be readily cross-linked to robust polyester materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A spectroscopic and theoretical investigation of the proton-transfer laser. [Fisetin and 3-hydroxyflavone

    Energy Technology Data Exchange (ETDEWEB)

    Parthenopoulos, D.A.

    1988-01-01

    The lasing characteristics and the spectroscopy of intramolecular proton-transfer molecules were investigated in nonpolar and polar solvents. In addition, molecular orbital calculations on intramolecular proton-transfer molecules were performed. The efficient generation of coherent stimulated emission from 3-hydroxyflavone (3-HF) and fisetin, two molecules that exhibit intramolecular proton transfer was shown. Amplified spontaneous emission from 3-HF is achieved in polar aprotic and moderately protic solvents. The observed shifts of the tautomer fluorescence are attributed to hydrogen bonding interactions with the solvent. In contrast, 3-hydroxychromone does not exhibit amplified spontaneous emission in various solvents and concentrations. Picosecond transient absorption experiments reveal the existence of absorption bands overlapping the emission, which leads to high-loss terms in the gain equation.

  3. Microsecond light-induced proton transfer to flavin in the blue light sensor plant cryptochrome.

    Science.gov (United States)

    Langenbacher, Thomas; Immeln, Dominik; Dick, Bernhard; Kottke, Tilman

    2009-10-14

    Plant cryptochromes are blue light photoreceptors that regulate key responses in growth and daily rhythm of plants and might be involved in magnetoreception. They show structural homology to the DNA repair enzyme photolyase and bind flavin adenine dinucleotide as chromophore. Blue light absorption initiates the photoreduction from the oxidized dark state of flavin to the flavin neutral radical, which is the signaling state of the sensor. Previous time-resolved studies of the photoreduction process have been limited to observation of the decay of the radical in the millisecond time domain. We monitored faster, light-induced changes in absorption of an algal cryptochrome covering a spectral range of 375-750 nm with a streak camera setup. Electron transfer from tryptophan to flavin is completed before 100 ns under formation of the flavin anion radical. Proton transfer takes place with a time constant of 1.7 micros leading to the flavin neutral radical. Finally, the flavin radical and a tryptophan neutral radical decay with a time constant >200 micros in the millisecond and second time domain. The microsecond proton transfer has not been observed in animal cryptochromes from insects or photolyases. Furthermore, the strict separation in time of electron and proton transfer is novel in the field of flavin-containing photoreceptors. The reaction rate implies that the proton donor is not in hydrogen bonding distance to the flavin N5. Potential candidates for the proton donor and the involvement of the tryptophan triad are discussed.

  4. Cation-modulated electron-transfer channel: H-atom transfer vs proton-coupled electron transfer with a variable electron-transfer channel in acylamide units.

    Science.gov (United States)

    Chen, Xiaohua; Bu, Yuxiang

    2007-08-08

    The mechanism of proton transfer (PT)/electron transfer (ET) in acylamide units was explored theoretically using density functional theory in a representative model (a cyclic coupling mode between formamide and the N-dehydrogenated formamidic radical, FF). In FF, PT/ET normally occurs via a seven-center cyclic proton-coupled electron transfer (PCET) mechanism with a N-->N PT and an O-->O ET. However, when different hydrated metal ions are bound to the two oxygen sites of FF, the PT/ET mechanism may significantly change. In addition to their inhibition of PT/ET rate, the hydrated metal ions can effectively regulate the FF PT/ET cooperative mechanism to produce a single pathway hydrogen atom transfer (HAT) or a flexible proton coupled electron transfer (PCET) mechanism by changing the ET channel. The regulation essentially originates from the change in the O...O bond strength in the transition state, subject to the binding ability of the hydrated metal ions. In general, the high valent metal ions and those with large binding energies can promote HAT, and the low valent metal ions and those with small binding energies favor PCET. Hydration may reduce the Lewis acidity of cations, and thus favor PCET. Good correlations among the binding energies, barrier heights, spin density distributions, O...O contacts, and hydrated metal ion properties have been found, which can be used to interpret the transition in the PT/ET mechanism. These findings regarding the modulation of the PT/ET pathway via hydrated metal ions may provide useful information for a greater understanding of PT/ET cooperative mechanisms, and a possible method for switching conductance in nanoelectronic devices.

  5. Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

    Science.gov (United States)

    Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

    1994-08-01

    The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

  6. Proton-coupled electron transfer promotes the reduction of ferrylmyoglobin by uric acid under physiological conditions

    DEFF Research Database (Denmark)

    de Zawadzki, Andressa; Cardoso, Daniel R.; Skibsted, Leif Horsfelt

    2017-01-01

    The hypervalent muscle pigment ferrylmyoglobin, MbFe(IV)]O, is not reduced by urate monoanions at physiological conditions despite a strong driving force of around 30 kJ mol1 while for low pH, uric acid was found to reduce protonated ferrylmyoglobin, MbFe(IV)]O,H+, efficiently in a bimolecular...... for reduction of hypervalent heme iron, where initial proton transfer to oxo-iron initiates the intermolecular electron transfer from urate to ferrylmyoglobin. The concentration of the powerful prooxidant ferrylmyoglobin increases strongly during digestion of red meat in the stomach. A concomitant increase...

  7. Long range electronic transport in microbial nanowires bridging an electrode and scanned probe

    Science.gov (United States)

    Veazey, Joshua; Lampa-Pastirk, Sanela; Walsh, Kathy; Sun, Jiebing; Zhang, Pengpeng; Reguera, Gemma; Tessmer, Stuart

    2011-03-01

    The filament-like appendages known as pili, expressed by the bacterium Geobacter sulfurreducens, are believed to act as electrically conductive nanowires. Previously, we used scanning tunneling microscopy to study the local density of states at different positions along the wire. However, the long range electron transfer believed to occur in this protein has not been directly observed. Here we discuss a system for verifying long range transport using a scanning probe technique. Transport at distances of more than a few nanometers would require a novel biological electron transfer process. The authors gratefully acknowledge support from the National Science Foundation (MCB-1021948) and the Michigan State University Foundation (Strategic Partnership Grant).

  8. Electrostatic models of electron-driven proton transfer across a lipid membrane

    Energy Technology Data Exchange (ETDEWEB)

    Smirnov, Anatoly Yu; Nori, Franco [Advanced Science Institute, RIKEN, Wako-shi, Saitama, 351-0198 (Japan); Mourokh, Lev G [Department of Physics, Queens College, The City University of New York, Flushing, NY 11367 (United States)

    2011-06-15

    We present two models for electron-driven uphill proton transport across lipid membranes, with the electron energy converted to the proton gradient via the electrostatic interaction. In the first model, associated with the cytochrome c oxidase complex in the inner mitochondria membranes, the electrostatic coupling to the site occupied by an electron lowers the energy level of the proton-binding site, making proton transfer possible. In the second model, roughly describing the redox loop in a nitrate respiration of E. coli bacteria, an electron displaces a proton from the negative side of the membrane to a shuttle, which subsequently diffuses across the membrane and unloads the proton to its positive side. We show that both models can be described by the same approach, which can be significantly simplified if the system is separated into several clusters, with strong Coulomb interaction inside each cluster and weak transfer couplings between them. We derive and solve the equations of motion for the electron and proton creation/annihilation operators, taking into account the appropriate Coulomb terms, tunnel couplings, and the interaction with the environment. For the second model, these equations of motion are solved jointly with a Langevin-type equation for the shuttle position. We obtain expressions for the electron and proton currents and determine their dependence on the electron and proton voltage build-ups, on-site charging energies, reorganization energies, temperature, and other system parameters. We show that the quantum yield in our models can be up to 100% and the power-conversion efficiency can reach 35%.

  9. Nonadiabatic dynamics of photoinduced proton-coupled electron transfer in a solvated phenol-amine complex.

    Science.gov (United States)

    Goyal, Puja; Schwerdtfeger, Christine A; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-02-12

    Photoinduced concerted electron-proton transfer (EPT), denoted photo-EPT, is important for a wide range of energy conversion processes. Transient absorption and Raman spectroscopy experiments on the hydrogen-bonded p-nitrophenylphenol-t-butylamine complex, solvated in 1,2-dichloroethane, suggested that this complex may undergo photo-EPT. The experiments probed two excited electronic states that were interpreted as an intramolecular charge transfer (ICT) state and an EPT state. Herein mixed quantum mechanical/molecular mechanical nonadiabatic surface hopping dynamics is used to investigate the relaxation pathways following photoexcitation. The potential energy surface is generated on the fly with a semiempirical floating occupation molecular orbital complete active space configuration interaction method for the solute molecule and a molecular mechanical force field for the explicit solvent molecules. The free energy curves along the proton transfer coordinate illustrate that proton transfer is thermodynamically and kinetically favorable on the lower-energy excited state but not on the higher-energy excited state, supporting the characterization of these states as EPT and ICT, respectively. The nonadiabatic dynamics simulations indicate that the population decays from the ICT state to the EPT state in ∼100 fs and from the EPT state to the ground state on the slower time scale of ∼1 ps, qualitatively consistent with the experimental measurements. For ∼54% of the trajectories, the proton transfers from the phenol to the amine in ∼400 fs on the EPT state and then transfers back to the phenol rapidly upon decay to the ground state. Thus, these calculations augment the original interpretation of the experimental data by providing evidence of proton transfer on the EPT state prior to decay to the ground state. The fundamental insights obtained from these simulations are also relevant to other photo-EPT processes.

  10. Structural conversion and intramolecular electron transfer in ferrocenylanthraquinones triggered by Keggin type of heteropoly acid serving as proton source

    Institute of Scientific and Technical Information of China (English)

    LIU Shuxia; LI Dehui; SU Zhongmin; WANG Enbo

    2004-01-01

    Intramolecular electron transfer triggered by proton and the mechanism of structural conversion in a ethynylene-bridged ferrocene-anthraquinone organic electron donor(D)-acceptor(A) g-conjugated system (1-FcAq) in the presence of a Keggin type heteropoly acid as proton source are discussed. Heteropoly acids can stabilize the protonated ethynylene-bridged ferrocene-anthraquinone conjugated complex, and the stable protonated complex has been isolated in air and characterized by elemental analyses, IR,1H NMR, and CV. Upon the inducement of proton, electron transfer from ferrocene moiety (Fc) to anthraquinone moiety (Aq) causes the rearrangement of the conjugated system to create a fulvene-cumulene structuere.

  11. New acceptor-bridge-donor strategy for enhancing NLO response with long-range excess electron transfer from the NH2...M/M3O donor (M = Li, Na, K) to inside the electron hole cage C20F19 acceptor through the unusual σ chain bridge (CH2)4.

    Science.gov (United States)

    Bai, Yang; Zhou, Zhong-Jun; Wang, Jia-Jun; Li, Ying; Wu, Di; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

    2013-04-01

    Using the strong electron hole cage C20F19 acceptor, the NH2...M/M3O (M = Li, Na, and K) complicated donors with excess electron, and the unusual σ chain (CH2)4 bridge, we construct a new kind of electride molecular salt e(-)@C20F19-(CH2)4-NH2...M(+)/M3O(+) (M = Li, Na, and K) with excess electron anion inside the hole cage (to be encapsulated excess electron-hole pair) serving as a new A-B-D strategy for enhancing nonlinear optical (NLO) response. An interesting push-pull mechanism of excess electron generation and its long-range transfer is exhibited. The excess electron is pushed out from the (super)alkali atom M/M3O by the lone pair of NH2 in the donor and further pulled inside the hole cage C20F19 acceptor through the efficient long σ chain (CH2)4 bridge. Owing to the long-range electron transfer, the new designed electride molecular salts with the excess electron-hole pair exhibit large NLO response. For the e(-)@C20F19-(CH2)4-NH2...Na(+), its large first hyperpolarizability (β0) reaches up to 9.5 × 10(6) au, which is about 2.4 × 10(4) times the 400 au for the relative e(-)@C20F20...Na(+) without the extended chain (CH2)4-NH2. It is shown that the new strategy is considerably efficient in enhancing the NLO response for the salts. In addition, the effects of different bridges and alkali atomic number on β0 are also exhibited. Further, three modulating factors are found for enhancing NLO response. They are the σ chain bridge, bridge-end group with lone pair, and (super)alkali atom. The new knowledge may be significant for designing new NLO materials and electronic devices with electrons inside the cages. They may also be the basis of establishing potential organic chemistry with electron-hole pair.

  12. Nanoimprinted Long-range Surface Plasmon Polariton Waveguide Components

    DEFF Research Database (Denmark)

    Johansen, Dan Mario; Boltasseva, A.; Nielsen, Theodor

    2006-01-01

    We report on the fabrication by nanoimprint lithography (NIL) and performance of metal stripe waveguides embedded in a polymer, capable of supporting long-range surface plasmon polariton (LRSPP) propagation.......We report on the fabrication by nanoimprint lithography (NIL) and performance of metal stripe waveguides embedded in a polymer, capable of supporting long-range surface plasmon polariton (LRSPP) propagation....

  13. Report of the Long-Range Planning Committee

    Energy Technology Data Exchange (ETDEWEB)

    1984-07-01

    This is the final report of the Long-Range Planning Committee of the Lawrence Livermore National Laboratory. It describes the make-up, purpose, working assumptions, and activities of the Committee and discusses the work done by the Committee on defense matters, energy, a number of additional topics, and future long-range planning activities.

  14. Degeneracy and long-range correlation: A simulation study

    Directory of Open Access Journals (Sweden)

    Marmelat Vivien

    2011-12-01

    Full Text Available We present in this paper a simulation study that aimed at evidencing a causal relationship between degeneracy and long-range correlations. Long-range correlations represent a very specific form of fluctuations that have been evidenced in the outcomes time series produced by a number of natural systems. Long-range correlations are supposed to sign the complexity, adaptability and flexibility of the system. Degeneracy is defined as the ability of elements that are structurally different to perform the same function, and is presented as a key feature for explaining the robustness of complex systems. We propose a model able to generate long-range correlated series, and including a parameter that account for degeneracy. Results show that a decrease in degeneracy tends to reduce the strength of long-range correlation in the series produced by the model.

  15. Long-Range Reconnaissance Imager on New Horizons

    CERN Document Server

    Cheng, A F; Conard, S J; Morgan, M F; Barnouin-Jha, O; Boldt, J D; Cooper, K A; Darlington, E H; Grey, M P; Hayes, J R; Kosakowski, K E; Magee, T; Rossano, E; Sampath, D; Schlemm, C; Taylor, H W

    2007-01-01

    The LOng-Range Reconnaissance Imager (LORRI) is the high resolution imaging instrument for the New Horizons mission to Pluto, its giant satellite Charon, its small moons Nix and Hydra, and the Kuiper Belt, which is the vast region of icy bodies extending roughly from Neptune's orbit out to 50 astronomical units (AU). New Horizons launched on January 19, 2006 as the inaugural mission in NASA's New Frontiers program. LORRI is a narrow angle (field of view=0.29 deg), high resolution (4.95 microrad pixels), Ritchey-Chretien telescope with a 20.8 cm diameter primary mirror, a focal length of 263 cm, and a three lens field-flattening assembly. A 1024 x 1024 pixel (optically active region), thinned, backside-illuminated charge-coupled device (CCD) detector is used in the focal plane unit and is operated in frame transfer mode. LORRI provides panchromatic imaging over a bandpass that extends approximately from 350 nm to 850 nm. LORRI operates in an extreme thermal environment, situated inside the warm spacecraft with...

  16. Status of the proton and electron transfer lines for the AWAKE Experiment at CERN

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, J.S., E-mail: janet.schmidt@cern.ch [CERN, Geneva (Switzerland); Bauche, J. [CERN, Geneva (Switzerland); Biskup, B. [CERN, Geneva (Switzerland); Czech Technical University, Prague (Czech Republic); Bracco, C.; Doebert, S.; Goddard, B.; Gschwendtner, E.; Jensen, L.K.; Jones, O.R.; Mazzoni, S.; Meddahi, M.; Pepitone, K.; Petrenko, A.; Velotti, F.M.; Vorozhtsov, A. [CERN, Geneva (Switzerland)

    2016-09-01

    The AWAKE project at CERN is planned to study proton driven plasma wakefield acceleration with an externally injected electron beam. Therefore two transfer lines are being designed in order to provide the proton beam from the SPS and the electron beam from an RF gun to the plasma cell. The commissioning of the proton line will take place in 2016 for the first phase of the experiment, which is focused on the self-modulation of a 12 cm long proton bunch in the plasma. The electron line will be added for the second phase of AWAKE in 2017, when the wakefield will be probed with an electron beam of 10–20 MeV/c. The challenge for these transfer lines lies in the parallel operation of the proton, electron and laser beam used to ionize the plasma and seed the self-modulation. These beams, of different characteristics, need to be synchronized and positioned for optimized injection conditions into the wakefield. This task requires great flexibility in the transfer line optics. The status of these designs will be presented in this paper.

  17. Status of the proton and electron transfer lines for the AWAKE Experiment at CERN

    Science.gov (United States)

    Schmidt, J. S.; Bauche, J.; Biskup, B.; Bracco, C.; Doebert, S.; Goddard, B.; Gschwendtner, E.; Jensen, L. K.; Jones, O. R.; Mazzoni, S.; Meddahi, M.; Pepitone, K.; Petrenko, A.; Velotti, F. M.; Vorozhtsov, A.

    2016-09-01

    The AWAKE project at CERN is planned to study proton driven plasma wakefield acceleration with an externally injected electron beam. Therefore two transfer lines are being designed in order to provide the proton beam from the SPS and the electron beam from an RF gun to the plasma cell. The commissioning of the proton line will take place in 2016 for the first phase of the experiment, which is focused on the self-modulation of a 12 cm long proton bunch in the plasma. The electron line will be added for the second phase of AWAKE in 2017, when the wakefield will be probed with an electron beam of 10-20 MeV/c. The challenge for these transfer lines lies in the parallel operation of the proton, electron and laser beam used to ionize the plasma and seed the self-modulation. These beams, of different characteristics, need to be synchronized and positioned for optimized injection conditions into the wakefield. This task requires great flexibility in the transfer line optics. The status of these designs will be presented in this paper.

  18. Molecular dynamics simulations reveal proton transfer pathways in cytochrome C-dependent nitric oxide reductase.

    Directory of Open Access Journals (Sweden)

    Andrei V Pisliakov

    Full Text Available Nitric oxide reductases (NORs are membrane proteins that catalyze the reduction of nitric oxide (NO to nitrous oxide (N(2O, which is a critical step of the nitrate respiration process in denitrifying bacteria. Using the recently determined first crystal structure of the cytochrome c-dependent NOR (cNOR [Hino T, Matsumoto Y, Nagano S, Sugimoto H, Fukumori Y, et al. (2010 Structural basis of biological N2O generation by bacterial nitric oxide reductase. Science 330: 1666-70.], we performed extensive all-atom molecular dynamics (MD simulations of cNOR within an explicit membrane/solvent environment to fully characterize water distribution and dynamics as well as hydrogen-bonded networks inside the protein, yielding the atomic details of functionally important proton channels. Simulations reveal two possible proton transfer pathways leading from the periplasm to the active site, while no pathways from the cytoplasmic side were found, consistently with the experimental observations that cNOR is not a proton pump. One of the pathways, which was newly identified in the MD simulation, is blocked in the crystal structure and requires small structural rearrangements to allow for water channel formation. That pathway is equivalent to the functional periplasmic cavity postulated in cbb(3 oxidase, which illustrates that the two enzymes share some elements of the proton transfer mechanisms and confirms a close evolutionary relation between NORs and C-type oxidases. Several mechanisms of the critical proton transfer steps near the catalytic center are proposed.

  19. Thermodynamic view of activation energies of proton transfer in various gramicidin A channels.

    Science.gov (United States)

    Chernyshev, Anatoly; Cukierman, Samuel

    2002-01-01

    The temperature dependencies (range: 5-45 degrees C) of single-channel proton conductances (g(H)) in native gramicidin A (gA) and in two diastereoisomers (SS and RR) of the dioxolane-linked gA channels were measured in glycerylmonooleate/decane (GMO) and diphytanoylphosphatidylcholine/decane (DiPhPC) bilayers. Linear Arrhenius plots (ln (g(H)) versus K(-1)) were obtained for the native gA and RR channels in both types of bilayers, and for the SS channel in GMO bilayers only. The Arrhenius plot for proton transfer in the SS channel in DiPhPC bilayers had a break in linearity around 20 degrees C. This break seems to occur only when protons are the permeating cations in the SS channel. The activation energies (E(a)) for proton transfer in various gA channels (approximately 15 kJ/mol) are consistent with the rate-limiting step being in the channel and/or at the membrane-channel/solution interface, and not in bulk solution. E(a) values for proton transfer in gA channels are considerably smaller than for the permeation of nonproton currents in gA as well as in various other ion channels. The E(a) values for proton transfer in native gA channels are nearly the same in both GMO and DiPhPC bilayers. In contrast, for the dioxolane linked gA dimers, E(a) values were strongly modulated by the lipid environment. The Gibbs activation free energies (Delta G(#)(o)) for protons in various gA channels are within the range of 27-29 kJ/mol in GMO bilayers and of 20-22 kJ/mol in DiPhPC bilayers. The largest difference between Delta G(#)(o) for proton currents occurs between native gA (or SS channels) and the RR channel. In general, the activation entropy (Delta S) is mostly responsible for the differences between g(H) values in various gA channels, and also in distinct bilayers. However, significant differences between the activation enthalpies (Delta H(#)(o)) for proton transfer in the SS and RR channels occur in distinct membranes.

  20. Two-photon exchange correction to muon-proton elastic scattering at low momentum transfer

    Energy Technology Data Exchange (ETDEWEB)

    Tomalak, Oleksandr [Johannes Gutenberg Universitaet, Institut fuer Kernphysik, Mainz (Germany); Johannes Gutenberg-Universitaet, PRISMA Cluster of Excellence, Mainz (Germany); Taras Shevchenko National University of Kyiv, Department of Physics, Kiev (Ukraine); Vanderhaeghen, Marc [Johannes Gutenberg Universitaet, Institut fuer Kernphysik, Mainz (Germany); Johannes Gutenberg-Universitaet, PRISMA Cluster of Excellence, Mainz (Germany)

    2016-03-15

    We evaluate the two-photon exchange (TPE) correction to the muon-proton elastic scattering at small momentum transfer. Besides the elastic (nucleon) intermediate state contribution, which is calculated exactly, we account for the inelastic intermediate states by expressing the TPE process approximately through the forward doubly virtual Compton scattering. The input in our evaluation is given by the unpolarized proton structure functions and by one subtraction function. For the latter, we provide an explicit evaluation based on a Regge fit of high-energy proton structure function data. It is found that, for the kinematics of the forthcoming muon-proton elastic scattering data of the MUSE experiment, the elastic TPE contribution dominates, and the size of the inelastic TPE contributions is within the anticipated error of the forthcoming data. (orig.)

  1. Polarization-transfer measurement to a large-virtuality bound proton in the deuteron

    CERN Document Server

    Yaron, I; Achenbach, P; Arenhövel, H; Beričič, J; Böhm, R; Bosnar, D; Debenjak, L; \\, M; Distler, O; Esser, A; Friščić, I; Gilman, R; Korover, I; Lichtenstadt, J; Merkel, H; Middleton, D G; Mihovilovič, M; Müller, U; Piasetzky, E; Širca, S; Strauch, S; Pochodzalla, J; Ron, G; \\, B; Schlimme, S; Schoth, M; Schulz, F; Sfienti, C; Thiel, M; Tyukin, A; Weber, A

    2016-01-01

    Possible differences between free and bound protons may be observed in the ratio of polarization-transfer components, $P'_x/P'_z$. We report the measurement of $P'_x/P'_z$, in the $^2\\textrm{H}(\\vec{e},e^{\\prime}\\vec{p})n$ reaction at low and high missing momenta. Observed increasing deviation of $P'_x/P'_z$ from that of a free proton as a function of the virtuality, similar to that observed in \\hefour, indicates that the effect in nuclei is due to the virtuality of the knock-out proton and not due to the average nuclear density. The measured differences from calculations assuming free-proton form factors ($\\sim10\\%$), may indicate in-medium modifications.

  2. Two-photon exchange correction to muon-proton elastic scattering at small momentum transfer

    CERN Document Server

    Tomalak, O

    2015-01-01

    We evaluate the two-photon exchange (TPE) correction to the muon-proton elastic scattering at small momentum transfer. Besides the elastic (nucleon) intermediate state contribution, which is calculated exactly, we account for the inelastic intermediate states by expressing the TPE process approximately through the forward doubly virtual Compton scattering. The input in our evaluation is given by the unpolarized proton structure functions and by one subtraction function. For the latter, we provide an explicit evaluation based on a Regge fit of high-energy proton structure function data. It is found that,for the kinematics of the forthcoming muon-proton elastic scattering data of the MUSE experiment, the elastic TPE contribution dominates, and the size of the inelastic TPE contributions is within the anticipated error of the forthcoming data.

  3. Proton transfer in histidine-tryptophan heterodimers embedded in helium droplets

    Energy Technology Data Exchange (ETDEWEB)

    Bellina, Bruno; Merthe, Daniel J.; Kresin, Vitaly V. [Department of Physics and Astronomy, University of Southern California, Los Angeles, California 90089-0484 (United States)

    2015-03-21

    We used cold helium droplets as nano-scale reactors to form and ionize, by electron bombardment and charge transfer, aromatic amino acid heterodimers of histidine with tryptophan, methyl-tryptophan, and indole. The molecular interaction occurring through an N–H ⋅ ⋅ ⋅ N hydrogen bond leads to a proton transfer from the indole group of tryptophan to the imidazole group of histidine in a radical cationic environment.

  4. Proton transfer in histidine-tryptophan heterodimers embedded in helium droplets

    CERN Document Server

    Bellina, Bruno; Kresin, Vitaly V

    2015-01-01

    We used cold helium droplets as nano-scale reactors to form and ionize, by electron bombardment and charge transfer, aromatic amino acid heterodimers of histidine with tryptophan, methyl-tryptophan, and indole. The molecular interaction occurring through an N-H...N hydrogen bond leads to a proton transfer from the indole group of tryptophan to the imidazole group of histidine in a radical cationic environment.

  5. Excited-state proton transfer of firefly dehydroluciferin.

    Science.gov (United States)

    Presiado, Itay; Erez, Yuval; Simkovitch, Ron; Shomer, Shay; Gepshtein, Rinat; Pinto da Silva, Luís; Esteves da Silva, Joaquim C G; Huppert, Dan

    2012-11-08

    Steady-state and time-resolved emission techniques were used to study the protolytic processes in the excited state of dehydroluciferin, a nonbioluminescent product of the firefly enzyme luciferase. We found that the ESPT rate coefficient is only 1.1 × 10(10) s(-1), whereas those of d-luciferin and oxyluciferin are 3.7 × 10(10) and 2.1 × 10(10) s(-1), respectively. We measured the ESPT rate in water-methanol mixtures, and we found that the rate decreases nonlinearly as the methanol content in the mixture increases. The deprotonated form of dehydroluciferin has a bimodal decay with short- and long-time decay components, as was previously found for both D-luciferin and oxyluciferin. In weakly acidic aqueous solutions, the deprotonated form's emission is efficiently quenched. We attribute this observation to the ground-state protonation of the thiazole nitrogen, whose pK(a) value is ~3.

  6. Hydrogen bonding: a channel for protons to transfer through acid-base pairs.

    Science.gov (United States)

    Wu, Liang; Huang, Chuanhui; Woo, Jung-Je; Wu, Dan; Yun, Sung-Hyun; Seo, Seok-Jun; Xu, Tongwen; Moon, Seung-Hyeon

    2009-09-10

    Different from H(3)O(+) transport as in the vehicle mechanism, protons find another channel to transfer through the poorly hydrophilic interlayers in a hydrated multiphase membrane. This membrane was prepared from poly(phthalazinone ether sulfone kentone) (SPPESK) and H(+)-form perfluorosulfonic resin (FSP), and poorly hydrophilic electrostatically interacted acid-base pairs constitute the interlayer between two hydrophilic phases (FSP and SPPESK). By hydrogen bonds forming and breaking between acid-base pairs and water molecules, protons transport directly through these poorly hydrophilic zones. The multiphase membrane, due to this unique transfer mechanism, exhibits better electrochemical performances during fuel cell tests than those of pure FSP and Nafion-112 membranes: 0.09-0.12 S cm(-1) of proton conductivity at 25 degrees C and 990 mW cm(-2) of the maximum power density at a current density of 2600 mA cm(-2) and a cell voltage of 0.38 V.

  7. A new type of excited-state intramolecular proton transfer: proton transfer from phenol OH to a carbon atom of an aromatic ring observed for 2-phenylphenol.

    Science.gov (United States)

    Lukeman, Matthew; Wan, Peter

    2002-08-14

    The photochemical deuterium incorporation at the 2'- and 4'-positions of 2-phenylphenol (4) and equivalent positions of related compounds has been studied in D(2)O (CH(3)OD)-CH(3)CN solutions with varying D(2)O (CH(3)OD) content. Predominant exchange was observed at the 2'-position with an efficiency that is independent of D(2)O (MeOD) content. Exchange at the 2'-position (but not at the 4'-position) was also observed when crystalline samples of 4-OD were irradiated. Data are presented consistent with a mechanism of exchange that involves excited-state intramolecular proton transfer (ESIPT) from the phenol to the 2'-carbon position of the benzene ring not containing the phenol, to generate the corresponding keto tautomer (an o-quinone methide). This is the first explicit example of a new class of ESIPT in which an acidic phenolic proton is transferred to an sp(2)-hybridized carbon of an aromatic ring. The complete lack of exchange observed for related substrates 6-9 and for planar 4-hydroxyfluorene (10) is consistent with a mechanism of ESIPT that requires an initial hydrogen bonding interaction between the phenol proton and the benzene pi-system. Similar exchange was observed for 2,2'-biphenol (5), suggesting that this new type of ESIPT is a general reaction for unconstrained 2'-aryl-substituted phenols and other related hydroxyarenes.

  8. Theoretical study of the mechanism of proton transfer in tautomeric systems: Alloxan

    Indian Academy of Sciences (India)

    Rita Kakkar; Bhupendra K Sarma; Vandana katoch

    2001-08-01

    Semiempirical SCF-MO studies of tautomerism in alloxan preclude the possibility of direct proton transfer in the gas phase due to the strain in the four-centred transition state, in which the proton being transferred is forced to come close to the positively charged carbon atom at the opposite corner of the four-membered ring. However, in aqueous solution, the activation barrier reduces appreciably, not only due to reduction in strain, but also due to charge separation in the transition state, which is stabilized due to ionic resonance. The N-H bond is almost broken, while the O-H bond is only partially formed in the transition state. The other stabilizing effect in aqueous solution is due to bulk solvent dielectric effects, which stabilize the transition state to a greater extent due to its higher dipole moment. Although the transition states for proton transfer to the neighbouring oxygen atoms on either side have comparable energies, as the mechanisms of proton transfer leading to the formation of the 2-hydroxy and 4-hydroxy tautomers are similar, bulk solvent effects are larger in the latter due to the higher dipole moment of the transition state. The reason is the almost complete separation of the two entities, i.e. the alloxan anion and the hydronium ion in the latter case, indicating that in this case a dissociative mechanism of the kind encountered in acid-base equilibria is operating.

  9. Offline thermal-desorption proton-transfer-reaction mass spectrometry to study composition of organic aerosol

    NARCIS (Netherlands)

    Timkovsky, J.; Dusek, U.; Henzing, J. S.; Kuipers, T. L.; Röckmann, T.; Holzinger, R.

    2015-01-01

    We present a novel approach to study the organic composition of aerosol filter samples using thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS) in the laboratory. The method is tested and validated based on the comparison with in situ TD-PTR-MS measurements. In general, we obs

  10. Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity

    Science.gov (United States)

    Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

    2016-01-01

    CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2. We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis. PMID:27450088

  11. Excited-state proton transfer and ion pair formation in a Cinchona organocatalyst

    NARCIS (Netherlands)

    Kumpulainen, T.; Brouwer, A.M.

    2012-01-01

    The excited-state proton transfer and subsequent intramolecular ion pair formation of a cupreidine-derived Cinchona organocatalyst (BnCPD) were studied in THF-water mixtures using picosecond time-resolved fluorescence together with global analysis. Full spectral and kinetic characterization of all t

  12. Conductivity properties of proton transfer and influence of temperature on it in hydrogen-bonded systems

    Institute of Scientific and Technical Information of China (English)

    PANGXiao-feng; YUJia-feng

    2004-01-01

    We study and calculate the mobility and oonductivity of proton transfer and influence of temperature on it by pang's dynamic model in hydrogen bonded systems, which ooincide with experiments. We further study the mechanism of magnetization of ciguid water in the basis of this model.

  13. Conductivity properties of proton transfer and influence of temperature on it in hydrogen-bonded systems

    Institute of Scientific and Technical Information of China (English)

    PANG Xiao-feng; YU Jia-feng

    2004-01-01

    We study and calculate the mobility and conductivity of proton transfer and influence of temperature on it by pang's dynamic model in hydrogen bonded systems, which coincide with experiments. We further study the mechanism of magnetization of ciguid water in the basis of this model.

  14. Links between potential energy structures and quantum cumulative reaction probabilities of double proton transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Horsten, H.F. von [Institut fuer Physikalische Chemie, Christian-Albrechts-Universitaet, Olshausenstrasse 40, 24098 Kiel (Germany); Hartke, B. [Institut fuer Physikalische Chemie, Christian-Albrechts-Universitaet, Olshausenstrasse 40, 24098 Kiel (Germany)], E-mail: hartke@phc.uni-kiel.de

    2007-09-25

    Double proton transfer reactions of pyrazole-guanidine species exhibit unusual energy profiles of a plateau form, different from the standard single and double barrier shapes. We have demonstrated earlier that this leads to a characteristically different quantum dynamical behavior of plateau reactions, when measured appropriately. Here we show that these differences also carry over to traditional measures of reaction probability.

  15. STATISTICAL PROPERTIES OF LONG-RANGE CONTACTS IN GLOBULAR PROTEINS

    Institute of Scientific and Technical Information of China (English)

    Xiang-hong Wang; Jian-hong Ke; Mang-xiao Hu

    2004-01-01

    The analysis of residue-residue contacts in protein structures can shed some light on our understanding of the folding and stability of proteins. In this paper, we study the statistical properties of long-range and short-range residueresidue contacts of 91 globular proteins using CSU software and analyze the importance of long-range contacts in globular protein structure. There are many short-range and long-range contacts in globular proteins, and it is found that the average number of long-range contacts per residue is 5.63 and the percentage of residue-residue contacts which are involved in longrange ones is 59.4%. In more detail, the distribution of long-range contacts in different residue intervals is investigated and it is found that the residues occurring in the interval range of 4-10 residues apart in the sequence contribute more long-range contacts to the stability of globular protein. The number of long-range contacts per residue, which is a measure of ability to form residue-residue contacts, is also calculated for 20 different amino acid residues. It is shown that hydrophobic residues (including Leu, Val, Ile, Met, Phc, Tyr, Cys and Trp) having a large number of long-range contacts easily form long-range contacts, while the hydrophilic amino acids (including Ala, Gly, Thr, His, Glu, Gin, Asp, Asn, Lys, Ser, Arg, and Pro) form long-range contacts with more difficulty. The relationship between the Fauchere-Pliska hydrophobicity scale (FPH) and the number of short-range and long-range contacts per residue for 20 amino acid residues is also studied. An approximately linear relationship between the Fauchere-Pliska hydrophobicity scale (FPH) and the number of long-range contacts per residue CL is found and can be expressed as CiL= a + b x FPHwhere a = 5.04 and b = 1.23. These results can help us to understand the role of residue-residue contacts in globular protein structure.

  16. EFFECTS OF LONG-RANGE INTERACTIONS ON THE FERROELECTRIC FILM

    Institute of Scientific and Technical Information of China (English)

    吴银忠; 李振亚

    2001-01-01

    The effect of long-range interactions on the spontaneous polarization and the Curie temperature of the ferroelectricfilm is investigated by use of the Landau theory. On the assumption that the nearest-n eighbour interaction remains constant, we find that the spontaneous polarization and the phase transition temperature increase with the enhancement of the long-range interactions. In the case of positive extrapolation length, the critical thickness of the ferroelectric film,in which a size-driven phase transition occurs, decreases with the enhancement of the long-range interactions.

  17. Truncated Long-Range Percolation on Oriented Graphs

    Science.gov (United States)

    van Enter, A. C. D.; de Lima, B. N. B.; Valesin, D.

    2016-07-01

    We consider different problems within the general theme of long-range percolation on oriented graphs. Our aim is to settle the so-called truncation question, described as follows. We are given probabilities that certain long-range oriented bonds are open; assuming that the sum of these probabilities is infinite, we ask if the probability of percolation is positive when we truncate the graph, disallowing bonds of range above a possibly large but finite threshold. We give some conditions in which the answer is affirmative. We also translate some of our results on oriented percolation to the context of a long-range contact process.

  18. Picosecond dynamics of proton transfer of a 7-hydroxyflavylium salt in aqueous-organic solvent mixtures.

    Science.gov (United States)

    Freitas, Adilson A; Quina, Frank H; Maçanita, António A L

    2011-10-13

    The intermediacy of the geminate base-proton pair (A*···H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH(+)* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base-proton pair A*···H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*···H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec), of A*···H(+)) from the diffusion controlled rates (dissociation, k(diss), and formation, k(diff)[H(+)], of A*···H(+)), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

  19. Excited-state proton coupled charge transfer modulated by molecular structure and media polarization.

    Science.gov (United States)

    Demchenko, Alexander P; Tang, Kuo-Chun; Chou, Pi-Tai

    2013-02-01

    Charge and proton transfer reactions in the excited states of organic dyes can be coupled in many different ways. Despite the complementarity of charges, they can occur on different time scales and in different directions of the molecular framework. In certain cases, excited-state equilibrium can be established between the charge-transfer and proton-transfer species. The interplay of these reactions can be modulated and even reversed by variations in dye molecular structures and changes of the surrounding media. With knowledge of the mechanisms of these processes, desired rates and directions can be achieved, and thus the multiple emission spectral features can be harnessed. These features have found versatile applications in a number of cutting-edge technological areas, particularly in fluorescence sensing and imaging.

  20. First-principles molecular dynamics study of proton transfer mechanism in bovine cytochrome c oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Kamiya, Katsumasa [Center for Computational Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Boero, Mauro [Center for Computational Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Tateno, Masaru [Center for Computational Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Shiraishi, Kenji [CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Oshiyama, Atsushi [Center for Computational Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan)

    2007-09-12

    Density functional based first-principles molecular dynamics calculations, performed on a model system extracted from the bovine cytochrome c oxidase, have been performed in an attempt to inspect the proton transfer mechanism across a peptide group. Our model system includes the specific Tyr440-Ser441 peptide group involved in a novel proton transfer path and shows that the Y440-S441 enol peptide group [-C(OH) = N-], which is a structural isomer of a keto form [-CO-NH-], is the product of the deprotonation of an imidic acid [-C(OH)-NH-] occurring in the vicinity of the deprotonated aspartic acid residue. For the subsequent enol-to-keto tautomerization, a direct H{sup +} transfer path in the Y440-S441 peptide group has been identified, in which the transition state takes a distorted four-membered ring structure.

  1. Long-range interaction effects on calcium-wave propagation

    Science.gov (United States)

    Kepseu, W. D.; Woafo, P.

    2008-07-01

    In this paper, numerical simulation of calcium waves in a network of cells coupled together by a paracrine signaling is investigated. The model takes into account the long-range interaction between cells due to the action of extracellular messengers, which provide links between first-neighbor cells, but also on cells located far away from the excited cell. When considering bidirectional coupling, the long-range interaction influences neither the frequency nor the amplitude of oscillations, contrary to one-directional coupling. The long-range interaction influences the speed of propagation of Ca2+ waves in the network and induces enlargement of the transition zone before the steady regime of propagation is attained. We also investigate the long-range effects on the colonization of a given niche by a pathogenic microorganism signal on calcium wave propagation in the network.

  2. Tewaukon National Wildlife Refuge : Long Range Water Management Plan

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This Long-Range Water Management Plan for Tewaukon National Wildlife Refuge begins with a history of precipitation, water levels, wildlife use, disease, water...

  3. Long Range Water Management Plan : Lacreek National Wildlife Refuge

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This Long-Range Water Management Plan for Lacreek National Wildlife Refuge begins with a history of precipitation, water levels, wildlife use, disease, water...

  4. Long-Range and Strategic Planning at Michigan State.

    Science.gov (United States)

    Carlisle, E. Fred

    1986-01-01

    On Feb. 6, 1961, the Board of Trustees of Michigan State University declared that MSU was "in a state of financial crisis". The development and implementation of long-range planning at Michigan State since the crisis is discussed. (MLW)

  5. Exciton-Phonon Dynamics with Long-Range Interaction

    CERN Document Server

    Laskin, Nick

    2011-01-01

    Exciton-phonon dynamics on a 1D lattice with long-range exciton-exciton interaction have been introduced and elaborated. Long-range interaction leads to a nonlocal integral term in the motion equation of the exciton subsystem if we go from discrete to continuous space. In some particular cases for power-law interaction, the integral term can be expressed through a fractional order spatial derivative. A system of two coupled equations has been obtained, one is a fractional differential equation for the exciton subsystem, the other is a standard differential equation for the phonon subsystem. These two equations present a new fundamental framework to study nonlinear dynamics with long-range interaction. New approaches to model the impact of long-range interaction on nonlinear dynamics are: fractional generalization of Zakharov system, Hilbert-Zakharov system, Hilbert-Ginzburg-Landau equation and nonlinear Hilbert-Schrodinger equation. Nonlinear fractional Schrodinger equation and fractional Ginzburg-Landau equa...

  6. Insights into the Proton Transfer Mechanism of a Bilin Reductase PcyA Following Neutron Crystallography.

    Science.gov (United States)

    Unno, Masaki; Ishikawa-Suto, Kumiko; Kusaka, Katsuhiro; Tamada, Taro; Hagiwara, Yoshinori; Sugishima, Masakazu; Wada, Kei; Yamada, Taro; Tomoyori, Katsuaki; Hosoya, Takaaki; Tanaka, Ichiro; Niimura, Nobuo; Kuroki, Ryota; Inaka, Koji; Ishihara, Makiko; Fukuyama, Keiichi

    2015-04-29

    Phycocyanobilin, a light-harvesting and photoreceptor pigment in higher plants, algae, and cyanobacteria, is synthesized from biliverdin IXα (BV) by phycocyanobilin:ferredoxin oxidoreductase (PcyA) via two steps of two-proton-coupled two-electron reduction. We determined the neutron structure of PcyA from cyanobacteria complexed with BV, revealing the exact location of the hydrogen atoms involved in catalysis. Notably, approximately half of the BV bound to PcyA was BVH(+), a state in which all four pyrrole nitrogen atoms were protonated. The protonation states of BV complemented the protonation of adjacent Asp105. The "axial" water molecule that interacts with the neutral pyrrole nitrogen of the A-ring was identified. His88 Nδ was protonated to form a hydrogen bond with the lactam O atom of the BV A-ring. His88 and His74 were linked by hydrogen bonds via H3O(+). These results imply that Asp105, His88, and the axial water molecule contribute to proton transfer during PcyA catalysis.

  7. Long-range eye tracking: A feasibility study

    Energy Technology Data Exchange (ETDEWEB)

    Jayaweera, S.K.; Lu, Shin-yee

    1994-08-24

    The design considerations for a long-range Purkinje effects based video tracking system using current technology is presented. Past work, current experiments, and future directions are thoroughly discussed, with an emphasis on digital signal processing techniques and obstacles. It has been determined that while a robust, efficient, long-range, and non-invasive eye tracking system will be difficult to develop, such as a project is indeed feasible.

  8. Lagrangian formulation of continuum with internal long-range interactions

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Based on a new definition of nonlocal variable,this paper establishes the Lagrangian formulation for continuum with internal long-range interactions.Distinguished from the existing theories,the nonlocal term in the Lagrangian formulation automatically satisfies the zero mean condition determined by the action and reaction law.By this formulation,elastic wave in a rod with the internal long-range interactions is investigated.The dispersion of the elastic wave is predicted.

  9. Long-range correlations in ALICE at the LHC

    CERN Document Server

    Altsybeev, Igor

    2016-01-01

    Long-range correlations between particles separated by a pseudorapidity gap are a powerful tool to explore the initial stages and evolution of the medium created in hadron-hadron collisions. An overview of the long-range correlations measured by the ALICE detector in pp, p-Pb and Pb-Pb will be presented. This includes analyses of forward-backward, two- and multi-particle correlations with the use of the central barrel and forward detectors.

  10. Observed Orbit Effects during Long Range Beam-Beam Studies

    CERN Document Server

    Alemany, R; Buffat, X; Calaga, R; Fitterer, M; Giachino, R; Hemelsoet, GH; Herr, W; Papotti, G; Pieloni, T; Poyer, M; Schaumann, M; Trad, G; Wollmann, D

    2012-01-01

    Possible limitations due to long range beam-beam effects at the LHC have been studied and are presented in this note. With a larger number of bunches and collisions in all interaction points, the crossing angles were reduced to enhance long range beam-beam effects. The analysis of the effects on the dynamic aperture and losses are documented in [1]. This note concentrates on the bunch-by-bunch orbit effects observed during the experiment.

  11. Current fluctuations in stochastic systems with long-range memory

    Energy Technology Data Exchange (ETDEWEB)

    Harris, R J; Touchette, H [School of Mathematical Sciences, Queen Mary University of London, Mile End Road, London, E1 4NS (United Kingdom)], E-mail: rosemary.harris@qmul.ac.uk, E-mail: h.touchette@qmul.ac.uk

    2009-08-28

    We propose a method to calculate the large deviations of current fluctuations in a class of stochastic particle systems with history-dependent rates. Long-range temporal correlations are seen to alter the speed of the large deviation function in analogy with long-range spatial correlations in equilibrium systems. We give some illuminating examples and discuss the applicability of the Gallavotti-Cohen fluctuation theorem. (fast track communication)

  12. Properties of Proton Transfer in Hydrogen-Bonded Systems at Finite Temperature

    Institute of Scientific and Technical Information of China (English)

    PANG Xiao-Feng

    2002-01-01

    The properties of proton transfer along hydrogen-bonded molecular systems are studied at finite temperature. The dynamic equations of the proton transport along the systems are obtained by using a completely quantummechanics method. From the dynamic equations and its soliton solutions we find out specific heat arising from the motionof solitons in the systems with finite temperature and the critical temperature of the soliton in the protein molecules,which is about 318 K. This shows that we can continuously study some biological phenomena in the living systems bythis model.

  13. Quantum Transition State Theory for proton transfer reactions in enzymes

    CERN Document Server

    Bothma, Jacques P; McKenzie, Ross H

    2009-01-01

    We consider the role of quantum effects in the transfer of hyrogen-like species in enzyme-catalysed reactions. This study is stimulated by claims that the observed magnitude and temperature dependence of kinetic isotope effects imply that quantum tunneling below the energy barrier associated with the transition state significantly enhances the reaction rate in many enzymes. We use a path integral approach which provides a general framework to understand tunneling in a quantum system which interacts with an environment at non-zero temperature. Here the quantum system is the active site of the enzyme and the environment is the surrounding protein and water. Tunneling well below the barrier only occurs for temperatures less than a temperature $T_0$ which is determined by the curvature of potential energy surface near the top of the barrier. We argue that for most enzymes this temperature is less than room temperature. For physically reasonable parameters quantum transition state theory gives a quantitative descr...

  14. Infrared Laser Driven Double Proton Transfer. An Optimal Control Theory Study

    CERN Document Server

    Abdel-Latif, Mahmoud

    2009-01-01

    Laser control of ultrafast double proton transfer is investigated for a two-dimensional model system describing stepwise and concerted transfer pathways. The pulse design has been done by employing optimal control theory in combination with the multiconfiguration time-dependent Hartree wave packet propagation. The obtained laser fields correspond to multiple pump-dump pulse sequences. Special emphasis is paid to the relative importance of stepwise and concerted transfer pathways for the driven wave packet and its dependence on the parameters of the model Hamiltonian as well as on the propagation time. While stepwise transfer is dominating in all cases considered, for high barrier systems concerted transfer proceeding via tunneling can make a contribution.

  15. Infrared laser driven double proton transfer. An optimal control theory study

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Latif, Mahmoud K. [Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef (Egypt); Institut fuer Physik, Universitaet Rostock, D-18051 Rostock (Germany); Kuehn, Oliver, E-mail: oliver.kuehn@uni-rostock.de [Institut fuer Physik, Universitaet Rostock, D-18051 Rostock (Germany)

    2010-02-18

    Laser control of ultrafast double proton transfer is investigated for a two-dimensional model system describing stepwise and concerted transfer pathways. The pulse design has been done by employing optimal control theory in combination with the multiconfiguration time-dependent Hartree wave packet propagation. The obtained laser fields correspond to multiple pump-dump pulse sequences. Special emphasis is paid to the relative importance of stepwise and concerted transfer pathways for the driven wave packet and its dependence on the parameters of the model Hamiltonian as well as on the propagation time. While stepwise transfer is dominating in all cases considered, for high barrier systems concerted transfer proceeding via tunneling can make a contribution.

  16. Coupled electron and proton transfer processes in 4-dimethylamino-2-hydroxy-benzaldehyde.

    Science.gov (United States)

    Zgierski, Marek Z; Fujiwara, Takashige; Lim, Edward C

    2011-09-08

    TDDFT calculations, picosecond transient absorption, and time-resolved fluorescence studies of 4-dimethylamino-2-hydroxy-benzaldehyde (DMAHBA) have been carried out to study the electron and proton transfer processes in polar (acetonitrile) and nonpolar (n-hexane) solvents. In n-hexane, the transient absorption (TA) as well as the fluorescence originate from the ππ* state of the keto form (with the carbonyl group in the benzaldehyde ring), which is produced by an intramolecular proton transfer from the initially excited ππ* state of the enol form (OH group in the ring). The decay rate of TA and fluorescence are essentially identical in n-hexane. In acetonitrile, on the other hand, the TA exhibits features that can be assigned to the highly polar twisted intramolecular charge transfer (TICT) states of enol forms, as evidenced by the similarity of the absorption to the TICT-state absorption spectra of the closely related 4-dimethylaminobenzaldehyde (DMABA). As expected, the decay rate of the TICT-state of DMAHBA is different from the fluorescence lifetime of the ππ* state of the keto form. The occurrence of the proton and electron transfers in acetonitrile is in good agreement with the predictions of the TDDFT calculations. The very short-lived (∼1 ps) fluorescence from the ππ* state of the enol form has been observed at about 380 nm in n-hexane and at about 400 nm in acetonitrile.

  17. Proton transfer pathways, energy landscape, and kinetics in creatine-water systems.

    Science.gov (United States)

    Ivchenko, Olga; Whittleston, Chris S; Carr, Joanne M; Imhof, Petra; Goerke, Steffen; Bachert, Peter; Wales, David J

    2014-02-27

    We study the exchange processes of the metabolite creatine, which is present in both tumorous and normal tissues and has NH2 and NH groups that can transfer protons to water. Creatine produces chemical exchange saturation transfer (CEST) contrast in magnetic resonance imaging (MRI). The proton transfer pathway from zwitterionic creatine to water is examined using a kinetic transition network constructed from the discrete path sampling approach and an approximate quantum-chemical energy function, employing the self-consistent-charge density-functional tight-binding (SCC-DFTB) method. The resulting potential energy surface is visualized by constructing disconnectivity graphs. The energy landscape consists of two distinct regions corresponding to the zwitterionic creatine structures and deprotonated creatine. The activation energy that characterizes the proton transfer from the creatine NH2 group to water was determined from an Arrhenius fit of rate constants as a function of temperature, obtained from harmonic transition state theory. The result is in reasonable agreement with values obtained in water exchange spectroscopy (WEX) experiments.

  18. Simulation and optimization of beam losses during continuous transfer extraction at the CERN Proton Synchrotron

    CERN Document Server

    Garcia, J B

    2011-01-01

    The proton beams used for the fixed target physics at the Super Proton Synchrotron (SPS) are extracted from the Proton Synchrotron ( PS) by a multiturn technique called continuous transfer (CT). During the CT extraction, large losses are observed in locations where the machine aperture should be large enough to accommodate the circulating beam. This limits the maximum intensity deliverable due to the induced stray radiation outside the PS tunnel. Scattered particles from the interaction with the electrostatic septum are identified as the possible source of these losses. This article presents a detailed study aiming to understand the origin of losses and propose possible cures. The simulations could reproduce accurately the beam loss pattern measured in real machine operation and determine the beam shaving, intrinsic to the extraction process, as the cause for the unexpected losses. Since these losses are unavoidable, the proposed solution implies a new optics scheme displacing the losses to a region with bett...

  19. Proton transfer reactions between nitric acid and acetone, hydroxyacetone, acetaldehyde and benzaldehyde in the solid phase.

    Science.gov (United States)

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-12-01

    The heterogeneous and homogeneous reactions of acetone, hydroxyacetone, acetaldehyde and benzaldehyde with solid nitric acid (HNO(3)) films have been studied with Reflection-Absorption Infrared Spectroscopy (RAIRS) under Ultra-High Vacuum (UHV) conditions in the 90-170 K temperature range. In the bulk or at the surface of the films, nitric acid transfers its proton to the carbonyl function of the organic molecules, producing protonated acetone-H(+), hydroxyacetone-H(+), acetaldehyde-H(+) and benzaldehyde-H(+), and nitrate anions NO(3)(-), a reaction not observed when nitric acid is previously hydrated [J. Lasne, C. Laffon and Ph. Parent, Phys. Chem. Chem. Phys., 2012, 14, 697]. This provides a molecular-scale description of the carbonyl protonation reaction in an acid medium, the first step of the acid-catalyzed condensation of carbonyl compounds, fuelling the growth of secondary organic aerosols (SOA) in the atmosphere.

  20. Localization in the Anderson model with long-range correlated hopping and on-site disorders

    Science.gov (United States)

    Lotfallahzadeh, Shiva; Anvari, Mehrnaz; Ekhtiary, Niko; Esmailpour, Ayoub; Rahimi Tabar, M. Reza

    2015-01-01

    We study the metal-insulator transition in one-dimensional Anderson binary alloy with long-range disordered hopping integrals and on-site energies using the transfer matrix method. In this model, the on-site energies and hopping integrals are distributed randomly with long-range correlations characterized by power spectrum of the type ?, with different exponents ? and ?, respectively. We determine the critical value of long-range correlation exponent of hopping integral ? in the presence of only off-diagonal disorder in which the transition from localized to extended states occurs in thermodynamic limit. When both of the on-site energies and hopping integrals are disordered, there are two parameters ? and ? that control the metal-insulator transition in the system. We draw the phase diagram which separates the localized regime from extended one and it shows the critical values of ? for a given value of ?.

  1. Proton transfer step in the carbon dioxide capture by monoethanol amine: a theoretical study at the molecular level.

    Science.gov (United States)

    Iida, Kenji; Sato, Hirofumi

    2012-02-23

    An aqueous solution of monoethanol amine (MEA) has been utilized in an industrial process of CO(2) absorption. The chemical reaction between CO(2) and MEA, which is employed in the process, consists of two steps. After the formation of the MEA-CO(2) complex ("capture"), a proton transfers from the complex to give a final product. In the present study, the overall mechanism of the reaction is discussed, especially focusing on the proton transfer step. Using RISM-SCF-SEDD, a hybrid method of electronic structure theory and statistical mechanics for molecular liquid, we clarified that the role of MEA as a base is crucial in the proton transfer step.

  2. Theoretical study on the mechanism of double proton transfer in porphycene by path-integral molecular dynamics simulations

    Science.gov (United States)

    Yoshikawa, Takehiro; Sugawara, Shuichi; Takayanagi, Toshiyuki; Shiga, Motoyuki; Tachikawa, Masanori

    2010-08-01

    Full-dimensional path-integral molecular dynamics simulations were performed to determine whether the double proton transfer tautomerization of porphycene is a concerted or a stepwise process. We employed an on-the-fly direct dynamics technique at the semiempirical PM6 method whose parameters were determined so as that the relative energies of the stationary points approximately reproduce previously reported electronic structure calculations. It was found that double proton transfer occurs dominantly through the concerted pathway via the second-order saddle point structure and that contribution of the stepwise mechanism increases with a temperature increase. Nuclear quantum effects play essential roles in determining the proton transfer mechanism.

  3. Ion intensity and thermal proton transfer in ultraviolet matrix-assisted laser desorption/ionization.

    Science.gov (United States)

    Lu, I-Chung; Lee, Chuping; Chen, Hui-Yuan; Lin, Hou-Yu; Hung, Sheng-Wei; Dyakov, Yuri A; Hsu, Kuo-Tung; Liao, Chih-Yu; Lee, Yin-Yu; Tseng, Chien-Ming; Lee, Yuan-Tseh; Ni, Chi-Kung

    2014-04-17

    The ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) was investigated by measuring the total cation intensity (not including sodiated and potasiated ions) as a function of analyte concentration (arginine, histidine, and glycine) in a matrix of 2,4,6-trihydroxyacetophenone (THAP). The total ion intensity increased up to 55 times near the laser fluence threshold as the arginine concentration increased from 0% to 1%. The increases were small for histidine, and a minimal increase occurred for glycine. Time-resolved fluorescence intensity was employed to investigate how analytes affected the energy pooling of the matrix. No detectable energy pooling was observed for pure THAP and THAP/analyte mixtures. The results can be described by using a thermal proton transfer model, which suggested that thermally induced proton transfer is crucial in the primary ion generation in UV-MALDI.

  4. Internal Stark effect mediates intramolecular excited-state proton transfer in 3-hydroxyflavone derivatives

    Science.gov (United States)

    Klymchenko, Andriy S.; Demchenko, Alexander P.

    2002-12-01

    Internal Stark effect in electronic spectra is the effect that is observed when the electronic bands shift udner the influence of promixal charges. In order to study the possible involvement of this effect in modulating the intramolecular proton transfer reactions in the excited state, we designed and studied several derivatives of 3-hydroxyflavone. They include the species containing neutral and positively charged substituents in 6 position of chromone ring. These compounds were studied in solvents of different polarities. In these experiments the shifts of both normal and tautomer flurosence bands are clearly observed in a manner predicted by Stark effect theory. In addition, a dramatic effect of suppression by introduced charge of intramolecular excited-state proton transfer was observed.

  5. A role of proton transfer in peroxidase-catalyzed process elucidated by substrates docking calculations

    Directory of Open Access Journals (Sweden)

    Ziemys Arturas

    2001-08-01

    Full Text Available Abstract Background Previous kinetic investigations of fungal-peroxidase catalyzed oxidation of N-aryl hydroxamic acids (AHAs and N-aryl-N-hydroxy urethanes (AHUs revealed that the rate of reaction was independent of the formal redox potential of substrates. Moreover, the oxidation rate was 3–5 orders of magnitude less than for oxidation of physiological phenol substrates, though the redox potential was similar. Results To explain the unexpectedly low reactivity of AHAs and AHUs we made ab initio calculations of the molecular structure of the substrates following in silico docking in the active center of the enzyme. Conclusions AHAs and AHUs were docked at the distal side of heme in the sites formed by hydrophobic amino acid residues that retarded a proton transfer and finally the oxidation rate. The analogous phenol substrates were docked at different sites permitting fast proton transfer in the relay of distal His and water that helped fast substrate oxidation.

  6. Photoproduction of the ω Meson on the Proton at Large Momentum Transfer

    Science.gov (United States)

    Battaglieri, M.; Brunoldi, M.; de Vita, R.; Laget, J. M.; Osipenko, M.; Ripani, M.; Taiuti, M.; Adams, G.; Amaryan, M. J.; Anciant, E.; Anghinolfi, M.; Armstrong, D. S.; Asavapibhop, B.; Asryan, G.; Audit, G.; Auger, T.; Avakian, H.; Barrow, S.; Beard, K.; Bektasoglu, M.; Berman, B. L.; Bersani, A.; Bianchi, N.; Biselli, A. S.; Boiarinov, S.; Bouchigny, S.; Bradford, R.; Branford, D.; Briscoe, W. J.; Brooks, W. K.; Burkert, V. D.; Calarco, J. R.; Capitani, G. P.; Carman, D. S.; Carnahan, B.; Cazes, A.; Cetina, C.; Cole, P. L.; Coleman, A.; Cords, D.; Corvisiero, P.; Crabb, D.; Crannell, H.; Cummings, J. P.; Desanctis, E.; Degtyarenko, P. V.; Demirchyan, R.; Denizli, H.; Dennis, L.; Dharmawardane, K. V.; Dhuga, K. S.; Djalali, C.; Dodge, G. E.; Doughty, D.; Dragovitsch, P.; Dugger, M.; Dytman, S.; Eckhause, M.; Egiyan, H.; Egiyan, K. S.; Elouadrhiri, L.; Farhi, L.; Feuerbach, R. J.; Ficenec, J.; Forest, T. A.; Freyberger, A. P.; Frolov, V.; Funsten, H.; Gaff, S. J.; Gai, M.; Garcon, M.; Gavalian, G.; Gilad, S.; Gilfoyle, G. P.; Giovanetti, K. L.; Golovach, E.; Griffioen, K.; Guidal, M.; Guillo, M.; Guo, L.; Gyurjyan, V.; Hadjidakis, C.; Hancock, D.; Hardie, J.; Heddle, D.; Hersman, F. W.; Hicks, K.; Hicks, R. S.; Holtrop, M.; Hyde-Wright, C. E.; Ito, M. M.; Joo, K.; Kelley, J. H.; Khandaker, M.; Kim, W.; Klein, A.; Klein, F. J.; Klimenko, A. V.; Klusman, M.; Kossov, M.; Kramer, L. H.; Kuang, Y.; Kuhn, S. E.; Lachniet, J.; Lawrence, D.; Lucas, M.; Lukashin, K.; Major, R. W.; Manak, J. J.; Marchand, C.; McAleer, S.; McCarthy, J.; McNabb, J. W.; Mecking, B. A.; Mestayer, M. D.; Meyer, C. A.; Mikhailov, K.; Mirazita, M.; Miskimen, R.; Mokeev, V.; Morrow, S.; Mozer, M. U.; Muccifora, V.; Mueller, J.; Mutchler, G. S.; Napolitano, J.; Nelson, S. O.; Niccolai, S.; Niczyporuk, B. B.; Niyazov, R. A.; Nozar, M.; O'Brien, J. T.; Opper, A. K.; Peterson, G.; Philips, S. A.; Pivnyuk, N.; Pocanic, D.; Pogorelko, O.; Polli, E.; Preedom, B. M.; Price, J. W.; Protopopescu, D.; Qin, L. M.; Raue, B. A.; Reolon, A. R.; Riccardi, G.; Ricco, G.; Ritchie, B. G.; Ronchetti, F.; Rossi, P.; Rowntree, D.; Rubin, P. D.; Sabourov, K.; Salgado, C.; Sapunenko, V.; Schumacher, R. A.; Serov, V. S.; Shafi, A.; Sharabian, Y. G.; Shaw, J.; Skabelin, A. V.; Smith, E. S.; Smith, T.; Smith, L. C.; Sober, D. I.; Spraker, M.; Stavinsky, A.; Stepanyan, S.; Stoler, P.; Taylor, S.; Tedeschi, D. J.; Todor, L.; Thoma, U.; Thompson, R.; Vineyard, M. F.; Vlassov, A. V.; Wang, K.; Weinstein, L. B.; Weller, H.; Weygand, D. P.; Whisnant, C. S.; Wolin, E.; Wood, M.; Yegneswaran, A.; Yun, J.; Zhang, B.; Zhao, J.; Zhou, Z.

    2003-01-01

    The differential cross section, dσ/dt, for ω meson exclusive photoproduction on the proton above the resonance region (2.6transfer -t=5 GeV2 using the CLAS detector at Jefferson Laboratory. The ω channel was identified by detecting a proton and π+ in the final state and using the missing mass technique. While the low momentum transfer region shows the typical diffractive pattern expected from Pomeron and Reggeon exchange, at large -t the differential cross section has a flat behavior. This feature can be explained by introducing quark interchange processes in addition to the QCD-inspired two-gluon exchange.

  7. Facilitated ion transfer of protonated primary organic amines studied by square wave voltammetry and chronoamperometry.

    Science.gov (United States)

    Torralba, E; Ortuño, J A; Molina, A; Serna, C; Karimian, F

    2014-05-15

    The transfer of the protonated forms of heptylamine, octylamine, decylamine, procaine and procainamide facilitated by dibenzo-18-crown-6 from water to a solvent polymeric membrane has been investigated by using cyclic square wave voltammetry. The experimental voltammograms obtained are in good agreement with theoretical predictions. The values of the standard ion transfer potential, complexation constant and diffusion coefficient in water have been obtained from these experiments, and have been used to draw some conclusions about the lipophilicity of these species and the relative stability of the organic ammonium complexes with dibenzo-18-crown-6. The results have been compared with those provided by linear sweep voltammetry. Calibration graphs were obtained with both techniques. An interesting chronoamperometric method for the determination of the diffusion coefficient of the target ion in the membrane has been developed and applied to all these protonated amines.

  8. Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities.

    Science.gov (United States)

    Miller, David C; Tarantino, Kyle T; Knowles, Robert R

    2016-06-01

    Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter, we aim to highlight the origins, development, and evolution of the PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups.

  9. Long-range interactions in lattice field theory

    Energy Technology Data Exchange (ETDEWEB)

    Rabin, J.M.

    1981-06-01

    Lattice quantum field theories containing fermions can be formulated in a chirally invariant way provided long-range interactions are introduced. It is established that in weak-coupling perturbation theory such a lattice theory is renormalizable when the corresponding continuum theory is, and that the continuum theory is indeed recovered in the perturbative continuum limit. In the strong-coupling limit of these theories one is led to study an effective Hamiltonian describing a Heisenberg antiferromagnet with long-range interactions. Block-spin renormalization group methods are used to find a critical rate of falloff of the interactions, approximately as inverse distance squared, which separates a nearest-neighbor-antiferromagnetic phase from a phase displaying identifiable long-range effects. A duality-type symmetry is present in some block-spin calculations.

  10. Understanding Long-Range Correlations in DNA sequences

    CERN Document Server

    Li, W; Kaneko, K; Wentian Li; Thomas G Marr; Kunihiko Kaneko

    1994-01-01

    Abstract: In this paper, we review the literature on statistical long-range correlation in DNA sequences. We examine the current evidence for these correlations, and conclude that a mixture of many length scales (including some relatively long ones) in DNA sequences is responsible for the observed 1/f-like spectral component. We note the complexity of the correlation structure in DNA sequences. The observed complexity often makes it hard, or impossible, to decompose the sequence into a few statistically stationary regions. We suggest that, based on the complexity of DNA sequences, a fruitful approach to understand long-range correlation is to model duplication, and other rearrangement processes, in DNA sequences. One model, called ``expansion-modification system", contains only point duplication and point mutation. Though simplistic, this model is able to generate sequences with 1/f spectra. We emphasize the importance of DNA duplication in its contribution to the observed long-range correlation in DNA sequen...

  11. Long-range oil and gas forecasting methodologies: literature survey

    Energy Technology Data Exchange (ETDEWEB)

    Cherniavsky, E.A.

    1980-08-01

    Performance of long-range energy system analyses requires the capability to project conventional domestic oil and gas supplies in the long term. The objective of the Long-range Forecasting Methodology project is to formulate an approach to this problem which will be compatible with the principal tool employed by the Energy Information Administration of the Department of Energy for long-range energy system analyses, the Long-term Energy Analysis Package (LEAP). This paper reports on projection methodologies that have appeared in the literature, evaluates them in terms of their applicability to the LEAP framework, and discusses the principal determinants of conventional domestic oil and gas supply in the long run.

  12. Exploring Autoionization and Photoinduced Proton-Coupled Electron Transfer Pathways of Phenol in Aqueous Solution.

    Science.gov (United States)

    Oliver, Thomas A A; Zhang, Yuyuan; Roy, Anirban; Ashfold, Michael N R; Bradforth, Stephen E

    2015-10-15

    The excited state dynamics of phenol in water have been investigated using transient absorption spectroscopy. Solvated electrons and vibrationally cold phenoxyl radicals are observed upon 200 and 267 nm excitation, but with formation time scales that differ by more than 4 orders of magnitude. The impact of these findings is assessed in terms of the relative importance of autoionization versus proton-coupled electron transfer mechanisms in this computationally tractable model system.

  13. Detection of Boronic Acids through Excited-State Intramolecular Proton-Transfer Fluorescence

    Science.gov (United States)

    Aronoff, Matthew R.; VanVeller, Brett

    2013-01-01

    Boronic acids are versatile reagents for the chemical synthesis of organic molecules. They and other boron-containing compounds can be detected readily by the interruption of the excited-state intramolecular proton transfer (ESIPT) of 10-hydroxybenzo[h]quinolone. This method is highly sensitive and selective, and useful for monitoring synthetic reactions and detecting boron-containing compounds on a solid support. PMID:24099104

  14. A novel salt of antidiabetic drug metformin resulting from a proton transfer reaction: Synthesis, characterization, crystal structure and solution studies

    Science.gov (United States)

    Ghasemi, Fatemeh; Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Refahi, Masoud; García-Granda, Santiago; Mendoza-Meroño, Rafael

    2017-03-01

    Reaction between N,N-dimethylebiguanidine, Met = Metformin, and 4-hydroxy-2,6-pyridinedicarboxylic acid, HO-dipicH2, results in the formation of a novel proton transfer compound, [MetH2][HO-dipicH]2·H2O, 1. The characterization was performed using FTIR, UV-Vis, 1H and 13C NMR spectroscopy and X-ray crystallography. The crystal system is triclinic with space group P 1 bar and two molecules per unit cell. The protonation constants of O-dipic and Met, in all of probability protonated forms, and the equilibrium constants for the O-dipic-Met proton transfer system were investigated by the potentiometric pH titration method using the Hyperquad2008 program. The stoichiometry of the proton transfer species in solution were in agreement with the solid state result.

  15. Long-range stresses associated with boundaries in deformed materials

    DEFF Research Database (Denmark)

    Leffers, T.

    1995-01-01

    around the boundaries, a population which, because of the long-range stresses associated, does not represent a perfect LEDS, but the deviation is moderate. For polycrystals with flat grains and for polycrystals with the grains subdivided into flat bands the geometrically necessary dislocations may remain...... in the (grain or band) boundaries, but they still represent a certain, moderate deviation from LEDS. A distinction is made between two contributions from the geometrically necessary dislocations to hardening: conservative hardening which is associated with long-range stresses and frictional hardening which...

  16. Study of beam-beam long range compensation with octupoles

    CERN Document Server

    Barranco Garcia, Javier; Buffat, Xavier; Tambasco, Claudia

    2017-01-01

    Long range beam-beam effects are responsible for particle losses and define fundamental operational parameters of colliders (i.e. crossing angles, intensities, emittances, ${\\beta}$${^∗}$). In this study we propose octuple magnets as a possible scheme to efficiently compensate long-range beam-beam interactions with a global correction scheme. The impact and improvements on the dynamic aperture of colliding beams together with estimates of the luminosity potentials are dis- cussed for the HL-LHC upgrade and extrapolations made for the FCC project.

  17. Long-range dependence in interest rates and monetary policy

    Science.gov (United States)

    Cajueiro, Daniel O.; Tabak, Benjamin M.

    2008-01-01

    This Letter studies the dynamics of Brazilian interest rates for short-term maturities. The Letter employs developed techniques in the econophysics literature and tests for long-range dependence in the term structure of these interest rates for the last decade. Empirical results suggest that the degree of long-range dependence has changed over time due to changes in monetary policy, specially in the short-end of the term structure of interest rates. Therefore, we show that it is possible to identify monetary arrangements using these techniques from econophysics.

  18. Long-range dependence in Interest Rates and Monetary Policy

    CERN Document Server

    Cajueiro, D O; Cajueiro, Daniel O.; Tabak, Benjamin M.

    2006-01-01

    This paper studies the dynamics of Brazilian interest rates for short-term maturities. The paper employs developed techniques in the econophysics literature and tests for long-range dependence in the term structure of these interest rates for the last decade. Empirical results suggest that the degree of long-range dependence has changed over time due to changes in monetary policy, specially in the short-end of the term structure of interest rates. Therefore, we show that it is possible to identify monetary arrangements using these techniques from econophysics.

  19. In what time scale proton transfer takes place in a live CHO cell?

    Science.gov (United States)

    Mojumdar, Supratik Sen; Chowdhury, Rajdeep; Mandal, Amit Kumar; Bhattacharyya, Kankan

    2013-06-01

    Excited state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulfonate, HPTS) in a live Chinese hamster ovary (CHO) cell is studied by time resolved confocal microscopy. The cytoplasm region of the cell is stained by a photoacid, HPTS (HA). The time constant of initial proton transfer (τPT) in the cell is found to be ˜10 times longer than that in bulk water, while the time constants of recombination (τrec) and dissociation (τdiss) in the cell are ˜3 times and ˜2 times longer, respectively. The slower rate of proton transfer (˜10 times) inside the CHO cell compared to that in bulk water is ascribed to slower solvation dynamics, lower availability of free water molecules, and disruption of hydrogen-bond network inside the cell. Translational and rotational diffusion of HPTS inside a single CHO cell have been investigated by fluorescence correlation spectroscopy (FCS) and picosecond anisotropy measurement, respectively. Both the translational and rotational diffusion slow down inside the live cell. FCS studies indicate that HPTS remains tightly bound to a macromolecule inside the cell.

  20. Theoretical study of intermolecular proton transfer reaction in isolated 5-hydroxyisoxazole-water complexes

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China)], E-mail: yonghliang@hotmail.com; Tang, Zhen Q. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China)

    2006-03-20

    A systematic investigation in isolated 5-hydroxyisoxazole-water complexes (5-HIO . (H{sub 2}O) {sub n} n = 1-3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K{sub 2} is the most stable isomer in the gas phase, and the tautomer K{sub 1} to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WE {sub cis} {r_reversible} 3WK{sub 1} and 2WE {sub trans} {r_reversible} 2WK{sub 2} is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between E {sub cis} and K{sub 1} cannot happen without solvent-assisted.

  1. Intramolecular proton transfer and tunnelling reactions of hydroxyphenylbenzoxazole derivatives in Xenon at 15 K

    Energy Technology Data Exchange (ETDEWEB)

    Walla, Peter J. [Max-Planck-Institute for Biophysical Chemistry, Department 010, Spectroscopy and Photochemical Kinetics, Am Fassberg 11, D-37077 Goettingen (Germany) and Department for Biophysical Chemistry, Technical University of Brunswick, Institute for Physical and Theoretical Chemistry, Hans-Sommerstr. 10, D-38106 Braunschweig (Germany)]. E-mail: pwalla@gwdg.de; Nickel, Bernhard [Max-Planck-Institute for Biophysical Chemistry, Department 010, Spectroscopy and Photochemical Kinetics, Am Fassberg 11, D-37077 Goettingen (Germany)

    2005-06-06

    We investigated the site dependence and the tunnelling processes of the intramolecular proton and deuteron transfer in the triplet state of the compounds 2-(2'-hydroxy-4'-methylphenyl)benzoxazole (m-MeHBO) and 2-(2'-hydroxy-3'-methylphenyl)benzoxazoles (o-MeHBO) and their deuterio-oxy analogues in a solid xenon matrix. After singlet excitation there occurs an ultrafast intramolecular enol {yields} keto proton transfer and subsequent intersystem crossing mainly to the keto triplet state. In the triplet state of m-MeHBO, the proton transfer back to the lower enol triplet state is governed by tunnelling processes. In o-MeHBO, however, the enol triplet state is higher and therefore normally no tunnel reaction can be observed. Because of the external heavy atom-effect in a xenon matrix, we were able to investigate the reverse enol-keto-tunnelling after exciting directly the enol triplet state of deuterated o-MeHBO. The time constants of the reverse enol-keto tautomerization are similar to those of the normal keto-enol tautomerization. In a xenon matrix, the observed site-selective phosphorescence spectra are very well-resolved vibrationally. This allowed the study of the tunnel rates in different well-defined sites. The vibrational energies obtained in the spectra are in good agreement with vibrational energies found in resonant Raman and IR spectra of 2-(2'-hydroxyphenyl)benzoxazole (HBO)

  2. Comparative study of stimulated proton-transfer luminescence of three chromones

    Energy Technology Data Exchange (ETDEWEB)

    Parthenopoulos, D.A.; Kasha, M. (Florida State Univ., Tallahassee (United States)); McMorrow, D. (Naval Research Lab., Washington, DC (United States))

    1991-04-04

    The contrasting behavior of three related chromones with respect to amplified spontaneous emission (ASE) and laser action as intramolecular proton-transfer laser systems at room temperature is investigated. The intramolecular proton-transfer laser is considered a chemical laser in which the excited tautomer species is produced by a chemical reaction after photon-pumping activating a four-level laser system. The three chromones studied are 2-methyl-3-hydroxychromone, 2-phenyl-3-hydroxychromone (3-hydroxyflavone), and the natural product fisetin (3,3{prime},4{prime},7-tetrahydroxyflavone), each of which exhibits good proton-transfer fluorescences in the 500-nm region, with respective quantum yields of 0.29 (MCH), 0.36 (MCH), and 0.16 (dioxane). Low-temperature spectroscopic study and picosecond transient absorption spectroscopy reveals that fluorescence quenching from molecular aggregation and transient parasitic S{sub n}{prime} {l arrow} S{sub 1}{prime} absorption of the tautomer both contribute to nonobservability of ASE and lasing action in the 2-methyl-3-hydroxychromone, in contrast to excellent ASE/lasing characteristics of the 3-hydroxyflavone and fisetin under comparable conditions.

  3. Redox-coupled proton transfer mechanism in nitrite reductase revealed by femtosecond crystallography.

    Science.gov (United States)

    Fukuda, Yohta; Tse, Ka Man; Nakane, Takanori; Nakatsu, Toru; Suzuki, Mamoru; Sugahara, Michihiro; Inoue, Shigeyuki; Masuda, Tetsuya; Yumoto, Fumiaki; Matsugaki, Naohiro; Nango, Eriko; Tono, Kensuke; Joti, Yasumasa; Kameshima, Takashi; Song, Changyong; Hatsui, Takaki; Yabashi, Makina; Nureki, Osamu; Murphy, Michael E P; Inoue, Tsuyoshi; Iwata, So; Mizohata, Eiichi

    2016-03-15

    Proton-coupled electron transfer (PCET), a ubiquitous phenomenon in biological systems, plays an essential role in copper nitrite reductase (CuNiR), the key metalloenzyme in microbial denitrification of the global nitrogen cycle. Analyses of the nitrite reduction mechanism in CuNiR with conventional synchrotron radiation crystallography (SRX) have been faced with difficulties, because X-ray photoreduction changes the native structures of metal centers and the enzyme-substrate complex. Using serial femtosecond crystallography (SFX), we determined the intact structures of CuNiR in the resting state and the nitrite complex (NC) state at 2.03- and 1.60-Å resolution, respectively. Furthermore, the SRX NC structure representing a transient state in the catalytic cycle was determined at 1.30-Å resolution. Comparison between SRX and SFX structures revealed that photoreduction changes the coordination manner of the substrate and that catalytically important His255 can switch hydrogen bond partners between the backbone carbonyl oxygen of nearby Glu279 and the side-chain hydroxyl group of Thr280. These findings, which SRX has failed to uncover, propose a redox-coupled proton switch for PCET. This concept can explain how proton transfer to the substrate is involved in intramolecular electron transfer and why substrate binding accelerates PCET. Our study demonstrates the potential of SFX as a powerful tool to study redox processes in metalloenzymes.

  4. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Benjamin Joel [Univ. of California, Berkeley, CA (United States)

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in ~240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH2I2 and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  5. Proton coupled electron transfer from the excited state of a ruthenium(II) pyridylimidazole complex.

    Science.gov (United States)

    Pannwitz, Andrea; Wenger, Oliver S

    2016-04-28

    Proton coupled electron transfer (PCET) from the excited state of [Ru(bpy)2pyimH](2+) (bpy = 2,2'-bipyridine; pyimH = 2-(2'-pyridyl)imidazole) to N-methyl-4,4'-bipyridinium (monoquat, MQ(+)) was studied. While this complex has been investigated previously, our study is the first to show that the formal bond dissociation free energy (BDFE) of the imidazole-N-H bond decreases from (91 ± 1) kcal mol(-1) in the electronic ground state to (43 ± 5) kcal mol(-1) in the lowest-energetic (3)MLCT excited state. This makes the [Ru(bpy)2pyimH](2+) complex a very strong (formal) hydrogen atom donor even when compared to metal hydride complexes, and this is interesting for light-driven (formal) hydrogen atom transfer (HAT) reactions with a variety of different substrates. Mechanistically, formal HAT between (3)MLCT excited [Ru(bpy)2pyimH](2+) and monoquat in buffered 1 : 1 (v : v) CH3CN/H2O was found to occur via a sequence of reaction steps involving electron transfer from Ru(ii) to MQ(+) coupled to release of the N-H proton to buffer base, followed by protonation of reduced MQ(+) by buffer acid. Our study is relevant in the larger contexts of photoredox catalysis and light-to-chemical energy conversion.

  6. A Molecular Dynamic Simulation of Hydrated Proton Transfer in Perfluorosulfonate Ionomer Membranes (Nafion 117

    Directory of Open Access Journals (Sweden)

    Hong Sun

    2015-01-01

    Full Text Available A molecular dynamic model based on Lennard-Jones Potential, the interaction force between two particles, molecular diffusion, and radial distribution function (RDF is presented. The diffusion of the hydrated ion, triggered by both Grotthuss and vehicle mechanisms, is used to study the proton transfer in Nafion 117. The hydrated ion transfer mechanisms and the effects of the temperature, the water content in the membrane, and the electric field on the diffusion of the hydrated ion are analyzed. The molecular dynamic simulation results are in good agreement with those reported in the literature. The modeling results show that when the water content in Nafion 117 is low, H3O+ is the main transfer ion among the different hydrated ions. However, at higher water content, the hydrated ion in the form of H+(H2O2 is the main transfer ion. It is also found that the negatively charged sulfonic acid group as the fortified point facilitates the proton transfer in Nafion 117 better than the free water molecule. The diffusion of the hydrated ion can be improved by increasing the cell temperature, the water content in Nafion, and the electric field intensity.

  7. Comprehensive studies on an overall proton transfer cycle of the ortho-green fluorescent protein chromophore.

    Science.gov (United States)

    Hsieh, Cheng-Chih; Chou, Pi-Tai; Shih, Chun-Wei; Chuang, Wei-Ti; Chung, Min-Wen; Lee, Junghwa; Joo, Taiha

    2011-03-09

    Initiated by excited-state intramolecular proton transfer (ESIPT) reaction, an overall reaction cycle of 4-(2-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (o-HBDI), an analogue of the core chromophore of the green fluorescent protein (GFP), has been investigated. In contrast to the native GFP core, 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (p-HBDI), which requires hydrogen-bonding relay to accomplish proton transfer in vivo, o-HBDI possesses a seven-membered-ring intramolecular hydrogen bond and thus provides an ideal system for mimicking an intrinsic proton-transfer reaction. Upon excitation, ESIPT takes place in o-HBDI, resulting in a ∼600 nm proton-transfer tautomer emission. The o-HBDI tautomer emission, resolved by fluorescence upconversion, is comprised of an instantaneous rise to a few hundred femtosecond oscillation in the early relaxation stage. Frequency analysis derived from ultrashort pulse gives two low-frequency vibrations at 115 and 236 cm(-1), corresponding to skeletal deformation motions associated with the hydrogen bond. The results further conclude that ESIPT in o-HBDI is essentially triggered by low-frequency motions and may be barrierless along the reaction coordinate. Femtosecond UV/vis transient absorption spectra also provide supplementary evidence for the structural evolution during the reaction. In CH(3)CN, an instant rise of a 530 nm transient is resolved, which then undergoes 7.8 ps decay, accompanied by the growth of a rather long-lived 580 nm transient species. It is thus concluded that following ESIPT the cis-proton transfer isomer undergoes cis-trans-isomerization. The results of viscosity-dependent dynamics are in favor of the one-bond-flip mechanism, which is in contrast to the volume-conserving isomerization behavior for cis-stilbene and p-HBDI. Further confirmation is given by the picosecond-femtosecond transient IR absorption spectra, where several new and long-lived IR bands in the range of 1400

  8. Proton transfer assisted charge transfer phenomena in photochromic Schiff bases and effect of -NEt2 groups to the anil Schiff bases.

    Science.gov (United States)

    Jana, Sankar; Dalapati, Sasanka; Guchhait, Nikhil

    2012-11-15

    Photochromic Schiff bases 5-diethylamino-2-[(4-diethylamino-benzylidene)-hydrazonomethyl]-phenol (DDBHP) and N,N'-bis(4-N,N-diethylaminosalisalidene) hydrazine (DEASH) with both the proton and charge transfer moieties have been synthesized, and their photophysical properties such as excited state intramolecular charge transfer (ICT) and proton transfer (ESIPT) processes have been reported on the basis of steady-state and time-resolved spectral measurement in various solvents. The ground-state six-membered intramolecular hydrogen bonding network at the proton transfer site accelerates the ESIPT process for these compounds. Both the compounds show large Stokes-shifted emission bands for proton transfer and charge transfer processes. The hydrogen bonding solvents play a crucial role in these photophysical processes. Excited-state dipole moment of DDBHP and DEASH calculated by the solvatochromic method supports the polar character of the charge transfer excited state. Introduction of -NEt(2) groups to the reported salicylaldehyde azine (SAA) Schiff base results an increase in fluorescence lifetime from femtosecond to picosecond time scale for the proton transfer process.

  9. TRANSFER

    African Journals Online (AJOL)

    “Chemistry Department, Kenyatta University, P. 0. Box 43844 ... harvester (X) [L 2] in a manner consistent with the following Forster equation for long range energy transfer [3-7]. .... sensitive foods, chemical reactors and essences. Recently we ...

  10. Isotope effect maximum for proton transfer between normal acids and bases

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, N.A. (Univ. of Goeteborg); Chiang, Y.; Kresge, A.J.

    1978-08-30

    Kinetic isotope effects were determined for the reaction between p-methylbenzaldehyde and methoxylamine in the presence of thirteen carboxylic acid catalysts and ammonium ions using deuterium oxide as the solvent for k/sub D/ measurements. The ratio of k/sub H//k/sub D/ = 1 for the relatively strong acids, CNCH/sub 2/CO/sub 2/H and HCO/sub 2/H, rise to a maximum approaching 3 for CNCH/sub 2/CH/sub 2/NH/sub 3//sup +/, O(CH/sub 2/CH/sub 2/)/sub 2/NH/sub 2//sup +/, and C/sub 6/H/sub 5/CH/sub 2/NH/sub 3//sup +/, and decrease to less than 2 for CH/sub 3/OCH/sub 2/CH/sub 2/CH/sub 2/NH/sub 3//sup +/, and CH/sub 3/CH/sub 2/CH/sub 2/NH/sub 3//sup +/. The authors state that the maximum observed can not be the result of solvent and secondary isotope effects, but must be caused by a rate determining step involving the proton transfer from the catalyst to the alkoxide oxygen of the first-formed zwitterion intermediate. From a discussion of the pKa's of the proton donor and the protonated proton acceptor (for these systems, pKa = 0), the authors conclude that the experimental data are consistent with a model in which encounter, proton transfer, and separation occur at approximately equal rates.

  11. ATP binding and aspartate protonation enhance photoinduced electron transfer in plant cryptochrome.

    Science.gov (United States)

    Cailliez, Fabien; Müller, Pavel; Gallois, Michaël; de la Lande, Aurélien

    2014-09-17

    Cryptochromes are flavoproteins encountered in most vegetal and animal species. They play a role of blue-light receptors in plants and in invertebrates. The putative resting state of the FAD cofactor in these proteins is its fully oxidized form, FADox. Upon blue-light excitation, the isoalloxazine ring (ISO) may undergo an ultrafast reduction by a nearby tryptophan residue W400. This primary reduction triggers a cascade of electron and proton transfers, ultimately leading to the formation of the FADH° radical. A recent experimental study has shown that the yield of FADH° formation in Arabidopsis cryptochrome can be strongly modulated by ATP binding and by pH, affecting the protonation state of D396 (proton donor to FAD°(-)). Here we provide a detailed molecular analysis of these effects by means of combined classical molecular dynamics simulations and time-dependent density functional theory calculations. When ATP is present and D396 protonated, FAD remains in close contact with W400, thereby enhancing electron transfer (ET) from W400 to ISO*. In contrast, deprotonation of D396 and absence of ATP introduce flexibility to the photoactive site prior to FAD excitation, with the consequence of increased ISO-W400 distance and diminished tunneling rate by almost two orders of magnitude. We show that under these conditions, ET from the adenine moiety of FAD becomes a competitive relaxation pathway. Overall, our data suggest that the observed effects of ATP and pH on the FAD photoreduction find their roots in the earliest stage of the photoreduction process; i.e., ATP binding and the protonation state of D396 determine the preferred pathway of ISO* relaxation.

  12. Long range node-strut analysis of trabecular bone microarchitecture

    DEFF Research Database (Denmark)

    Schmah, Tanya; Marwan, Norbert; Thomsen, Jesper Skovhus

    2011-01-01

    PURPOSE: We present a new morphometric measure of trabecular bone microarchitecture, called mean node strength (NdStr), which is part of a newly developed approach called long range node-strut analysis. Our general aim is to describe and quantify the apparent "latticelike" microarchitecture of th...

  13. Helioseismology with long-range dark matter-baryon interactions

    DEFF Research Database (Denmark)

    Lopes, I.; Panci, Paolo; Silk, J.

    2014-01-01

    the agreement between the best solar model and the helioseismic data without being excluded by direct detection experiments. In particular, the LUX detector will soon be able to either constrain or confirm our best-fit solar model in the presence of a dark sector with long-range interactions that reconcile...

  14. Algebraic Approach to the N-Body Long Range Scattering

    Science.gov (United States)

    Dereziński, Jan

    It is proven that if J, h are bounded continuous functions and H is an N-body Schrödinger operator then there exists s-lim limits {t-> ±∞ } eitH J ((x)/(t))h (H)e-itH. Limits of this form are used to study the N-body long range scattering.

  15. Air Force B-21 Long Range Strike Bomber

    Science.gov (United States)

    2016-04-14

    Congressional Research Service 7 Industrial Base Northrop Grumman intends to build the B-21 at its facilities at Air Force Plant 42 in Palmdale, CA, which were...DefenseNews.com, March 2, 2016. 32 A useful discussion of these issues can be found in Andrew Hunter , “Long Range Strike: 3 Lessons from Defense

  16. Homogeneous cooling with repulsive and attractive long-range interactions

    NARCIS (Netherlands)

    Müller, M.K; Masami, Nakagawa; Luding, Stefan

    2009-01-01

    In granular matter, consisting of discrete particles, long-range interactions imply that each of the particles is interacting with all others. For many charged granular materials with Coulomb repulsion or large-scale gravitationally attractive systems, a Molecular Dynamics environment is developed.

  17. Strategic Long Range Planning for Universities. AIR Forum 1980 Paper.

    Science.gov (United States)

    Baker, Michael E.

    The use of strategic long-range planning at Carnegie-Mellon University (CMU) is discussed. A structure for strategic planning analysis that integrates existing techniques is presented, and examples of planning activities at CMU are included. The key concept in strategic planning is competitive advantage: if a university has a competitive…

  18. Effect of Wind on Long Range Propagation in Shallow Water

    NARCIS (Netherlands)

    Ainslie, M.A.

    2004-01-01

    Long range acoustic propagation in isothermal conditions is considered, involving multiple reflections from the sea surface. If the sea is calm there is almost perfect reflection and hence low loss. The effect of wind is to increase propagation loss due to the interaction with near-surface bubble cl

  19. Directional couplers using long-range surface plasmon polariton waveguides

    DEFF Research Database (Denmark)

    Boltasseva, Alexandra; Bozhevolnyi, Sergey I.

    2006-01-01

    We present an experimental study of guiding and routing of electromagnetic radiation along the nanometer-thin and micrometer-wide gold stripes embedded in a polymer via excitation of long-range surface plasmon polaritons (LR-SPPs) in a very broad wavelength range from 1000 to 1650 mn. For straight...

  20. Long-range interactions in dilute granular systems

    NARCIS (Netherlands)

    Müller, Micha-Klaus

    2008-01-01

    In this thesis, on purpose, we focussed on the most challenging, longest ranging potentials. We analyzed granular media of low densities obeying 1/r long-range interaction potentials between the granules. Such systems are termed granular gases and differ in their behavior from ordinary gases by diss

  1. The long-range electromobility; Die Langstrecken-Elektromobilitaet

    Energy Technology Data Exchange (ETDEWEB)

    Burkert, Andreas

    2013-05-01

    The recent advances in the fuel cell technology prompted the automotive developers to bring to design hybrid electric vehicles with a fuel cell and a lithium-ion battery. Thus, the long-range electric mobility is possible at a short refueling time simultaneously. In addition, the lithium battery is suitable for preconditioning of the hydrogen fuel cell.

  2. Long-range Cerebral Plasticity of the Human Brain after Contralateral C7 Nerve Transfer%臂丛损伤健侧C7神经移位术后大脑运动皮质远期功能重组

    Institute of Scientific and Technical Information of China (English)

    刘彬; 华续赟; 刘含秋; 汤伟军; 张俊海; 冯晓源

    2012-01-01

    Purpose: To assess the characteristics of long-range cerebral plasticity of the human brain cortex after the seventh contralateral cervical nerve transfer by using functional MRI(fMRI). Methods: Nine healthy male volunteers and 8 male patients with total brachial plexus traction injuries (more than 2 years after contralateral C7 nerve transfer) were studied by using fMRI. Functional brain images were acquired under the condition of hand grasping of unilateral hand. Results: All healthy volunteers' unilateral hand movement generated strong signal change in the contralateral sensorimotor cortex and the laterality index of every healthy control was positive. Group analysis of the control group showed the same result as single subject analysis. Movement of the affected hand of patient was associated with a bilateral network activation, but the laterality index was positive, which implied that the main activated areas were located in the contralateral cortex. Group analysis of the 5 right brachial plexus injury patients and single subject analysis of the 3 left brachial plexus injury patients revealed the same results. Conclusion: The brain may try to restore the control of an injured limb to its original cortex after the seventh contralateral cervical nerve transfer.%目的:运用功能磁共振成像方法研究臂丛根性撕脱伤并行健侧C7神经移位术后大脑运动功能的远期变化.方法:8例经临床检查和手术证实一侧全臂丛根性撕脱伤男性患者(健侧C7术后两年以上)以及9名健康男性被试接受磁共振扫描.运动任务为单侧手的抓握运动.结果:健康对照组单侧手运动时所有被试均主要激活对侧初级运动区和辅助运动区而且偏侧化系数均大于0.组分析结果同样显示单侧手运动主要激活对侧大脑半球运动脑区.患者患肢运动激活双侧运动皮质,但偏侧化系数大干0,提示患肢运动主要激活对侧运动皮质(M1和SMA).5例右侧臂丛损伤患者

  3. Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

    Science.gov (United States)

    de Eulate, Eva Alvarez; Silvester, Debbie S; Arrigan, Damien W M

    2015-12-01

    At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  4. Excited state intramolecular proton transfer and charge transfer dynamics of a 2-(2'-hydroxyphenyl)benzoxazole derivative in solution.

    Science.gov (United States)

    Kim, Chul Hoon; Park, Jaehun; Seo, Jangwon; Park, Soo Young; Joo, Taiha

    2010-05-13

    Excited state intramolecular proton transfer (ESIPT) and subsequent intramolecular charge transfer (ICT) dynamics of a 2-(2'-hydroxyphenyl)benzoxazole derivative conjugated with an electron withdrawing group (HBOCE) in solutions and a polymer film has been investigated by femtosecond time-resolved fluorescence (TRF) and TRF spectra measurements without the conventional spectral reconstruction method. TRF with high enough resolution (benzoxazole groups is invoked to account for the dispersive ESIPT dynamics in liquids. From the TRF spectra of both the enol and keto isomers, we have identified the ICT reaction of the keto isomer occurring subsequent to the ESIPT. The ICT proceeds also by two time constants of near instantaneous and 2.7 ps. Since the ICT dynamics of HBOCE is rather close to the polar solvation dynamics, we argue that the ICT is barrierless and determined mostly by the solvent fluctuation.

  5. Model system-bath Hamiltonian and nonadiabatic rate constants for proton-coupled electron transfer at electrode-solution interfaces.

    Science.gov (United States)

    Navrotskaya, Irina; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2008-06-28

    An extension of the Anderson-Newns-Schmickler model for electrochemical proton-coupled electron transfer (PCET) is presented. This model describes reactions in which electron transfer between a solute complex in solution and an electrode is coupled to proton transfer within the solute complex. The model Hamiltonian is derived in a basis of electron-proton vibronic states defined within a double adiabatic approximation for the electrons, transferring proton, and bath modes. The interaction term responsible for electronic transitions between the solute complex and the electrode depends on the proton donor-acceptor vibrational mode within the solute complex. This model Hamiltonian is used to derive the anodic and cathodic rate constants for nonadiabatic electrochemical PCET. The derivation is based on the master equations for the reduced density matrix of the electron-proton subsystem, which includes the electrons of the solute complex and the electrode, as well as the transferring proton. The rate constant expressions differ from analogous expressions for electrochemical electron transfer because of the summation over electron-proton vibronic states and the dependence of the couplings on the proton donor-acceptor vibrational motion. These differences lead to additional contributions to the total reorganization energy, an additional exponential temperature-dependent prefactor, and a temperature-dependent term in the effective activation energy that has different signs for the anodic and cathodic processes. This model can be generalized to describe both nonadiabatic and adiabatic electrochemical PCET reactions and provides the framework for the inclusion of additional effects, such as the breaking and forming of other chemical bonds.

  6. Intermolecular hydrogen bonds: From temperature-driven proton transfer in molecular crystals to denaturation of DNA

    Indian Academy of Sciences (India)

    Mark Johnson

    2008-11-01

    We have combined neutron scattering and a range of numerical simulations to study hydrogen bonds in condensed matter. Two examples from a recent thesis will be presented. The first concerns proton transfer with increasing temperature in short inter-molecular hydrogen bonds [1,2]. These bonds have unique physical and chemical properties and are thought to play a fundamental role in processes like enzymatic catalysis. By combining elastic and inelastic neutron scattering results with ab initio, lattice dynamics and molecular dynamics simulations, low frequency lattice modes are identified which modulate the potential energy surface of the hydrogen bond proton and drive proton transfer. The second example concerns base-pair opening in DNA which is the fundamental physical process underlying biological processes like denaturation and transcription. We have used an emprical force field and a large scale, all-atom phonon calculation to gain insight into the base-pair opening modes and the apparent `energy gap' between the accepted frequencies for these modes (∼ 100 cm-1 or ∼ 140 K) and the temperature of the biological processes (room temperature to 100° C) [3]. Inelastic neutron scattering spectra on aligned, highly crystalline DNA samples, produced at the ILL, provide the reference data for evaluating the precision of these simulation results.

  7. Excited-state intramolecular proton transfer and photoswitching in hydroxyphenyl-imidazopyridine derivatives: A theoretical study

    Science.gov (United States)

    Omidyan, Reza; Iravani, Maryam

    2016-11-01

    The MP2/CC2 and CASSCF theoretical approaches have been employed to determine the excited state proton transfer and photophysical nature of the four organic compounds, having the main frame of hydroxyphenyl-imidzaopyridine (HPIP). The nitrogen insertion effect, in addition to amine (-NH2) substitution has been investigated extensively by following the transition energies and deactivation pathways of resulted HPIP derivatives. It has been predicted that the excited state intramolecular proton transfer with or without small barrier is the most important feature of these compounds. Also, for all of the considered HPIP derivatives, a conical intersection (CI) between ground and the S1 excited state has been predicted. The strong non-adiabatic coupling in the CI (S1/S0), drives the system back to the ground state in which the proton may either return to the phenoxy unit and thus close the photocycle, or the system can continue the twisting motion that results in formation of a γ-photochromic species. This latter species can be responsible for photochromism of HPIP derivative systems.

  8. Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.

    Science.gov (United States)

    Amorati, Riccardo; Baschieri, Andrea; Morroni, Gloria; Gambino, Rossana; Valgimigli, Luca

    2016-06-01

    The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay.

  9. White light generation by carbonyl based indole derivatives due to proton transfer: an efficient fluorescence sensor.

    Science.gov (United States)

    Singla, Nidhi; Bhadram, Venkata Srinu; Narayana, Chandrabhas; Chowdhury, Papia

    2013-04-01

    The motivation of the present work is to understand the optical, chemical, and electrical aspects of the proton transfer mechanism of indole (I) and some carbonyl based indole derivatives: indole-3-carboxaldehyde (I3C) and indole-7-carboxaldehyde (I7C) for both powder form and their liquid solution. Structural information for indole derivatives (isolated molecule and in solution) is obtained with density functional theory (DFT) and time dependent DFT (TD-DFT) methods. Calculated transition energies are used to generate UV-vis, FTIR, Raman, and NMR spectra which are later verified with the experimental spectra. The occurrence of different conformers [cis (N(c)), trans (N(t)), and zwitterion (Z*)] have been interpreted by Mulliken charge, natural bond orbital (NBO) analysis, and polarization versus electric field (P-E loop) studies. (1)H and (13)C NMR and molecular vibrational frequencies of the fundamental modes established the stability of Nc due to the presence of intramolecular hydrogen bonding (IHB) in the ground state (S0). Computed/experimental UV-vis absorption/emission studies reveal the creation of new species: zwitterion (Z*) and anion (A*) in the excited state (S1) due to excited state intramolecular and intermolecular proton transfer (ESI(ra)PT and ESI(er)PT). Increased electrical conductivity (σ(ac)) with temperature and increased ferroelectric polarization at higher field verifies proton conduction in I7C.

  10. Neutron structure of human carbonic anhydrase II: implications for proton transfer.

    Science.gov (United States)

    Fisher, S Zoë; Kovalevsky, Andrey Y; Domsic, John F; Mustyakimov, Marat; McKenna, Robert; Silverman, David N; Langan, Paul A

    2010-01-26

    Human carbonic anhydrase II (HCA II) catalyzes the reversible hydration of carbon dioxide to form bicarbonate and a proton. Despite many high-resolution X-ray crystal structures, mutagenesis, and kinetic data, the structural details of the active site, especially the proton transfer pathway, are unclear. A large HCA II crystal was prepared at pH 9.0 and subjected to vapor H-D exchange to replace labile hydrogens with deuteriums. Neutron diffraction studies were conducted at the Protein Crystallography Station at Los Alamos National Laboratory. The structure to 2.0 A resolution reveals several interesting active site features: (1) the Zn-bound solvent appearing to be predominantly a D(2)O molecule, (2) the orientation and hydrogen bonding pattern of solvent molecules in the active site cavity, (3) the side chain of His64 being unprotonated (neutral) and predominantly in an inward conformation pointing toward the zinc, and (4) the phenolic side chain of Tyr7 appearing to be unprotonated. The implications of these details are discussed, and a proposed mechanism for proton transfer is presented.

  11. Proton and charge transfer reactions dynamics of a hydroxyflavone derivative in a polar solvent and in a cyclodextrin nanocavity

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, M.; Organero, J.A. [Departamento de Quimica Fisica, Seccion de Quimicas, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avda. Carlos III, S.N., 45071 Toledo (Spain); Douhal, A. [Departamento de Quimica Fisica, Seccion de Quimicas, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avda. Carlos III, S.N., 45071 Toledo (Spain)], E-mail: Abderrazzak.douhal@uclm.es

    2007-09-25

    In this work, we report on the observation of ultrafast intramolecular charge- and proton-transfer reactions of 4'-dimethylaminoflavonol (DMAF) in N,N-dimethyl formamide and in {gamma}-cyclodextrin ({gamma}-CD) solution. Upon femtosecond excitation an intramolecular charge transfer (ICT) reaction takes place to produce an ICT structure in {approx}200 fs. This structure may undergo a proton transfer reaction to generate a zwitterionic (Z) form in 2-3 ps, or relaxes in its potential energy well, to later equilibrate with that of Z in hundreds of ps. Addition of {gamma}-CD does not significantly affect the fast dynamics of the formed anion. The fs-emission signals of the parent molecule, 3-hydroxyflavone, indicate that the dimethyl amino group in DMAF enhances the rate constant of intermolecular proton-transfer and intramolecular charge-transfer reactions.

  12. A quantum chemical study of the mechanism for proton-coupled electron transfer leading to proton pumping in cytochrome c oxidase

    Science.gov (United States)

    Blomberg, Margareta R. A.; Siegbahn, Per E. M.

    2010-10-01

    The proton pumping mechanism in cytochrome c oxidase, the terminal enzyme in the respiratory chain, has been investigated using hybrid DFT with large chemical models. In previous studies, a gating mechanism was suggested based on electrostatic interpretations of kinetic experiments. The predictions from that analysis are tested here. The main result is that the suggestion of a positively charged transition state for proton transfer is confirmed, while some other suggestions for the gating are not supported. It is shown that a few critical relative energy values from the earlier studies are reproduced with quite high accuracy using the present model calculations. Examples are the forward barrier for proton transfer from the N-side of the membrane to the pump-loading site when the heme a cofactor is reduced, and the corresponding back leakage barrier when heme a is oxidised. An interesting new finding is an unexpected double-well potential for proton transfer from the N-side to the pump-loading site. In the intermediate between the two transition states found, the proton is bound to PropD on heme a. A possible purpose of this type of potential surface is suggested here. The accuracy of the present values are discussed in terms of their sensitivity to the choice of dielectric constant. Only one energy value, which is not critical for the present mechanism, varies significantly with this choice and is therefore less certain.

  13. Proton transfer in the K-channel analog of B-type Cytochrome c oxidase from Thermus thermophilus.

    Science.gov (United States)

    Woelke, Anna Lena; Wagner, Anke; Galstyan, Gegham; Meyer, Tim; Knapp, Ernst-Walter

    2014-11-04

    A key enzyme in aerobic metabolism is cytochrome c oxidase (CcO), which catalyzes the reduction of molecular oxygen to water in the mitochondrial and bacterial membranes. Substrate electrons and protons are taken up from different sides of the membrane and protons are pumped across the membrane, thereby generating an electrochemical gradient. The well-studied A-type CcO uses two different entry channels for protons: the D-channel for all pumped and two consumed protons, and the K-channel for the other two consumed protons. In contrast, the B-type CcO uses only a single proton input channel for all consumed and pumped protons. It has the same location as the A-type K-channel (and thus is named the K-channel analog) without sharing any significant sequence homology. In this study, we performed molecular-dynamics simulations and electrostatic calculations to characterize the K-channel analog in terms of its energetic requirements and functionalities. The function of Glu-15B as a proton sink at the channel entrance is demonstrated by its rotational movement out of the channel when it is deprotonated and by its high pKA value when it points inside the channel. Tyr-244 in the middle of the channel is identified as the valve that ensures unidirectional proton transfer, as it moves inside the hydrogen-bond gap of the K-channel analog only while being deprotonated. The electrostatic energy landscape was calculated for all proton-transfer steps in the K-channel analog, which functions via proton-hole transfer. Overall, the K-channel analog has a very stable geometry without large energy barriers.

  14. Entropy and long-range correlations in random symbolic sequences

    CERN Document Server

    Melnik, S S

    2014-01-01

    The goal of this paper is to develop an estimate for the entropy of random long-range correlated symbolic sequences with elements belonging to a finite alphabet. As a plausible model, we use the high-order additive stationary ergodic Markov chain. Supposing that the correlations between random elements of the chain are weak we express the differential entropy of the sequence by means of the symbolic pair correlation function. We also examine an algorithm for estimating the differential entropy of finite symbolic sequences. We show that the entropy contains two contributions, the correlation and fluctuation ones. The obtained analytical results are used for numerical evaluation of the entropy of written English texts and DNA nucleotide sequences. The developed theory opens the way for constructing a more consistent and sophisticated approach to describe the systems with strong short- and weak long-range correlations.

  15. One-dimensional long-range percolation: A numerical study

    Science.gov (United States)

    Gori, G.; Michelangeli, M.; Defenu, N.; Trombettoni, A.

    2017-07-01

    In this paper we study bond percolation on a one-dimensional chain with power-law bond probability C /rd +σ , where r is the distance length between distinct sites and d =1 . We introduce and test an order-N Monte Carlo algorithm and we determine as a function of σ the critical value Cc at which percolation occurs. The critical exponents in the range 0 introduction of a suitably defined effective dimension deff relating the long-range model with a short-range one in dimension deff. We finally present a formulation of our algorithm for bond percolation on general graphs, with order N efficiency on a large class of graphs including short-range percolation and translationally invariant long-range models in any spatial dimension d with σ >0 .

  16. Travel: a long-range goal of retired women.

    Science.gov (United States)

    Staats, Sara; Pierfelice, Loretta

    2003-09-01

    The authors surveyed retired persons (predominately women) with regard to their immediate, intermediate, and long-range activities following retirement. As predicted, leisure travel emerged as a frequent long-range goal for persons retired more than 5 years. The travel activity preferences of long-retired older women present challenges and opportunities to both researchers and marketers. Length of trips and frequency of trips have been predicted from regression models, with trip length in particular being well predicted by the problem of daily life hassles. A theoretical model of continued post-retirement travel is presented as a variant of Solomon's opponent process theory of affect (R. L. Solomon, 1980). The authors suggest that to the degree that places traveled to are varied and different, older people may remain stimulated and continue to enjoy retirement.

  17. Long-range boundary effects in simple fluids

    Science.gov (United States)

    Nieuwoudt, J. C.; Kirkpatrick, T. R.; Dorfman, J. R.

    1984-01-01

    We discuss long-range boundary effects in simple two- or three-dimensional fluids. These boundary effects are due to the existence of long-range correlations in nonequilibrium fluids and can be computed either by means of kinetic theory or phenomenological mode-coupling theories. In particular, we use kinetic theory to compute the stress tensor and heat flux vector for a fluid in a nonequilibrium steady state in a finite geometry and show that both the effective shear viscosity and effective heat conductivity have contributions due to the walls of the container that influence the behavior of the system far into the fluid. We also show that the mechanocaloric effect is present in the bulk of a three-dimensional fluid and that there are normal stresses in a fluid whenever the temperature gradient is nonzero.

  18. SEGMENTATION AND QUALITY ANALYSIS OF LONG RANGE CAPTURED IRIS IMAGE

    Directory of Open Access Journals (Sweden)

    Anand Deshpande

    2016-05-01

    Full Text Available The iris segmentation plays a major role in an iris recognition system to increase the performance of the system. This paper proposes a novel method for segmentation of iris images to extract the iris part of long range captured eye image and an approach to select best iris frame from the iris polar image sequences by analyzing the quality of iris polar images. The quality of iris image is determined by the frequency components present in the iris polar images. The experiments are carried out on CASIA-long range captured iris image sequences. The proposed segmentation method is compared with Hough transform based segmentation and it has been determined that the proposed method gives higher accuracy for segmentation than Hough transform.

  19. Conformal invariance in the long-range Ising model

    Energy Technology Data Exchange (ETDEWEB)

    Paulos, Miguel F. [CERN, Theory Group, Geneva (Switzerland); Rychkov, Slava, E-mail: slava.rychkov@lpt.ens.fr [CERN, Theory Group, Geneva (Switzerland); Laboratoire de Physique Théorique de l' École Normale Supérieure (LPTENS), Paris (France); Faculté de Physique, Université Pierre et Marie Curie (UPMC), Paris (France); Rees, Balt C. van [CERN, Theory Group, Geneva (Switzerland); Zan, Bernardo [Institute of Physics, Universiteit van Amsterdam, Amsterdam (Netherlands)

    2016-01-15

    We consider the question of conformal invariance of the long-range Ising model at the critical point. The continuum description is given in terms of a nonlocal field theory, and the absence of a stress tensor invalidates all of the standard arguments for the enhancement of scale invariance to conformal invariance. We however show that several correlation functions, computed to second order in the epsilon expansion, are nontrivially consistent with conformal invariance. We proceed to give a proof of conformal invariance to all orders in the epsilon expansion, based on the description of the long-range Ising model as a defect theory in an auxiliary higher-dimensional space. A detailed review of conformal invariance in the d-dimensional short-range Ising model is also included and may be of independent interest.

  20. Conformal invariance in the long-range Ising model

    Directory of Open Access Journals (Sweden)

    Miguel F. Paulos

    2016-01-01

    Full Text Available We consider the question of conformal invariance of the long-range Ising model at the critical point. The continuum description is given in terms of a nonlocal field theory, and the absence of a stress tensor invalidates all of the standard arguments for the enhancement of scale invariance to conformal invariance. We however show that several correlation functions, computed to second order in the epsilon expansion, are nontrivially consistent with conformal invariance. We proceed to give a proof of conformal invariance to all orders in the epsilon expansion, based on the description of the long-range Ising model as a defect theory in an auxiliary higher-dimensional space. A detailed review of conformal invariance in the d-dimensional short-range Ising model is also included and may be of independent interest.

  1. Optical measurements of long-range protein vibrations

    Science.gov (United States)

    Acbas, Gheorghe; Niessen, Katherine A.; Snell, Edward H.; Markelz, A. G.

    2014-01-01

    Protein biological function depends on structural flexibility and change. From cellular communication through membrane ion channels to oxygen uptake and delivery by haemoglobin, structural changes are critical. It has been suggested that vibrations that extend through the protein play a crucial role in controlling these structural changes. While nature may utilize such long-range vibrations for optimization of biological processes, bench-top characterization of these extended structural motions for engineered biochemistry has been elusive. Here we show the first optical observation of long-range protein vibrational modes. This is achieved by orientation-sensitive terahertz near-field microscopy measurements of chicken egg white lysozyme single crystals. Underdamped modes are found to exist for frequencies >10 cm-1. The existence of these persisting motions indicates that damping and intermode coupling are weaker than previously assumed. The methodology developed permits protein engineering based on dynamical network optimization.

  2. Temperature inversion in long-range interacting systems.

    Science.gov (United States)

    Teles, Tarcísio N; Gupta, Shamik; Di Cintio, Pierfrancesco; Casetti, Lapo

    2015-08-01

    Temperature inversions occur in nature, e.g., in the solar corona and in interstellar molecular clouds: Somewhat counterintuitively, denser parts of the system are colder than dilute ones. We propose a simple and appealing way to spontaneously generate temperature inversions in systems with long-range interactions, by preparing them in inhomogeneous thermal equilibrium states and then applying an impulsive perturbation. In similar situations, short-range systems would typically relax to another thermal equilibrium, with a uniform temperature profile. By contrast, in long-range systems, the interplay between wave-particle interaction and spatial inhomogeneity drives the system to nonequilibrium stationary states that generically exhibit temperature inversion. We demonstrate this mechanism in a simple mean-field model and in a two-dimensional self-gravitating system. Our work underlines the crucial role the range of interparticle interaction plays in determining the nature of steady states out of thermal equilibrium.

  3. Observation of Prethermalization in Long-Range Interacting Spin Chains

    CERN Document Server

    Neyenhuis, B; Lee, A C; Zhang, J; Richerme, P; Hess, P W; Gong, Z -X; Gorshkov, A V; Monroe, C

    2016-01-01

    Statistical mechanics can predict thermal equilibrium states for most classical systems, but for an isolated quantum system there is no general understanding on how equilibrium states dynamically emerge from the microscopic Hamiltonian. For instance, quantum systems that are near-integrable usually fail to thermalize in an experimentally realistic time scale and, instead, relax to quasi-stationary prethermal states that can be described by statistical mechanics when approximately conserved quantities are appropriately included in a generalized Gibbs ensemble (GGE). Here we experimentally study the relaxation dynamics of a chain of up to 22 spins evolving under a long-range transverse field Ising Hamiltonian following a sudden quench. For sufficiently long-ranged interactions the system relaxes to a new type of prethermal state that retains a strong memory of the initial conditions. In this case, the prethermal state cannot be described by a GGE, but rather arises from an emergent double-well potential felt by...

  4. Learning Long-range Terrain Perception for Autonomous Mobile Robots

    Directory of Open Access Journals (Sweden)

    Mingjun Wang

    2010-02-01

    Full Text Available Long-range terrain perception has a high value in performing efficient autonomous navigation and risky intervention tasks for field robots, such as earlier recognition of hazards, better path planning, and higher speeds. However, Stereo-based navigation systems can only perceive near-field terrain due to the nearsightedness of stereo vision. Many near-to-far learning methods, based on regions' appearance features, are proposed to predict the far-field terrain. We proposed a statistical prediction framework to enhance long-range terrain perception for autonomous mobile robots. The main difference between our solution and other existing methods is that our framework not only includes appearance features as its prediction basis, but also incorporates spatial relationships between terrain regions in a principled way. The experiment results show that our framework outperforms other existing approaches in terms of accuracy, robustness and adaptability to dynamic unstructured outdoor environments.

  5. Emergent long-range couplings in arrays of fluid cells

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Douglas Bruce [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2014-08-07

    We present a system exhibiting extraordinarily long-range cooperative effects, on a length scale far exceeding the bulk correlation length. We give a theoretical explanation of these phenomena based on the mesoscopic picture of phase coexistence in finite systems, which is confirmedly Monte Carlo (MC) simulation studies. Our work demonstrates that such action-at-a-distance can occur in classical systems involving simple or complex fluids, such as colloid-polymer mixtures, or ferromagnets.

  6. Long Range Microimage Transmission Techniques Study for AFMPC

    Science.gov (United States)

    1979-10-01

    of MIT Cambridge, Massa- chusetts, and EPSCO Laboratories ( now defunct) in Wilton, Connecticut. Their results indicate that the long range... EPSCO Laboratories (now defunrt) in Wilton, Connecticut. The NOSC effort was sponsored by the Bureau of Naval Personnel, the ESL effort was conducted...in support of the Library of Congress and the EPSCO Laboratory effort was sponsored by RADC in support of the Foreign Technology Division at Wright

  7. Long range anti-ferromagnetic spin model for prebiotic evolution

    Energy Technology Data Exchange (ETDEWEB)

    Nokura, Kazuo [Shonan Institute of Technology, Fujisawa 251-8511 (Japan)

    2003-11-28

    I propose and discuss a fitness function for one-dimensional binary monomer sequences of macromolecules for prebiotic evolution. The fitness function is defined by the free energy of polymers in the high temperature random coil phase. With repulsive interactions among the same kind of monomers, the free energy in the high temperature limit becomes the energy function of the one-dimensional long range anti-ferromagnetic spin model, which is shown to have a dynamical phase transition and glassy states.

  8. The long range distributed fiber raman photon temperature sensor

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A 31 km long range distributed optical fiber Raman photon temperature sensor (DOFRPTS) system have been developed based on temperature effect of the amplified spontaneous Raman scattering in fiber, and using fiber laser as a pumped source. The results show that temperature measuring uncertainty is ±2 ℃, temperature resolution is 0.1 ℃, measurement time is 432 s, spatial resolution is less than 4 m.

  9. Extreme long range process effects characterization and compensation

    Science.gov (United States)

    Figueiro, Thiago; Browning, Clyde; Thornton, Martin J.; Vannuffel, Cyril; Choi, Kang-Hoon; Hohle, Christoph; Tortai, Jean-Herve; Schiavone, Patrick

    2013-10-01

    Proximity Effects in electron beam lithography impact feature dimensions, pattern fidelity and uniformity. These effects are addressed using a mathematical model representing the radial exposure intensity distribution induced by a point electron source, commonly named as the Point Spread Function (PSF). PSF models are usually employed for predicting and compensating for effects up to 15μm. It is well known that there are also some process related phenomena that impact pattern uniformity that have a longer range, namely CMP effects, fogging, etc. Performing proximity effects corrections can result in lengthy run times as file size and pattern densities continue to increase exponentially per technology node. Running corrections for extreme long range phenomena becomes computational and file size prohibitive. Nevertheless, since extreme long range may reach up several millimeters, and new technology nodes require a high level of precision, a strategy for predicting and compensating these phenomena is crucial. In this paper a set of test patterns are presented in order to verify and calibrate the so called extreme long range effects in the electron beam lithography. Moreover, a strategy to compensate for extreme long range effects based on the pattern density is presented. Since the evaluation is based on a density map instead of the actual patterns, the computational effort is feasible. The proposed method may be performed off-line (in contrast to machine standard in-line correction). The advantage of employing off-line compensation relies on enhancing the employ of dose and/or geometry modulation. This strategy also has the advantage of being completely decoupled from other e-beam writer's internal corrections (like Fogging Effect Correction - FEC).

  10. On the search for new long-range forces

    CERN Document Server

    Okun, Lev Borisovich

    1980-01-01

    The hypothesis is discussed of the existence of new long-range forces in addition to gravitational and electromagnetic forces. It is assumed that the forces act between massive elementary particles of a new type which have not been observed hitherfore experimentally. A search for such particles could be carried out by means of exact and systematic gravimetric measurements on the surface of the Earth as well as in the solar system. (11 refs).

  11. ENSEMBLE methods to reconcile disparate national long range dispersion forecasting

    Energy Technology Data Exchange (ETDEWEB)

    Mikkelsen, T.; Galmarini, S.; Bianconi, R.; French, S. (eds.)

    2003-11-01

    ENSEMBLE is a web-based decision support system for real-time exchange and evaluation of national long-range dispersion forecasts of nuclear releases with cross-boundary consequences. The system is developed with the purpose to reconcile among disparate national forecasts for long-range dispersion. ENSEMBLE addresses the problem of achieving a common coherent strategy across European national emergency management when national long-range dispersion forecasts differ from one another during an accidental atmospheric release of radioactive material. A series of new decision-making 'ENSEMBLE' procedures and Web-based software evaluation and exchange tools have been created for real-time reconciliation and harmonisation of real-time dispersion forecasts from meteorological and emergency centres across Europe during an accident. The new ENSEMBLE software tools is available to participating national emergency and meteorological forecasting centres, which may choose to integrate them directly into operational emergency information systems, or possibly use them as a basis for future system development. (au)

  12. Acceleration of Evolutionary Spread by Long-Range Dispersal

    Science.gov (United States)

    Hallatschek, Oskar

    2014-03-01

    The spreading of evolutionary novelties across populations is the central element of adaptation. Unless population are well-mixed (like bacteria in a shaken test tube), the spreading dynamics not only depends on fitness differences but also on the dispersal behavior of the species. Spreading at a constant speed is generally predicted when dispersal is sufficiently short-ranged. However, the case of long-range dispersal is unresolved: While it is clear that even rare long-range jumps can lead to a drastic speedup, it has been difficult to analyze the ensuing stochastic growth process. We present a simple self-consistent argument supported by simulations that accurately predicts evolutionary spread for broad distributions of long distance dispersal. In contrast to the exponential laws predicted by deterministic ``mean-field'' models, spread is either according to a super-linear power-law or a stretched exponential law, depending on the tails of the dispersal kernel. Fluctuations and the relation to supercritical long-range percolation are discussed. Due to the simplicity of our model, which lacks any complex interactions between individuals, we expect our results to be applicable to a wide range of spreading processes. Our results may be used, in particular, to estimate the spread of modern human epidemics, which are greatly accelerated by the human aviation. Based on joint work with Daniel S. Fisher, Stanford.

  13. Admission control with long-range dependence traffic input

    Institute of Scientific and Technical Information of China (English)

    RAO Yun-hua; ZOU Xue-cheng

    2005-01-01

    The admission control scheme is investigated for a FIFO self-similar queuing system with Quality of Service (QoS) performance guarantees. Since the self-similar queuing system performance analysis is often carried out under the condition of infinite buffer, it is difficult to deduce the upper boundary of buffer overflow probability. To overcome this shortcoming, a simple overflow condition is proposed, which defines a buffer overflow occurrence whenever the arrival rate exceeds the service rate. The analytic formula for the buffer overflow probability upper boundary is easily obtained under this condition. The required bandwidth upper boundary with long-range dependence input and determined overflow probability is then derived from this formula. Based on the above analytic formulas, the upper boundaries of the admission control regions for homogeneous and heterogeneous long-range dependence traffic sources are separately obtained. Finally, an effective admission control scheme for long-range dependence input is proposed. Simulation studies with real traffic have confirmed the validity of these results.

  14. Long-range electrostatic screening in ionic liquids.

    Science.gov (United States)

    Gebbie, Matthew A; Dobbs, Howard A; Valtiner, Markus; Israelachvili, Jacob N

    2015-06-16

    Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems.

  15. Long-Range Forces in Direct Dark Matter Searches

    CERN Document Server

    Fornengo, N; Regis, M

    2011-01-01

    We discuss the positive indications of a possible dark matter signal in direct detection experiments in terms of a mechanism of interaction between the dark matter particle and the nuclei occurring via the exchange of a light mediator, resulting in a long-range interaction. We analyze the annual modulation results observed by the DAMA and CoGeNT experiments and the observed excess of events of CRESST. In our analysis, we discuss the relevance of uncertainties related to the velocity distribution of galactic dark matter and to the channeling effect in NaI. We find that a long-range force is a viable mechanism, which can provide full agreement between the reconstructed dark matter properties from the various experimental data sets, especially for masses of the light mediator in the 10-30 MeV range and a light dark matter with a mass around 10 GeV. The relevant bounds on the light mediator mass and scattering cross section are then derived, should the annual modulation effects be due to this class of long-range ...

  16. CALCULATION OF THE PROTON-TRANSFER RATE USING DENSITY-MATRIX EVOLUTION AND MOLECULAR-DYNAMICS SIMULATIONS - INCLUSION OF THE PROTON EXCITED-STATES

    NARCIS (Netherlands)

    MAVRI, J; BERENDSEN, HJC

    1995-01-01

    The methodology for treatment of proton transfer processes by density matrix evolution (DME) with inclusion of many excited states is presented. The DME method (Berendsen, H. J. C.; Mavri, J. J. Phys. Chem. 1993, 97, 13464) that simulates the dynamics of quantum systems embedded in a classical envir

  17. Proton-coupled electron transfers: pH-dependent driving forces? Fundamentals and artifacts.

    Science.gov (United States)

    Bonin, Julien; Costentin, Cyrille; Robert, Marc; Routier, Mathilde; Savéant, Jean-Michel

    2013-09-25

    Besides its own interest, tryptophan oxidation by photogenerated Ru complexes is one of the several examples where concerted proton-electron transfer (CPET) to water as proton acceptor endowed with a pH-dependent driving force has been invoked to explain the data. Since this notion is contrary to the very basic principles of chemical physics, it was interesting to attempt uncovering the source of this contradiction with an easily accessible substrate. Careful examination of the oxidation of the tryptophan (ethyl ester derivative) bearing a NH3(+)/NH2 group showed that there is no trace of such an unconventional H2O-CPET with a pH-dependent driving force. The reaction mechanism simply consists, with both the NH3(+) acid and NH2 basic forms of the tryptophan derivative, in a rate-determining electron-transfer step followed by deprotonation steps. The same is true with the ethyl ester-methyl amide derivative of tryptophan, whose behavior is even simpler since the molecule does not bear an acid-base group. No such unconventional H2O-CPET was found with phenol, another easily accessible substrate. It may thus be inferred that the same applies to less easily available systems in which electron transfer occurs intramolecularly. These observations help to rid the road of such artificial obstacles and improve present models of H2O-CPET reactions, a landmark towards the understanding of the role of water chains in natural systems.

  18. Excited-state charge coupled proton transfer reaction in dipole-functionalized salicylideneaniline

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Kew-Yu, E-mail: kyuchen@fcu.edu.tw; Hu, Jiun-Wei

    2015-03-15

    Based on design and synthesis of salicylideneaniline derivatives 1–4, we demonstrate an exceedingly useful system to investigate the excited-state intramolecular charge transfer (ESICT) coupled with excited-state intramolecular proton transfer (ESIPT) reaction via the dipolar functionality of Schiff base salicylideneaniline. In solid and aprotic solvents 1–4 exist mainly as E conformers that possess a strong intramolecular six-membered-ring hydrogen bond. Compounds 2–4 exhibit solely a long-wavelength proton-transfer tautomer emission, while dipole-functionalized Schiff base 1 exhibits remarkable dual emission due to the different solvent-polarity environments between ESICT and ESIPT states. Moreover, the geometric structures, frontier molecular orbitals (MOs) and the potential energy curves for 1–4 in the ground and the first singlet excited state were fully rationalized by density functional theory (DFT) and time-dependent DFT calculations. - Highlights: • A dipole-functionalized salicylideneaniline derivative was synthesized. • The Schiff base exhibits remarkable dual emission. • A novel ESICT/ESIPT coupled system was created.

  19. Evidence of coupled photoinduced proton transfer and intramolecular charge transfer reaction in para-N,N-dimethylamino orthohydroxy benzaldehyde: Spectroscopic and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Mahanta, Subrata; Singh, Rupashree Balia; Kar, Samiran [Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700009 (India); Guchhait, Nikhil [Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700009 (India)], E-mail: nguchhait@yahoo.com

    2008-12-10

    Steady state and time resolved fluorescence spectroscopy and quantum chemical calculations have been used to study excited state properties of para-N,N-dimethylamino orthohydroxy benzaldehyde (PDOHBA). Spectral characteristics of PDOHBA support the existence of both donor-acceptor charge transfer (CT) and proton transfer (PT) reaction in the excited state. Structural calculations at Hartree Fock and Density Functional Theory (DFT) levels and theoretical potential energy surfaces (PESs) along the proton transfer and donor twisting coordinates using DFT and Time Dependent Density Functional Theory point towards the possibility of barrierless PT and CT reaction in the first excited state of PDOHBA.

  20. Excited-state proton transfer of photoexcited pyranine in water observed by femtosecond stimulated Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Han, Fangyuan; Liu, Weimin; Fang, Chong, E-mail: Chong.Fang@oregonstate.edu

    2013-08-30

    Highlights: • A number of low – frequency modes are sequentially observed in photoexcited HPTS. • Evidence of coherent quantum beat in several low – frequency modes with anharmonic coupling. • The most transient low – frequency mode is the symmetric ring breathing of HPTS. • Excited – state proton transfer occurs nonadiabatically on the 5–200 ps timescale. • Kinetic isotope effect is 3–4 for the two-stage ESPT components in water. - Abstract: We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm{sup −1}), and is facilitated by HPTS ring wagging (108 cm{sup −1}) and ring-H out-of-plane motions (321, 362, 952 cm{sup −1}), which largely decay within ∼1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate–water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3–4 in aqueous solution on the 5–200 ps timescale.

  1. Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

    Science.gov (United States)

    Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

    2016-11-01

    Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

  2. HYPERBRANCHED EPOXY RESINS PREPARED BY PROTON TRANSFER POLYMERIZATION FROM AN A2 + B3 SYSTEM

    Institute of Scientific and Technical Information of China (English)

    Li-jie Ma; Hai-qiao Wang; Li fan He; Xiao-yu Li

    2011-01-01

    Epoxy-terminated hyperbranched polymers (EHBPs) were prepared by proton transfer polymerization and characterized by FT-IR, 1H-NMR and GPC. The solution and thermal properties of the uncured samples and mechanical properties of cured samples were examined. The thermo-stable products had good solubility in polar solvents, low solution viscosity and Tgs ranging from 15℃ to 33℃ depending on their molecular weights. The mechanical properties of cured films were studied and compared with those of a bisphenol-A type epoxy resin. The films of EHBPs had good impact resistance and high gloss values without sacrificing hardness and adhesion.

  3. Resonant electron transfer in slow collisions of protons with Rydberg hydrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Joachain, C.J.; Nedeljkovic, N.N.

    1984-05-01

    The resonant charge-transfer reaction of protons on highly excited hydrogen atoms is considered by taking into account both the tunneling (under-barrier) and the over-barrier (classically allowed) electron transitions. It is demonstrated that in a wide range of variation of the reduced ve- locity v = vn, the classical transition mechanism is predominant. Cross-section calculations for principal quantum numbers n between 10 and 50 are presented. The results for 45< or =n< or =50 are compared with the available experimental data and with other theoretical calculations.

  4. Femtosecond Dynamics of Fundamental Reaction Processes in Liquids: Proton Transfer, Geminate Recombination, Isomerization and Vibrational Relaxation.

    Science.gov (United States)

    Schwartz, Benjamin Joel

    Femtosecond and picosecond transient absorption spectroscopy are used to probe several fundamental aspects of chemical reactivity in the condensed phase including proton transfer, germinate recombination, isomerization and vibrational relaxation. The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured for the first time, and the effects of external hydrogen-bonding interactions on the proton transfer are studied in detail. The proton transfer takes place in ~240 fsec in non-polar environments, but becomes faster than the instrumental resolution of 110 fsec in methanol solutions. A simple model is proposed to explain these results. The dynamics following photodissociation of CH _2I_2 and other small molecules provide the first direct observations of germinate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results also show that recombination yields but not rates depend on the molecular details of the solvent environment and suggest that recombination kinetics are dominated by a single collision with the surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. The data show no simple correlation between the hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes. This strongly implies that the isomerization of these systems does not provide a suitable testing ground for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in the photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial

  5. Interplay between excited-state intramolecular proton transfer and charge transfer in flavonols and their use as protein-binding-site fluorescence probes

    Energy Technology Data Exchange (ETDEWEB)

    Sytnik, A.; Gormin, D.; Kasha, M. (Florida State Univ., Tallahassee, FL (United States))

    1994-12-06

    A comparative study is presented of competitive fluorescences of three flavonols, 3-hydroxyflavone, 3,3[prime],4[prime],7-tetrahydroxyflavone (fisetin), and 4[prime]-diethylamino-3-hydroxyflavone (DHF). The normal fluorescence S[sub 1] [yields] S[sub 0] (400-nm region) is largely replaced by the proton-transfer tautomer fluorescence S[prime][sub 1] [yields] S[prime][sub 0] in the 550-nm region for all three of the flavonols in aprotic solvents at room temperature. For DHF in polar solvents the normal fluorescence becomes a charge-transfer fluorescence (460-500 nm) which competes strongly with the still dominant proton-transfer fluorescence (at 570 nm). In protic solvents, and at 77 K, the interference with intramolecular hydrogen bonding gives rise to greatly enhanced normal fluorescence, lowering the quantum yield of proton-transfer fluorescence. The utility of DHF as a discriminating fluorescence probe for protein binding sites is suggested by the strong dependence of the charge-transfer fluorescence on polarity of the environment and by various static and dynamic parameters of the charge-transfer and proton-transfer fluorescence which can be determined. 49 refs., 6 figs., 1 tab.

  6. Proposed linear energy transfer areal detector for protons using radiochromic film

    Science.gov (United States)

    Mayer, Rulon; Lin, Liyong; Fager, Marcus; Douglas, Dan; McDonough, James; Carabe, Alejandro

    2015-04-01

    Radiation therapy depends on predictably and reliably delivering dose to tumors and sparing normal tissues. Protons with kinetic energy of a few hundred MeV can selectively deposit dose to deep seated tumors without an exit dose, unlike x-rays. The better dose distribution is attributed to a phenomenon known as the Bragg peak. The Bragg peak is due to relatively high energy deposition within a given distance or high Linear Energy Transfer (LET). In addition, biological response to radiation depends on the dose, dose rate, and localized energy deposition patterns or LET. At present, the LET can only be measured at a given fixed point and the LET spatial distribution can only be inferred from calculations. The goal of this study is to develop and test a method to measure LET over extended areas. Traditionally, radiochromic films are used to measure dose distribution but not for LET distribution. We report the first use of these films for measuring the spatial distribution of the LET deposited by protons. The radiochromic film sensitivity diminishes for large LET. A mathematical model correlating the film sensitivity and LET is presented to justify relating LET and radiochromic film relative sensitivity. Protons were directed parallel to radiochromic film sandwiched between solid water slabs. This study proposes the scaled-normalized difference (SND) between the Treatment Planning system (TPS) and measured dose as the metric describing the LET. The SND is correlated with a Monte Carlo (MC) calculation of the LET spatial distribution for a large range of SNDs. A polynomial fit between the SND and MC LET is generated for protons having a single range of 20 cm with narrow Bragg peak. Coefficients from these fitted polynomial fits were applied to measured proton dose distributions with a variety of ranges. An identical procedure was applied to the protons deposited from Spread Out Bragg Peak and modulated by 5 cm. Gamma analysis is a method for comparing the calculated

  7. Acceleration of evolutionary spread by long-range dispersal.

    Science.gov (United States)

    Hallatschek, Oskar; Fisher, Daniel S

    2014-11-18

    The spreading of evolutionary novelties across populations is the central element of adaptation. Unless populations are well mixed (like bacteria in a shaken test tube), the spreading dynamics depend not only on fitness differences but also on the dispersal behavior of the species. Spreading at a constant speed is generally predicted when dispersal is sufficiently short ranged, specifically when the dispersal kernel falls off exponentially or faster. However, the case of long-range dispersal is unresolved: Although it is clear that even rare long-range jumps can lead to a drastic speedup--as air-traffic-mediated epidemics show--it has been difficult to quantify the ensuing stochastic dynamical process. However, such knowledge is indispensable for a predictive understanding of many spreading processes in natural populations. We present a simple iterative scaling approximation supported by simulations and rigorous bounds that accurately predicts evolutionary spread, which is determined by a trade-off between frequency and potential effectiveness of long-distance jumps. In contrast to the exponential laws predicted by deterministic "mean-field" approximations, we show that the asymptotic spatial growth is according to either a power law or a stretched exponential, depending on the tails of the dispersal kernel. More importantly, we provide a full time-dependent description of the convergence to the asymptotic behavior, which can be anomalously slow and is relevant even for long times. Our results also apply to spreading dynamics on networks with a spectrum of long-range links under certain conditions on the probabilities of long-distance travel: These are relevant for the spread of epidemics.

  8. INEL D&D long-range plan

    Energy Technology Data Exchange (ETDEWEB)

    Buckland, R.J.; Kenoyer, D.J.; LaBuy, S.A.

    1995-09-01

    This Long-Range Plan presents the Decontamination and Dismantlement (D&D) Program planning status for facilities at the Idaho National Engineering Laboratory (INEL). The plan provides a general description of the D&D Program objectives, management criteria, and policy; discusses current activities; and documents the INEL D&D Program cost and schedule estimate projections for the next 15 years. Appendices are included that provide INEL D&D project historical information, a comprehensive descriptive summary of each current D&D surplus facility, and a summary database of all INEL contaminated facilities awaiting or undergoing the facility transition process.

  9. Copulas and time series with long-ranged dependences

    CERN Document Server

    Chicheportiche, Rémy

    2013-01-01

    We review ideas on temporal dependences and recurrences in discrete time series from several areas of natural and social sciences. We revisit existing studies and redefine the relevant observables in the language of copulas (joint laws of the ranks). We propose that copulas provide an appropriate mathematical framework to study non-linear time dependences and related concepts - like aftershocks, Omori law, recurrences, waiting times. We also critically argue using this global approach that previous phenomenological attempts involving only a long-ranged autocorrelation function lacked complexity in that they were essentially mono-scale.

  10. Long-range exchange interaction between magnetic impurities in graphene

    Science.gov (United States)

    Agarwal, M.; Mishchenko, E. G.

    2017-02-01

    The effective spin exchange RKKY coupling between impurities (adatoms) on graphene mediated by conduction electrons is studied as a function of the strength of the potential part of the on-site energy U of the electron-adatom interaction. With increasing U , the exchange coupling becomes long range, determined largely by the impurity levels with energies close to the Dirac points. When adatoms reside on opposite sublattices, their exchange coupling, normally antiferromagnetic, becomes ferromagnetic and resonantly enhanced at a specific distance where an impurity level crosses the Dirac point.

  11. Political Mechanisms for Long-Range Survival and Development

    Science.gov (United States)

    Marshall, W.

    As the first species aware of extinction and capable of proactively ensuring our long-term survival and development, it is striking that we do not do so with the rigor, formality, and foresight it requires. Only from a reactive posture have we responded to the challenges of global warfare, human rights, environmental concerns, and sustainable development. Despite our awareness of the possibility for extinction and apocalyptic set-backs to our evolution, and despite the existence of long-range studies-which must still be dramatically increased-proactive global policy implementation regarding our long-term survival and development is arguably non-existent. This lack of long-term policy making can be attributed in part to the lack of formal political mechanisms to facilitate longer-range policy making that extends 30 years or more into the future. Political mechanisms for infusing long-range thinking, research, and strategic planning into the policy-making process can help correct this shortcoming and provide the motivation needed to adequately address long-term challenges with the political rigor required to effectively establish and implement long-term policies. There are some efforts that attempt to address longer-range issues, but those efforts often do not connect to the political process, do not extend 30 or more years into the future, are not well-funded, and are not sufficiently systemic. Political mechanisms for long-range survival and prosperity could correct these inadequacies by raising awareness, providing funding, and most importantly, leveraging political rigor to establish and enforce long-range strategic planning and policies. The feasibility of such mechanisms should first be rigorously studied and assessed in a feasibility study, which could then inform implementation. This paper will present the case for such a study and suggest some possible political mechanisms that should be investigated further in the proposed study. This work is being further

  12. Long-range correlations and coherent structures in magnetohydrodynamic equilibria.

    Science.gov (United States)

    Weichman, Peter B

    2012-12-01

    The equilibrium theory of the 2D magnetohydrodynamic equations is derived, accounting for the full infinite hierarchies of conserved integrals. An exact description in terms of two coupled elastic membranes emerges, producing long-ranged correlations between the magnetic and velocity fields. This is quite different from the results of previous variational treatments, which relied on a local product ansatz for the thermodynamic Gibbs distribution. The equilibria display the same type of coherent structures, such as compact eddies and zonal jets, previously found in pure fluid equilibria. Possible consequences of this for recent simulations of the solar tachocline are discussed.

  13. Sensitivity in the trajectory of long-range -particle

    Indian Academy of Sciences (India)

    P V Kunhikrishnan; A Rajan Nambiar; K P Santhosh

    2012-09-01

    The factors influencing the trajectory of long-range -particle in the cold ternary fission of 252Cf are discussed. The trajectory of the -particle is studied by considering the influence of the force on the -particle due to Coulomb and proximity potentials and is found to have sensitive dependence on the initial position and initial energy of the -particle. The sensitivity to initial conditions signifies the presence of deterministic chaos which is characterized by Lyapunov exponent (LE). The LE is calculated using Wolf’s algorithm and found positive which implies that the objectives of trajectory calculations are restricted.

  14. Long-range dependence and sea level forecasting

    CERN Document Server

    Ercan, Ali; Abbasov, Rovshan K

    2013-01-01

    This study shows that the Caspian Sea level time series possess long range dependence even after removing linear trends, based on analyses of the Hurst statistic, the sample autocorrelation functions, and the periodogram of the series. Forecasting performance of ARMA, ARIMA, ARFIMA and Trend Line-ARFIMA (TL-ARFIMA) combination models are investigated. The forecast confidence bands and the forecast updating methodology, provided for ARIMA models in the literature, are modified for the ARFIMA models. Sample autocorrelation functions are utilized to estimate the differencing lengths of the ARFIMA

  15. Method of coupled mode for long-range bottom reverberation

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The theory of coupled mode is used for modeling the long-range bottom reverberation in shallow water caused by bottom roughness. The distant bottom reverberation level and spatial coherence of impulsive source are both derived. The results agree with those from the classical reverberation model, and are compared with the experimental data. The influence of source bandwidth and the distance between sources and receivers on the intensity of bottom reverberation are particularly discussed. The method is shown to be available for both the monoand the bi-static cases.

  16. ATHLETE Mobility Performance in Long-Range Traverse

    Science.gov (United States)

    Townsend, Julie

    2011-01-01

    The All-Terrain Hex-Limbed Extra-Terrestrial Explorer (ATHLETE) is a modular mobility and manipulation platform being developed to support NASA operations in a variety of missions, including exploration of planetary surfaces. The agile system consists of a symmetrical arrangement of six limbs, each with seven articulated degrees of freedom and a powered wheel. This design enables transport of bulky payloads over a wide range of terrains and is envisioned as a tool to mobilize habitats, power-generation equipment, and other supplies for long-range exploration and outpost construction.

  17. Long-range plasmonic waveguides with hyperbolic cladding.

    Science.gov (United States)

    Babicheva, Viktoriia E; Shalaginov, Mikhail Y; Ishii, Satoshi; Boltasseva, Alexandra; Kildishev, Alexander V

    2015-11-30

    We study plasmonic waveguides with dielectric cores and hyperbolic multilayer claddings. The proposed design provides better performance in terms of propagation length and mode confinement in comparison to conventional designs, such as metal-insulator-metal and insulator-metal-insulator plasmonic waveguides. We show that the proposed structures support long-range surface plasmon modes, which exist when the permittivity of the core matches the transverse effective permittivity component of the metamaterial cladding. In this regime, the surface plasmon polaritons of each cladding layer are strongly coupled, and the propagation length can be on the order of a millimeter.

  18. Long-range plasmonic waveguides with hyperbolic cladding

    DEFF Research Database (Denmark)

    Babicheva, Viktoriia E.; Shalaginov, Mikhail Y.; Ishii, Satoshi;

    2015-01-01

    We study plasmonic waveguides with dielectric cores and hyperbolic multilayer claddings. The proposed design provides better performance in terms of propagation length and mode confinement in comparison to conventional designs, such as metal-insulator-metal and insulator-metal-insulator plasmonic...... waveguides. We show that the proposed structures support long-range surface plasmon modes, which exist when the permittivity of the core matches the transverse effective permittivity component of the metamaterial cladding. In this regime, the surface plasmon polaritons of each cladding layer are strongly...

  19. Long range node-strut analysis of trabecular bone microarchitecture

    DEFF Research Database (Denmark)

    Schmah, Tanya; Marwan, Norbert; Thomsen, Jesper Skovhus

    2011-01-01

    of the trabecular bone network. METHODS: Similar in some ways to the topological node-strut analysis introduced by Garrahan et al. [J. Microsc. 142, 341-349 (1986)], our method is distinguished by an emphasis on long-range trabecular connectivity. Thus, while the topological classification of a pixel (after...... skeletonization) as a node, strut, or terminus, can be determined from the 3 × 3 neighborhood of that pixel, our method, which does not involve skeletonization, takes into account a much larger neighborhood. In addition, rather than giving a discrete classification of each pixel as a node, strut, or terminus, our...

  20. Network resource allocation attack detection with long range dependence

    Institute of Scientific and Technical Information of China (English)

    WANG Xin; FANG Bin-xing

    2007-01-01

    The approach of traffic abnormality detection of network resource allocation attack did not have reliable signatures to depict abnormality and identify them. However, it is crucial for us to detect attacks accurately.The technique that we adopted is inspired by long range dependence ideas. We use the number of packet arrivals of a flow in fixed-length time intervals as the signal and attempt to extend traffic invariant "self-similarity".We validate the effectiveness of the approach with simulation and trace analysis.

  1. Anisotropic blockade using pendular long-range Rydberg molecules

    Science.gov (United States)

    Eiles, Matthew T.; Lee, Hyunwoo; Pérez-Ríos, Jesús; Greene, Chris H.

    2017-05-01

    We propose an experiment to demonstrate a blockade mechanism caused by long-range anisotropic interactions in an ultracold dipolar gas composed of the recently observed "butterfly" Rydberg molecules. At the blockade radius, the strong intermolecular interaction between two adjacent molecules shifts their molecular states out of resonance with the photoassociation laser, preventing their simultaneous excitation. When the molecules are prepared in a quasi-one-dimensional (Q1D) trap, the interaction's strength can be tuned via a weak external field. The molecular density thus depends strongly on the angle between the trap axis and the field. The available Rydberg and internal molecular states provide a wide range of tunability.

  2. Microbuckling in fibrin networks enables long-range cell mechanosensing

    CERN Document Server

    Notbohm, Jacob; Rosakis, Phoebus; Tirrell, David A; Ravichandran, Guruswami

    2014-01-01

    We show that cells in a fibrous matrix induce deformation fields that propagate over a longer range than predicted by linear elasticity. Synthetic, linear elastic hydrogels used in many mechanotrans- duction studies fail to capture this effect. We develop a nonlinear microstructural finite element model for a fiber network to simulate localized deformations induced by cells. The model captures measured cell-induced matrix displacements from experiments and identifies an important mech- anism for long range cell mechanosensing: loss of compression stiffness due to microbuckling of individual fibers. We show evidence that cells sense each other through the formation of localized intercellular bands of tensile deformations caused by this mechanism.

  3. Multifractal analysis of the long-range correlations in the cardiac dynamics of Drosophila melanogaster

    CERN Document Server

    Vitanov, N K; Vitanov, Nikolay K.; Yankulova, Elka D.

    2006-01-01

    Time series of heartbeat activity of humans can exhibit long-range correlations. In this paper we show that such kind of correlations can exist for the heartbeat activity of much simpler species like Drosophila melanogaster. By means of the method of multifractal detrended fluctuation analysis (MFDFA) we calculate fractal spectra $f(\\alpha)$ and $h(q)$ and investigate the correlation properties of heartbeat activity of Drosophila with genetic hearth defects for three consequent generations of species. We observe that opposite to the case of humans the time series of the heartbeat activity of healtly Drosophila do not have scaling properties. Time series from flies with genetic defects can be long-range correllated and can have multifractal properties. The fractal heartbeat dynamics of Drosophila is transferred from generation to generation.

  4. Observation of three behaviors in confined liquid water within a nanopool hosting proton-transfer reactions.

    Science.gov (United States)

    Douhal, Abderrazzak; Angulo, Gonzalo; Gil, Michal; Organero, Juan Angel; Sanz, Mikel; Tormo, Laura

    2007-05-17

    In this contribution, we report on studies of rotational and diffusional dynamics of 7-hydroxyquinoline (7HQ) within a reverse micelle (RM) containing different amounts of water. Analyzed in terms of the wobbling-in-a-cone model, the data reveal structural and dynamical properties of the nanopool. We clearly observed three regions in the behavior of confined water molecules within the RM hosting a double proton-transfer reaction between the probe and water. This observation remarkably reproduces the change of calculated water density within this life-mimicking medium. The number of water molecules per AOT head in the transition regions changes from 2 to 5, the latter being very near to the full solvation number (6) of the RM heads. Moreover, the H-bonds breaking and making within the RM to give new structures of the probe strongly affect the environment fluidization in different extents, reflected in different relaxation times of these structures; however, they are of similar sizes. We discuss the role of RM confinement and the proton-transfer dynamics on the behavior of water and their relationships to the packing of water molecules in the studied range of concentrations.

  5. Proton transfer in hydrogen-bonded network of phenol molecules: intracluster formation of water.

    Science.gov (United States)

    Lengyel, Jozef; Gorejová, Radka; Herman, Zdeněk; Fárník, Michal

    2013-11-07

    Electron ionization and time-of-flight mass spectrometry was used to investigate the phenol clusters (PhOH)n of different size from single molecule to large clusters: in coexpansion with He, the dimers n = 2 are mostly generated; in Ar, large species of n ≥ 10 also occur. Besides [(PhOH)n](+•) cluster ion series, hydrated phenol cluster ions [(PhOH)n·xH2O](+•) with up to x = 3 water molecules and dehydrated phenol clusters [(PhOH)n-H2O](+•) were observed. The hydrated phenol series exhibits minima and maxima that are interpreted as evidence for proton transfer between the hydrogen bonded cluster ions of cyclic structures. The proton transfer leads to a water generation within the clusters, and subsequent elimination of the diphenyl ether molecule(s) from the cluster yields the hydrated phenol cluster ions. Alternatively, a water molecule release yields a series of dehydrated phenols, among which the diphenyl ether ion [PhOPh](+•) (n = 2) constitutes the maximum.

  6. Thermal proton transfer reactions in ultraviolet matrix-assisted laser desorption/ionization.

    Science.gov (United States)

    Chu, Kuan Yu; Lee, Sheng; Tsai, Ming-Tsang; Lu, I-Chung; Dyakov, Yuri A; Lai, Yin Hung; Lee, Yuan-Tseh; Ni, Chi-Kung

    2014-03-01

    One of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10(-4)) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10(-7) at a high laser fluence and less than 10(-7) at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI.

  7. Excited-state proton transfer of fluorescein anion as an ionic liquid component.

    Science.gov (United States)

    Rodrigues, Catarina A B; Graça, Cátia; Maçôas, Ermelinda; Fedorov, Alexander; Afonso, Carlos A M; Martinho, José M G

    2013-11-14

    Fluorescent ionic liquids (FILs) incorporating the fluorescein anion have been prepared by anion exchange of the parent quaternary ammonium chloride (Quat(+)Cl(-)) ionic liquid. By controlling the molar ratio of fluorescein to Quat(+)Cl(-), ionic liquids incorporating different prototropic forms of fluorescein were prepared. The 1:1 molar ratio ionic liquid (FIL1) is essentially composed of monoanionic fluorescein, while dianionic fluorecein is predominant in the FIL with a 1:2 molar ratio (FIL2). The fluorescence excitation spectrum of FIL2 is markedly different from its absorption spectrum. Absorption features the fluorescein dianion, while the excitation spectrum is exclusively due to the monoanion. In FIL1, the absorption and excitation spectra are both characteristic of the monoanion. In both FILs, emission of the dianion is observed upon excitation of the monoanion. This unusual behavior is interpreted in the context of a fast deprotonation of the monoanion in the excited state. The presence of residual water in the ionic liquid is important for the proton transfer process. By lowering the pH of FIL1, the transient proton transfer is inhibited, and the emission of the monoanion could be observed. The FILs have completely different spectroscopic properties from solvated fluorescein in Quat(+)Cl(-), where the prototropic equilibrium is shifted toward the neutral forms.

  8. Excited-state proton transfer of photoexcited pyranine in water observed by femtosecond stimulated Raman spectroscopy

    Science.gov (United States)

    Han, Fangyuan; Liu, Weimin; Fang, Chong

    2013-08-01

    We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm-1), and is facilitated by HPTS ring wagging (108 cm-1) and ring-H out-of-plane motions (321, 362, 952 cm-1), which largely decay within ∼1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate-water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3-4 in aqueous solution on the 5-200 ps timescale.

  9. Doing the Limbo with a Low Barrier: Hydrogen Bonding and Proton Transfer in Hydroxyformylfulvene

    Science.gov (United States)

    Vealey, Zachary; Nemchick, Deacon; Vaccaro, Patrick

    2016-06-01

    Model compounds continue to play crucial roles for elucidating the ubiquitous phenomena of hydrogen bonding and proton transfer, often yielding invaluable insights into kindred processes taking place in substantially larger species. The symmetric double-minimum topography that characterizes the potential-energy landscape for an important subset of these systems allows unambiguous signatures of molecular dynamics (in the form of tunneling-induced bifurcations) to be extracted directly from spectral measurements. As a relatively unexplored member of this class, 6-hydroxy-2-formylfulvene (HFF) contains an intramolecular O-H···O interaction that has participating atoms from the hydroxylic (donor) and ketonic (acceptor) moieties closely spaced in a quasi-linear configuration. This unusual arrangement suggests proton transduction to occur with minimal encumbrance, possibly leading to a pronounced dislocation of the shuttling hydron commensurate with the concepts of low-barrier hydrogen bonding (which are distinguished by great strength, short distance, and vanishingly small potential barriers). A variety of spectroscopic probes built primarily upon the techniques of laser-induced fluorescence and dispersed fluorescence have been enlisted to acquire the first vibronically resolved information reported for the ground [tilde{X}1A1] and lowest-lying singlet excited [tilde{A}1B{2} (π*π)] electronic manifolds of HFF entrained in a cold supersonic free-jet expansion. These experimental findings will be discussed and compared to those obtained for related proton-transfer systems, with complimentary quantum-chemical calculations serving to unravel the unique bonding motifs and reactive pathways inherent to HFF.

  10. Long range node-strut analysis of trabecular bone microarchitecture

    CERN Document Server

    Schmah, T; Thomsen, J S; Saparin, P

    2015-01-01

    Purpose: We present a new morphometric measure of trabecular bone microarchitecture, called mean node strength (NdStr), which is part of a newly developed approach called long range node-strut analysis. Our general aim is to describe and quantify the apparent "latticelike" microarchitecture of the trabecular bone network. Methods: Similar in some ways to the topological node-strut analysis introduced by Garrahan et al. [J. Microsc. 142, 341-349 (1986)], our method is distinguished by an emphasis on long-range trabecular connectivity. Thus, while the topological classification of a pixel (after skeletonization) as a node, strut, or terminus, can be determined from the 3x3 neighborhood of that pixel, our method, which does not involve skeletonization, takes into account a much larger neighborhood. In addition, rather than giving a discrete classification of each pixel as a node, strut, or terminus, our method produces a continuous variable, node strength. The node strength is averaged over a region of interest ...

  11. Discovery of large genomic inversions using long range information.

    Science.gov (United States)

    Eslami Rasekh, Marzieh; Chiatante, Giorgia; Miroballo, Mattia; Tang, Joyce; Ventura, Mario; Amemiya, Chris T; Eichler, Evan E; Antonacci, Francesca; Alkan, Can

    2017-01-10

    Although many algorithms are now available that aim to characterize different classes of structural variation, discovery of balanced rearrangements such as inversions remains an open problem. This is mainly due to the fact that breakpoints of such events typically lie within segmental duplications or common repeats, which reduces the mappability of short reads. The algorithms developed within the 1000 Genomes Project to identify inversions are limited to relatively short inversions, and there are currently no available algorithms to discover large inversions using high throughput sequencing technologies. Here we propose a novel algorithm, VALOR, to discover large inversions using new sequencing methods that provide long range information such as 10X Genomics linked-read sequencing, pooled clone sequencing, or other similar technologies that we commonly refer to as long range sequencing. We demonstrate the utility of VALOR using both pooled clone sequencing and 10X Genomics linked-read sequencing generated from the genome of an individual from the HapMap project (NA12878). We also provide a comprehensive comparison of VALOR against several state-of-the-art structural variation discovery algorithms that use whole genome shotgun sequencing data. In this paper, we show that VALOR is able to accurately discover all previously identified and experimentally validated large inversions in the same genome with a low false discovery rate. Using VALOR, we also predicted a novel inversion, which we validated using fluorescent in situ hybridization. VALOR is available at https://github.com/BilkentCompGen/VALOR.

  12. The Frontiers of Nuclear Science: A Long-Range Plan

    Energy Technology Data Exchange (ETDEWEB)

    None, None

    2007-12-01

    In a letter dated July 17, 2006, the Department of Energy’s (DOE) Office of Science for Nuclear Physics and the National Science Foundation’s (NSF) Mathematical and Physical Sciences Directorate charged the Nuclear Science Advisory Committee (NSAC) to “conduct a study of the opportunities and priorities for U.S. nuclear physics research and recommend a long range plan that will provide a framework for coordinated advancement of the nation’s nuclear science research programs over the next decade.” This request set in motion a bottom-up review and forward look by the nuclear science community. With input from this community-wide process, a 59 member working group, which included the present NSAC members, gathered at the beginning of May, 2007, to develop guidance on how to optimize the future research directions for the field based on the projected resources outlined in the charge letter from DOE and NSF. A new long range plan—The Frontiers of Nuclear Science—grew out of this meeting. For the last decade, the top priority for nuclear science has been to utilize the flagship facilities that were built with investments by the nation in the 1980s and 1990s. Research with these facilities has led to many significant new discoveries that have changed our understanding of the world in which we live. But new discoveries demand new facilities, and the successes cannot continue indefinitely without new investment.

  13. On the Long-Range Directed Polymer Model

    Science.gov (United States)

    Wei, Ran

    2016-10-01

    We study the long-range directed polymer model on Z in a random environment, where the underlying random walk lies in the domain of attraction of an α -stable process for some α in (0,2]. Similar to the more classic nearest-neighbor directed polymer model, as the inverse temperature β increases, the model undergoes a transition from a weak disorder regime to a strong disorder regime. We extend most of the important results known for the nearest-neighbor directed polymer model on Z^d to the long-range model on Z. More precisely, we show that in the entire weak disorder regime, the polymer satisfies an analogue of invariance principle, while in the so-called very strong disorder regime, the polymer end point distribution contains macroscopic atoms and under some mild conditions, the polymer has a super-α -stable motion. Furthermore, for α in (1,2], we show that the model is in the very strong disorder regime whenever β >0, and we give explicit bounds on the free energy.

  14. Surface tension and long range corrections of cylindrical interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bourasseau, E. [CEA/DAM DIF, F-91297 Arpajon Cedex (France); Malfreyt, P. [Université Clermont Auvergne, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand (France); Ghoufi, A., E-mail: aziz.ghoufi@univ-rennes1.fr [Institut de Physique de Rennes, UMR 6251 CNRS, Université de Rennes 1, 263 avenue Général Leclerc, 35042 Rennes (France)

    2015-12-21

    The calculation of the surface tension of curved interfaces has been deeply investigated from molecular simulation during this last past decade. Recently, the thermodynamic Test-Area (TA) approach has been extended to the calculation of surface tension of curved interfaces. In the case of the cylindrical vapour-liquid interfaces of water and Lennard-Jones fluids, it was shown that the surface tension was independent of the curvature of the interface. In addition, the surface tension of the cylindrical interface is higher than that of the planar interface. Molecular simulations of cylindrical interfaces have been so far performed (i) by using a shifted potential, (ii) by means of large cutoff without periodic boundary conditions, or (iii) by ignoring the long range corrections to the surface tension due to the difficulty to estimate them. Indeed, unlike the planar interfaces there are no available operational expressions to consider the tail corrections to the surface tension of cylindrical interfaces. We propose here to develop the long range corrections of the surface tension for cylindrical interfaces by using the non-exponential TA (TA2) method. We also extend the formulation of the Mecke-Winkelmann corrections initially developed for planar surfaces to cylindrical interfaces. We complete this study by the calculation of the surface tension of cylindrical surfaces of liquid tin and copper using the embedded atom model potentials.

  15. Long-range response in ac electricity grids

    Science.gov (United States)

    Jung, Daniel; Kettemann, Stefan

    2016-07-01

    Local changes in the topology of electricity grids can cause overloads far away from the disturbance [D. Witthaut and M. Timme, Eur. Phys. J. B 86, 377 (2013), 10.1140/epjb/e2013-40469-4], making the prediction of the robustness against changes in the topology—for example, caused by power outages or grid extensions—a challenging task. The impact of single-line additions on the long-range response of dc electricity grids has recently been studied [D. Labavić, R. Suciu, H. Meyer-Ortmanns, and S. Kettemann, Eur. Phys. J.: Spec. Top. 223, 2517 (2014), 10.1140/epjst/e2014-02273-0]. By solving the real part of the static ac load flow equations, we conduct a similar investigation for ac grids. In a regular two-dimensional grid graph with cyclic boundary conditions, we find a power law decay for the change of power flow as a function of distance to the disturbance over a wide range of distances. The power exponent increases and saturates for large system sizes. By applying the same analysis to the German transmission grid topology, we show that also in real-world topologies a long-ranged response can be found.

  16. Long-range synchrony and emergence of neural reentry

    Science.gov (United States)

    Keren, Hanna; Marom, Shimon

    2016-11-01

    Neural synchronization across long distances is a functionally important phenomenon in health and disease. In order to access the basis of different modes of long-range synchrony, we monitor spiking activities over centimetre scale in cortical networks and show that the mode of synchrony depends upon a length scale, λ, which is the minimal path that activity should propagate through to find its point of origin ready for reactivation. When λ is larger than the physical dimension of the network, distant neuronal populations operate synchronously, giving rise to irregularly occurring network-wide events that last hundreds of milliseconds to several seconds. In contrast, when λ approaches the dimension of the network, a continuous self-sustained reentry propagation emerges, a regular seizure-like mode that is marked by precise spatiotemporal patterns (‘synfire chains’) and may last many minutes. Termination of a reentry phase is preceded by a decrease of propagation speed to a halt. Stimulation decreases both propagation speed and λ values, which modifies the synchrony mode respectively. The results contribute to the understanding of the origin and termination of different modes of neural synchrony as well as their long-range spatial patterns, while hopefully catering to manipulation of the phenomena in pathological conditions.

  17. Disordered Kitaev chains with long-range pairing

    Science.gov (United States)

    Cai, Xiaoming

    2017-03-01

    We study the competition of disorder and superconductivity for a generalized Kitaev model in incommensurate potentials. The generalized Kitaev model describes one dimensional spinless fermions with long-range p-wave superconducting pairing, which decays with distance l as a power law  ∼1/{{l}α} . We focus on the transition from the topological superconducting phase to the topologically trivial Anderson localized phase, and effects of the exponent α on this phase transition. In the topological superconducting phase, for a system under open boundary condition the amplitude of zero-mode Majorana fermion has a hybrid exponential-algebraic decay as the distance increases from the edge. In the Anderson localized phase, some single-particle states remain critical for very strong disorders and the number of critical states increases as α decreases. In addition, except for critical disorders, the correlation function always has an exponential decay at the short range and an algebraic decay at the long range. Phase transition points are also numerically determined and the topological phase transition happens earlier at a smaller disorder strength for a system with smaller α.

  18. Short and Long Range Screening of Optical Singularities

    CERN Document Server

    Kessler, David A

    2007-01-01

    Screening of topological charges (singularities) is discussed for paraxial optical fields with short and with long range correlations. For short range screening the charge variance in a circular region with radius $R$ grows linearly with $R$, instead of with $R^{2}$ as expected in the absence of screening; for long range screening it grows faster than $R$: for a field whose autocorrelation function is the zero order Bessel function J_{0}, the charge variance grows as R ln R$. A J_{0} correlation function is not attainable in practice, but we show how to generate an optical field whose correlation function closely approximates this form. The charge variance can be measured by counting positive and negative singularities inside the region A, or more easily by counting signed zero crossings on the perimeter of A. \\For the first method the charge variance is calculated by integration over the charge correlation function C(r), for the second by integration over the zero crossing correlation function Gamma(r). Usin...

  19. Phase transitions in simplified models with long-range interactions

    Science.gov (United States)

    Rocha Filho, T. M.; Amato, M. A.; Mello, B. A.; Figueiredo, A.

    2011-10-01

    We study the origin of phase transitions in several simplified models with long-range interactions. For the self-gravitating ring model, we are unable to observe a possible phase transition predicted by Nardini and Casetti [Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.80.060103 80, 060103R (2009).] from an energy landscape analysis. Instead we observe a sharp, although without any nonanalyticity, change from a core-halo to a core-only configuration in the spatial distribution functions for low energies. By introducing a different class of solvable simplified models without any critical points in the potential energy we show that a behavior similar to the thermodynamics of the ring model is obtained, with a first-order phase transition from an almost homogeneous high-energy phase to a clustered phase and the same core-halo to core configuration transition at lower energies. We discuss the origin of these features for the simplified models and show that the first-order phase transition comes from the maximization of the entropy of the system as a function of energy and an order parameter, as previously discussed by Hahn and Kastner [Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.72.056134 72, 056134 (2005); Eur. Phys. J. BEPJBFY1434-602810.1140/epjb/e2006-00100-7 50, 311 (2006)], which seems to be the main mechanism causing phase transitions in long-range interacting systems.

  20. Anomalous excited-state dynamics of lucifer yellow CH in solvents of high polarity: evidence for an intramolecular proton transfer.

    Science.gov (United States)

    Panda, Debashis; Mishra, Padmaja P; Khatua, Saumyakanti; Koner, Apurba L; Sunoj, Raghavan B; Datta, Anindya

    2006-05-04

    The photophysics of the fluorescent probe Lucifer yellow CH has been investigated using fluorescence spectroscopic and computational techniques. The nonradiative rate is found to pass through a minimum in solvents of intermediate empirical polarity. This apparently anomalous behavior is rationalized by considering the possibility of predominance of different kinds of nonradiative processes, viz. intersystem crossing (ISC) and excited-state proton transfer (ESPT), in solvents of low and high empirical polarity, respectively. The feasibility of the proton transfer is examined by the structure determined by the density functional theory (DFT) calculations. The predicted energy levels based on the time-dependent density functional theory (TD-DFT) method in the gas phase identifies the energy gap between the S(1) and nearest triplet state to be close enough to facilitate ISC. Photophysical investigation in solvent mixtures and in deuterated solvents clearly indicates the predominance of the solvent-mediated intramolecular proton transfer in the excited state of the fluorophore in protic solvents.

  1. Photoinduced proton transfer coupled with energy transfer: Mechanism of sensitized luminescence of terbium ion by salicylic acid doped in polymer.

    Science.gov (United States)

    Misra, Vinita; Mishra, Hirdyesh

    2008-06-28

    In the present work, excited state intramolecular proton transfer (ESIPT) in salicylic acid (SA) monoanion and subsequent sensitization of Tb(3+) ion in polyvinyl alcohol (PVA) have been studied. The study has been carried out both by steady state and time domain fluorescence measurement techniques at room temperature. It is found that the SA completely ionizes and exists as monoanion in PVA. It exhibits a large Stokes shifted blue emission (10 000 cm(-1)) due to ESIPT and shows a decay time of 6.85 ns. On the other hand, Tb(3+) ion shows a very weak green emission and a decay time of approximately 641 mus in PVA film. Upon incorporating Tb(3+) ion in SA doped PVA film, both intensity and decay time of SA decrease and sensitized emission from Tb(+3) ion along with 3.8 mus rise time is observed. Energy transfer is found to take place both from excited singlet as well as triplet states. A brief description of the properties of the present system from the viewpoint of luminescent solar collector material is addressed.

  2. Reservoir shore development in long range terrestrial laser scanning monitoring.

    Science.gov (United States)

    Kaczmarek, Halina

    2016-04-01

    Shore zones of reservoirs are in most cases very active, getting transformed as a result of coastal processes and mass movements initiated on the slopes surrounding the reservoir. From the point of view of the users of water reservoirs shore recession strongly undesirable as it causes destruction to infrastructure and buildings located in the immediate vicinity of the reservoir. For this reason, reservoir shores require continuous geodetic monitoring. Fast and accurate geodetic measurements covering shore sections several kilometers long, often in poorly accessible areas, are available using long range terrestrial laser scanning (TLS). The possibilities of using long range terrestrial laser scanning are shown on the example of the reservoir Jeziorsko on the Warta River (Central Poland). This reservoir, created in the years 1986-1992, is a typical retention reservoir, the annual fluctuations of which reach 5 m. Depending on the water level its surface area ranges from 42.3 to 19.6 km2. The width of the reservoir is 2.5 km. The total shore length of the reservoir, developed in Quaternary till and sand-till sediments, is 44.3 km, including 30.1 km of the unreinforced shore. Out of the unreinforced shore 27% is subject to coastal erosion. The cliff heights vary from a few cm to 12.5 meters, and the current rate of the cliff recession ranges from 0 to 1.12 m/y. The study used a terrestrial long range laser scanner Riegl VZ-4000 of a range of up to 4000 m. It enabled conducting the measurements of the cliff recession from the opposite shore of the reservoir, with an angular resolution of 0.002°, which gives about 50 measurement points per 1 m2. The measurements were carried out in the years 2014-2015, twice a year, in early spring before high water level, and in late autumn at a dropping water level. This allowed the separation of the impact of coastal processes and frost weathering on the cliff recession and their quantitative determination. The size and nature of

  3. Long-Range Lepton Flavor Interactions and Neutrino Oscillations

    Energy Technology Data Exchange (ETDEWEB)

    Davoudiasl, H.; Lee, H-S; Marciano, W.

    2011-03-31

    Recent results from the MINOS accelerator neutrino experiment suggest a possible difference between {nu}{sub {mu}} and {bar {nu}}{sub {mu}} disappearance oscillation parameters, which one may ascribe to a new long distance potential acting on neutrinos. As a specific example, we consider a model with gauged B - L{sub e} - 2L{sub {tau}} number which contains an extremely light new vector boson, m{sub Z}, < 10{sup -18} eV and extraordinarily weak coupling {alpha}{prime} {approx}< 10{sup -52}. In that case, differences between {nu}{sub {mu}} {yields} {nu}{sub {tau}} and {bar {nu}}{sub {mu}} {yields} {bar {nu}}{sub {tau}} oscillations can result from a long-range potential due to neutrons in the Earth and the Sun that distinguishes {nu}{sub {mu}} and {nu}{sub {tau}} on Earth, with a potential difference of {approx} 6 x 10{sup -14} eV, and changes sign for anti-neutrinos. We show that existing solar, reactor, accelerator, and atmospheric neutrino oscillation constraints can be largely accommodated for values of parameters that help explain the possible MINOS anomaly by this new physics, although there is some tension with atmospheric constraints. A long-range interaction, consistent with current bounds, could have very pronounced effects on atmospheric neutrino disappearance in the 20-50 GeV range that will be studied with the IceCube DeepCore array, currently in operation, and can have a significant effect on future high-precision long-baseline oscillation experiments which aim for {+-}1% sensitivity, in {nu}{sub {mu}} and {bar {nu}}{sub {mu}} disappearance, separately. Together, these experiments can extend the reach for new long-distance effects well beyond current bounds and test their relevance to the aforementioned MINOS anomaly. We also point out that long-range potentials originating from the Sun could lead to annual modulations of neutrino data at the percent level, due to the variation of the Earth-Sun distance. A similar phenomenology is shown to apply to

  4. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture.

    Science.gov (United States)

    Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

    2015-05-28

    The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol(-1). On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol(-1). The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  5. Selective 4e-/4H+ O2 reduction by an iron(tetraferrocenyl)porphyrin complex: from proton transfer followed by electron transfer in organic solvent to proton coupled electron transfer in aqueous medium.

    Science.gov (United States)

    Mittra, Kaustuv; Chatterjee, Sudipta; Samanta, Subhra; Dey, Abhishek

    2013-12-16

    An iron porphyrin catalyst bearing four ferrocenes and a hydrogen bonding distal pocket is found to catalyze 4e(-)/4H(+) oxygen reduction reaction (ORR) in organic solvent under homogeneous conditions in the presence of 2-3 equiv of Trifluoromethanesulphonic acid. Absorption spectroscopy, electron paramagnetic resonance (EPR), and resonance Raman data along with H2O2 assay indicate that one out of the four electrons necessary to reduce O2 to H2O is donated by the ferrous porphyrin while three are donated by the distal ferrocene residues. The same catalyst shows 4e(-)/4H(+) reduction of O2 in an aqueous medium, under heterogeneous conditions, over a wide range of pH. Both the selectivity and the rate of ORR are found to be pH independent in an aqueous medium. The ORR proceeds via a proton transfer followed by electron transfer (PET) step in an organic medium and while a 2e(-)/1H(+) proton coupled electron transfer (PCET) step determines the electrochemical potential of ORR in an aqueous medium.

  6. Long range properties of $1S$-bottomonium states

    CERN Document Server

    Brambilla, Nora; Castellà, Jaume Tarrús; Vairo, Antonio

    2015-01-01

    We derive an analytical expression for the chromo-polarizability of $1S$-bottomonium states using weakly-coupled pNRQCD. In this setting the intermediate octet states have Coulombic continuum wavefunctions. We use the QCD trace anomaly to obtain the two-pion production amplitude for the chromo-polarizability operator and match the result to a Chiral Effective Field Theory (EFT) with $1S$-bottomonium states and pions as degrees-of-freedom. In this chiral EFT we compute long range properties of the $1S$-bottomonium generated by the pion coupling such as the leading chiral log to the $1S$-bottomonium mass and the van der Waals potential between two $1S$-bottomonium states.

  7. Photoassociation of long-range $nD$ Rydberg molecules

    CERN Document Server

    Anderson, David A; Raithel, Georg

    2014-01-01

    We observe long-range homonuclear diatomic $nD$ Rydberg molecules photoassociated out of an ultracold gas of $^{87}$Rb atoms for 34$\\le n \\le$40. The measured ground-state binding energies of $^{87}$Rb$(nD-5S_{1/2})$ molecular states are larger than those of their $^{87}$Rb$(nS-5S_{1/2})$ counterparts, showing the dependence of the molecular bond on the angular momentum of the Rydberg atom. We exhibit the transition of $^{87}$Rb$(nD-5S_{1/2})$ molecules from a molecular-binding-dominant regime at low $n$ to a fine-structure-dominant regime at high $n$ [akin to Hund's cases (a) and (c), respectively]. In the analysis the fine structure of the $nD$ Rydberg atom and the hyperfine structure of the $5S_{1/2}$ atom are included.

  8. On the origin of long-range correlations in texts

    CERN Document Server

    Altmann, Eduardo G; Esposti, Mirko Degli

    2012-01-01

    The complexity of human interactions with social and natural phenomena is mirrored in the way we describe our experiences through natural language. In order to retain and convey such a high dimensional information, the statistical properties of our linguistic output has to be highly correlated in time. An example are the robust observations, still largely not understood, of correlations on arbitrary long scales in literary texts. In this paper we explain how long-range correlations flow from highly structured linguistic levels down to the building blocks of a text (words, letters, etc..). By combining calculations and data analysis we show that correlations take form of a bursty sequence of events once we approach the semantically relevant topics of the text. The mechanisms we identify are fairly general and can be equally applied to other hierarchical settings.

  9. Theory of long-range ultracold atom-molecule photoassociation

    CERN Document Server

    Pérez-Ríos, Jesús; Dulieu, Olivier

    2015-01-01

    The creation of ultracold molecules is currently limited to diatomic species. In this letter we present a theoretical description of the photoassociation of ultracold atoms and molecules to create ultracold excited triatomic molecules, thus being a novel example of light-assisted ultracold chemical reaction. The calculation of the photoassociation rate of ultracold Cs atoms with ultracold Cs$_2$ molecules in their rovibrational ground state is reported, based on the solution of the quantum dynamics involving the atom-molecule long-range interactions, and assuming a model potential for the short-range physics. The rate for the formation of excited Cs$_3$ molecules is predicted to be comparable with currently observed atom-atom photoassociation rates. We formulate an experimental proposal to observe this process relying on the available techniques of optical lattices and standard photoassociation spectroscopy.

  10. Long-range effects in electron scattering by polar molecules

    Science.gov (United States)

    Fabrikant, Ilya I.

    2016-11-01

    We review long-range effects in electron collisions with polar molecules, starting with elastic scattering. We then go to rotationally and vibrationally inelastic processes and dissociative electron attachment. The last two are strongly affected by vibrational Feshbach resonances which have been observed and described theoretically in many systems from simple diatomic molecules to more complex polyatomics, biologically relevant molecules, and van der Waals clusters. We then review environmental effects which include electron interaction with molecules adsorbed on surfaces and molecules in cluster environments. We concentrate on physics rather than on listing results of ab initio calculations. With increasing complexity of targets and processes model approaches become more relevant. We demonstrate their success in the theoretical description of electron attachment to polyatomic molecules and to molecules in complex environments.

  11. Traveling Solitons in Long-Range Oscillator Chains

    CERN Document Server

    Miloshevich, George; Dauxois, Thierry; Khomeriki, Ramaz; Ruffo, Stefano

    2016-01-01

    We investigate the existence and propagation of solitons in a long-range extension of the quartic Fermi-Pasta-Ulam (FPU) chain of anharmonic oscillators. The coupling in the linear term decays as a power-law with an exponent greater than 1 and less than 3. We obtain an analytic perturbative expression of traveling envelope solitons by introducing a Non Linear Schrodinger (NLS) equation for the slowly varying amplitude of short wavelength modes. Due to the non analytic properties of the dispersion relation, it is crucial to develop the theory using discrete difference operators. Those properties are also the ultimate reason why kink-solitons may exist but are unstable, at variance with the short-range FPU model. We successfully compare these approximate analytic results with numerical simulations.

  12. Effective field theory for long-range properties of bottomonium

    Science.gov (United States)

    Krein, Gastão

    2017-03-01

    In this communication we present selected results from a recent study [N. Brambilla, G. Krein, J. Tarrús Castellà and A. Vairo, Phys. Rev. D 93, 054002 (2016)] of long-range properties of bottomonium. An analytical expression for the chromopolarizability of 1S bottomonium states is derived within the framework of potential nonrelativistic QCD (pNRQCD). Next, after integrating out the ultrasoft scale associated with the binding energy of bottomonium, the QCD trace anomaly is used to obtain the two-pion production amplitude for the chromopolarizability operator and the result is matched to a chiral effective field theory having bottomonium states and pions as degrees of freedom. We present results for the leading chiral logarithm correction to the mass of the 1S bottomonium and the van der Waals potential between two bottomonium states.

  13. An Autonomous Long Range Monitoring System For Emergency Operators

    CERN Document Server

    Lanati, Matteo; Secco, Emanuele Lindo; Magenes, Giovanni; Gamba, Paolo

    2011-01-01

    Miniaturization and portability of new electronics lead up to wearable devices embedded within garments: a European program called ProeTEX developed multi-purpose sensors integrated within emergency operators' garments in order to monitor their health state and the surrounding environment. This work deals with the development of an autonomous Long Range communication System (LRS), suitable to transmit data between operators' equipment and the local command post, where remote monitoring software is set up. The LRS infrastructure is based on Wi-Fi protocol and modular architecture. Field tests carried out on the developed prototype showed a high reliability in terms of correctly exchanged data and recovering capabilities in case of temporary disconnection, due to the operator's movements.

  14. Contactless nonlinear optics mediated by long-range Rydberg interactions

    Science.gov (United States)

    Busche, Hannes; Huillery, Paul; Ball, Simon W.; Ilieva, Teodora; Jones, Matthew P. A.; Adams, Charles S.

    2017-07-01

    In conventional nonlinear optics, linear quantum optics, and cavity quantum electrodynamics to create effective photon-photon interactions photons must have, at one time, interacted with matter inside a common medium. In contrast, in Rydberg quantum optics, optical photons are coherently and reversibly mapped onto collective atomic Rydberg excitations, giving rise to dipole-mediated effective photon-photon interactions that are long range. Consequently, a spatial overlap between the light modes is no longer required. We demonstrate such a contactless coupling between photons stored as collective Rydberg excitations in spatially separate optical media. The potential induced by each photon modifies the retrieval mode of its neighbour, leading to correlations between them. We measure these correlations as a function of interaction strength, distance and storage time, demonstrating an effective interaction between photons separated by 15 times their wavelength. Contactless effective photon-photon interactions are relevant for scalable multichannel photonic devices and the study of strongly correlated many-body dynamics using light.

  15. Long range prediction of Indian summer monsoon rainfall

    Indian Academy of Sciences (India)

    A A Munot; K Krishna Kumar

    2007-02-01

    The search for new parameters for predicting the all India summer monsoon rainfall (AISMR) has been an important aspect of long range prediction of AISMR. In recent years NCEP/NCAR reanalysis has improved the geographical coverage and availability of the data and this can be easily updated. In this study using NCEP/NCAR reanalysis data on temperature, zonal and meridional wind at different pressure levels, few predictors are identified and a prediction scheme is developed for predicting AISMR. The regression coeffcients are computed by stepwise multiple regression procedure. The final equation explained 87% of the variance with multiple correlation coeffcient (MCC), 0.934. The estimated rainfall in the El-Nino year of 1997 was -1.7% as against actual of 4.4%. The estimated rainfall deficiency in both the recent deficient years of 2002 and 2004 were -19.5% and -8.5% as against observed -20.4% and -11.5% respectively.

  16. Long-range interactions in antiferromagnetic quantum spin chains

    Science.gov (United States)

    Bravo, B.; Cabra, D. C.; Gómez Albarracín, F. A.; Rossini, G. L.

    2017-08-01

    We study the role of long-range dipolar interactions on antiferromagnetic spin chains, from the classical S →∞ limit to the deep quantum case S =1 /2 , including a transverse magnetic field. To this end, we combine different techniques such as classical energy minima, classical Monte Carlo, linear spin waves, bosonization, and density matrix renormalization group (DMRG). We find a phase transition from the already reported dipolar ferromagnetic region to an antiferromagnetic region for high enough antiferromagnetic exchange. Thermal and quantum fluctuations destabilize the classical order before reaching magnetic saturation in both phases, and also close to zero field in the antiferromagnetic phase. In the extreme quantum limit S =1 /2 , extensive DMRG computations show that the main phases remain present with transition lines to saturation significatively shifted to lower fields, in agreement with the bosonization analysis. The overall picture maintains a close analogy with the phase diagram of the anisotropic XXZ spin chain in a transverse field.

  17. Kinetic Gaussian Model with Long-Range Interactions

    Institute of Scientific and Technical Information of China (English)

    KONGXiang-Mu; YANGZhan-Ru

    2004-01-01

    In this paper dynamical critical phenomena of the Gaussian model with long-range interactions decayingas 1/rd+δ (δ>0) on d-dimensional hypercubic lattices (d = 1, 2, and 3) are studied. First, the critical points are exactly calculated, and it is found that the critical points depend on the value of δ and the range of interactions. Then the critical dynamics is considered. We calculate the time evolutions of the local magnetizations and the spin-spin correlation functions, and further the dynamic critical exponents are obtained. For one-, two- and three-dimensional lattices, it is found that the dynamic critical exponents are all z = 2 if δ > 2, which agrees with the result when only considering nearest neighboring interactions, and that they are all δ if 0 < δ < 2. It shows that the dynamic critical exponents are independent of the spatial dimensionality but depend on the value of δ.

  18. Kinetic Gaussian Model with Long-Range Interactions

    Institute of Scientific and Technical Information of China (English)

    KONG Xiang-Mu; YANG Zhan-Ru

    2004-01-01

    In this paper dynamical critical phenomena of the Gaussian model with long-range interactions decaying as 1/rd+δ (δ> 0) on d-dimensional hypercubic lattices (d = 1, 2, and 3) are studied. First, the critical points are exactly calculated, and it is found that the critical points depend on the value of δ and the range of interactions. Then the critical dynamics is considered. We calculate the time evolutions of the local magnetizations and the spin-spin correlation functions, and further the dynamic critical exponents are obtained. For one-, two- and three-dimensional lattices, it is found that the dynamic critical exponents are all z = 2 if δ> 2, which agrees with the result when only considering nearest neighboring interactions, and that they are all δ if 0 <δ< 2. It shows that the dynamic critical exponents are independent of the spatial dimensionality but depend on the value of δ.

  19. On the origin of long-range correlations in texts.

    Science.gov (United States)

    Altmann, Eduardo G; Cristadoro, Giampaolo; Esposti, Mirko Degli

    2012-07-17

    The complexity of human interactions with social and natural phenomena is mirrored in the way we describe our experiences through natural language. In order to retain and convey such a high dimensional information, the statistical properties of our linguistic output has to be highly correlated in time. An example are the robust observations, still largely not understood, of correlations on arbitrary long scales in literary texts. In this paper we explain how long-range correlations flow from highly structured linguistic levels down to the building blocks of a text (words, letters, etc..). By combining calculations and data analysis we show that correlations take form of a bursty sequence of events once we approach the semantically relevant topics of the text. The mechanisms we identify are fairly general and can be equally applied to other hierarchical settings.

  20. Phantom energy mediates a long-range repulsive force.

    Science.gov (United States)

    Amendola, Luca

    2004-10-29

    Scalar field models with nonstandard kinetic terms have been proposed in the context of k inflation, of Born-Infeld Lagrangians, of phantom energy and, more in general, of low-energy string theory. In general, scalar fields are expected to couple to matter inducing a new interaction. In this Letter I derive the cosmological perturbation equations and the Yukawa correction to gravity for such general models. I find three interesting results: first, when the field behaves as phantom energy (equation of state less than -1), then the coupling strength is negative, inducing a long-range repulsive force; second, the dark-energy field might cluster on astrophysical scales; third, applying the formalism to a Brans-Dicke theory with a general kinetic term it is shown that its Newtonian effects depend on a single parameter that generalizes the Brans-Dicke constant.

  1. Long-Range Correlations in Small Atomic Clusters

    Science.gov (United States)

    Nayak, Saroj K.; Ramaswamy, R.

    We study the power spectrum of fluctuations in the potential energy of atoms in small rare-gas clusters. At temperatures when the cluster is in a liquid-like state the spectra have a “1/f” dependence over a wide range of frequency f. This behavior is distinctly different from both the solid phase of clusters or bulk liquid, and is indicative of long-range temporal correlations. The origins of this phenomenon is explored by studying the individual potential-energy distributions in pure and mixed rare-gas clusters, Xe55 and ArXe54, via molecular dynamics simulations. Substitution of atomic impurities acts as an effective probe of the dynamics, and we observe that long-lived memory effects have their origins in hierarchical relaxation processes arising in the motion of the atoms from the surface to the core and vice-versa.

  2. Vlasov equation for long-range interactions on a lattice

    CERN Document Server

    Bachelard, Romain; De Ninno, Giovanni; Ruffo, Stefano; Staniscia, F

    2011-01-01

    We show that, in the continuum limit, the dynamics of Hamiltonian systems defined on a lattice with long-range couplings is well described by the Vlasov equation. This equation can be linearized around the homogeneous state and a dispersion relation, that depends explicitly on the Fourier modes of the lattice, can be derived. This allows to compute the stability thresholds of the homogeneous state, which turn out to depend on the mode number. When this state is unstable, the growth rates are also function of the mode number. Explicit calculations are performed for the $\\alpha$-HMF model with $0 \\leq \\alpha <1$, for which the zero mean-field mode is always found to dominate the exponential growth. The theoretical predictions are successfully compared with numerical simulations performed on a finite lattice.

  3. Vlasov equation for long-range interactions on a lattice.

    Science.gov (United States)

    Bachelard, R; Dauxois, T; De Ninno, G; Ruffo, S; Staniscia, F

    2011-06-01

    We show that, in the continuum limit, the dynamics of Hamiltonian systems defined on a lattice with long-range couplings is well described by the Vlasov equation. This equation can be linearized around the homogeneous state, and a dispersion relation, which depends explicitly on the Fourier modes of the lattice, can be derived. This allows one to compute the stability thresholds of the homogeneous state, which turns out to depend on the mode number. When this state is unstable, the growth rates are also functions of the mode number. Explicit calculations are performed for the α-Hamiltonian mean field model with 0≤α<1, for which the mean-field mode is always found to dominate the exponential growth. The theoretical predictions are successfully compared with numerical simulations performed on a finite lattice.

  4. Stable swarming using adaptive long-range interactions

    Science.gov (United States)

    Gorbonos, Dan; Gov, Nir S.

    2017-04-01

    Sensory mechanisms in biology, from cells to humans, have the property of adaptivity, whereby the response produced by the sensor is adapted to the overall amplitude of the signal, reducing the sensitivity in the presence of strong stimulus, while increasing it when it is weak. This property is inherently energy consuming and a manifestation of the nonequilibrium nature of living organisms. We explore here how adaptivity affects the effective forces that organisms feel due to others in the context of a uniform swarm, in both two and three dimensions. The interactions between the individuals are taken to be attractive and long-range and of power-law form. We find that the effects of adaptivity inside the swarm are dramatic, where the effective forces decrease (or remain constant) with increasing swarm density. Linear stability analysis demonstrates how this property prevents collapse (Jeans instability), when the forces are adaptive. Adaptivity therefore endows swarms with a natural mechanism for self-stabilization.

  5. Effects of proton acceptors on formation of a non-heme iron(IV)-oxo complex via proton-coupled electron transfer.

    Science.gov (United States)

    Nishida, Yusuke; Morimoto, Yuma; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi

    2013-03-18

    Rates of formation of a non-heme iron(IV)-oxo complex, [Fe(IV)(O)(N4Py)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), via electron-transfer oxidation of [Fe(III)(OH)(N4Py)](2+) in acetonitrile (MeCN) containing H2O (0.56 M) were accelerated as much as 390-fold by addition of proton acceptors such as CF3COO(-), TsO(-) (p-MeC6H4SO3(-)), NsO(-) (o-NO2C6H4SO3(-)), DNsO(-) (2,4-(NO2)2C6H3SO3(-)), and TfO(-) (CF3SO3(-)). The acceleration effect of proton acceptors increases with increasing basicity of the proton acceptors. The one-electron oxidation potential of [Fe(III)(OH)(N4Py)](2+) was shifted from 1.24 to 0.96 V vs SCE in the presence of TsO(-) (10 mM). The electron-transfer oxidation of Fe(III)-OH complex was coupled with the deprotonation process by proton acceptors in which deuterium kinetic isotope effects were observed when H2O was replaced by D2O.

  6. Incoherent shock waves in long-range optical turbulence

    Science.gov (United States)

    Xu, G.; Garnier, J.; Faccio, D.; Trillo, S.; Picozzi, A.

    2016-10-01

    Considering the nonlinear Schrödinger (NLS) equation as a representative model, we report a unified presentation of different forms of incoherent shock waves that emerge in the long-range interaction regime of a turbulent optical wave system. These incoherent singularities can develop either in the temporal domain through a highly noninstantaneous nonlinear response, or in the spatial domain through a highly nonlocal nonlinearity. In the temporal domain, genuine dispersive shock waves (DSW) develop in the spectral dynamics of the random waves, despite the fact that the causality condition inherent to the response function breaks the Hamiltonian structure of the NLS equation. Such spectral incoherent DSWs are described in detail by a family of singular integro-differential kinetic equations, e.g. Benjamin-Ono equation, which are derived from a nonequilibrium kinetic formulation based on the weak Langmuir turbulence equation. In the spatial domain, the system is shown to exhibit a large scale global collective behavior, so that it is the fluctuating field as a whole that develops a singularity, which is inherently an incoherent object made of random waves. Despite the Hamiltonian structure of the NLS equation, the regularization of such a collective incoherent shock does not require the formation of a DSW - the regularization is shown to occur by means of a different process of coherence degradation at the shock point. We show that the collective incoherent shock is responsible for an original mechanism of spontaneous nucleation of a phase-space hole in the spectrogram dynamics. The robustness of such a phase-space hole is interpreted in the light of incoherent dark soliton states, whose different exact solutions are derived in the framework of the long-range Vlasov formalism.

  7. Formation of the long range Dpp morphogen gradient.

    Directory of Open Access Journals (Sweden)

    Gerald Schwank

    2011-07-01

    Full Text Available The TGF-β homolog Decapentaplegic (Dpp acts as a secreted morphogen in the Drosophila wing disc, and spreads through the target tissue in order to form a long range concentration gradient. Despite extensive studies, the mechanism by which the Dpp gradient is formed remains controversial. Two opposing mechanisms have been proposed: receptor-mediated transcytosis (RMT and restricted extracellular diffusion (RED. In these scenarios the receptor for Dpp plays different roles. In the RMT model it is essential for endocytosis, re-secretion, and thus transport of Dpp, whereas in the RED model it merely modulates Dpp distribution by binding it at the cell surface for internalization and subsequent degradation. Here we analyzed the effect of receptor mutant clones on the Dpp profile in quantitative mathematical models representing transport by either RMT or RED. We then, using novel genetic tools, experimentally monitored the actual Dpp gradient in wing discs containing receptor gain-of-function and loss-of-function clones. Gain-of-function clones reveal that Dpp binds in vivo strongly to the type I receptor Thick veins, but not to the type II receptor Punt. Importantly, results with the loss-of-function clones then refute the RMT model for Dpp gradient formation, while supporting the RED model in which the majority of Dpp is not bound to Thick veins. Together our results show that receptor-mediated transcytosis cannot account for Dpp gradient formation, and support restricted extracellular diffusion as the main mechanism for Dpp dispersal. The properties of this mechanism, in which only a minority of Dpp is receptor-bound, may facilitate long-range distribution.

  8. Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    A. Guenther

    2009-04-01

    Full Text Available The ability to measure sesquiterpenes (SQT; C15H24 by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS was investigated. SQT calibration standards were prepared by a capillary diffusion method and the PTR-MS-estimated mixing ratios were derived from the counts of product ions and proton transfer reaction constants. These values were compared with mixing ratios determined by a calibrated Gas Chromatograph (GC coupled to a Flame Ionization Detector (GC-FID. Product ion distributions from soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+, out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+, are accounted for. Considerable fragmentation of bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, cause the accuracy to be reduced to 50% if only the parent ion (m/z 205+ is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport research station in 2005. Inferred average daytime ecosystem scale mixing ratios (fluxes of isoprene, sum of monoterpenes (MT, and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1, 1.2 μg m−3 (0.21 mg m−2 h−1, and 0.0016 μg m−3 (0.10 mg m−2 h−1, respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly

  9. Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    S. Kim

    2008-12-01

    Full Text Available The ability to measure sesquiterpenes (SQT; C15H24 by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS was investigated with SQT standards, prepared by a capillary diffusion method, and the estimated mixing ratios, derived from the counts of product ions and proton transfer reaction constants were intercompared with measured mixing ratios, measured by a complementary Gas Chromatograph (GC coupled to a Flame Ionization Detector (GC-FID. Product ion distributions due to soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+ out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+ are accounted for. Bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, showed considerable fragmentation causing the accuracy of their analysis to be reduced to 50% if only the parent ion (m/z 205 is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport research station in 2005. Inferred Average daytime ecosystem scale mixing ratios (fluxes of isoprene, sum of monoterpenes (MT, and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1, 1.2 μg m−3 (0.21 mg m−2 h−1 and 0.0016 μg m−3 (0.10 mgm−2 h−1 respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly underestimated OH

  10. Designing a multicolor long range nanoscopic ruler for the imaging of heterogeneous tumor cells

    Science.gov (United States)

    Chavva, Suhash Reddy; Viraka Nellore, Bhanu Priya; Pramanik, Avijit; Sinha, Sudarson Sekhar; Jones, Stacy; Ray, Paresh Chandra

    2016-07-01

    Tumor heterogeneity is one of the biggest challenges in cancer treatment and diagnosis. A multicolor optical ruler is essential to address the heterogeneous tumor cell complexity. Driven by this need, the current article reports the design of a multicolor long range nanoscopic ruler for screening tumor heterogeneity by accurately identifying epithelial cells and cancer stem cells (CSCs) simultaneously. A nanoscopic surface energy transfer (NSET) ruler has been developed using blue fluorescence polymer dots (PDs) and red fluorescence gold cluster dots (GCDs) as multicolor fluorescence donor and plasmonic gold nanoparticle (GNP) acts as an excellent acceptor. Reported experimental results demonstrated that the multicolor nanoscopic ruler's working window is above 35 nm distances, which is more than three times farther than that of Förster resonance energy transfer (FRET) distance limit. Theoretical modeling using Förster dipole-dipole coupling and dipole to nanoparticle surface energy transfer have been used to discuss the possible mechanism for multicolor nanoscopic ruler's long-range capability. Using RNA aptamers that are specific for the target cancer cells, experimental data demonstrate that the nanoscopic ruler can be used for screening epithelial and CSCs simultaneously from a whole blood sample with a detection capability of 10 cells per mL. Experimental data show that the nanoscopic ruler can distinguish targeted cells from non-targeted cells.

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

    Science.gov (United States)

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

    2016-01-05

    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.

  12. Structure and dynamics of proton transfer in liquid imidazole. A molecular dynamics simulation.

    Science.gov (United States)

    Li, Ailin; Cao, Zhen; Li, Yao; Yan, Tianying; Shen, Panwen

    2012-10-25

    Proton transfer (PT) via the Grotthuss mechanism in liquid imidazole (im) at 393 K is studied with molecular dynamics simulation using a reactive multistate empirical valence bond (MS-EVB) model. It is found that the proton is tightly binded to an imidazole to form an imidazolium (imH(+)), which is solvated in a distorted Eigen-like complex (im-imH(+)-im), whereas the Zundel-like complex (im-H(+)-im) is rare. PT occurs via an Eigen-Zundel-Eigen scenario for switching the identity of imH(+) from an Eigen-like complex to another, intermediated by a Zundel-like complex. Structural and dynamical analyses demonstrate that PT in imidazole can be considered as a local event with very short spatial/temporal correlation, characterized by a few "rattling" or recurrent PT events. At long time scale, the trend of the PT correlation function may be recast with the diffusion model of reversible geminate recombination toward the power-law decay. The formation of the hydrogen bonds (HBs) for the imidazole molecules between the first and second solvation shell of imH(+) is crucial to pave the PT pathway. The above features may be understood by the flexibility of the HBs in liquid imidazole, as a stable HB network is essential for the Grotthuss mechanism.

  13. To Tunnel or not to Tunnel, Proton Transfer is the Question.

    Science.gov (United States)

    Chew, Kathryn; Nemchick, Deacon; Vaccaro, Patrick

    2014-06-01

    The transduction of protons between donor and acceptor sites, as mediated by the action of adjoining hydrogen bonds, represents one of the most ubiquitous of chemical transformations. While the basic mechanisms underlying such phenomena often can be ascribed to simple acid-base chemistry, the putative roles of selective nuclear and electronic displacements should not be discounted, especially when the presence of a sizeable potential barrier impedes classical hydron-migration pathways. The vibrational and isotopic specificity of hindered intramolecular proton transfer taking place within the ground (˜{X1}{A}1) and the lowest-lying excited (˜{A1}B2 (π *π) electronic states of the prototypical tropolone (TrOH) system has been probed by implementing multiple-color variants of resonant four-wave mixing (RFWM) spectroscopy, with polarization-resolved detection allowing for the extraction of quantitative rotation-tunneling information. The marked dependence of unimolecular dynamics on the extent and the type of excitation deposited into TrOH internal degrees of freedom will be discussed. Experimentally observed trends and propensities for tunneling-mediated reactivity will be interpreted through use of accompanying quantum-chemical calculations.

  14. Topological Influence of Lyotropic Liquid Crystalline Systems on Excited-State Proton Transfer Dynamics.

    Science.gov (United States)

    Roy, Bibhisan; Satpathi, Sagar; Hazra, Partha

    2016-03-29

    In the present work, we have investigated the excited-state proton transfer (ESPT) dynamics inside lipid-based reverse hexagonal (HII), gyroid Ia3d, and diamond Pn3m LLC phases. Polarized light microscopy (PLM) and small-angle X-ray scattering (SAXS) techniques have been employed for the characterization of LLC systems. Time-resolved fluorescence results reveal the retarded ESPT dynamics inside liquid crystalline systems compared to bulk water, and it follows the order HII water and it follows the order H2O constant and different channel diameters of these LLC systems. However, the dissociation dynamics is found to be slower than bulk water and it follows the order HII dissociation dynamics in these liquid crystalline systems.

  15. Lead chloride-based layered perovskite incorporated with an excited state intramolecular proton transfer dye

    Energy Technology Data Exchange (ETDEWEB)

    Sakai, Ken-ichi, E-mail: k-sakai@photon.chitose.ac.j [Department of Bio- and Material Photonics, Chitose Institute of Science and Technology, Bibi, Chitose 066-8655 (Japan); Takemura, Motohiro; Kawabe, Yutaka [Department of Bio- and Material Photonics, Chitose Institute of Science and Technology, Bibi, Chitose 066-8655 (Japan)

    2010-12-15

    We successfully fabricated thin films of organic-inorganic layered perovskite-type compound (AEHBA){sub 2}PbCl{sub 4}, where AEHBA stands for N-(2-aminoethyl)-2-hydroxybenzamide, a blue fluorescent dye that shows excited state intramolecular proton transfer (ESIPT) reaction. The formation of its highly ordered structure was readily achieved by the spin-coating of N,N-dimethylformamide solution dissolving PbCl{sub 2} and the AEHBA hydrogen chloride salt. X-ray diffraction analysis of the films revealed that organic AEHBA and inorganic PbCl{sub 4} perovskite layers were alternately stacked parallel to the substrate. In the absorption spectrum, exciton formation within the perovskite layers was confirmed by the appearance of a characteristic sharp band, while the photoluminescence spectrum showed a large Stokes-shifted band of AEHBA, indicating that it underwent an ESIPT.

  16. Detailed theoretical investigation of excited-state intramolecular proton transfer mechanism of a new chromophore II

    Science.gov (United States)

    Cui, Yanling; Li, Yafei; Dai, Yumei; Verpoort, Francis; Song, Peng; Xia, Lixin

    2016-02-01

    In the present work, TDDFT has been used to investigate the excited state intramolecular proton transfer (ESIPT) mechanism of a new chromophore II [Sensors and Actuators B: Chemical. 202 (2014) 1190]. The calculated absorption and fluorescence spectra agree well with experimental results. In addition, two types of II configurations are found in the first excited state (S1), which can be ascribed to the ESIPT reaction. Based on analysis of the calculated infrared (IR) spectra of O-H stretching vibration as well as the hydrogen bonding energies, the strengthening of the hydrogen bond in the S1 state has been confirmed. The frontier molecular orbitals (MOs), Hirshfeld charge distribution and the Natural bond orbital (NBO) have also been analyzed, which displays the tendency of the ESIPT process. Finally, potential energy curves of the S0 and S1 states were constructed, demonstrating that the ESIPT reaction can be facilitated based on the photo-excitation.

  17. Excited-state solvation and proton transfer dynamics of DAPI in biomimetics and genomic DNA.

    Science.gov (United States)

    Banerjee, Debapriya; Pal, Samir Kumar

    2008-08-14

    The fluorescent probe DAPI (4',6-diamidino-2-phenylindole) is an efficient DNA binder. Studies on the DAPI-DNA complexes show that the probe exhibits a wide variety of interactions of different strengths and specificities with DNA. Recently the probe has been used to report the environmental dynamics of a DNA minor groove. However, the use of the probe as a solvation reporter in restricted environments is not straightforward. This is due to the presence of two competing relaxation processes (intramolecular proton transfer and solvation stabilization) in the excited state, which can lead to erroneous interpretation of the observed excited-state dynamics. In this study, the possibility of using DAPI to unambiguously report the environmental dynamics in restricted environments including DNA is explored. The dynamics of the probe is studied in bulk solvents, biomimetics like micelles and reverse micelles, and genomic DNA using steady-state and picosecond-resolved fluorescence spectroscopies.

  18. Polarization transfer for inclusive proton-nucleus inelastic scattering at 800 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Fergerson, R.; McGill, J.; Glashausser, C.; Jones, K.; Nanda, S.; Sun Zuxun; Barlett, M.; Hoffmann, G.; Marshall, J.; McClelland, J.; and others

    1988-11-01

    The polarization-transfer observables D/sub N//sub N/, D/sub S//sub S/, D/sub L//sub L/, D/sub L//sub S/, and D/sub S//sub L/ have been measured at 800 MeV for polarized proton inelastic scattering from /sup 1/H, /sup 2/H, and /sup 12/C with energy losses up to about 400 MeV. The scattering angles in the laboratory were 5/sup 0/, 11/sup 0/, and 20/sup 0/. No large differences between the observables for the three targets were seen. The data for /sup 12/C in the quasielastic region are reasonably well explained by nonrelativistic and relativistic models of one-step quasifree scattering. Specifically nuclear effects appear small in both the quasielastic and delta regions.

  19. Radiative charge transfer in cold and ultracold Sulfur atoms colliding with Protons

    CERN Document Server

    Shen, G; Wang, J G; McCann, J F; McLaughlin, B M

    2015-01-01

    Radiative decay processes at cold and ultra cold temperatures for Sulfur atoms colliding with protons are investigated. The MOLPRO quantum chemistry suite of codes was used to obtain accurate potential energies and transition dipole moments, as a function of internuclear distance, between low-lying states of the SH$^{+}$ molecular cation. A multi-reference configuration-interaction (MRCI) approximation together with the Davidson correction is used to determine the potential energy curves and transition dipole moments, between the states of interest, where the molecular orbitals (MO's) are obtained from state-averaged multi configuration-self-consistent field (MCSCF) calculations. The collision problem is solved approximately using an optical potential method to obtain radiative loss, and a fully two-channel quantum approach for radiative charge transfer. Cross sections and rate coefficients are determined for the first time for temperatures ranging from 10 $\\mu$ K up to 10,000 K. Results are obtained for all ...

  20. Excited state proton transfer effect of 7-hydroxyquinoline in dimethyl sulfoxide solvent

    Institute of Scientific and Technical Information of China (English)

    GUO Yang-xue; LI Xiang-ping; ZHENG Jia-jin; ZHANG Gui-lan; LIU Jing-jiang; CHEN Wen-ju

    2006-01-01

    7-hydroxyquinoline (7-HQ) is a kind of organic molecule with excited state proton transfer (ESPT) effect,and can be used as the material for all optical switching.This optical switching takes place via the ESPT effect depending on its intermolecular hydrogen bond formed with the solvent,and can have the effect of all optical switching.7-HQ can not form intermolecular hydrogen bond with dimethyl sulfoxide (DMSO),so 7-HQ in DMSO solution cannot display the ESPT effect.However,after the solution was radiated by an UV laser, we found that 7-HQ could have ESPT effect.This phenomenon is reported and the mechanism is investigated for the first time in this paper.

  1. Colorimetric Sensors for Anion Recognition Based on the Proton Transfer Signaling Mechanism

    Institute of Scientific and Technical Information of China (English)

    HUANG Xiaohuan; HE Yongbing; CHEN Zhihong; HU Chenguang

    2009-01-01

    Phenolic hydroxyl based sensors N,N-bi(salicylidene)-1,2-phenylenediamine (1),2-[(4-nitrophenylimino)methyl] phenol (2) and 2-[p-tdylimino methyl] phenol (3) bearing Schiff-base groups can act as selective colorimetric sensors for anions,which exhibit distinct color changes in the presence of fluoride,but show no response to other halogen anions.They also give response to acetate,which is clearly visible to the naked eyes.The selectivity can be rationalized on the proton transfer signaling mechanism.The sensor 1 containing plural phenolic groups undergoes stepwise deprotonation of the two O-H fragments when it interacts with excess fluoride,which is confirmed by UV-Vis,1H NMR and 19F NMR spectroscopic methods.

  2. Proton transfer from 1,4-pentadiene to superoxide radical anion: a QTAIM analysis

    Directory of Open Access Journals (Sweden)

    Angela Rodríguez-Serrano

    2014-04-01

    Full Text Available We studied the bis-allylic proton transferreaction from 1,4-pentadiene to superoxideradical anion (O2·־. Minima andtransition state geometries, as well asthermochemical parameters were computedat the B3LYP/6-311+G(3df,2plevel of theory. The electronic wavefunctions of reactants, intermediates,and products were analyzed within theframework of the Quantum Theory ofAtoms in Molecules. The results showthe formation of strongly hydrogen bondedcomplexes between the 1,4-pentadien-3-yl anion and the hydroperoxylradical as the reaction products. Theseproduct complexes (PCs are more stablethan the isolated reactants and muchmore stable than the isolated products.This reaction occurs via pre-reactivecomplexes which are more stable thanthe PCs and the transition states. This isin agreement with the fact that the netproton transfer reaction that leads to freeproducts is an endothermic and nonspontaneousprocess.

  3. RF Wire Compensator of Long-Range Beam-Beam Effects

    CERN Document Server

    Dorda, U; Kroyer, T; Zimmermann, F

    2008-01-01

    The dynamic aperture of the proton beam circulating in the Large Hadron Collider (LHC) is expected to be limited by up to 120 long-range beam-beam encounters. In order to perfectly compensate the LHC long-range beambeam effect for nominal as well as for so-called "PACMAN" bunches, i.e. bunches at the start or end of a bunch train, the strength of a wire compensator should be adjusted for each bunch individually. Here an RF-based compensator is proposed as a practical solution for the PACMAN compensation. We show that this approach also allows relaxing the power and precision requirements compared with those of a pulsed DC device, to a level within the state-of-the-art of RF technology. Furthermore it permits the use of a passive circulator in the tunnel close to the beam and thus a significant reduction of the transmission line length and of the associated multiple reflections. Simulations of dynamic aperture and emittance growth, issues related to RF phase noise, and first experimental results from laborator...

  4. In-flight sleep, pilot fatigue and Psychomotor Vigilance Task performance on ultra-long range versus long range flights.

    Science.gov (United States)

    Gander, Philippa H; Signal, T Leigh; van den Berg, Margo J; Mulrine, Hannah M; Jay, Sarah M; Jim Mangie, Captain

    2013-12-01

    This study evaluated whether pilot fatigue was greater on ultra-long range (ULR) trips (flights >16 h on 10% of trips in a 90-day period) than on long range (LR) trips. The within-subjects design controlled for crew complement, pattern of in-flight breaks, flight direction and departure time. Thirty male Captains (mean age = 54.5 years) and 40 male First officers (mean age = 48.0 years) were monitored on commercial passenger flights (Boeing 777 aircraft). Sleep was monitored (actigraphy, duty/sleep diaries) from 3 days before the first study trip to 3 days after the second study trip. Karolinska Sleepiness Scale, Samn-Perelli fatigue ratings and a 5-min Psychomotor Vigilance Task were completed before, during and after every flight. Total sleep in the 24 h before outbound flights and before inbound flights after 2-day layovers was comparable for ULR and LR flights. All pilots slept on all flights. For each additional hour of flight time, they obtained an estimated additional 12.3 min of sleep. Estimated mean total sleep was longer on ULR flights (3 h 53 min) than LR flights (3 h 15 min; P(F) = 0.0004). Sleepiness ratings were lower and mean reaction speed was faster at the end of ULR flights. Findings suggest that additional in-flight sleep mitigated fatigue effectively on longer flights. Further research is needed to clarify the contributions to fatigue of in-flight sleep versus time awake at top of descent. The study design was limited to eastward outbound flights with two Captains and two First Officers. Caution must be exercised when extrapolating to different operations.

  5. Proton-transfer reaction dynamics and energetics in calcification and decalcification.

    Science.gov (United States)

    Suwa, Ryota; Hatta, Masayuki; Ichikawa, Kazuhiko

    2014-10-13

    CaCO3 -saturated saline waters at pH values below 8.5 are characterized by two stationary equilibrium states: reversible chemical calcification/decalcification associated with acid dissociation, Ca(2+) +HCO3 (-) ⇌CaCO3 +H(+) ; and reversible static physical precipitation/dissolution, Ca(2+) +CO3 (2-) ⇌CaCO3 . The former reversible reaction was determined using a strong base and acid titration. The saturation state described by the pH/PCO2 -independent solubility product, [Ca(2+) ][CO3 (2-) ], may not be observed at pH below 8.5 because [Ca(2+) ][CO3 (2-) ]/([Ca(2+) ][HCO3 (-) ]) ≪1. Since proton transfer dynamics controls all reversible acid dissociation reactions in saline waters, the concentrations of calcium ion and dissolved inorganic carbon (DIC) were expressed as a function of dual variables, pH and PCO2 . The negative impact of ocean acidification on marine calcifying organisms was confirmed by applying the experimental culture data of each PCO2 /pH-dependent coral polyp skeleton weight (Wskel) to the proton transfer idea. The skeleton formation of each coral polyp was performed in microspaces beneath its aboral ectoderm. This resulted in a decalcification of 14 weight %, a normalized CaCO3 saturation state Λ of 1.3 at PCO2 ≈400 ppm and pH ≈8.0, and serious decalcification of 45 % and Λ 2.5 at PCO2 ≈1000 ppm and pH ≈7.8.

  6. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Hongying; Huang, Guangming, E-mail: gmhuang@ustc.edu.cn

    2015-03-31

    Graphical abstract: Direct and humidity independent mass spectrometry analysis of gas phase chemicals could be achieved via ambient proton transfer ionization, ion intensity was found to be stable with humidity ranged from ∼10% to ∼100%. - Highlights: • A humidity independent mass spectrometric method for gas phase samples analysis. • A universal and good sensitivity method. • The method can real time identify plant released raw chemicals. - Abstract: In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m{sup −3}, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  7. Stereochemistry of 1,2-elimination and proton-transfer reactions: toward a unified understanding.

    Science.gov (United States)

    Mohrig, Jerry R

    2013-07-16

    Many mechanistic and stereochemical studies have focused on the breaking of the C-H bond through base-catalyzed elimination reactions. When we began our research, however, chemists knew almost nothing about the stereospecificity of addition-elimination reactions involving conjugated acyclic carbonyl compounds, even though the carbonyl group is a pivotal functional group in organic chemistry. Over the last 25 years, we have studied the addition-elimination reactions of β-substituted acyclic esters, thioesters, and ketones in order to reach a comprehensive understanding of how electronic effects influence their stereochemistry. This Account brings together our understanding of the stereochemistry of 1,2-elimination and proton-transfer reactions, describing how each study has built upon previous work and contributed to our understanding of this field. When we began, chemists thought that anti stereospecificity in base-catalyzed 1,2-elimination reactions occurred via concerted E2 mechanisms, which provide a smooth path for anti elimination. Unexpectedly, we discovered that some E1cBirrev reactions produce the same anti stereospecificity as E2 reactions even though they proceed through diffusionally equilibrated, "free" enolate-anion intermediates. This result calls into question the conventional wisdom that anti stereochemistry must result from a concerted mechanism. While carrying out our research, we developed insights ranging from the role of historical contingency in the evolution of hydratase-dehydratase enzymes to the influence of buffers on the stereochemistry of H/D exchange in D2O. Negative hyperconjugation is the most important concept for understanding our results. This idea provides a unifying view for the largely anti stereochemistry in E1cBirrev elimination reactions and a basis for understanding the stereoelectronic influence of electron-withdrawing β-substituents on proton-transfer reactions.

  8. Classical investigation of long-range coherence in biological systems

    Science.gov (United States)

    Preto, Jordane

    2016-12-01

    Almost five decades ago, H. Fröhlich [H. Fröhlich, "Long-range coherence and energy storage in biological systems," Int. J. Quantum Chem. 2(5), 641-649 (1968)] reported, on a theoretical basis, that the excitation of quantum modes of vibration in contact with a thermal reservoir may lead to steady states, where under high enough rate of energy supply, only specific low-frequency modes of vibration are strongly excited. This nonlinear phenomenon was predicted to occur in biomolecular systems, which are known to exhibit complex vibrational spectral properties, especially in the terahertz frequency domain. However, since the effects of terahertz or lower-frequency modes are mainly classical at physiological temperatures, there are serious doubts that Fröhlich's quantum description can be applied to predict such a coherent behavior in a biological environment, as suggested by the author. In addition, a quantum formalism makes the phenomenon hard to investigate using realistic molecular dynamics simulations (MD) as they are usually based on the classical principles. In the current paper, we provide a general classical Hamiltonian description of a nonlinear open system composed of many degrees of freedom (biomolecular structure) excited by an external energy source. It is shown that a coherent behaviour similar to Fröhlich's effect is to be expected in the classical case for a given range of parameter values. Thus, the supplied energy is not completely thermalized but stored in a highly ordered fashion. The connection between our Hamiltonian description, carried out in the space of normal modes, and a more standard treatment in the physical space is emphasized in order to facilitate the prediction of the effect from MD simulations. It is shown how such a coherent phenomenon may induce long-range resonance effects that could be of critical importance at the biomolecular level. The present work is motivated by recent experimental evidences of long-lived excited low

  9. Electron and proton transfer assemblies and new porous materials from nanometer-scale building blocks

    Science.gov (United States)

    Johnson, Stacy Ann

    Elegant examples of molecular engineering are found in nature that make our current small devices seem primitive. By using naturally occurring examples we can better imagine how to construct useful three dimensional nanoscaled devices. Electron and proton transfer composites were prepared using a multilayer film growth technique, in which single anionic sheets derived from inorganic solids are interleaved with cationic polyelectrolytes. This method allows for the growth of concentric monolayers of redox-active polymers on high-surface-area silica supports, and for vectorial electron transfer reactions through the layers of the "onion." Photoinduced charge separation has been observed in composites consisting of an inner polycationic layer of poly(styrene- co-N-vinylbenzyl-N'-methyl-4,4 '-bipyridine), and an outer polycationic layer of poly[Ru(bpy) 2(vbpy)]2+, vbpy = 4-vinyl-4'-methyl- 2,2'-bipyridine, bpy = 2,2' -bipyridine, which are separated by a thin inorganic sheet of Zr(HOPO 3)2·H2O. Following the logic of the proton transport mechanism found in biological membranes, a photosensitive proton pump was constructed using the same electrostatic adsorption technique. This composite was prepared with a polymeric form of a luminescent ruthenium complex, poly[Ru(bpy) 2(bpm)]2+, bpy = 2,2'-bipyridine bpm = 2,2'-bipyrimidine. The pH of a solution in which the composites were suspended changed reversibly when irradiated with visible light. A series of microporous polymer replicas were synthesized using inorganic templates. Zeolites were used as templates to prepare microporous polymer replicas with nanometer sized pore networks. Phenol-formaldehyde polymers were synthesized and cured within the channel networks of zeolites Y, beta, and L. Dissolution of the aluminosilicate framework in aqueous IHF yields an organic replica. The zeolite template exerts important topological effects on the structure and physical properties of the replica. A similar process is described

  10. Quantification of diesel exhaust gas phase organics by a thermal desorption proton transfer reaction mass spectrometer

    Directory of Open Access Journals (Sweden)

    M. H. Erickson

    2012-02-01

    Full Text Available A new approach was developed to measure the total abundance of long chain alkanes (C12 and above in urban air using thermal desorption with a proton transfer reaction mass spectrometer (PTR-MS. These species are emitted in diesel exhaust and may be important precursors to secondary organic aerosol production in urban areas. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The yield of the fragment ions is a function of drift conditions. At a drift field strength of 80 Townsends, the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Higher drift field strengths yield greater normalized sensitivity implying that the proton affinity of the long chain n-alkanes is less than H2O. Analysis of diesel fuel shows the mass spectrum was dominated by alkanes (CnH2n+1, monocyclic aromatics, and an ion group with formula CnH2n−1 (m/z 97, 111, 125, 139. The PTR-MS was deployed in Sacramento, CA during the Carbonaceous Aerosols and Radiative Effects Study field experiment in June 2010. The ratio of the m/z 97 to 85 ion intensities in ambient air matched that found in diesel fuel. Total diesel exhaust alkane concentrations calculated from the measured abundance of m/z 85 ranged from the method detection limit of ~1 μg m−3 to 100 μg m−3 in several air pollution episodes. The total diesel exhaust alkane concentration determined by this method was on average a factor of 10 greater than the sum of alkylbenzenes associated with spark ignition vehicle exhaust.

  11. Amide proton transfer imaging in clinics: Basic concepts and current and future use in brain tumors and stoke

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ji Eun [Dept. of Radiology and Research Institute of Radiology, University of Ulsan College of Medicine, Asan Medical Center, Seoul (Korea, Republic of); Jahng, Geon Ho [Dept. of Radiology, Kyung Hee University Hospital at Gangdong, College of Medicine, Kyung Hee University, Seoul (Korea, Republic of); Jeong, Ha Kyu [Philips Korea, Seoul (Korea, Republic of)

    2016-12-15

    Amide proton transfer (APT) imaging is gaining attention as a relatively new in vivo molecular imaging technique that has higher sensitivity and spatial resolution than magnetic resonance spectroscopy imaging. APT imaging is a subset of the chemical exchange saturation transfer mechanism, which can offer unique image contrast by selectively saturating protons in target molecules that get exchanged with protons in bulk water. In this review, we describe the basic concepts of APT imaging, particularly with regard to the benefit in clinics from the current literature. Clinical applications of APT imaging are described from two perspectives: in the diagnosis and monitoring of the treatment response in brain glioma by reflecting endogenous mobile proteins and peptides, and in the potential for stroke imaging with respect to tissue acidity.

  12. Sequential Proton Loss Electron Transfer in Deactivation of Iron(IV) Binding Protein by Tyrosine Based Food Components

    DEFF Research Database (Denmark)

    Tang, Ning; Skibsted, Leif Horsfelt

    2017-01-01

    The iron(IV) binding protein ferrylmyoglobin, MbFe(IV)=O, was found to be reduced by tyrosine based food components in aqueous solution through a sequential proton loss electron transfer reaction mechanism without binding to the protein as confirmed by isothermal titration calorimetry. Dopamine...... by protonation of ferrylmyoglobin and facilitated proton transfer at acidic conditions. Enthalpy-entropy compensation effects were observed for the activation parameters (ΔH† and ΔS†), indicating the common reaction mechanism. Moreover, principal component analysis combined with heat map were performed...... to understand the relationship between density functional theory calculated molecular descriptors and kinetic data, which was further modeled by partial least squares for quantitative structure-activity relationship analysis. In addition, a three tyrosine residue containing protein, lysozyme, was also found...

  13. Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Soumya; Soudackov, Alexander; Hammes-Schiffer, Sharon

    2016-06-14

    Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play an essential role in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We present a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This approach incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectric continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganization energies in close agreement with experimental values for two experimentally studied PCET systems. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  14. Long-range spin Seebeck effect and acoustic spin pumping.

    Science.gov (United States)

    Uchida, K; Adachi, H; An, T; Ota, T; Toda, M; Hillebrands, B; Maekawa, S; Saitoh, E

    2011-10-01

    Imagine that a metallic wire is attached to a part of a large insulator, which itself exhibits no magnetization. It seems impossible for electrons in the wire to register where the wire is positioned on the insulator. Here we found that, using a Ni₈₁Fe₁₉/Pt bilayer wire on an insulating sapphire plate, electrons in the wire recognize their position on the sapphire. Under a temperature gradient in the sapphire, surprisingly, the voltage generated in the Pt layer is shown to reflect the wire position, although the wire is isolated both electrically and magnetically. This non-local voltage is due to the coupling of spins and phonons: the only possible carrier of information in this system. We demonstrate this coupling by directly injecting sound waves, which realizes the acoustic spin pumping. Our finding provides a persuasive answer to the long-range nature of the spin Seebeck effect, and it opens the door to 'acoustic spintronics' in which sound waves are exploited for constructing spin-based devices.

  15. Entropy production in systems with long range interactions

    Science.gov (United States)

    Pakter, Renato; Levin, Yan

    2017-04-01

    On a fine grained scale the Gibbs entropy of an isolated system remains constant throughout its dynamical evolution. This is a consequence of Liouville’s theorem for Hamiltonian systems and appears to contradict the second law of thermodynamics. In reality, however, there is no problem since the thermodynamic entropy should be associated with the Boltzmann entropy, which for non-equilibrium systems is different from Gibbs entropy. The Boltzmann entropy accounts for the microstates which are not accessible from a given initial condition, but are compatible with a given macrostate. In a sense the Boltzmann entropy is a coarse grained version of the Gibbs entropy and will not decrease during the dynamical evolution of a macroscopic system. In this paper we will explore the entropy production for systems with long range interactions. Unlike for short range systems, in the thermodynamic limit, the probability density function for these systems decouples into a product of one particle distribution functions and the coarse grained entropy can be calculated explicitly. We find that the characteristic time for the entropy production scales with the number of particles as {{N}α} , with α >0 , so that in the thermodynamic limit entropy production takes an infinite amount of time.

  16. Record length requirement of long-range dependent teletraffic

    Science.gov (United States)

    Li, Ming

    2017-04-01

    This article contributes the highlights mainly in two folds. On the one hand, it presents a formula to compute the upper bound of the variance of the correlation periodogram measurement of teletraffic (traffic for short) with long-range dependence (LRD) for a given record length T and a given value of the Hurst parameter H (Theorems 1 and 2). On the other hand, it proposes two formulas for the computation of the variance upper bound of the correlation periodogram measurement of traffic of fractional Gaussian noise (fGn) type and the generalized Cauchy (GC) type, respectively (Corollaries 1 and 2). They may constitute a reference guideline of record length requirement of traffic with LRD. In addition, record length requirement for the correlation periodogram measurement of traffic with either the Schuster type or the Bartlett one is studied and the present results about it show that both types of periodograms may be used for the correlation measurement of traffic with a pre-desired variance bound of correlation estimation. Moreover, real traffic in the Internet Archive by the Special Interest Group on Data Communication under the Association for Computing Machinery of US (ACM SIGCOMM) is analyzed in the case study in this topic.

  17. Long-range correlations and the momentum distribution in nuclei

    CERN Document Server

    Amir-Azimi-Nili, K; Skouras, L D; Polls, A

    1996-01-01

    The influence of correlations on the momentum distribution of nucleons in nuclei is evaluated starting from a realistic nucleon-nucleon interaction. The calculations are performed directly for the finite nucleus \\,^{16}O making use of the Green's function approach. The emphasis is focused on the correlations induced by the excitation modes at low energies described within a model-space of shell-model configurations including states up to the sdg shell. Our analysis demonstrates that these long-range correlations do not produce any significant enhancement of the momentum distribution at high missing momenta and low missing energies. This is in agreement with high resolution (e,e'p) experiments for this nucleus. We also try to simulate the corresponding effects in large nuclei by quenching the energy-spacing between single-particle orbits. This yields a sizable enhancement of the spectral function at large momenta and small energy. Such behavior could explain the deviation of the momentum distribution from the ...

  18. Ultracold Long-Range Rydberg Molecules with Complex Multichannel Spectra

    Science.gov (United States)

    Eiles, Matthew; Greene, Chris

    2016-05-01

    A generalized class of exotic long-range Rydberg molecules consisting of a multichannel Rydberg atom bound to a distant ground state atom by the Rydberg electron is predicted. These molecules are characterized by the rich physics provided by the strongly perturbed multichannel Rydberg spectra of divalent atoms, in contrast to the regular Rydberg series of the alkali atoms used to form Rydberg molecules to date. These multichannel Rydberg molecules exhibit favorable properties for laser excitation, because states exist where the quantum defect varies strongly with the principal quantum number n. In particular, the nd Rydberg state of calcium becomes nearly degenerate with states of high orbital angular momentum over the range 17 molecular states are predicted to occur in the low- J states of silicon, which are strongly perturbed due to channel interactions between Rydberg series leading to the spin-orbit split ionization thresholds. These interactions manifest themselves in potential curves exhibiting two distinct length scales, providing novel opportunities for quantum manipulation. Supported in part by the National Science Foundation under Grant No. PHY-1306905.

  19. Long-range interacting systems in the unconstrained ensemble

    Science.gov (United States)

    Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

    2017-01-01

    Completely open systems can exchange heat, work, and matter with the environment. While energy, volume, and number of particles fluctuate under completely open conditions, the equilibrium states of the system, if they exist, can be specified using the temperature, pressure, and chemical potential as control parameters. The unconstrained ensemble is the statistical ensemble describing completely open systems and the replica energy is the appropriate free energy for these control parameters from which the thermodynamics must be derived. It turns out that macroscopic systems with short-range interactions cannot attain equilibrium configurations in the unconstrained ensemble, since temperature, pressure, and chemical potential cannot be taken as a set of independent variables in this case. In contrast, we show that systems with long-range interactions can reach states of thermodynamic equilibrium in the unconstrained ensemble. To illustrate this fact, we consider a modification of the Thirring model and compare the unconstrained ensemble with the canonical and grand-canonical ones: The more the ensemble is constrained by fixing the volume or number of particles, the larger the space of parameters defining the equilibrium configurations.

  20. ORNL long-range environmental and waste management plan

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, J.S.; Bates, L.D.; Brown, C.H.; Easterday, C.A.; Hill, L.G.; Kendrick, C.M.; McNeese, L.E.; Myrick, T.E.; Payne, T.L.; Pepper, C.E.; Robinson, S.M.; Rohwer, P.S.; Scanlan, T.F.; Smith, M.A.; Stratton, L.E.; Trabalka, J.R.

    1989-09-01

    This report, the ORNL Long-Range Environmental and Waste Management Plan, is the annual update in a series begun in fiscal year 1985. Its primary purpose is to provide a thorough and systematic planning document to reflect the continuing process of site assessment, strategy development, and planning for the current and long-term control of environmental issues, waste management practices, and remedial action requirements. The document also provides an estimate of the resources required to implement the current plan. This document is not intended to be a budget document; it is, however, intended to provide guidance to both Martin Marietta Energy Systems, Inc., and the US Department of Energy (DOE) management as to the near order of magnitude of the resources (primarily funding requirements) and the time frame required to execute the strategy in the present revision of the plan. As with any document of this nature, the near-term (one to three years) part of the plan is a pragmatic assessment of the current program and ongoing capital projects and reflects the efforts perceived to be necessary to comply with all current state and federal regulations and DOE orders. It also should be in general agreement with current budget (funding) requests and obligations for these immediate years. 55 figs., 72 tabs.

  1. Long-range interacting systems in the unconstrained ensemble.

    Science.gov (United States)

    Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

    2017-01-01

    Completely open systems can exchange heat, work, and matter with the environment. While energy, volume, and number of particles fluctuate under completely open conditions, the equilibrium states of the system, if they exist, can be specified using the temperature, pressure, and chemical potential as control parameters. The unconstrained ensemble is the statistical ensemble describing completely open systems and the replica energy is the appropriate free energy for these control parameters from which the thermodynamics must be derived. It turns out that macroscopic systems with short-range interactions cannot attain equilibrium configurations in the unconstrained ensemble, since temperature, pressure, and chemical potential cannot be taken as a set of independent variables in this case. In contrast, we show that systems with long-range interactions can reach states of thermodynamic equilibrium in the unconstrained ensemble. To illustrate this fact, we consider a modification of the Thirring model and compare the unconstrained ensemble with the canonical and grand-canonical ones: The more the ensemble is constrained by fixing the volume or number of particles, the larger the space of parameters defining the equilibrium configurations.

  2. Experimental perspectives for systems based on long-range interactions

    CERN Document Server

    Bachelard, Romain; De Buyl, Pierre; Staniscia, F; Cataliotti, F S; De Ninno, G; Fanelli, Duccio; Piovella, Nicola

    2010-01-01

    The possibility of observing phenomena peculiar to long-range interactions, and more specifically in the so-called Quasi-Stationary State (QSS) regime is investigated within the framework of two devices, namely the Free-Electron Laser (FEL) and the Collective Atomic Recoil Laser (CARL). The QSS dynamics has been mostly studied using the Hamiltonian Mean-Field (HMF) toy model, demonstrating in particular the presence of first versus second order phase transitions from magnetized to unmagnetized regimes in the case of HMF. Here, we give evidence of the strong connections between the HMF model and the dynamics of the two mentioned devices, and we discuss the perspectives to observe some specific QSS features experimentally. In particular, a dynamical analog of the phase transition is present in the FEL and in the CARL in its conservative regime. Regarding the dissipative CARL, a formal link is established with the HMF model. For both FEL and CARL, calculations are performed with reference to existing experimenta...

  3. Isolation Platform for Long Range Optical Communications Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Optical communication links provide higher data transfer rates with lower mass, power, and volume than conventional radio-frequency links. For deep space...

  4. Vibration Isolation Platform for Long Range Optical Communications Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Optical communication links provide higher data transfer rates with lower mass, power, and volume than conventional radio-frequency links. For deep space...

  5. Detection of trace gases from fermentation processes using photoacoustic spectroscopy and proton-transfer-reaction mass spectrometry

    NARCIS (Netherlands)

    Boamfă-Ivan, Elena Iuliana

    2005-01-01

    This thesis presents novel interdisciplinary Physics - Biology research work that employed Photoacoustic Spectroscopy and Proton-Transfer-Reaction Mass Spectrometry. Both techniques were used in biological studies of trace gasses emitted by crop plants and fruit under stress situations. The findings

  6. Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

    NARCIS (Netherlands)

    Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

    2012-01-01

    Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive

  7. Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

    NARCIS (Netherlands)

    Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

    2012-01-01

    Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive fr

  8. Geographical provenancing of purple grape juices from different farming systems by proton transfer reaction mass spectrometry using supervised statistical techniques

    NARCIS (Netherlands)

    Granato, Daniel; Koot, Alex; Ruth, van S.M.

    2015-01-01

    BACKGROUND: Organic, biodynamic and conventional purple grape juices (PGJ; n = 79) produced in Brazil and Europe were characterized by volatile organic compounds (m/z 20-160) measured by proton transfer reaction mass spectrometry (PTR-MS), and classification models were built using supervised sta

  9. 10-hydroxybenzo[h]quinoline: Switching between single and double-well proton transfer through structural modifications

    DEFF Research Database (Denmark)

    Hristova, S; Dobrikov, G; Kamounah, F. S.;

    2015-01-01

    Proton transfer in 10-hydroxybenzo[h]quinoline (HBQ) and structurally modified compounds was investigated experimentally (steady state UV-Vis absorption and emission spectroscopy, NMR and advanced chemometric techniques) and theoretically (DFT and TD-DFT M06-2X/TZVP calculations) in the ground...

  10. Short- and long-range corrected hybrid density functionals with the D3 dispersion corrections

    CERN Document Server

    Wang, Chih-Wei; Chai, Jeng-Da

    2016-01-01

    We propose a short- and long-range corrected (SLC) hybrid scheme employing 100% Hartree-Fock (HF) exchange at both zero and infinite interelectronic distances, wherein three SLC hybrid density functionals with the D3 dispersion corrections (SLC-LDA-D3, SLC-PBE-D3, and SLC-B97-D3) are developed. SLC-PBE-D3 and SLC-B97-D3 are shown to be accurate for a very diverse range of applications, such as core ionization and excitation energies, thermochemistry, kinetics, noncovalent interactions, dissociation of symmetric radical cations, vertical ionization potentials, vertical electron affinities, fundamental gaps, and valence, Rydberg, and long-range charge-transfer excitation energies. Relative to omegaB97X-D, SLC-B97-D3 provides significant improvement for core ionization and excitation energies and noticeable improvement for the self-interaction, asymptote, energy-gap, and charge-transfer problems, while performing similarly for thermochemistry, kinetics, and noncovalent interactions.

  11. The investigation of excited state proton transfer mechanism in water-bridged 7-azaindole

    Science.gov (United States)

    Zhang, Yong-Jia; Zhao, Jin-Feng; Li, Yong-Qing

    2016-01-01

    Based on the time-dependent density functional theory (TDDFT), the excited-state intermolecular proton transfer (ESIPT) mechanism of water-bridged 7-azaindole has been investigated theoretically. The calculations of primary bond lengths and the IR vibrational spectra between the S0 state and the S1 state that verified the intramolecular hydrogen bond were strengthened. The fact that reproduced experimental absorbance and fluorescence emission spectra well theoretically demonstrate that the TDDFT theory we adopted is reasonable and effective. In addition, intramolecular charge transfer based on the frontier molecular orbitals demonstrated the indication of the ESIPT reaction. The constructed potential energy curves of ground state and the first excited state based on keeping the H2···O3 and H6···N7 distances fixed at a series of values have been used to illustrate the ESIPT process. A relative lower barrier of 5.94 kcal/mol in the S1 state potential energy curve for type II (lower than that of 9.82 kcal/mol in the S1 state for type I) demonstrates that type II ESIPT process occurs firstly in 7Al-2H2O complex.

  12. Characterizing amide proton transfer imaging in haemorrhage brain lesions using 3T MRI

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Ha-Kyu [Philips Korea, Seoul (Korea, Republic of); Korea Basic Science Institute, Chungcheongbuk-do (Korea, Republic of); Han, Kyunghwa [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, Seodaemun-gu, Seoul (Korea, Republic of); Yonsei University College of Medicine, Yonsei Biomedical Research Institute, Seoul (Korea, Republic of); Zhou, Jinyuan [Johns Hopkins University School of Medicine, Division of MRI Research, Department of Radiology, Baltimore, MD (United States); Zhao, Yansong [Philips Healthcare, MR Clinical Science, Cleveland, OH (United States); Choi, Yoon Seong; Lee, Seung-Koo; Ahn, Sung Soo [Yonsei University College of Medicine, Department of Radiology and Research Institute of Radiological Science, Seodaemun-gu, Seoul (Korea, Republic of)

    2017-04-15

    The aim of this study was to characterize amide proton transfer (APT)-weighted signals in acute and subacute haemorrhage brain lesions of various underlying aetiologies. Twenty-three patients with symptomatic haemorrhage brain lesions including tumorous (n = 16) and non-tumorous lesions (n = 7) were evaluated. APT imaging was performed and analyzed with magnetization transfer ratio asymmetry (MTR{sub asym}). Regions of interest were defined as the enhancing portion (when present), acute or subacute haemorrhage, and normal-appearing white matter based on anatomical MRI. MTR{sub asym} values were compared among groups and components using a linear mixed model. MTR{sub asym} values were 3.68 % in acute haemorrhage, 1.6 % in subacute haemorrhage, 2.65 % in the enhancing portion, and 0.38 % in normal white matter. According to the linear mixed model, the distribution of MTR{sub asym} values among components was not significantly different between tumour and non-tumour groups. MTR{sub asym} in acute haemorrhage was significantly higher than those in the other regions regardless of underlying pathology. Acute haemorrhages showed high MTR{sub asym} regardless of the underlying pathology, whereas subacute haemorrhages showed lower MTR{sub asym} than acute haemorrhages. These results can aid in the interpretation of APT imaging in haemorrhage brain lesions. (orig.)

  13. Electron attachment to the guanine-cytosine nucleic acid base pair and the effects of monohydration and proton transfer.

    Science.gov (United States)

    Gupta, Ashutosh; Jaeger, Heather M; Compaan, Katherine R; Schaefer, Henry F

    2012-05-17

    The guanine-cytosine (GC) radical anion and its interaction with a single water molecule is studied using ab initio and density functional methods. Z-averaged second-order perturbation theory (ZAPT2) was applied to GC radical anion for the first time. Predicted spin densities show that the radical character is localized on cytosine. The Watson-Crick monohydrated GC anion is compared to neutral GC·H2O, as well as to the proton-transferred analogue on the basis of structural and energetic properties. In all three systems, local minima are identified that correspond to water positioned in the major and minor grooves of macromolecular DNA. On the anionic surface, two novel structures have water positioned above or below the GC plane. On the neutral and anionic surfaces, the global minimum can be described as water interacting with the minor groove. These structures are predicted to have hydration energies of 9.7 and 11.8 kcal mol(-1), respectively. Upon interbase proton-transfer (PT), the anionic global minimum has water positioned in the major groove, and the hydration energy increases to 13.4 kcal mol(-1). PT GC·H2O(•-) has distonic character; the radical character resides on cytosine, while the negative charge is localized on guanine. The effects of proton transfer are further investigated through the computed adiabatic electron affinities (AEA) of GC and monohydrated GC, and the vertical detachment energies (VDE) of the corresponding anions. Monohydration increases the AEAs and VDEs by only 0.1 eV, while proton-transfer increases the VDEs substantially (0.8 eV). The molecular charge distribution of monohydrated guanine-cytosine radical anion depends heavily on interbase proton transfer.

  14. Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons.

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2011-05-01

    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of nonequivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolite phantoms with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: (i) on-resonance SL is most sensitive to chemical exchanges in the intermediate-exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. (ii) Offset frequency-dependent SL and CEST spectra are very similar and can be explained well with an SL model recently developed by Trott and Palmer (J Magn Reson 2002;154:157-160). (iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. (iv) The asymmetry of the magnetization transfer ratio (MTR(asym)) is highly dependent on the choice of saturation pulse power. In the intermediate-exchange regime, MTR(asym) becomes complicated and should be interpreted with care.

  15. Observing Proton Transfer Reactions Inside the MALDI Plume: Experimental and Theoretical Insight into MALDI Gas-Phase Reactions

    Science.gov (United States)

    Mirabelli, Mario F.; Zenobi, Renato

    2017-08-01

    We evaluated the contribution of gas-phase in-plume proton transfer reactions to the formation of protonated and deprotonated molecules in the MALDI process. A split sample holder was used to separately deposit two different samples, which avoids any mixing during sample preparation. The two samples were brought very close to each other and desorbed/ionized by the same laser pulse. By using a combination of deuterated and non-deuterated matrices, it was possible to observe exclusively in-plume proton transfer processes. The hydrogen/deuterium exchange (HDX) kinetics were evaluated by varying the delayed extraction (DE) time, allowing the desorbed ions and neutrals to interact inside the plume for a variable period of time before being extracted and detected. Quantum mechanical calculations showed that the HDX energy barriers are relatively low for such reactions, corroborating the importance of gas-phase proton transfer in the MALDI plume. The experimental results, supported by theoretical simulations, confirm that the plume is a very reactive environment, where HDX reactions could be observed from 0 ns up to 400 ns after the laser pulse. These results could be used to evaluate the relevance of previously proposed (and partially conflicting) ionization models for MALDI.

  16. Multifractal Geophysical Extremes: Nonstationarity and Long Range Correlations

    Science.gov (United States)

    Tchiguirinskaia, I.; Schertzer, D.; Lovejoy, S.

    2012-04-01

    Throughout the world, extremes in environmental sciences are of prime importance. They are key variables not only for risk assessments and engineering designs (e.g. of dams and bridges), but also for resource management (e.g. water and energy) and for land use. A better understanding of them is more and more indispensable in settling the debate on their possible climatological evolution. Whereas it took decades before a uniform technique for estimating flow frequencies within a stationary framework, it is often claimed that « stationarity is dead ! ». The fact that geophysical and environmental fields are variable over a wider range of scales than previously thought require to go beyond the limits of the (classical) Extreme Value Theory (EVT). Indeed, long-range correlations are beyond the scope of the classical EVT theory. We show that multifractal concepts and techniques are particularly appealing because they can effectively deal with a cascade of interactions concentrating for instance energy, liquid water, etc. into smaller and smaller space-time domains. Furthermore, a general outcome of these cascade processes -which surprisingly was realized only rather recently- is that rather independently of their details they yield probability distributions with power-law fall-offs, often called (asymptotic) Pareto or Zipf laws. We discuss the corresponding probability distributions of their maxima and its relationship with the Frechet law. We use these multifractal techniques to investigate the possibility of using very short or incomplete data records for reliable statistical predictions of the extremes. In particular we assess the multifractal parameter uncertainty with the help of long synthetic multifractal series and their sub-samples, in particular to obtain an approximation of confidence intervals that would be particularly important for the predictions of multifractal extremes. We finally illustrate the efficiency of this approach with its application to

  17. Long-range transport of air pollution into the Arctic

    Science.gov (United States)

    Stohl, A.; Berg, T.; Breivik, K.; Burkhart, J. F.; Eckhardt, S.; Fjæraa, A.; Forster, C.; Herber, A.; Lunder, C.; McMillan, W. W.; None, N.; Manø, S.; Oltmans, S.; Shiobara, M.; Stebel, K.; Hirdman, D.; Stroem, J.; Tørseth, K.; Treffeisen, R.; Virkkunen, K.; Yttri, K. E.; Andrews, E.; Kowal, D.; Mefford, T.; Ogren, J. A.; Sharma, S.; Spichtinger, N.; Stone, R.; Hoch, S.; Wehrli, C.

    2007-12-01

    This paper presents an overview of air pollution transport into the Arctic. The major transport processes will be highlighted, as well as their seasonal, interannual, and spatial variability. The source regions of Arctic air pollution will be discussed, with a focus on black carbon (BC) sources, as BC can produce significant radiative forcing in the Arctic. It is found that Europe is the main source region for BC in winter, whereas boreal forest fires are the strongest source in summer, especially in years of strong burning. Two case studies of recent extreme Arctic air pollution events will be presented. In summer 2004, boreal forest fires in Alaska and Canada caused pan-Arctic enhancements of black carbon. The BC concentrations measured at Barrow (Alaska), Alert (Canada), Summit (Greenland) and Zeppelin (Spitsbergen) were all episodically elevated, as a result of the long-range transport of the biomass burning emissions. Aerosol optical depth was also episodically elevated at these stations, with an almost continuous elevation over more than a month at Summit. During the second episode in spring 2006, new records were set for all measured air pollutant species at the Zeppelin station (Spitsbergen) as well as for ozone in Iceland. At Zeppelin, BC, AOD, aerosol mass, ozone, carbon monoxide and other compounds all reached new record levels, compared to the long-term monitoring record. The episode was caused by transport of polluted air masses from Eastern Europe deep into the Arctic, a consequence of the unusual warmth in the European Arctic during the episode. While fossil fuel combustion sources certainly contributed to this episode, smoke from agricultural fires in Eastern Europe was the dominant pollution component. We also suggest a new revolatilization mechanism for persistent organic pollutants (POPs) stored in soils and vegetation by fires, as POPs were strongly elevated during both episodes. All this suggests a considerable influence of biomass burning on

  18. Proton Exchange in a Paramagnetic Chemical Exchange Saturation Transfer Agent from Experimental Studies and ab Initio Metadynamics Simulation.

    Science.gov (United States)

    Pollet, Rodolphe; Bonnet, Célia S; Retailleau, Pascal; Durand, Philippe; Tóth, Éva

    2017-03-27

    The proton-exchange process between water and a carbamate has been studied experimentally and theoretically in a lanthanide-based paramagnetic chemical exchange saturation transfer agent endowed with potential multimodality detection capabilities (optical imaging, or T1 MRI for the Gd(III) analogue). In addition to an in-depth structural analysis by a combined approach (using X-ray crystallography, NMR, and molecular dynamics), our ab initio simulation in aqueous solution sheds light on the reaction mechanism for this proton exchange, which involves structural Grotthuss diffusion.

  19. Femtosecond and temperature-dependent picosecond dynamics of ultrafast excited-state proton transfer in water-dioxane mixtures.

    Science.gov (United States)

    Freitas, Adilson A; Quina, Frank H; Maçanita, António A L

    2014-11-13

    Synthetic flavylium salts like the 7-hydroxy-4-methylflavylium (HMF) cation have been used as prototypes to study the chemistry and photochemistry of anthocyanins, the major group of water-soluble pigments in the plant kingdom. In this work, a combination of fluorescence upconversion with femtosecond time resolution and time-correlated single photon counting (TCSPC) with picosecond time resolution have been employed to investigate in details the excited-state proton transfer (ESPT) of HMF in water and in binary water/1,4-dioxane mixtures. TCSPC measurements as a function of temperature provide activation parameters for all of the individual rate constants involved in the proton transfer, including those for dissociation and recombination of the geminate excited base-proton pair (A*···H(+)) that can be detected in the water/dioxane mixtures (but not in water). Unlike the other rate constants, the deprotonation rate constant kd shows a non-Arrhenius dependence on temperature in both water and water/dioxane mixtures. At low temperatures kd is close to the dielectric relaxation rate of the solvent with a barrier of ca. 8 kJ mol(-1), suggesting that the solvent reorganization is the rate-limiting step. At higher temperatures (>30 °C) the proton transfer process is nearly barrierless and solvent-dependent. Fluorescence upconversion results in H2O, D2O, and water/dioxane mixtures confirm the two-step model for the ESPT of HMF and provide additional details of the early events prior to the onset of proton transfer, attributed to conformational relaxation and solvent reaccommodation around the initially formed excited state. The results are consistent with DFT calculations that indicate that charge redistribution occurs after rather than prior to the onset of the ESPT process.

  20. Stepwise vs concerted excited state tautomerization of 2-hydroxypyridine: Ammonia dimer wire mediated hydrogen/proton transfer

    Energy Technology Data Exchange (ETDEWEB)

    Esboui, Mounir, E-mail: mounir.esboui@fst.rnu.tn [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications, Département de Physique, Faculté des Sciences de Tunis, 2092 Tunis (Tunisia); Technical and Vocational Training Corporation, Hail College of Technology, P.O. Box 1960, Hail 81441 (Saudi Arabia)

    2015-07-21

    The stepwise and concerted excited state intermolecular proton transfer (PT) and hydrogen transfer (HT) reactions in 2-hydroxypyridine-(NH{sub 3}){sub 2} complex in the gas phase under Cs symmetry constraint and without any symmetry constraints were performed using quantum chemical calculations. It shows that upon excitation, the hydrogen bonded in 2HP-(NH{sub 3}){sub 2} cluster facilitates the releasing of both hydrogen and proton transfer reactions along ammonia wire leading to the formation of the 2-pyridone tautomer. For the stepwise mechanism, it has been found that the proton and the hydrogen may transfer consecutively. These processes are distinguished from each other through charge translocation analysis and the coupling between the motion of the proton and the electron density distribution along ammonia wire. For the complex under Cs symmetry, the excited state HT occurs on the A″({sup 1}πσ{sup ∗}) and A′({sup 1}nσ{sup ∗}) states over two accessible energy barriers along reaction coordinates, and excited state PT proceeds mainly through the A′({sup 1}ππ{sup ∗}) and A″({sup 1}nπ{sup ∗}) potential energy surfaces. For the unconstrained complex, potential energy profiles show two {sup 1}ππ{sup ∗}-{sup 1}πσ{sup ∗} conical intersections along enol → keto reaction path indicating that proton and H atom are localized, respectively, on the first and second ammonia of the wire. Moreover, the concerted excited state PT is competitive to take place with the stepwise process, because it proceeds over low barriers of 0.14 eV and 0.11 eV with respect to the Franck-Condon excitation of enol tautomer, respectively, under Cs symmetry and without any symmetry constraints. These barriers can be probably overcome through tunneling effect.

  1. Proton transfer reactions associated with the reaction of the fully reduced, purified cytochrome C oxidase with molecular oxygen and ferricyanide.

    Science.gov (United States)

    Capitanio, Nazzareno; Capitanio, Giuseppe; De Nitto, Emanuele; Boffoli, Domenico; Papa, Sergio

    2003-04-29

    A study is presented on proton transfer associated with the reaction of the fully reduced, purified bovine heart cytochrome c oxidase with molecular oxygen or ferricyanide. The proton consumption associated with aerobic oxidation of the four metal centers changed significantly with pH going from approximately 3.0 H(+)/COX at pH 6.2-6.3 to approximately 1.2 H(+)/COX at pH 8.0-8.5. Rereduction of the metal centers was associated with further proton uptake which increased with pH from approximately 1.0 H(+)/COX at pH 6.2-6.3 to approximately 2.8 H(+)/COX at pH 8.0-8.5. Anaerobic oxidation of the four metal centers by ferricyanide resulted in the net release of 1.3-1.6 H(+)/COX in the pH range 6.2-8.2, which were taken up by the enzyme on rereduction of the metal centers. The proton transfer elicited by ferricyanide represents the net result of deprotonation/protonation reactions linked to anaerobic oxidoreduction of the metal centers. Correction for the ferricyanide-induced pH changes of the proton uptake observed in the oxidation and rereduction phase of the reaction of the reduced oxidase with oxygen gave a measure of the proton consumption in the reduction of O(2) to 2H(2)O. The results show that the expected stoichiometric proton consumption of 4H(+) in the reduction of O(2) to 2H(2)O is differently associated, depending on the actual pH, with the oxidation and reduction phase of COX. Two H(+)/COX are initially taken up in the reduction of O(2) to two OH(-) groups bound to the binuclear Fe a(3)-Cu(B) center. At acidic pHs the third and fourth protons are also taken up in the oxidative phase with formation of 2H(2)O. At alkaline pHs the third and fourth protons are taken up with formation of 2H(2)O only upon rereduction of COX.

  2. Proton transfer from water to ketyl radical anion: Assessment of critical size of hydrated cluster and free energy barrier in solution from first principles simulations

    Science.gov (United States)

    Biswas, Sohag; Dasgupta, Teesta; Mallik, Bhabani S.

    2016-09-01

    We present the reactivity of an organic intermediate by studying the proton transfer process from water to ketyl radical anion using gas phase electronic structure calculations and the metadynamics method based first principles molecular dynamics (FPMD) simulations. Our results indicate that during the micro solvation of anion by water molecules systematically, the presence of minimum three water molecules in the gas phase cluster is sufficient to observe the proton transfer event. The analysis of trajectories obtained from initial FPMD simulation of an aqueous solution of the anion does not show any evident of complete transfer of the proton from water. The cooperativity of water molecules and the relatively weak anion-water interaction in liquid state prohibit the full release of the proton. Using biasing potential through first principles metadynamics simulations, we report the observation of proton transfer reaction from water to ketyl radical anion with a barrier height of 16.0 kJ/mol.

  3. Assessment of ischemic penumbra in patients with hyperacute stroke using amide proton transfer (APT) chemical exchange saturation transfer (CEST) MRI.

    Science.gov (United States)

    Tietze, Anna; Blicher, Jakob; Mikkelsen, Irene Klaerke; Østergaard, Leif; Strother, Megan K; Smith, Seth A; Donahue, Manus J

    2014-02-01

    Chemical exchange saturation transfer (CEST)-derived, pH-weighted, amide proton transfer (APT) MRI has shown promise in animal studies for the prediction of infarction risk in ischemic tissue. Here, APT MRI was translated to patients with acute stroke (1-24 h post-symptom onset), and assessments of APT contrast, perfusion, diffusion, disability and final infarct volume (23-92 days post-stroke) are reported. Healthy volunteers (n = 5) and patients (n = 10) with acute onset of symptoms (0-4 h, n = 7; uncertain onset diffusion- and perfusion-weighted MRI, fluid-attenuated inversion recovery (FLAIR) and CEST. Traditional asymmetry and a Lorentzian-based APT index were calculated in the infarct core, at-risk tissue (time-to-peak, TTP; lengthening) and final infarct volume. On average (mean ± standard deviation), control white matter APT values (asymmetry, 0.019 ± 0.005; Lorentzian, 0.045 ± 0.006) were not significantly different (p > 0.05) from APT values in normal-appearing white matter (NAWM) of patients (asymmetry, 0.022 ± 0.003; Lorentzian, 0.048 ± 0.003); however, ischemic regions in patients showed reduced (p = 0.03) APT effects compared with NAWM. Representative cases are presented, whereby the APT contrast is compared quantitatively with contrast from other imaging modalities. The findings vary between patients; in some patients, a trend for a reduction in the APT signal in the final infarct region compared with at-risk tissue was observed, consistent with tissue acidosis. However, in other patients, no relationship was observed in the infarct core and final infarct volume. Larger clinical studies, in combination with focused efforts on sequence development at clinically available field strengths (e.g. 3.0 T), are necessary to fully understand the potential of APT imaging for guiding the hyperacute management of patients.

  4. Laser induced autofluorescence in the monitoring of β-mercaptoethanol mediated photo induced proton coupled electron transfer in proteins.

    Science.gov (United States)

    Manjunath, S; Satish Rao, B S; Satyamoorthy, K; Mahato, K K

    2015-01-01

    Photo induced proton coupled electron transfer (PCET) is an important process that many organisms use for progression of catalytic reactions leading to energy conversion. In the present study, the influence of SDS and BME on the redox properties of tyrosine and tryptophan for five different globular proteins, BSA, HSA, RNase-A, trypsin and lysozyme were studied using laser induced autofluorescence. The proteins were subjected to denaturation under SDS, SDS plus heat and SDS plus β-mercaptoethanol (BME) plus heat and the corresponding fluorescence were recorded. The influence of BME on the autofluorescence properties of the proteins were evaluated upon tris-2-corboxy-ethyl phosphine (TCEP) denaturation. The BSA and HSA when exposed to SDS alone, exhibited hydrophobic collapse around their tryptophan moieties. However, these proteins when treated with SDS plus BME plus heat, an unusual red shift in the emission was observed, may be due to proton transfer from hydroxyl group of the excited tyrosine residues to the local microenvironments. The observation was further confirmed with similar proton transfer in absence of tryptophan in RNase-A showing involvement of tyrosine in the process. A drastic quenching of fluorescence in all of the proteins under study were also observed, may be due to photo-induced electron transfer (PET) from BME to the intrinsic fluorophores resulting in radical ions formation, evaluated upon DCFDA measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. 2006 Long Range Development Plan Final Environmental ImpactReport

    Energy Technology Data Exchange (ETDEWEB)

    Philliber, Jeff

    2007-01-22

    This environmental impact report (EIR) has been prepared pursuant to the applicable provisions of the California Environmental Quality Act (CEQA) and its implementing guidelines (CEQA Guidelines), and the Amended University of California Procedures for Implementation of the California Environmental Quality Act (UC CEQA Procedures). The University of California (UC or the University) is the lead agency for this EIR, which examines the overall effects of implementation of the proposed 2006 Long Range Development Plan (LRDP; also referred to herein as the 'project' for purposes of CEQA) for Lawrence Berkeley National Laboratory (LBNL; also referred to as 'Berkeley Lab,' 'the Laboratory,' or 'the Lab' in this document). An LRDP is a land use plan that guides overall development of a site. The Lab serves as a special research campus operated by the University employees, but it is owned and financed by the federal government and as such it is distinct from the UC-owned Berkeley Campus. As a campus operated by the University of California, the Laboratory is required to prepare an EIR for an LRDP when one is prepared or updated pursuant to Public Resources Code Section 21080.09. The adoption of an LRDP does not constitute a commitment to, or final decision to implement, any specific project, construction schedule, or funding priority. Rather, the proposed 2006 LRDP describes an entire development program of approximately 980,000 gross square feet of new research and support space construction and 320,000 gross square feet of demolition of existing facilities, for a total of approximately 660,000 gross square feet of net new occupiable space for the site through 2025. Specific projects will undergo CEQA review at the time proposed to determine what, if any, additional review is necessary prior to approval. As described in Section 1.4.2, below, and in Chapter 3 of this EIR (the Project Description), the size of the project has been

  6. Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations.

    Science.gov (United States)

    Xia, Shu-Hua; Xie, Bin-Bin; Fang, Qiu; Cui, Ganglong; Thiel, Walter

    2015-04-21

    Excited-state intramolecular proton transfer (ESIPT) between two highly electronegative atoms, for example, oxygen and nitrogen, has been intensely studied experimentally and computationally, whereas there has been much less theoretical work on ESIPT to other atoms such as carbon. We have employed CASSCF, MS-CASPT2, RI-ADC(2), OM2/MRCI, DFT, and TDDFT methods to study the mechanistic photochemistry of 2-phenylphenol, for which such an ESIPT has been observed experimentally. According to static electronic structure calculations, irradiation of 2-phenylphenol populates the bright S1 state, which has a rather flat potential in the Franck-Condon region (with a shallow enol minimum at the CASSCF level) and may undergo an essentially barrierless ESIPT to the more stable S1 keto species. There are two S1/S0 conical intersections that mediate relaxation to the ground state, one in the enol region and one in the keto region, with the latter one substantially lower in energy. After S1 → S0 internal conversion, the transient keto species can return back to the S0 enol structure via reverse ground-state hydrogen transfer in a facile tautomerization. This mechanistic scenario is verified by OM2/MRCI-based fewest-switches surface-hopping simulations that provide detailed dynamic information. In these trajectories, ESIPT is complete within 118 fs; the corresponding S1 excited-state lifetime is computed to be 373 fs in vacuum. Most of the trajectories decay to the ground state via the S1/S0 conical intersection in the keto region (67%), and the remaining ones via the enol region (33%). The combination of static electronic structure computations and nonadiabatic dynamics simulations is expected to be generally useful for understanding the mechanistic photophysics and photochemistry of molecules with intramolecular hydrogen bonds.

  7. Proton-detected MAS NMR experiments based on dipolar transfers for backbone assignment of highly deuterated proteins

    Science.gov (United States)

    Chevelkov, Veniamin; Habenstein, Birgit; Loquet, Antoine; Giller, Karin; Becker, Stefan; Lange, Adam

    2014-05-01

    Proton-detected solid-state NMR was applied to a highly deuterated insoluble, non-crystalline biological assembly, the Salmonella typhimurium type iii secretion system (T3SS) needle. Spectra of very high resolution and sensitivity were obtained at a low protonation level of 10-20% at exchangeable amide positions. We developed efficient experimental protocols for resonance assignment tailored for this system and the employed experimental conditions. Using exclusively dipolar-based interspin magnetization transfers, we recorded two sets of 3D spectra allowing for an almost complete backbone resonance assignment of the needle subunit PrgI. The additional information provided by the well-resolved proton dimension revealed the presence of two sets of resonances in the N-terminal helix of PrgI, while in previous studies employing 13C detection only a single set of resonances was observed.

  8. Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections

    CERN Document Server

    Lin, You-Sheng; Mao, Shan-Ping; Chai, Jeng-Da

    2012-01-01

    By incorporating the improved empirical atom-atom dispersion corrections from DFT-D3 [Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104], two long-range corrected (LC) hybrid density functionals are proposed. Our resulting LC hybrid functionals, omegaM06-D3 and omegaB97X-D3, are shown to be accurate for a very wide range of applications, such as thermochemistry, kinetics, noncovalent interactions, frontier orbital energies, fundamental gaps, and long-range charge-transfer excitations, when compared with common global and LC hybrid functionals. Relative to omegaB97X-D [Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615], omegaB97X-D3 (reoptimization of omegaB97X-D with improved dispersion corrections) is shown to be superior for non-bonded interactions, and similar in performance for bonded interactions, while omegaM06-D3 is shown to be superior for general applications.

  9. Excited state proton transfer in 9-aminoacridine carboxamides in water and in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Charles A. [Iowa State Univ., Ames, IA (United States)

    1995-09-26

    The 9-aminoacridine molecule is important in several different fields of chemistry. The absorption and fluorescence spectra of this compound are pH sensitive and it is this property that allowed it to be used as a pH probe in different chemical environments. The compound exhibits proton transfer reactions which are among the most fundamental of chemical reactions. The planarity of 9-aminoacridine allows it to intercalate into DNA. Intercalation is a process in which the aromatic flat surface of the intercalator inserts between adjacent base pairs of DNA. The large surface area of 9-aminoacridine`s fused tricyclic ring system allows strong intercalative binding through van der Waals attractions. 9-aminoacridine and many of its derivatives have been tried as possible antitumor drugs. The cytotoxicity of an antitumor agent can be dramatically increased through the addition of one or two cationic side chains. This increase in cytotoxicity using the 9-aminoacridine compound as a parent molecule has been investigated through various derivatives with cationic side chains consisting of different number of carbon atoms between the proximal and distal N atoms. Similar derivatives varied the position of the carboxamide side chain on the aromatic ring system. The objective of this work is to first create a baseline study of the excited state kinetics of the 9-aminoacridine carboxamides in the absence of DNA. The baseline study will allow the excited state kinetics of these antitumor drugs when placed in DNA to be more fully understood.

  10. A complete description of tunnelling using direct quantum dynamics simulation: Salicylaldimine proton transfer

    Energy Technology Data Exchange (ETDEWEB)

    Polyak, Iakov; Allan, Charlotte S. M.; Worth, Graham A., E-mail: g.a.worth@bham.ac.uk [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2015-08-28

    We demonstrate here conclusively that the variational multiconfiguration Gaussian (vMCG) method converges to the grid based full quantum dynamics multiconfiguration time-dependent Hartree result for a tunnelling problem in many dimensions, using the intramolecular proton transfer in salicylaldimine as a model system. The 13-dimensional model potential energy surface was obtained from Hartree Fock energies with the 6-31G* basis set and the expectation value of the flux operator along the transition mode was used as a benchmark characteristic. As well as showing excellent convergence of the vMCG method on the model surface using a local harmonic approximation and a moderate number of basis functions, we show that the direct dynamics version of the vMCG also performs very well, usually needs the same number of Gaussians to converge, and converges to exact results if those are obtained on an accurately fitted surface. Finally, we make an important observation that the width of the Gaussian basis functions must be chosen very carefully to obtain accurate results with the use of the frozen-width approximation.

  11. Amide proton transfer-weighted MRI detection of traumatic brain injury in rats.

    Science.gov (United States)

    Zhang, Hong; Wang, Wenzhu; Jiang, Shanshan; Zhang, Yi; Heo, Hye-Young; Wang, Xianlong; Peng, Yun; Wang, Jian; Zhou, Jinyuan

    2017-01-01

    The purpose of this study was to explore the capability and uniqueness of amide proton transfer-weighted (APTw) imaging in the detection of primary and secondary injury after controlled cortical impact (CCI)-induced traumatic brain injury (TBI) in rats. Eleven adult rats had craniotomy plus CCI surgery under isoflurane anesthesia. Multi-parameter MRI data were acquired at 4.7 T, at eight time points (1, 6 h, and 1, 2, 3, 7, 14, and 28 days after TBI). At one and six hours post-injury, average APTw signal intensities decreased significantly in the impacted and peri-lesional areas due to tissue acidosis. A slightly high APTw signal was seen in the core lesion area with respect to the peri-lesional area, which was due to hemorrhage, as shown by T2*w. After the initial drop, the APTw signals dramatically increased in some peri-lesional areas at two and three days post-injury, likely due to the secondary inflammatory response. The use of APTw MRI has the potential to introduce a novel molecular neuroimaging approach for the simultaneous detection of ischemia, hemorrhage, and neuroinflammation in TBI.

  12. Rapid tomato volatile profiling by using proton-transfer reaction mass spectrometry (PTR-MS).

    Science.gov (United States)

    Farneti, Brian; Cristescu, Simona M; Costa, Guglielmo; Harren, Frans J M; Woltering, Ernst J

    2012-05-01

    The availability of rapid and accurate methods to assess fruit flavor is of utmost importance to support quality control especially in the breeding phase. Breeders need more information and analytical tools to facilitate selection for complex multigenic traits such as flavor quality. In this study, it is shown that proton-transfer reaction mass spectrometry (PTR-MS) is a suitable method to monitor at high sensitivity the emission of volatiles determining the tomato aromatic profile such as hexanal, hexenals, methanol, ethanol, and acetaldehyde. The volatiles emitted by 14 tomato varieties (at red stage) were analyzed by 2 solvent-free headspace methods: solid-phase microextraction/gas chromatography MS and PTR-MS. Multivariate statistics (principal component analysis and cluster analysis) of the PTR-MS results allow an unambiguous separation between varieties, especially with a clear fingerprinting separation between the different tomato types: round truss, cocktail, and cherry tomatoes. PTR-MS was also successfully used to monitor the changes in volatile profiles during postharvest ripening and storage.

  13. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

    Science.gov (United States)

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.

  14. Initial processes of proton transfer in salicylideneaniline studied by time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Sekikawa, Taro; Schalk, Oliver; Wu, Guorong; Boguslavskiy, Andrey E; Stolow, Albert

    2013-04-11

    Excited-state intramolecular proton transfer (ESIPT) in salicylideneaniline (SA) and selected derivatives substituted in the para position of the anilino group have been investigated by femtosecond time-resolved photoelectron spectroscopy (TRPES) and time-dependent density functional theory (TDDFT). SA has a twisted structure at the energetic minimum of the ground state, but ESIPT is assumed to take place through a planar structure, although this has not been fully established. The TRPES studies revealed that the excited-state dynamics within the S1 band varied significantly with excitation wavelength. At finite temperatures, the ground state was found to sample a broad range of torsional angles, from planar to twisted. At lower photon energies (370 nm), only the planar ground-state molecules were excited, and the excited-state reaction took place within 50 fs. At higher energies (350 and 330 nm), predominantly twisted ground-state molecules were excited: they had to planarize before ESIPT could occur. This process was found to be slower in methylated SA but did not change significantly in the brominated and nitrated SAs. These substitution effects on the decay dynamics can be explained by modifications of the potential barriers, as predicted by the TDDFT calculations, and support the mechanism of a twisting motion of the anilino ring prior to ESIPT. The contribution of another pathway leading to internal conversion within the enol form was found to be minor at the excitation wavelengths considered here.

  15. Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer

    Energy Technology Data Exchange (ETDEWEB)

    Yoder, Bruce L., E-mail: bruce.yoder@phys.chem.ethz.ch; West, Adam H. C.; Signorell, Ruth [Laboratory of Physical Chemistry, ETH Zürich, Zürich 8093 (Switzerland); Bravaya, Ksenia B. [Department of Chemistry, Boston University, Boston, Massachusetts 02215-2521 (United States); Bodi, Andras [Molecular Dynamics Group, Paul Scherrer Institut, Villigen 5232 (Switzerland); Sztáray, Bálint [Department of Chemistry, University of the Pacific, Stockton, California 95211 (United States)

    2015-03-21

    We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME − h{sub 6}){sub n} and (DME − d{sub 6}){sub n}n = 1 and 2, in the 9–14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C–H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH{sub 3}OHCH{sub 3}{sup +} by the loss of CH{sub 2}OCH{sub 3} with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME − h{sub 6}){sub 2} and deuterated (DME − d{sub 6}){sub 2}, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME − d{sub 6} monomer.

  16. Influence of different environments on the excited-state proton transfer and dual fluorescence of fisetin

    Science.gov (United States)

    Guharay, Jayanti; Dennison, S. Moses; Sengupta, Pradeep K.

    1999-05-01

    The influence of different protic and aprotic solvent environments on the excited-state intramolecular proton transfer (ESIPT) leading to a dual fluorescence behaviour of a biologically important, naturally occurring, polyhydroxyflavone, fisetin (3,3',4',7-tetrahydroxyflavone), has been investigated. The normal fluorescence band, in particular, is extremely sensitive to solvent polarity with νmax shifting from 24 510 cm -1 in dioxane ( ET(30)=36.0) to 20 790 cm -1 in methanol ( ET(30)=55.5). This is rationalized in terms of solvent dipolar relaxation process, which also accounts for the red edge excitation shifts (REES) observed in viscous environments such as glycerol at low temperatures. Significant solvent dependence of the tautomer fluorescence properties ( νmax, yield and decay kinetics) reveals the influence of external hydrogen bonding perturbation on the internal hydrogen bond of the molecule. These excited-state relaxation phenomena and their relevant parameters have been used to probe the microenvironment of fisetin in a membrane mimetic system, namely AOT reverse micelles in n-heptane at different water/surfactant molar ratio ( w0).

  17. Amplified excited state intramolecular proton transfer fluorescence of butterfly-shaped bis-2,6-dibenzothiazolylphenol

    Science.gov (United States)

    Zhang, Xuan; Ma, Wei-Wei

    2017-06-01

    A butterfly-shaped benzothiazole derivative, bis-2,6-dibenzothiazolylphenol (2), was synthesized via 4-methylene bridging two 2,6-dibenzothiazolylphenol (1) molecules, and the excited-state intramolecular proton transfer (ESIPT) fluorescence of 1 and 2 were comparably investigated by steady-state spectroscopic experiments with the aid of theoretical simulations for structure and energy. It was found that 2 showed similar ESIPT emissions to those of 1 in solution and solid states, but the ESIPT fluorescence quantum yield was substantially amplified in the case of the more ‘integrated’ 2. In both tetrahydrofuran (THF) and CHCl3 solvents, ESIPT occurred and orange emissions at 580-590 nm from keto tautomers were observed, where the absolute fluorescence quantum yield was measured to be 0.28 and 0.41 for 1, as well as 0.41 and 0.59 for 2, respectively. In the solid state, 2 showed an ESIPT emission at 570 nm with an absolute fluorescence quantum yield of 0.38, which is substantially shorter and larger than the corresponding values of 1 (592 nm and 0.26) respectively. Furthermore, both 2 and 1 showed strongly blue-shifted green emissions around 520 nm from the deprotonated anion species in N,N-dimethyl formamide (DMF). A similar blue-shifted green emission was also found with the addition of fluoride in the THF solution of 2 or 1, suggesting that the competitive deprotonation makes the ESIPT impossible.

  18. Static and dynamic headspace analysis of instant coffee blends by proton-transfer-reaction mass spectrometry.

    Science.gov (United States)

    Romano, Andrea; Gaysinsky, Sylvia; Czepa, Andreas; Del Pulgar, José Sanchez; Cappellin, Luca; Biasioli, Franco

    2015-09-01

    Instant coffee is a widespread product, generally related to a high consumer acceptability, also because of its ease of preparation. The present work addresses the characterization of the headspace of freshly brewed instant coffees resulting from different blends, during and immediately after preparation. The sample set consisted of 10 coffees, obtained by mixing three different blends in different proportions. The employment of Proton Transfer Reaction-Mass Spectrometry (PTR-MS) allowed for direct and real-time sampling from the headspace, under conditions that mimic those that are encountered above the cup during and right after brewing. Different coffee brews were separated on the basis of the respective volatile profiles, and data showed good consistency with the respective blend compositions. When the headspace evolution was monitored during preparation, similar results were obtained in terms of blend separation; moreover, different blends displayed different and reproducible 'signatures' in terms of time evolution. A straightforward method for the prediction of headspace composition is proposed, allowing to predict the volatile profiles of two-component and three-component blends on the basis of the respective parent components. Overall, the results constitute a successful example of the applicability of PTR-MS as a tool for product development in food science. Copyright © 2015 John Wiley & Sons, Ltd.

  19. Experimental and computational studies on creatininium 4-nitrobenzoate - An organic proton transfer complex

    Science.gov (United States)

    Thirumurugan, R.; Anitha, K.

    2017-10-01

    A new organic proton transfer complex of creatininium 4-nitrobenzoate (C4NB) has been synthesized and its single crystals were grown successfully by slow evaporation technique. The grown single crystal was subjected to various characterization techniques like single crystal X-ray diffraction (SCXRD), FTIR, FT-Raman and Kurtz-Perry powder second harmonic generation (SHG). The SCXRD analysis revealed that C4NB was crystallized into orthorhombic crystal system, with noncentrosymmetric (NCS), P212121 space group. The creatininium cation and 4-nitrobenzoate anion were connected through a pair of N__H⋯O hydrogen bonds (N(3)__H(6) ⋯ O(3) (x+1, y, z) and N(2)__H(5) &ctdot O(2) (x-1/2, -y-1/2, -z+2)) and fashioned a R22(8) ring motif. The crystal structure was stabilized by strong N__H⋯O and weak C__H⋯O intermolecular interactions and it was quantitatively analysed by Hirshfeld surface and fingerprint (FP) analysis. FTIR and FT-Raman studies confirmed the vibrational modes of functional groups present in C4NB compound indubitably. SHG efficiency of grown crystal was 4.6 times greater than that of standard potassium dihydrogen phosphate (KDP) material. Moreover, density functional theory (DFT) studies such as Mulliken charge distribution, frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) map, natural bond orbital analysis (NBO) and first order hyperpolarizability (β0) were calculated to explore the structure-property relationship.

  20. Molecular Seesaw: How Increased Hydrogen Bonding Can Hinder Excited-State Proton Transfer.

    Science.gov (United States)

    Welsch, Ralph; Driscoll, Eric; Dawlaty, Jahan M; Miller, Thomas F

    2016-09-15

    A previously unexplained effect in the relative rate of excited-state intramolecular proton transfer (ESIPT) in related indole derivatives is investigated using both theory and experiment. Ultrafast spectroscopy [ J. Phys. Chem. A, 2015, 119, 5618-5625 ] found that although the diol 1,3-bis(2-pyridylimino)-4,7-dihydroxyisoindole exhibits two equivalent intramolecular hydrogen bonds, the ESIPT rate associated with tautomerization of either hydrogen bond is a factor of 2 slower than that of the single intramolecular hydrogen bond in the ethoxy-ol 1,3-bis(2-pyridylimino)-4-ethoxy-7-hydroxyisoindole. Excited-state electronic structure calculations suggest a resolution to this puzzle by revealing a seesaw effect in which the two hydrogen bonds of the diol are both longer than the single hydrogen bond in the ethoxy-ol. Semiclassical rate theory recovers the previously unexplained trends and leads to clear predictions regarding the relative H/D kinetic isotope effect (KIE) for ESIPT in the two systems. The theoretical KIE predictions are tested using ultrafast spectroscopy, confirming the seesaw effect.

  1. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

    Science.gov (United States)

    Barmet, P.; Dommen, J.; DeCarlo, P. F.; Tritscher, T.; Praplan, A. P.; Platt, S. M.; Prévôt, A. S. H.; Donahue, N. M.; Baltensperger, U.

    2012-03-01

    The hydroxyl free radical (OH) is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS). 3-pentanol, 3-pentanone and pinonaldehyde (PA) were used as OH tracers in α-pinene (AP) secondary organic aerosol (SOA) aging studies. In addition we tested butanol-d9 as a potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88) × 10-12 cm3 molecule-1 s-1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time) dimension: the OH clock, which corresponds to the integrated OH concentration over time.

  2. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

    Directory of Open Access Journals (Sweden)

    P. Barmet

    2011-12-01

    Full Text Available The hydroxyl free radical (OH is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS. 3-pentanol, 3-pentanone and pinonaldehyde (PA were used as OH tracers in α-pinene (AP secondary organic aerosol (SOA aging studies. In addition we tested butanol-d9 as potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88 · 10−12 cm3molecule−1s−1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time dimension:~the OH clock, which corresponds to the integrated OH concentration over time.

  3. OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

    Directory of Open Access Journals (Sweden)

    P. Barmet

    2012-03-01

    Full Text Available The hydroxyl free radical (OH is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS. 3-pentanol, 3-pentanone and pinonaldehyde (PA were used as OH tracers in α-pinene (AP secondary organic aerosol (SOA aging studies. In addition we tested butanol-d9 as a potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88 × 10−12 cm3 molecule−1 s−1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time dimension: the OH clock, which corresponds to the integrated OH concentration over time.

  4. Unraveling the mechanism of proton translocation in the extracellular half-channel of bacteriorhodopsin.

    Science.gov (United States)

    Ge, Xiaoxia; Gunner, M R

    2016-05-01

    Bacteriorhodopsin, a light activated protein that creates a proton gradient in halobacteria, has long served as a simple model of proton pumps. Within bacteriorhodopsin, several key sites undergo protonation changes during the photocycle, moving protons from the higher pH cytoplasm to the lower pH extracellular side. The mechanism underlying the long-range proton translocation between the central (the retinal Schiff base SB216, D85, and D212) and exit clusters (E194 and E204) remains elusive. To obtain a dynamic view of the key factors controlling proton translocation, a systematic study using molecular dynamics simulation was performed for eight bacteriorhodopsin models varying in retinal isomer and protonation states of the SB216, D85, D212, and E204. The side-chain orientation of R82 is determined primarily by the protonation states of the residues in the EC. The side-chain reorientation of R82 modulates the hydrogen-bond network and consequently possible pathways of proton transfer. Quantum mechanical intrinsic reaction coordinate calculations of proton-transfer in the methyl guanidinium-hydronium-hydroxide model system show that proton transfer via a guanidinium group requires an initial geometry permitting proton donation and acceptance by the same amine. In all the bacteriorhodopsin models, R82 can form proton wires with both the CC and the EC connected by the same amine. Alternatively, rare proton wires for proton transfer from the CC to the EC without involving R82 were found in an O' state where the proton on D85 is transferred to D212.

  5. Analytical framework for modeling of long-range transport of fungal plant epidemics

    Science.gov (United States)

    Kogan, Oleg; O'Keeffe, Kevin; Schneider, David; Myers, Christopher; Analytical FrameworksInfectious Disease Dynamics Team

    2015-03-01

    A new framework for the study of long-range transport of fungal plant epidemics is proposed. The null nonlinear model includes advective transport through the free atmosphere, spore production on the ground, and transfer of spores between the ground and the advective atmospheric layer. The competition between the growth wave on the ground and the effect of the wind is most strongly reflected in upwind fronts, which can propagate into the wind for exponential initial conditions. If the rate of spore transfer into the advective layer is below critical, this happens for initital conditions with arbitrary steepness. Upwind fronts from localized initial conditions will propagate in the direction of the wind above this critical parameter, and will not propagate below it. On the other hand, the speed of the downwind front does not have a strong dependence on the rate of spore transfer between the advective layer and the ground. Thus, even vanishingly small, but finite transfer rates result in a substantial epidemic wave in the direction of the wind. We also consider the effect of an additional, random-walk like mechanism of transport through the near-ground atmospheric boundary layer, and attempt to understand which route dominates the transport over long distances.

  6. 23 CFR 450.214 - Development and content of the long-range statewide transportation plan.

    Science.gov (United States)

    2010-04-01

    ... TRANSPORTATION PLANNING AND RESEARCH PLANNING ASSISTANCE AND STANDARDS Statewide Transportation Planning and... long-range statewide transportation plan should include capital, operations and management strategies... transportation system. The long-range statewide transportation plan may consider projects and strategies that...

  7. Low-threshold wavelength-switchable organic nanowire lasers based on excited-state intramolecular proton transfer.

    Science.gov (United States)

    Zhang, Wei; Yan, Yongli; Gu, Jianmin; Yao, Jiannian; Zhao, Yong Sheng

    2015-06-08

    Coherent light signals generated at the nanoscale are crucial to the realization of photonic integrated circuits. Self-assembled nanowires from organic dyes can provide both a gain medium and an effective resonant cavity, which have been utilized for fulfilling miniaturized lasers. Excited-state intramolecular proton transfer (ESIPT), a classical molecular photoisomerization process, can be used to build a typical four-level system, which is more favorable for population inversion. Low-power driven lasing in proton-transfer molecular nanowires with an optimized ESIPT energy-level process has been achieved. With high gain and low loss from the ESIPT, the wires can be applied as effective FP-type resonators, which generated single-mode lasing with a very low threshold. The lasing wavelength can be reversibly switched based on a conformation conversion of the excited keto form in the ESIPT process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Intramolecular proton transfer through the adjoining π-conjugated system in Shiff base: Application for colorimetric sensing of fluoride anion

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xudong, E-mail: 081022009@fudan.edu.cn [College of Chemistry and Material Sciences, Hebei Normal University, Yuhua Road 113, Shijiazhuang 050024 (China); College of Science and Hebei Research Center of Pharmaceutical and Chemical Engineering, Hebei University of Science and Technology, Yuhua Road 70, Shijiazhuang 050080 (China); Zhang, Ping [College of Chemistry and Material Sciences, Hebei Normal University, Yuhua Road 113, Shijiazhuang 050024 (China); Li, Yajuan; Zhen, Xiaoli; Geng, Lijun; Wang, Yanqiu [College of Science and Hebei Research Center of Pharmaceutical and Chemical Engineering, Hebei University of Science and Technology, Yuhua Road 70, Shijiazhuang 050080 (China); Ma, Zichuan, E-mail: ma7405@hebtu.edu.cn [College of Chemistry and Material Sciences, Hebei Normal University, Yuhua Road 113, Shijiazhuang 050024 (China)

    2014-07-01

    In this paper, a new kind of phenol-based chemsensor L2 comprised of a Schiff base and azo groups was rationally designed and synthesized. It could selectively recognize fluoride anion among tested anions such as F{sup −}, AcO{sup −}, H{sub 2}PO{sub 4}{sup −}, Cl{sup −}, Br{sup −}, and I{sup −} with obvious color changes from yellow to fuchsia. The intramolecular PT (proton transfer) in L1 and L2 was responsible for the sensing ability, which was certified by the {sup 1}H NMR and Uv–vis experiments. - Highlights: • The phenol derivative L2 could selectively sense F{sup −} among test anions. • Intramolecular proton transfer happened when L2 was bonded with F{sup −}. • It is the first antipyrine-based anion receptor.

  9. Theoretical Study on Proton-Transfer Reaction of Intracellular Second-messenger 3',5'-Cyclic Nucleotide

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ai-Hua; YANG Bao-Hua; LI Zong-He

    2008-01-01

    The gas-phase proton-transfer reaction mechanism of intracellular second-messenger 3',5'-cyclic nucleotide (cAMPm) has been theoretically investigated at the B3LYP/6-31G** level. One or two H2O molecules have been used to simulate the catalyst. It is found that H shift reaction between conformation Bm and conformation Dm of cAMPm involves a cyclic transition state with one or two water molecules as a shuttle. Furthermore, H shift reac- tion proceeds easily with the participation of two water molecules. The results provide evidence in theory to study proton-transfer reaction mechanism of related phosphodiesters. Our present calculations have rationalized all the possible reaction channels.

  10. Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization.

    Science.gov (United States)

    Lu, I-Chung; Chu, Kuan Yu; Lin, Chih-Yuan; Wu, Shang-Yun; Dyakov, Yuri A; Chen, Jien-Lian; Gray-Weale, Angus; Lee, Yuan-Tseh; Ni, Chi-Kung

    2015-07-01

    The ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer. The ion-to-neutral ratios of CHCA are three orders of magnitude larger than those of the other matrices at the same laser fluence. The ion-to-neutral ratios predicted using the thermal proton transfer model are similar to the experimental measurements, indicating that thermal proton transfer reactions play a major role in generating ions in ultraviolet-MALDI.

  11. Excited-state intramolecular proton transfer of 2-acetylindan-1,3-dione studied by ultrafast absorption and fluorescence spectroscopy

    Directory of Open Access Journals (Sweden)

    Pramod Kumar Verma

    2016-03-01

    Full Text Available We employ transient absorption from the deep-UV to the visible region and fluorescence upconversion to investigate the photoinduced excited-state intramolecular proton-transfer dynamics in a biologically relevant drug molecule, 2-acetylindan-1,3-dione. The molecule is a ß-diketone which in the electronic ground state exists as exocyclic enol with an intramolecular H-bond. Upon electronic excitation at 300 nm, the first excited state of the exocyclic enol is initially populated, followed by ultrafast proton transfer (≈160 fs to form the vibrationally hot endocyclic enol. Subsequently, solvent-induced vibrational relaxation takes place (≈10 ps followed by decay (≈390 ps to the corresponding ground state.

  12. Synthesis of metal-hydrazone complexes and vapochromic behavior of their hydrogen-bonded proton-transfer assemblies.

    Science.gov (United States)

    Kobayashi, Atsushi; Dosen, Masa-aki; Chang, Mee; Nakajima, Kiyohiko; Noro, Shin-ichiro; Kato, Masako

    2010-11-03

    We synthesized and investigated a new series of metal-hydrazone complexes, including deprotonated [MX(mtbhp)] and protonated forms [MX(Hmtbhp)](ClO(4)) (M = Pd(2+), Pt(2+); X = Cl(-), Br(-); Hmtbhp = 2-(2-(2-(methylthio)benzylidene)hydrazinyl)pyridine) and hydrogen-bonded proton-transfer (HBPT) assemblies containing [PdBr(mtbhp)] and bromanilic acid (H(2)BA). The mtbhp hydrazone ligand acts as a tridentate SNN ligand and provides a high proton affinity. UV-vis spectroscopy revealed that these metal-hydrazone complexes follow a reversible protonation-deprotonation reaction ([MX(mtbhp)] + H(+) ⇋ [MX(Hmtbhp)](+)), resulting in a remarkable color change from red to yellow. Reactions between proton acceptor [PdBr(mtbhp)] (A) and proton donor H(2)BA (D) afforded four types of HBPT assemblies with different D/A ratios: for D/A = 1:1, {[PdBr(Hmtbhp)](HBA)·Acetone} and {[PdBr(Hmtbhp)](HBA)·2(1,4-dioxane)}; for D/A = 1:2, [PdBr(Hmtbhp)](2)(BA); and for D/A = 3:2, {[PdBr(Hmtbhp)](2)(HBA)(2)(H(2)BA)·2Acetonitrile}. The proton donor gave at least one proton to the acceptor to form the hydrogen bonded A···D pair of [PdBr(Hmtbhp)](+)···HBA(-). The strength of the hydrogen bond in the pair depends on the kind of molecule bound to the free monoanionic bromanilate OH group. Low-temperature IR spectra (T < 150 K) showed that the hydrogen bond distance between [PdBr(Hmtbhp)](+) and bromanilate was short enough (ca. 2.58 Å) to induce proton migration in the [PdBr(Hmtbhp)](2)(BA) assembly in the solid state. The hydrogen bonds formed not only between [PdBr(Hmtbhp)](+) and HBA(-) but also between HBA(-) and neutral H(2)BA molecules in the {[PdBr(Hmtbhp)](2)(HBA)(2)(H(2)BA)·2Acetonitrile} assembly. The H(2)BA-based flexible hydrogen bond network and strong acidic host structure result in an interesting vapor adsorption ability and vapochromic behavior in this assembly because the vapor-induced rearrangement of the hydrogen bond network, accompanied by changes in

  13. Time-dependent calculations of transfer ionization by fast proton-helium collision in one-dimensional kinematics

    OpenAIRE

    Serov, Vladislav V.; Kheifets, A. S.

    2014-01-01

    We analyze a transfer ionization (TI) reaction in the fast proton-helium collision $\\rm H^+ + He \\to H^0 + He^{2+} + e^-$ by solving a time-dependent Schr\\"odinger equation (TDSE) under the classical projectile motion approximation in one-dimensional kinematics. In addition, we construct various time independent analogues of our model using lowest order perturbation theory in the form of the Born series. By comparing various aspects of the TDSE and the Born series calculations, we conclude th...

  14. Neutral transition metal hydrides as acids in hydrogen bonding and proton transfer: media polarity and specific solvation effects.

    Science.gov (United States)

    Levina, Vladislava A; Filippov, Oleg A; Gutsul, Evgenii I; Belkova, Natalia V; Epstein, Lina M; Lledos, Agusti; Shubina, Elena S

    2010-08-18

    Structural, spectroscopic, and electronic features of weak hydrogen-bonded complexes of CpM(CO)(3)H (M = Mo (1a), W (1b)) hydrides with organic bases (phosphine oxides R(3)PO (R = n-C(8)H(17), NMe(2)), amines NMe(3), NEt(3), and pyridine) are determined experimentally (variable temperature IR) and computationally (DFT/M05). The intermediacy of these complexes in reversible proton transfer is shown, and the thermodynamic parameters (DeltaH degrees , DeltaS degrees ) of each reaction step are determined in hexane. Assignment of the product ion pair structure is made with the help of the frequency calculations. The solvent effects were studied experimentally using IR spectroscopy in CH(2)Cl(2), THF, and CH(3)CN and computationally using conductor-like polarizable continuum model (CPCM) calculations. This complementary approach reveals the particular importance of specific solvation for the hydrogen-bond formation step. The strength of the hydrogen bond between hydrides 1 and the model bases is similar to that of the M-H...X hydrogen bond between 1 and THF (X = O) or CH(3)CN (X = N) or between CH(2)Cl(2) and the same bases. The latter competitive weak interactions lower the activities of both the hydrides and the bases in the proton transfer reaction. In this way, these secondary effects shift the proton transfer equilibrium and lead to the counterintuitive hampering of proton transfer upon solvent change from hexane to moderately polar CH(2)Cl(2) or THF.

  15. Rapid Detection of Meat Spoilage by Measuring Volatile Organic Compounds by Using Proton Transfer Reaction Mass Spectrometry

    OpenAIRE

    Mayr, D; Margesin, R.; Klingsbichel, E.; E. Hartungen; Jenewein, D.; Schinner, F.; Märk, T.D.

    2003-01-01

    The evolution of the microbial spoilage population for air- and vacuum-packaged meat (beef and pork) stored at 4°C was investigated over 11 days. We monitored the viable counts (mesophilic total aerobic bacteria, Pseudomonas spp., Enterobacteriaceae, lactic acid bacteria, and Enterococcus spp.) by the microbiological standard technique and by measuring the emission of volatile organic compounds (VOCs) with the recently developed proton transfer reaction mass spectrometry system. Storage time,...

  16. New methods for determining proton pumping ability and electron transfer activity of the cytochrome bc1 complex.

    Science.gov (United States)

    Qu, Yuangang; Dong, Fang

    2015-02-01

    It is important to determine the electron transfer activity and proton pumping ability of the cytochrome bc1 complex for better understanding its structure and function. In this study, several methods for determining the electron transfer and proton pumping of the bc1 complex, including the traditional and the new methods, are presented and evaluated. For determining the proton pumping ability of the bc1 complex, the new stopped-flow method has a higher accuracy than the traditional pH meter method, and the new spectrophotometer method is more convenient than the traditional pH meter method. In measuring the electron transfer activity of the bc1 complex, the new stopped-flow method is more accurate and has a higher separating capacity than the traditional spectrophotometer method. © The Author 2014. Published by ABBS Editorial Office in association with Oxford University Press on behalf of the Institute of Biochemistry and Cell Biology, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences.

  17. Excited-state intramolecular proton transfer molecules bearing o-hydroxy analogues of green fluorescent protein chromophore.

    Science.gov (United States)

    Chuang, Wei-Ti; Hsieh, Cheng-Chih; Lai, Chin-Hung; Lai, Cheng-Hsuan; Shih, Chun-Wei; Chen, Kew-Yu; Hung, Wen-Yi; Hsu, Yu-Hsiang; Chou, Pi-Tai

    2011-10-21

    o-Hydroxy analogues, 1a-g, of the green fluorescent protein chromophore have been synthesized. Their structures and electronic properties were investigated by X-ray single-crystal analyses, electrochemistry, and luminescence properties. In solid and nonpolar solvents 1a-g exist mainly as Z conformers that possess a seven-membered-ring hydrogen bond and undergo excited-state intramolecular proton transfer (ESIPT) reactions, resulting in a proton-transfer tautomer emission. Fluorescence upconversion dynamics have revealed a coherent type of ESIPT, followed by a fast vibrational/solvent relaxation (decay of a few to several tens of picoseconds was resolved in cyclohexane. Accordingly, the proton-transfer tautomer emission intensity is moderate (0.08 in 1e) to weak (∼10(-4) in 1a) in cyclohexane. The stronger intramolecular hydrogen bonding in 1g suppresses the rotation of the aryl-alkene bond, resulting in a high yield of tautomer emission (Φ(f) ≈ 0.2). In the solid state, due to the inhibition of exo-C(5)-C(4)-C(3) rotation, intense tautomer emission with a quantum yield of 0.1-0.9 was obtained for 1a-g. Depending on the electronic donor or acceptor strength of the substituent in either the HOMO or LUMO site, a broad tuning range of the emission from 560 (1g) to 670 nm (1a) has been achieved.

  18. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation. [Spiropyrans

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in [approximately]240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH[sub 2]I[sub 2] and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a [approximately]350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  19. Semiclassical study of quantum coherence and isotope effects in ultrafast electron transfer reactions coupled to a proton and a phonon bath.

    Science.gov (United States)

    Venkataraman, Charulatha

    2011-11-28

    The linearized semiclassical initial value representation is employed to describe ultrafast electron transfer processes coupled to a phonon bath and weakly coupled to a proton mode. The goal of our theoretical investigation is to understand the influence of the proton on the electronic dynamics in various bath relaxation regimes. More specifically, we study the impact of the proton on coherences and analyze if the coupling to the proton is revealed in the form of an isotope effect. This will be important in distinguishing reactions in which the proton does not undergo significant rearrangement from those in which the electron transfer is accompanied by proton transfer. Unlike other methodologies widely employed to describe nonadiabatic electron transfer, this approach treats the electronic and nuclear degrees of freedom consistently. However, due to the linearized approximation, quantum interference effects are not captured accurately. Our study shows that at small phonon bath reorganization energies, coherent oscillations and isotope effect are observed in both slow and fast bath regimes. The coherences are more substantially damped by deuterium in comparison to the proton. Further, in contrast to the dynamics of the spin-boson model, the coherences are not long-lived. At large bath reorganization energies, the decay is incoherent in the slow and fast bath regimes. In this case, the extent of the isotope effect depends on the relative relaxation timescales of the proton mode and the phonon bath. The isotope effect is magnified for baths that relax on picosecond timescales in contrast to baths that relax in femtoseconds.

  20. Escherichia coli Phosphoenolpyruvate-Dependent Phosphotransferase System : Stereospecificity of Proton Transfer in the Phosphorylation of Enzyme I from (Z)-Phosphoenolbutyrate

    NARCIS (Netherlands)

    Hoving, H; Nowak, Thomas; Robillard, George T.

    1983-01-01

    The stereochemistry of the proton transfer in the reaction of phosphoenolbutyrate with enzyme I has been established. During the reaction of the pure Z isomer of this analogue of phosphoenolpyruvate with enzyme I, to yield phosphoenzyme I and 2-oxobutyrate, the substrate is protonated at C-3 from th

  1. Calibration and intercomparison of acetic acid measurements using proton transfer reaction mass spectrometry (PTR-MS)

    Science.gov (United States)

    Haase, K.B.; Keene, W.C.; Pszenny, A.A.P.; Mayne, H.R.; Talbot, R.W.; Sive, B.C.

    2012-01-01

    Acetic acid is one of the most abundant organic acids in the ambient atmosphere, with maximum mixing ratios reaching into the tens of parts per billion by volume (ppbv) range. The identities and associated magnitudes of the major sources and sinks for acetic acid are poorly characterized, due in part to the limitation in available measurement techniques. This paper demonstrates that Proton Transfer Reaction Mass Spectrometry (PTR-MS) can reliably quantify acetic acid vapor in ambient air. Three different PTR-MS configurations were calibrated at low ppbv mixing ratios using permeation tubes, which yielded calibration factors between 7.0 and 10.9 normalized counts per second per ppbv (ncps ppbv−1) at a drift tube field strength of 132 townsend (Td). Detection limits ranged from 0.06 to 0.32 ppbv with dwell times of 5 s. These calibration factors showed negligible humidity dependence. Using the experimentally determined calibration factors, PTR-MS measurements of acetic acid during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign were validated against results obtained using Mist Chambers coupled with Ion Chromatography (MC/IC). An orthogonal least squares linear regression of paired data yielded a slope of 1.14 ± 0.06 (2σ), an intercept of 0.049 ± 20 (2σ) ppbv, and an R2 of 0.78. The median mixing ratio of acetic acid on Appledore Island, ME during the ICARTT campaign was 0.530 ± 0.025 ppbv with a minimum of 0.075 ± 0.004 ppbv, and a maximum of 3.555 ± 0.171 ppbv.

  2. Calibration and intercomparison of acetic acid measurements using proton transfer reaction mass spectrometry (PTR-MS

    Directory of Open Access Journals (Sweden)

    K. B. Haase

    2012-07-01

    Full Text Available Acetic acid is one of the most abundant organic acids in the ambient atmosphere, with maximum mixing ratios reaching into the tens of parts per billion by volume (ppbv range. The identities and associated magnitudes of the major sources and sinks for acetic acid are poorly characterized, due in part to the limitation in available measurement techniques. This paper demonstrates that Proton Transfer Reaction Mass Spectrometry (PTR-MS can reliably quantify acetic acid vapor in ambient air. Three different PTR-MS configurations were calibrated at low ppbv mixing ratios using permeation tubes, which yielded calibration factors between 7.0 and 10.9 normalized counts per second per ppbv (ncps ppbv−1 at a drift tube field strength of 132 townsend (Td. Detection limits ranged from 0.06 to 0.32 ppbv with dwell times of 5 s. These calibration factors showed negligible humidity dependence. Using the experimentally determined calibration factors, PTR-MS measurements of acetic acid during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT campaign were validated against results obtained using Mist Chambers coupled with Ion Chromatography (MC/IC. An orthogonal least squares linear regression of paired data yielded a slope of 1.14 ± 0.06 (2σ, an intercept of 0.049 ± 20 (2σ ppbv, and an R2 of 0.78. The median mixing ratio of acetic acid on Appledore Island, ME during the ICARTT campaign was 0.530 ± 0.025 ppbv with a minimum of 0.075 ± 0.004 ppbv, and a maximum of 3.555 ± 0.171 ppbv.

  3. The interplay of skeletal deformations and ultrafast excited-state intramolecular proton transfer: Experimental and theoretical investigation of 10-hydroxybenzo[h]quinoline

    Energy Technology Data Exchange (ETDEWEB)

    Schriever, Christian [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany)], E-mail: christian.schriever@physik.uni-muenchen.de; Barbatti, Mario [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria)], E-mail: mario.barbatti@univie.ac.at; Stock, Kai [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany); Aquino, Adelia J.A.; Tunega, Daniel [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria); Lochbrunner, Stefan [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany); Riedle, Eberhard [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany)], E-mail: eberhard.riedle@physik.uni-muenchen.de; Vivie-Riedle, Regina de [Department Chemie - Ludwig-Maximilians-Universitaet (LMU), Butenandt-Strasse 11, 81377 Muenchen (Germany)], E-mail: regina.de_vivie@cup.uni-muenchen.de; Lischka, Hans [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria)], E-mail: hans.lischka@univie.ac.at

    2008-05-23

    The excited-state intramolecular proton transfer in the aromatic polycycle 10-hydroxybenzo[h]quinoline is investigated by means of transient absorption experiments with 30 fs time resolution, classical dynamics and wavepacket dynamics. The experiments establish the ultrafast transfer after UV excitation and show signatures of coherent vibrational motion in the keto product. To elucidate details of the proton transfer mechanism, the classical dynamics is also performed for 2-(2'-hydroxyphenyl)benzothiazole and the results are compared. For both systems the proton transfer takes place on the ultrafast scale of 30-40 fs, with good agreement between the theoretical investigations and the measurements. The dynamics simulations show that for both molecules the proton is handed over by means of skeletal deformation of the molecule. Due to the more rigid structure of 10-hydroxybenzo[h]quinoline the hydrogen migration mode participates more actively than in 2-(2'-hydroxyphenyl)benzothiazole.

  4. Quantification of in vivo pH-weighted amide proton transfer (APT) MRI in acute ischemic stroke

    Science.gov (United States)

    Zhou, Iris Y.; Igarashi, Takahiro; Guo, Yingkun; Sun, Phillip Z.

    2015-03-01

    Amide proton transfer (APT) imaging is a specific form of chemical exchange saturation transfer (CEST) MRI that probes the pH-dependent amide proton exchange.The endogenous APT MRI is sensitive to tissue acidosis, which may complement the commonly used perfusion and diffusion scans for characterizing heterogeneous ischemic tissue damage. Whereas the saturation transfer asymmetry analysis (MTRasym) may reasonably compensate for direct RF saturation, in vivo MTRasym is however, susceptible to an intrinsically asymmetric shift (MTR'asym). Specifically, the reference scan for the endogenous APT MRI is 7 ppm upfield from that of the label scan, and subjects to concomitant RF irradiation effects, inclu