2004 DOE/BES Analysis Program Contractors' Meeting

Total Page:16

File Type:pdf, Size:1020Kb

2004 DOE/BES Analysis Program Contractors' Meeting 2004 DOE/BES Analysis Program Contractors’ Meeting Annapolis, Maryland February 12 – 14, 2004 Sponsored by The U.S. Department of Energy Office of Basic Energy Sciences Workshop Chair: John Miller 2004 DOE/BES Analysis Program Contractors’ Meeting Program and Abstracts Department of Energy Office of Science Office of Basic Energy Sciences Chemical Sciences, Geosciences and Biosciences Division FOREWORD This abstract booklet provides a record of the 2004 U.S. Department of Energy, Office of Basic Energy Sciences, Analysis Program Contractors’ Meeting. This group of scientists last met as part of the larger Separations and Analysis Program Contractors’ Meeting held in San Diego April 5-7, 2001. The agenda and abstracts of that meeting may be found on the web at http://www.sc.doe.gov/bes/chm/Publications/publications.html. There is wide agreement that a gathering of researchers with common interests and sponsorship provides a fruitful environment for exchange of research results, research techniques, and research opportunities. The primary means of communicating research achievements and perspectives at this meeting is oral presentations, formal discussion periods and informal breaks and meals. The agenda has been organized so that papers in related disciplines – such as mass spectrometry or optical spectroscopy – are loosely clustered together. I am pleased to have the privilege of organizing this meeting and of serving as the program manager of this world-class research program. In carrying out these tasks, I learn from the achievements, and share the excitement, of the research of the many sponsored scientists and students whose names appear on the papers in the following pages. It is also hoped that this meeting will enhance your research efforts and will nurture future collaborations and initiatives. Thanks are due to all of the researchers whose dedication and innovation have advanced our research and made this meeting possible and, I hope, productive. I am sure that all of you will build on your successes and that we will assemble in a very few years for our next meeting. I offer special thanks to Jody Shumpert of the Oak Ridge Institute for Science and Education and to Karen Talamini of the Chemical Sciences, Geosciences and Biosciences Division in DOE for assisting in the technical and logistical aspects of this meeting. John C. Miller 2004 DOE/BES Analysis Program Contractors’ Meeting AGENDA 2004 DOE/BES Analysis Program Contractors’ Meeting AGENDA (Note: Speakers are bolded - Other contributors are named in abstracts) Wednesday, February 11, 2004 7:00-9:00 pm Registration, Cash Bar and Light Hors d’oeuvres – Lobby Level, Room 260 Thursday, February 12, 2004 7:30-8:00 Registration and Continental Breakfast - Arundel C 8:00 Welcome – John C. Miller U.S. Department of Energy, Office of Science Chemical Sciences, Geosciences and Biosciences Division 8:15- 9:15 Plenary Lecture - Dr. Sune Svanberg, Lund Inst. of Tech., Sweden Chemical analysis by optical and laser spectroscopy ......................................................P1 9:15-9:45 Break Session 1 9:45-10:05 Richard E. Russo Laser Material Interactions (Ablation) for Chemical Analysis ........................................ S1-1 10:05-10:25 J. Thomas Dickinson UV Laser-Surface Interaction Relevant to Analytic Spectroscopy of ............................... S1-2 Wide Band Gap Materials 10:25-10:45 Nicolo Omenetto (with J.D. Winefordner and Ben Smith) Modeling, Diagnostic and Application of the Laser Induced Plasma .............................. S1-3 10:45-11:05 Akos Vertes Excitation, Relaxation and Internal Energy Content in Matrix-Assisted ......................... S1-4 Laser Desorption Ionization 11:05-11:25 Willard W. Harrison Laser Desorption/Discharge Ionization Sources for Mass Spectrometry......................... S1-5 11:25-11:45 Alla Zelenyuk Chemistry and Microphysics of Small Particles............................................................... S1-6 12:00-1:15 Lunch Session 2 1:15-1:35 Julia Laskin (with Jean H. Futrell) Surface-Induced Dissociation of Complex Polyatomic Ions............................................. S2-1 1:35-1:55 David H. Russell Fragmentation Chemistry of Peptide Ions as a Function of N-terminal Residue............. S2-2 and Charge Carrier: [M+H, Li, Na, K, or Cu(I)]+ 1:55-2:15 T. Gregory Schaaff Mass Spectrometry of Nanocrystal and Cluster Compounds ........................................... S2-3 2:15-2:35 Paul B. Farnsworth Ion Sampling and Transport in Plasma Source Mass Spectrometers............................... S2-4 2:35-2:55 Robert Noll (for Gary M. Hieftje) Fundamental Studies of the Inductively Coupled Plasma and Glow Discharge .............. S2-5 2:55-3:15 Akbar Montaser Fundamental Nebulization Processes and Analyte Transport in...................................... S2-6 High-Temperature Plasmas 3:15-3:30 Break Session 3 3:30-3:50 Richard M. Crooks Measurements of Mass Transport Rate Through Well-Defined Nanoscopic.................... S3-1 Tubes 3:50-4:10 Marc D. Porter Chemical Analysis at Nanodomains: Composition, Structure, and Function .................. S3-2 Relationships 4:10-4:30 Eric Borguet Fluorescence Labeling of Surface Species (FLOSS) a Key to Understanding ................. S3-3 the UV Photoreactivity of Alkylsiloxane SAMs 4:30-4:45 Move to Alternate Room – Calvert Ballroom 4:50-6:00 Discussion 6:00 Adjourn and Dinner (on your own) Friday, February 13, 2004 7:30-8:00 Registration and Continental Breakfast – Arundel C 8:00 Welcome - John C. Miller U.S. Department of Energy, Office of Science Chemical Sciences, Geosciences and Biosciences Division 8:15- 9:15 Plenary Lecture - Dr. Michael T. Bowers, University of California, Santa Barbara Ion Mobility: The Method and Its Applications to Problems in Materials and Biochemistry ..............................................................................................................P2 9:15-9:45 Break Session 4 9:45-10:05 Scott A. McLuckey The Dynamics and Thermodynamics of Gaseous Macro-ions.......................................... S4-1 10:05-10:25 Douglas E. Goeringer Physicochemical Processes in RF Quadrupole Ion Traps................................................ S4-2 10:25-10:45 R. S. Houk Inorganic Mass Spectrometry with ICP and Electrospray Ionization Sources ................ S4-3 10:45-11:05 Douglas C. Duckworth Mass Spectrometry of Room Temperature Ionic Liquids.................................................. S4-4 Gary J. Van Berkel Electrostatic and Electrochemical Processes in Electrospray ......................................... S4-5 11:05-11:25 James E. Delmore Surface Ionization Mass Spectrometry ............................................................................. S4-6 11:25-11:45 Gerardo Gamez (for R. Graham Cooks) Ion Motion and Ion Excitation in the Quadrupole Ion Trap Mass ................................... S4-7 Spectrometer: Simulation and Experiment Cooks 12:00-1:30 Lunch Session 5 1:30-1:50 Michael D. Barnes Oriented Polymer Nanostructures: New insights into intramolecular ............................. S5-1 structure and photophysics of conducing polymers 1:50-2:10 Bruce A. Bushaw Triple Resonance Ionization: From Ultra-trace Isotope Analysis to................................ S5-2 High Precision Spectroscopy 2:10-2:30 Jeanne E. Pemberton Vibrational Spectroscopy of Chromatographic Stationary Phases .................................. S5-3 2:30-2:50 Edward M. Eyring Characterization of Intermediates by Attenuated Total Reflectance ................................ S5-4 Infrared Spectroscopy 2:50-3:10 Janos H. Fendler Quantification of Interparticles Forces and Aggregation of Nanoparticles..................... S5-5 3:10-3:30 Robert J. Hurtubise Solid-Matrix Luminescence Analysis and Coupling Solid-Matrix.................................... S5-6 Luminescence with Separation Methodology 3:30-4:00 Break Session 6 4:00-4:20 Gary E. Maciel Multinuclear Magnetic Resonance Study of Silica and Modified Silica........................... S6-1 4:20-4:40 Gerald Diebold Thermal Diffusion Shock Waves ....................................................................................... S6-2 4:40-5:00 Bruce S. Hudson Inelastic Neutron Scattering and Periodic DFT Studies of Hydrogen ............................. S6-3 Bonded Structures 5:00-6:00 Discussion 7:00 Cash Bar and Dinner (provided by DOE) – Calvert AB Saturday, February 14, 2004 8:30-9:00 Continental Breakfast – Arundel C Session 7 9:00-9:20 Paul W. Bohn Molecular Aspects of Transport in Thin Films of Controlled Architecture...................... S7-1 9:20-9:40 Sheng Dai Novel separation processes via hierarchically structured materials and......................... S7-2 ionic liquids 9:40-10:00 George Guiochon Study of the Homogeneity of Adsorbent Surfaces ............................................................. S7-3 10:00-10:20 Frank Bright Studies of Solvation Processes in Supercritical Fluids..................................................... S7-4 10:20-10:50 Break 10:50-12:30 Discussion and Wrap Up 12:30 Adjourn 2004 DOE/BES Analysis Program Contractors’ Meeting Abstract Plenary Lecture 1 Abstract P-1 2004 DOE/BES Analysis Program Contractor´s Meeing Annapolis, Md., February 12-14 2004 Chemical analysis by optical and laser spectroscopy Sune Svanberg Department of Physics, Lund Institute of Technology, P.O. Box 118, S-221 00 Lund, Sweden [email protected] Optical spectroscopy, and in particular laser spectroscopy, provide many interesting possibilities
Recommended publications
  • Synthetic Applications of Dienes and Polyenes, Excluding Cycloadditions
    The Chemistry of Dienes and Polyenes. Volume 2 Edited by Zvi Rappoport Copyright 2000 John Wiley & Sons, Ltd. ISBN: 0-471-72054-2 CHAPTER 9 Synthetic applications of dienes and polyenes, excluding cycloadditions NANETTE WACHTER-JURCSAK Department of Chemistry, Biochemistry and Natural Science, Hofstra University, Hempstead, New York 11549-1090, USA Fax: (516) 463-6394; e-mail: [email protected] and KIMBERLY A. CONLON Department of Pharmacological Sciences, School of Medicine, State University of New York at Stony Brook, Stony Brook, New York 11794-8651, USA Fax: (516) 444-3218; e-mail: [email protected] I. INTRODUCTION ..................................... 693 II. ADDITION REACTIONS ............................... 694 III. OXIDATION REACTIONS ............................... 700 IV. COUPLING REACTIONS ............................... 710 A. Wittig Reactions of Dienes and Polyenes .................... 711 B. Coupling Promoted by Organometallic Reagents ............... 712 V. DIMERIZATION REACTIONS ............................ 718 VI. PREPARATION OF METAL–POLYENE COMPLEXES ........... 720 VII. REARRANGEMENTS .................................. 722 A. Cope Rearrangement ................................. 722 B. Claisen Rearrangement ............................... 728 VIII. REFERENCES ....................................... 736 I. INTRODUCTION The reactivity of polyenes is influenced by their substituents, and whether or not the multiple double bonds of the unsaturated hydrocarbon are conjugated or isolated from 693 694 Nanette Wachter-Jurcsak and Kimberly A. Conlon one another. The -system of a polyene may be fully conjugated, or there may be one or more pairs of conjugated double bonds isolated from the other -bonds in the molecule, or, alternatively, each of the carbon–carbon double bonds in the polyene may be isolated from one another. Conjugated -systems react differently with electrophiles than isolated double bonds. Addition of hydrogen to isolated double bonds has been previously discussed in this series and will not be addressed here1.
    [Show full text]
  • Curriculum Vitae
    1 CURRICULUM VITAE Robert Bau Born: February 10, 1944, Shanghai, China (naturalized U.S. citizen, 1974) Education: B.Sc., University of Hong Kong, June, 1964 Ph.D., University of California at Los Angeles, March, 1968 ` Postdoctoral Research Fellow, Harvard University, 1968-69 Positions Held Since Ph.D. Degree: 1977-present Professor of Chemistry, University of Southern California 1974-77 Associate Professor of Chemistry, University of Southern California 1969-74 Assistant Professor of Chemistry, University of Southern California Awards and Honors: Fellow of the Alfred P. Sloan Foundation, 1974-76 NIH Research Career Development Awardee, 1975-80 Recipient of USC Associates Award for Excellence in Teaching, 1974 Recipient of USC Associates Award for Excellence in Research, 1979 Fellow of the American Association for the Advancement of Science, 1982 Recipient of the Alexander van Humboldt Foundation, U.S. Senior Scientist Award, 1985 Visiting Professor of Chemistry, University of Grenoble, France, March-June, 1989 President, American Crystallographic Association, 2006 Research Interests: X-ray and Neutron Diffraction Studies of Covalent Metal Hydride Compounds Neutron Diffraction Studies on Molecules Having Chiral Methylene Groups (Molecules of the type CHDRR') Neutron Diffraction Studies of Small Proteins 2 PUBLICATION LIST Professor Robert Bau Department of Chemistry University of Southern California Los Angeles, California 90089-0744 1. "The Crystal Structure of HRe2Mn(CO)14. A Neutral, 'Electron Deficient', Polynuclear Carbonyl Hydride", H.D. Kaesz, R. Bau, and M.R. Churchill, J. Am. Chem. Soc., 89, 2775 (1967). 2. "Spectroscopic Studies of Isotopically Substituted Metal Carbonyls. I. Vibrational Analysis of Metal Pentacarbonyl Halides", H.D. Kaesz, R. Bau, D. Hendrickson and J.M.
    [Show full text]
  • Synthetic Advances in the C‐H Activation of Rigid Scaffold Molecules
    Synthesis Review Synthetic Advances in the C‐H Activation of Rigid Scaffold Molecules Nitika Grovera Mathias O. Senge*a a School of Chemistry, Trinity College Dublin, The University of Dublin, Trinity Biomedical Sciences Institute, 152–160 Pearse Street, Dublin 2, Ireland [email protected] Dedicated to Prof. Dr. Henning Hopf Received: only recall the epic endeavors involved in Eaton’s cubane Accepted: Published online: synthesis,3 Parquette’s preparation of dodecahedrane, DOI: Prinzbach’s pagodane route thereto, or Maier’s synthesis of Abstract The remarkable structural and electronic properties of rigid non‐ tetra-tert-butyltetrahedrane.4 conjugated hydrocarbons afford attractive opportunities to design molecular building blocks for both medicinal and material applications. The bridgehead positions provide the possibility to append diverse functional groups at specific angles and in specific orientations. The current review summarizes the synthetic development in CH functionalization of the three rigid scaffolds namely: (a) cubane, (b) bicyclo[1.1.1]pentane (BCP), (c) adamantane. 1 Introduction 2 Cubane 2.1 Cubane Synthesis 2.2 Cubane Functionalization 3 BCP 3.1 BCP Synthesis 3.2 BCP Functionalization 4 Adamantane 4.1 Adamantane Synthesis 4.2 Adamantane Functionalization 5 Conclusion and Outlook Key words Cubane, bicyclo[1.1.1]pentane, adamantane, rigid scaffolds, CH‐ functionalization. Figure 1 The structures of cubane, BCP and adamantane and the five platonic hydrocarbon systems. The fascinating architecture of these systems significantly 1 Introduction differs from scaffolds realized in natural compounds. Hence, they attracted considerable attention from synthetic and The practice of synthetic organic chemistry of non-natural physical organic chemists to investigate their properties and to compounds with rigid organic skeletons provides a deep establish possible uses.3,5 Significantly, over the past twenty understanding of bonding and reactivity.
    [Show full text]
  • Cyclopentane Synthesis
    Cyclopentane Synthesis Dan O’Malley Baran Group Meeting Cyclopentane Synthesis Group Meeting O'Malley 2/9/2005 This presentation is broken down into the following catagories. Some reactions either fit more than one Students of organic chemistry are taught a number of reactions for the synthesis of category or do not fit easily into any of them. Efforts have been made to place all such reactions in the cyclohexanes at a very early stage of their careers. Techniques for the creation of cyclopentanes, most appropriate category. however, are generally taught at a much later stage and are rarely given the same detailed treatment. This may be the result of the fact that there are no equivalents of reactions such as the Diels-Alder and I. General Information Robinson Annulation in terms of generality, extent of use, and historical importance. This may, in turn, II. Ionic Reactions be caused by the fact that the cyclopentane is an inherintly "umpoled" functionality, as illustrated below. III. Metal Mediated Reactions IV. Radical Reactions FG V. Pericyclic and Pseudo-pericyclic Reactions VI. Ring Expansion and Contraction Reactions I. General Information This situation is further exacerbated by the general lack of cheaply available cyclopentane compounds Baldwin's rules in the chiral pool; wheras a number of cyclohexane terpenes are readily available for elaboration, there Baldwin has divided ring closure reactions into those that are "favored" and those that are "disfavored". are no analogous cylcopentane natural products. Cyclopentanes are however, present in many Those that are disfavored are not always impossible, but are frequently much more difficult to effect.
    [Show full text]
  • Cyclophane. Do MM Calculations of Each of These
    10 52. Shown to the right are [2.2.2](1,3,5)-cyclophane and [2.2.2.2](1,2,3,5)-cyclophane. Do MM calculations of each of these as well as on all of the other two-carbon bridged structures: (1,2,3)-, (1,2,4)-, (1,2,3,4)-, (1,2,4,5)-, (1,2,3,4,5)-, and (1,2,3,4,5,6)-cyclophane; the latter is known as "superphane." Compare the computed angles and distances with those measured by X-ray crystallography (see the cited article). [Sekine, Y.; Boekelheide, V. J. Am. Chem. Soc. 1991, 103, 1777 and references cited therein; also Gleiter, R.; Kratz, D. Acc. Chem. Res. 1993, 26, 311.] 53. Shown to the right is [3.3](1,3)-cyclophane. There are at least five reasonable conformations for this compound (see the cited article). Use molecular mechanics to calculate the energy and geometry of each of these five conformations; assess which factors are responsible for the energy differences among the conformations. [Biali, S. E. J. Chem. Educ. 1990, 67, 1039.] 54. Use molecular mechanics to calculate the energies and geometries of a series of tetrasubstituted alkenes where R is H, Me, Et, iPr, or tBu. Compare your answers with those in Chart I and Table III of the first-cited reference. (Don't bother trying to reproduce the rotational barriers of Chart II because these are in doubt, as indicated by the second-cited reference.) [Clennan, E. L.; Chen, X.; Koola, J. J. J. Am. Chem. Soc. 1990, 112, 5193; Orfanopoulos, M.; Stratakis, M.; Elemes, Y.; Jensen, F.
    [Show full text]
  • NBO Applications, 2005
    NBO 2005 – 686 references Abbati, G. L.; Aragoni, M. C.; Arca, M.; Carrea, M. B.; Devillanova, F. A.; Garau, A.; Isaia, F.; Lippolis, V.; Marcelli, M.; Silvestru, C.; Verani, G. Gold(0) and gold(III) reactivity towards the tetraphenyldithioimidodiphosphinic acid, [Ph2P(S)NHP(S)Ph-2] European Journal of Inorganic Chemistry: 589-596 2005. Abirami, S.; Xing, Y. M.; Tsang, C. W.; Ma, N. L. Theoretical study of alpha/beta-alanine and their protonated/alkali metal cationized complexes Journal of Physical Chemistry A, (109): 500-506 2005. Adcock, W.; Graton, J.; Laurence, C.; Lucon, M.; Trout, N. Three-centre hydrogen bonding in the complexes of syn-2,4-difluoroadamantane with 4- fluorophenol and hydrogen fluoride Journal of Physical Organic Chemistry, (18): 227-234 2005. Afanas'yev, D. Y.; Prosyanik, A. V. Why N-methyleneformamide, CH2=N-CHO, prefers gauche-conformation? A DFT/NBO study Journal of Molecular Structure-Theochem, (130): 45-49 2005. Agou, T.; Kobayashi, J.; Kawashima, T. Dibenzophosphaborin: A hetero-pi-conjugated molecule with fluorescent properties based on intramolecular charge transfer between phosphorus and boron atoms Organic Letters, (7): 4373-4376 2005. Ahlquist, M.; Fabrizi, G.; Cacchi, S.; Norrby, P. O. Palladium(0) alkyne complexes as active species: a DFT investigation Chemical Communications: 4196-4198 2005. Alajarin, M.; Ortin, M. M.; Sanchez-Andrada, P.; Vidal, A.; Bautista, D. From ketenimines to ketenes to quinolones: Two consecutive pseudopericyclic events Organic Letters, (7): 5281-5284 2005. Alajarin, M.; Sanchez-Andrada, P.; Lopez-Leonardo, C.; Alvarez, A. On the mechanism of phthalimidine formation via o-phthalaldehyde monoimines. New [1,5]-H sigmatropic rearrangements in molecules with the 5-aza-2,4-pentadienal Journal of Organic Chemistry, (70): 7617-7623 2005.
    [Show full text]
  • 4.3.6 Strain Energies and Heats of Formation
    Results and Discussion • 183 ∆ –1 dramatically reduces the barrier to inversion ( Eplan drops from 58.6 to 7.4 kJ mol ). This might partly reflect the dramatic reduction in the energy difference between ‘pla- ∆ nar’ and tetrahedral-like structures for neopentane and spiropentane ( EPT = 880 and 440 kJ mol–1, respectively) (see Section 4.3.2). The introduction of a pair of methylene bridges between the caps then reduces this barrier to zero, giving a broadened potential energy well with an equilibrium structure with D2h symmetry. 4.3.6 Strain Energies and Heats of Formation Determining the total strain energies (SEs) of our novel hydrocarbons allows for a comparison with other strained hydrocarbons.43 We have chosen to use a method of cal- culating strain energies which has been used to great effect by Schulman and Disch.32 This method determines the strain energy as the negative of the calculated enthalpy change of a homodesmic reaction in which the number of quaternary (C), tertiary (CH) and secondary (CH2) carbons present in the target hydrocarbon are balanced with prod- uct neopentane, isobutane and propane molecules. The number of primary (CH3) car- bons on each side of the reaction is then balanced using ethane. This preserves the number and type of C–C bonds on each side of the reaction and is found to give good cancellation of errors when the MP2 method is used to calculate energies (see also Section 3.2 on page 97). If these product molecules are defined as being strain free (which is usual), the enthalpy change of this homodesmic reaction gives the total strain of the target hydrocarbon.
    [Show full text]
  • Prakash Vita-September 2018
    VITA G. K. Surya Prakash (October 2018) PERSONAL DATA Born: October 7, 1953, Bangalore, India Citizenship: USA (Naturalized) Married: 1981, Rama Devi Children: Archana, daughter (b. 1985), Arjun, son (b. 1991). Address: Home: 3412 Casco Court, Hacienda Heights, CA 91745, U. S. A Office: Loker Hydrocarbon Research Institute, University of Southern California, 837 Bloom Walk, Los Angeles, CA 90089- 1661, U.S.A. Telephone: (H) 626-333-734; (O) 213-740-5984; Fax: 213-740-6679 Email: [email protected] Web Address: http://chem.usc.edu/faculty/Prakash.html EDUCATION B. Sc (Honors) Chemistry, Bangalore University, India, 1972 M.Sc., Chemistry, Indian Institute of Technology (IIT), Madras, India, 1974 Ph. D., Chemistry, University of Southern California (Under Nobel Laureate, Professor George A. Olah), 1978 (Ph.D. work was carried out at Case Western Reserve University, 1974-1977) Postdoctoral, 1978-1979, University of Southern California (Nobel Laureate, Professor George A. Olah) ACADEMIC EXPERIENCE and POSITIONS Chairman, Department of Chemsitry, University of Southern California, 2017-present. Director, Loker Hydrocarbon Research Institute, University of Southern California, Sept. 2010- present. Scientific Director, Loker Hydrocarbon Research Institute, University of Southern California, Feb. 2000- August 2010. George A. & Judith A. Olah Nobel Laureate Chair in Hydrocarbon Chemistry, University of Southern California, Jan. 1997 – present. Professor of Chemistry, University of Southern California, Sept.1994 – present. Associate Professor of Chemistry, University of Southern California, Sept. 1990- Aug.1994, Tenured in 1993. Research Associate Professor of Chemistry, University of Southern California, Sept. 1984-Aug.1990. Research Assistant Professor of Chemistry, University of Southern California, Sept. 1981 – Aug. 1984. Junior Fellow, Loker Hydrocarbon Research Institute, University of Southern California, March 1979- Aug.1981.
    [Show full text]
  • 2 Korpus I Językoznawstwo Korpusowe 9
    Piotr Paryzek Pozyskiwanie danych leksykalnych z tekstów elektronicznych (na materiale czasopisma naukowego) Promotor: dr hab. Piotr Wierzchoń, prof. Uniwersytet im. Adama Mickiewicza w Poznaniu Instytut Językoznawstwa Poznań 2011 Panu Profesorowi Piotrowi Wierzchoniowi bardzo dziękuję za cierpliwość, trafne uwagi i opiekę nad pracą Spis treści 1 WSTĘP 7 2 KORPUS I JĘZYKOZNAWSTWO KORPUSOWE 9 2.1 Historia badań korpusowych 12 2.1.1 Krytycyzm Chomsky’ego 12 2.1.2 Rozwój badań korpusowych 14 2.2 Charakterystyka korpusów językowych 18 2.2.1 Sinclaira koncepcja konstruowania korpusów (1996) 18 2.2.2 Reprezentatywność 21 2.2.3 Koncepcja McEnery’ego i Wilsona (1996) 24 2.3 Typologia korpusów 27 2.3.1 Korpusy referencyjne i monitorujące 27 2.3.2 Korpusy ogólne i specjalistyczne 28 2.3.3 Korpusy pełnotekstowe i próbkowane 29 2.3.4 Korpusy języka pisanego i mówionego 30 2.3.5 Korpusy jednojęzyczne i wielojęzyczne, równoległe i porównywalne 31 2.3.6 Korpusy nieanotowane i anotowane 33 2.3.7 Korpusy synchroniczne i diachroniczne 35 2.4 Korpusy historyczne i współczesne 36 2.4.1 Korpusy ery przedkomputerowej 36 2.4.2 Wybrane korpusy komputerowe 38 2.4.2.1 Brown Corpus 38 2.4.2.2 British National Corpus 39 2.4.2.3 American National Corpus 40 2.4.2.4 Cobuild, Bank of English 40 2.4.2.5 International Corpus of English (ICE) 41 2.4.2.6 The Helsinki Corpus of English Texts 43 2.4.3 Korpusy w Polsce 43 2.4.3.1 PELCRA 43 2.4.3.2 Narodowy Korpus Języka Polskiego 45 3 2.4.3.3 Korpus Języka Polskiego PWN 46 2.4.3.4 Korpus IPI PAN 47 2.4.4 Zbiory tekstów 47
    [Show full text]
  • Topochemical Control of the Photodimerization of Aromatic Compounds by Γ-Cyclodextrin Thioethers in Aqueous Solution
    Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution Hai Ming Wang and Gerhard Wenz* Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2013, 9, 1858–1866. Organic Macromolecular Chemistry, Saarland University, Campus doi:10.3762/bjoc.9.217 Saarbrücken C4 2, 66123 Saarbrücken, Germany Received: 16 May 2013 Email: Accepted: 15 August 2013 Gerhard Wenz* - [email protected] Published: 12 September 2013 * Corresponding author This article is part of the Thematic Series "Superstructures with cyclodextrins: Chemistry and applications". Keywords: acenaphthylene; anthracene; coumarin; cyclodextrins; Guest Editor: H. Ritter photodimerization; quantum yield; stereoselectivity © 2013 Wang and Wenz; licensee Beilstein-Institut. License and terms: see end of document. Abstract The formation of soluble 1:2 complexes within hydrophilic γ-cyclodextrin (γ-CD) thioethers allows to perform photodimerizations of aromatic guests under controlled, homogenous reaction conditions. The quantum yields for unsubstituted anthracene, acenaph- thylene, and coumarin complexed in these γ-CD thioethers were found to be up to 10 times higher than in the non-complexed state. The configuration of the photoproduct reflected the configuration of the dimeric inclusion complex of the guest. Anti-parallel orien- tation of acenaphthylene within the CD cavity led to the exclusive formation of the anti photo-dimer in quantitative yield. Parallel orientation of coumarin within the complex of a CD thioether led to the formation of the syn head-to-head dimer. The degree of complexation of coumarin could be increased by employing the salting out effect. Introduction Photochemical reactions have been considered highly attractive solid state [3] or by various templates in solution has been the for a long time because they often lead to products that are best solution to this problem [4,5].
    [Show full text]
  • The Enthalpy of Sublimation of Cubane
    Thermochimica Acta xxx (2004) xxx–xxx 3 4 The enthalpy of sublimation of cubane a,1 b,∗ b b 5 A. Bashir-Hashemi , James S. Chickos , William Hanshaw , Hui Zhao , c c 6 Behzad S. Farivar , Joel F. Liebman 7 a Fluorochem, Inc., Azusa, CA 91702, USA 8 b Department of Chemistry and Biochemistry, University of Missouri at St. Louis, St. Louis, MO 63121, USA 9 c Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250, USA 10 Received 1 March 2004; received in revised form 6 May 2004; accepted 8 May 2004 11 This paper is dedicated to Philip E. Eaton and Thomas W. Cole, Jr. on the occasion of the 40th anniversary 12 of the first successful synthesis of cubane and any of its derivatives 13 Abstract 14 The sublimation enthalpy of cubane, a key reference material for force field and quantum mechanical computations, was measured by 15 combining the vaporization enthalpy at T = 298.15 K to the sum of the fusion enthalpy measured at T = 405 K and a solid–solid phase 16 transition that occurs at T = 394 K. The fusion and solid–solid phase transitions were measured previously. A sublimation enthalpy value of − 17 (55.2 ± 2.0) kJ mol 1 at T = 298.15 K was obtained. This value compares quite favorably the value obtained by comparing the sublimation 18 enthalpy of similar substances as a function of their molar masses but is at odds with earlier measurements. 19 © 2004 Published by Elsevier B.V. 20 Keywords: Cubane; Sublimation; Enthalpy 2 21 1.
    [Show full text]
  • Recent Developments in Arene Photocycloadditions
    HOT TOPICS 962 doi:10.2533/chimia.2008.962 CHIMIA 2008, 62, No. 12 Chimia 62 (2008) 962–966 © Schweizerische Chemische Gesellschaft ISSN 0009–4293 Recent Developments in Arene Photocycloadditions Ursula Streit and Christian G. Bochet* Abstract: The photocycloaddition of alkenes with aromatic systems may proceed through three reaction modes, affording different types of products: ortho, meta, and para. These reactions generate a considerable increase in complexity, and yield products arduously attainable by classical synthetic steps. Whereas the meta-photocyclo- addition has gained a lot of attention in the last decades because of its applicability in the total synthesis of numer- ous natural products, the ortho- and para-cycloadditions still have a great potential for further development. In this highlight, we review the latest advances in the field of photocycloaddition of alkenes to aromatic systems. Keywords: Arene photocycloaddition · Lacifodilactone F 1. Introduction [2+2] * [2+4] Aromaticity is a fascinating property, which has been the subject of many studies that ortho para were undertaken from all sorts of perspec- [3+2] meta tives. For the synthetic organic chemist, the extra stabilization of structures which feature cyclic arrays of 4n+2 conjugated π-electrons has been a very useful concept, in terms of a driving force for molecules able to access such a state, or in terms of their Scheme 1. resistance to aggressive reagents. The spe- cific case of benzenoid substrates has been extensively studied in the past century, and For example, benzenoid substrates rarely efficiently by means of classical thermal synthetic transformations of such cores are undergo Diels-Alder [4+2] cycloaddition reactions.
    [Show full text]