WorldWideScience

Sample records for polar organic molecules

  1. Adsorption of polar organic molecules on sediments: Case-study on Callovian-Oxfordian claystone.

    Science.gov (United States)

    Rasamimanana, S; Lefèvre, G; Dagnelie, R V H

    2017-08-01

    The release and transport of anthropogenic organic matter through the geosphere is often an environmental criterion of safety. Sedimentary rocks are widely studied in this context as geological barriers for waste management. It is the case of Callovian-Oxfordian claystone (COx), for which several studies report adsorption of anthropogenic organic molecules. In this study, we evaluated and reviewed adsorption data of polar organic molecules on COx claystone. Experiments were performed on raw claystone, decarbonated and clay fractions. Adsorption isotherms were measured with adsorbates of various polarities: adipate, benzoate, ortho-phthalate, succinate, gluconate, oxalate, EDTA, citrate. A significant adsorption was observed for multidentate polycarboxylic acids as evidenced with phthalate, succinate, oxalate, gluconate, EDTA and citrate (R d  = 1.53, 3.52, 8.4, 8.8, 12.4, 54.7 L kg -1 respectively). Multiple linear regression were performed as a statistical analysis to determine the predictors from these adsorption data. A linear correlation between adsorption data (R d ) and dipole moment (μ) of adsorbates was evidenced (R 2  = 0.91). Molecules with a high dipole moment, μ(D) > 2.5, displayed a significant adsorption, R d ≫1 L kg -1 . A qualitative correlation can be easily estimated using the water/octanol partition coefficient, P ow , of adsorbates (R 2  = 0.77). In this case, two opposite trends were distinguished for polar and apolar molecules. The use of organic carbon content in sediments is relevant for predicting adsorption of apolar compounds, log (P ow )>+1. The oxides/clays contents may be relevant regarding polar molecules, log ( apparent P ow )<-1. The proposed scheme offers a general methodology for investigation of geo-barriers towards heterogeneous organic plumes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Ultracold Polar Molecules

    Science.gov (United States)

    2016-04-01

    AFRL-AFOSR-UK-TR-2016-0005 Ultracold Polar Molecules Jeremy Hutson UNIVERSITY OF DURHAM Final Report 04/01/2016 DISTRIBUTION A: Distribution approved...DATES COVERED (From - To) 15-Jan-2010 to 14-Jul-2015 4. TITLE AND SUBTITLE Final Report on Grant FA8655-10-1-3033 on Ultracold Polar Molecules 5a...formation of ultracold 87RbCs molecules in their rovibrational ground state by magnetoassociation followed by STIRAP, resulting in 14 papers acknowledging

  3. Nuclear magnetic resonance of laser-polarized noble gases in molecules, materials and organisms

    Energy Technology Data Exchange (ETDEWEB)

    Goodson, Boyd McLean [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Conventional nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) are fundamentally challenged by the insensitivity that stems from the ordinarily low spin polarization achievable in even the strongest NMR magnets. However, by transferring angular momentum from laser light to electronic and nuclear spins, optical pumping methods can increase the nuclear spin polarization of noble gases by several orders of magnitude, thereby greatly enhancing their NMR sensitivity. This dissertation is primarily concerned with the principles and practice of optically pumped nuclear magnetic resonance (OPNMR). The enormous sensitivity enhancement afforded by optical pumping noble gases can be exploited to permit a variety of novel NMR experiments across many disciplines. Many such experiments are reviewed, including the void-space imaging of organisms and materials, NMR and MRI of living tissues, probing structure and dynamics of molecules in solution and on surfaces, and zero-field NMR and MRI.

  4. Nuclear magnetic resonance of laser-polarized noble gases in molecules, materials and organisms

    International Nuclear Information System (INIS)

    Goodson, Boyd M.

    1999-01-01

    Conventional nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) are fundamentally challenged by the insensitivity that stems from the ordinarily low spin polarization achievable in even the strongest NMR magnets. However, by transferring angular momentum from laser light to electronic and nuclear spins, optical pumping methods can increase the nuclear spin polarization of noble gases by several orders of magnitude, thereby greatly enhancing their NMR sensitivity. This dissertation is primarily concerned with the principles and practice of optically pumped nuclear magnetic resonance (OPNMR). The enormous sensitivity enhancement afforded by optical pumping noble gases can be exploited to permit a variety of novel NMR experiments across many disciplines. Many such experiments are reviewed, including the void-space imaging of organisms and materials, NMR and MRI of living tissues, probing structure and dynamics of molecules in solution and on surfaces, and zero-field NMR and MRI

  5. Organic molecules in the polar ice: from chemical analysis to environmental proxies

    Science.gov (United States)

    Barbante, Carlo; Zennaro, Piero; Giorio, Chiara; Kehrwald, Natalie; Benton, Alisa K.; Wolff, Eric W.; Kalberer, Markus; Kirchgeorg, Torben; Zangrando, Roberta; Barbaro, Elena; Gambaro, Andrea

    2015-04-01

    The molecular and isotopic compositions of organic matter buried in ice contains information that helps reconstruct past environmental conditions, evaluate histories of climate change, and assess impacts of humans on ecosystems. In recent years novel analytical techniques were developed to quantify molecular compounds in ice cores. As an example, biomass burning markers, including monosaccharide anhydrides, lightweight carboxylic acids, lignin and resin pyrolysis products, black carbon, and charcoal records help in reconstructing past fire activity across seasonal to millennial time scales. Terrestrial biomarkers, such as plant waxes (e.g. long-chain n-alkanes) are also a promising paleo vegetation proxy in ice core studies. Polycyclic aromatic hydrocarbons are ubiquitous pollutants recently detected in ice cores. These hydrocarbons primarily originate from incomplete combustion of organic matter and fossil fuels (e.g. diesel engines, domestic heating, industrial combustion) and therefore can be tracers of past combustion activities. In order to be suitable for paloeclimate purposes, organic molecular markers detected in ice cores should include the following important features. Markers have to be stable under oxidizing atmospheric conditions, and ideally should not react with hydroxyl radicals, during their transport to polar regions. Organic markers must be released in large amounts in order to be detected at remote distances from the sources. Proxies must be specific, in order to differentiate them from other markers with multiple sources. The extraction of glaciochemical information from ice cores is challenging due to the low concentrations of some impurities, thereby demanding rigorous control of external contamination sources and sensitive analytical techniques. Here, we review the analysis and use of organic molecules in ice as proxies of important environmental and climatic processes.

  6. Cold guided beams of polar molecules

    International Nuclear Information System (INIS)

    Motsch, Michael

    2010-01-01

    This thesis reports on experiments characterizing cold guided beams of polar molecules which are produced by electrostatic velocity filtering. This filtering method exploits the interaction between the polar molecules and the electric field provided by an electrostatic quadrupole guide to extract efficiently the slow molecules from a thermal reservoir. For molecules with large and linear Stark shifts such as deuterated ammonia (ND 3 ) or formaldehyde (H 2 CO), fluxes of guided molecules of 10 10 -10 11 molecules/s are produced. The velocities of the molecules in these beams are in the range of 10-200 m/s and correspond to typical translational temperatures of a few Kelvin. The maximum velocity of the guided molecules depends on the Stark shift, the molecular mass, the geometry of the guide, and the applied electrode voltage. Although the source is operated in the near-effusive regime, the number density of the slowest molecules is sensitive to collisions. A theoretical model, taking into account this velocity-dependent collisional loss of molecules in the vicinity of the nozzle, reproduces the density of the guided molecules over a wide pressure range. A careful adjustment of pressure allows an increase in the total number of molecules, whilst yet minimizing losses due to collisions of the sought-for slow molecules. This is an important issue for future applications. Electrostatic velocity filtering is suited for different molecular species. This is demonstrated by producing cold guided beams of the water isotopologs H 2 O, D 2 O, and HDO. Although these are chemically similar, they show linear and quadratic Stark shifts, respectively, when exposed to external electric fields. As a result, the flux of HDO is larger by one order of magnitude, and the flux of the individual isotopologs shows a characteristic dependence on the guiding electric field. The internal-state distribution of guided molecules is studied with a newly developed diagnostic method: depletion

  7. Decelerating and Trapping Large Polar Molecules.

    Science.gov (United States)

    Patterson, David

    2016-11-18

    Manipulating the motion of large polyatomic molecules, such as benzonitrile (C 6 H 5 CN), presents significant difficulties compared to the manipulation of diatomic molecules. Although recent impressive results have demonstrated manipulation, trapping, and cooling of molecules as large as CH 3 F, no general technique for trapping such molecules has been demonstrated, and cold neutral molecules larger than 5 atoms have not been trapped (M. Zeppenfeld, B. G. U. Englert, R. Glöckner, A. Prehn, M. Mielenz, C. Sommer, L. D. van Buuren, M. Motsch, G. Rempe, Nature 2012, 491, 570-573). In particular, extending Stark deceleration and electrostatic trapping to such species remains challenging. Here, we propose to combine a novel "asymmetric doublet state" Stark decelerator with recently demonstrated slow, cold, buffer-gas-cooled beams of closed-shell volatile molecules to realize a general system for decelerating and trapping samples of a broad range of volatile neutral polar prolate asymmetric top molecules. The technique is applicable to most stable volatile molecules in the 100-500 AMU range, and would be capable of producing trapped samples in a single rotational state and at a motional temperature of hundreds of mK. Such samples would immediately allow for spectroscopy of unprecedented resolution, and extensions would allow for further cooling and direct observation of slow intramolecular processes such as vibrational relaxation and Hertz-level tunneling dynamics. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules

    Science.gov (United States)

    Muppidi, Vamsee Krishna; Zacharias, Panthapally S.; Pal, Samudranil

    2007-01-01

    The physical properties of [CuL 12(H 2O)] ( 1) and [CuL 22(H 2O)] ( 2) and preparation and crystal structures of the inclusion compounds 1·( P)-C 2H 4Br 2, 2·( M)-C 2H 4Br 2, 1·CH 3CN and 2·CH 3CN are described. HL 1 and HL 2 (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-( R)- α-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-( S)- α-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuL n2(H 2O)] ( 1 and 2) molecules connected by O-H⋯O and C-H⋯O interactions form perfectly polar two-dimensional networks. In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed ( P) and the left-handed ( M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C-H⋯O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O-H⋯O and C-H⋯O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules.

  9. Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules

    International Nuclear Information System (INIS)

    Muppidi, Vamsee Krishna; Zacharias, Panthapally S.; Pal, Samudranil

    2007-01-01

    The physical properties of [CuL 1 2 (H 2 O)] (1) and [CuL 2 2 (H 2 O)] (2) and preparation and crystal structures of the inclusion compounds 1.(P)-C 2 H 4 Br 2 , 2.(M)-C 2 H 4 Br 2 , 1.CH 3 CN and 2.CH 3 CN are described. HL 1 and HL 2 (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-(R)-α-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-(S)-α-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuL n 2 (H 2 O)] (1 and 2) molecules connected by O-H...O and C-H...O interactions form perfectly polar two-dimensional networks. In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed (P) and the left-handed (M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C-H...O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O-H...O and C-H...O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules. - Graphical abstract: The square-pyramidal Cu(II) complexes [CuL n 2 (H 2 O)] with the bidentate HL n (HL 1 =N-(2-hydroxy-5-nitrobenzyl)-(R)-α-methyl-benzylamine and HL 2 =N-(2-hydroxy-5-nitrobenzyl)-(S)-α-methylbenzylamine) form 1:1 host-guest compounds with Br(CH 2 ) 2 Br and CH 3 CN. The X-ray structures of these species reveal the enantiospecific confinement of the chiral rotamers of Br(CH 2 ) 2 Br and perfectly polar ordering of both host and guest molecules in the crystal lattice. The figure shows the polar alignments of (a) [CuL 1 2 (H 2 O)].(P)-C 2 H 4 Br 2 and (b) [CuL 2 2 (H 2 O)].CH 3 CN

  10. The preparation of a poly (pentaerythritol tetraglycidyl ether-co-poly ethylene imine) organic monolithic capillary column and its application in hydrophilic interaction chromatography for polar molecules.

    Science.gov (United States)

    Chen, Ye; Shu, Yan; Yang, Zihui; Lv, Xumei; Tan, Wangming; Chen, Yingzhuang; Ma, Ming; Chen, Bo

    2017-10-02

    An easy single-step thermal treatment "one-pot" approach for the preparation of poly (pentaerythritol tetraglycidyl ether-co-poly ethylene imine) organic monolithic capillary columns was developed successfully. The column was prepared by the epoxy-amine ring-opening polymerization of pentaerythritol tetraglycidyl ether (PTE) with poly (ethylene imine) (PEI) using acetonitrile (ACN) and polyethylene glycol 600 (PEG 600) as the porogenic system at 60 °C for 12 h. The obtained monolith was homogeneous and permeable. It achieved the high-efficiency separation of polar molecules including amides, nucleosides, bases, phenols, and benzoic acids in capillary liquid chromatography (cLC). The highest column efficiency reached ca. 101,000 plates/m (for guanine) on monolith poly(PTE-co-PEI) at 0.64 mm/s, and satisfactory chromatographic performance with column efficiencies ranged from 45,500 to 97,000 plates/m was achieved for the four amides. A typical hydrophilic interaction liquid chromatography (HILIC) retention mechanism was observed with high organic solvent contents (>60% ACN). Also, the polymer-based monolithic column was successfully applied to separate the tumor markers. Furthermore, the poly(PTE-co-PEI) monolith could be easily modified with 1, 2-epoxydodecane, which reacted with the amino groups presented on the surface of the poly(PTE-co-PEI) monolith. Hydrophobic interactions were observed during the separation of alkylbenzenes and anilines on the post-modified poly(PTE-co-PEI) monolith. Together, these results confirm the feasibility of the epoxy-amine ring-opening polymerization reaction during the fabrication of a monolithic column with high efficiency for cLC applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Topological px+ipy superfluid phase of fermionic polar molecules

    NARCIS (Netherlands)

    Levinsen, J.; Cooper, N.R.; Shlyapnikov, G.V.

    2011-01-01

    We discuss the topological px+ipy superfluid phase in a 2D gas of single-component fermionic polar molecules dressed by a circularly polarized microwave field. This phase emerges because the molecules may interact with each other via a potential Vo(r) that has an attractive dipole-dipole 1/r^3 tail,

  12. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 17; Issue 10. Fascinating Organic Molecules from Nature - Some Exotic Red Pigments of Plant Origin. N R Krishnaswamy C N ... Keywords. Pigments of red sandalwood; Safflower; chica red; Brazil wood; Dragon's blood; Miro wood and Kamala dye.

  13. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 18; Issue 7. Fascinating Organic Molecules from Nature - Sweet Stimulants of the Olfactory Nerves - Muscone, Civetone and Related Compounds. N R Krishnaswamy C N Sundaresan. Series Article Volume 18 Issue 7 July 2013 pp 673-683 ...

  14. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 18; Issue 3. Fascinating Organic Molecules from Nature - Hunting with Poisoned Arrows: Story of Curare. N R Krishnaswamy C N Sundaresan. Series Article Volume 18 Issue 3 March 2013 pp 218-225 ...

  15. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 18; Issue 5. Fascinating Organic Molecules from Nature - Using a Natural Product to Catch Fish! The Chemistry of Rotenoids. N R Krishnaswamy C N Sundaresan. Series Article Volume 18 Issue 5 May 2013 pp 428-439 ...

  16. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 18; Issue 1. Fascinating Organic Molecules from Nature - Colours in Flight - Pigments from Bird Feathers and Butterfly Wings. N R Krishnaswamy C N Sundaresan. Series Article Volume 18 Issue 1 January 2013 pp 12-21 ...

  17. Small Molecule Organic Optoelectronic Devices

    Science.gov (United States)

    Bakken, Nathan

    Organic optoelectronics include a class of devices synthesized from carbon containing 'small molecule' thin films without long range order crystalline or polymer structure. Novel properties such as low modulus and flexibility as well as excellent device performance such as photon emission approaching 100% internal quantum efficiency have accelerated research in this area substantially. While optoelectronic organic light emitting devices have already realized commercial application, challenges to obtain extended lifetime for the high energy visible spectrum and the ability to reproduce natural white light with a simple architecture have limited the value of this technology for some display and lighting applications. In this research, novel materials discovered from a systematic analysis of empirical device data are shown to produce high quality white light through combination of monomer and excimer emission from a single molecule: platinum(II) bis(methyl-imidazolyl)toluene chloride (Pt-17). Illumination quality achieved Commission Internationale de L'Eclairage (CIE) chromaticity coordinates (x = 0.31, y = 0.38) and color rendering index (CRI) > 75. Further optimization of a device containing Pt-17 resulted in a maximum forward viewing power efficiency of 37.8 lm/W on a plain glass substrate. In addition, accelerated aging tests suggest high energy blue emission from a halogen-free cyclometalated platinum complex could demonstrate degradation rates comparable to known stable emitters. Finally, a buckling based metrology is applied to characterize the mechanical properties of small molecule organic thin films towards understanding the deposition kinetics responsible for an elastic modulus that is both temperature and thickness dependent. These results could contribute to the viability of organic electronic technology in potentially flexible display and lighting applications. The results also provide insight to organic film growth kinetics responsible for optical

  18. An electrostatic elliptical mirror for neutral polar molecules

    OpenAIRE

    Flórez, A. Isabel González; Meek, Samuel A.; Haak, Henrik; Conrad, Horst; Santambrogio, Gabriele; Meijer, Gerard

    2011-01-01

    Focusing optics for neutral molecules finds application in shaping and steering molecular beams. Here we present an electrostatic elliptical mirror for polar molecules consisting of an array of microstructured gold electrodes deposited on a glass substrate. Alternating positive and negative voltages applied to the electrodes create a repulsive potential for molecules in low-field-seeking states. The equipotential lines are parallel to the substrate surface, which is bent in an elliptical shap...

  19. An electrostatic elliptical mirror for neutral polar molecules.

    Science.gov (United States)

    González Flórez, A Isabel; Meek, Samuel A; Haak, Henrik; Conrad, Horst; Santambrogio, Gabriele; Meijer, Gerard

    2011-11-14

    Focusing optics for neutral molecules finds application in shaping and steering molecular beams. Here we present an electrostatic elliptical mirror for polar molecules consisting of an array of microstructured gold electrodes deposited on a glass substrate. Alternating positive and negative voltages applied to the electrodes create a repulsive potential for molecules in low-field-seeking states. The equipotential lines are parallel to the substrate surface, which is bent in an elliptical shape. The mirror is characterized by focusing a beam of metastable CO molecules and the results are compared to the outcome of trajectory simulations.

  20. Orienting Asymmetric Molecules by Laser Fields with Twisted Polarization

    Science.gov (United States)

    Gershnabel, E.; Averbukh, I. Sh.

    2018-02-01

    We study interaction of generic asymmetric molecules with laser fields having twisted polarization, using a pair of strong time-delayed short laser pulses with crossed linear polarizations as an example. We show that such an excitation not only provides unidirectional rotation of the most polarizable molecular axis, but also induces a directed torque along this axis, which results in a transient orientation of the molecules. The asymmetric molecules are chiral in nature and different molecular enantiomers experience the orienting action in opposite directions causing out-of-phase oscillations of their dipole moments. The resulting microwave radiation was recently suggested to be used for analysis or discrimination of chiral molecular mixtures. We reveal the mechanism behind this laser-induced orientation effect, show that it is classical in nature, and envision further applications of light with twisted polarization.

  1. Characterization of Interstellar Organic Molecules

    International Nuclear Information System (INIS)

    Gencaga, Deniz; Knuth, Kevin H.; Carbon, Duane F.

    2008-01-01

    Understanding the origins of life has been one of the greatest dreams throughout history. It is now known that star-forming regions contain complex organic molecules, known as Polycyclic Aromatic Hydrocarbons (PAHs), each of which has particular infrared spectral characteristics. By understanding which PAH species are found in specific star-forming regions, we can better understand the biochemistry that takes place in interstellar clouds. Identifying and classifying PAHs is not an easy task: we can only observe a single superposition of PAH spectra at any given astrophysical site, with the PAH species perhaps numbering in the hundreds or even thousands. This is a challenging source separation problem since we have only one observation composed of numerous mixed sources. However, it is made easier with the help of a library of hundreds of PAH spectra. In order to separate PAH molecules from their mixture, we need to identify the specific species and their unique concentrations that would provide the given mixture. We develop a Bayesian approach for this problem where sources are separated from their mixture by Metropolis Hastings algorithm. Separated PAH concentrations are provided with their error bars, illustrating the uncertainties involved in the estimation process. The approach is demonstrated on synthetic spectral mixtures using spectral resolutions from the Infrared Space Observatory (ISO). Performance of the method is tested for different noise levels.

  2. Dipolar collisions of polar molecules in the quantum regime.

    Science.gov (United States)

    Ni, K-K; Ospelkaus, S; Wang, D; Quéméner, G; Neyenhuis, B; de Miranda, M H G; Bohn, J L; Ye, J; Jin, D S

    2010-04-29

    Ultracold polar molecules offer the possibility of exploring quantum gases with interparticle interactions that are strong, long-range and spatially anisotropic. This is in stark contrast to the much studied dilute gases of ultracold atoms, which have isotropic and extremely short-range (or 'contact') interactions. Furthermore, the large electric dipole moment of polar molecules can be tuned using an external electric field; this has a range of applications such as the control of ultracold chemical reactions, the design of a platform for quantum information processing and the realization of novel quantum many-body systems. Despite intense experimental efforts aimed at observing the influence of dipoles on ultracold molecules, only recently have sufficiently high densities been achieved. Here we report the experimental observation of dipolar collisions in an ultracold molecular gas prepared close to quantum degeneracy. For modest values of an applied electric field, we observe a pronounced increase in the loss rate of fermionic potassium-rubidium molecules due to ultracold chemical reactions. We find that the loss rate has a steep power-law dependence on the induced electric dipole moment, and we show that this dependence can be understood in a relatively simple model based on quantum threshold laws for the scattering of fermionic polar molecules. In addition, we directly observe the spatial anisotropy of the dipolar interaction through measurements of the thermodynamics of the dipolar gas. These results demonstrate how the long-range dipolar interaction can be used for electric-field control of chemical reaction rates in an ultracold gas of polar molecules. Furthermore, the large loss rates in an applied electric field suggest that creating a long-lived ensemble of ultracold polar molecules may require confinement in a two-dimensional trap geometry to suppress the influence of the attractive, 'head-to-tail', dipolar interactions.

  3. Do Identical Polar Diatomic Molecules Form Stacked or Linear ...

    Indian Academy of Sciences (India)

    ias

    The interaction of two identical polar neutral molecules is modeled by two equal but oppositely charged point particles at a fixed distance of sep- aration. The total Coulomb potential energy of this system is calculated as a function of this dis- tance, x, and the distance, y, between their cen- ters of mass. We find that when the ...

  4. Dielectric relaxation phenomena of rigid polar liquid molecules ...

    Indian Academy of Sciences (India)

    journal of. October 2001 physics pp. 775–793. Dielectric relaxation phenomena of rigid polar liquid molecules under giga hertz electric field. K DUTTA, S K SIT and S ... BDH, England, n-hexane and n-heptane from M/s. E Merck ... used in medicine as drug to induce sleep and relieve pain and in the manufacture of D.D.T..

  5. Dielectric relaxation phenomena of rigid polar liquid molecules ...

    Indian Academy of Sciences (India)

    The dielectric relaxation phenomena of rigid polar liquid molecules chloral and ethyltrichloroacetate () in benzene, -hexane and -heptane () under 4.2, 9.8 and 24.6 GHz electric fields at 30°C are studied to show the possible existence of double relaxation times 2 and 1 for rotations of the whole and the flexible ...

  6. Do Identical Polar Diatomic Molecules Form Stacked or Linear ...

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 19; Issue 8. Do Identical Polar Diatomic Molecules Form Stacked or Linear Dimers?: Hydrogen Bonding is Not Just Dipole-Dipole Interactions. C W Williams Richard N Zare E Arunan. General Article Volume 19 Issue 8 August 2014 pp 704-712 ...

  7. Fermi liquid of two-dimensional polar molecules

    NARCIS (Netherlands)

    Lu, Z.K; Shlyapnikov, G.V.

    2012-01-01

    We study Fermi-liquid properties of a weakly interacting two-dimensional gas of single-component fermionic polar molecules with dipole moments d oriented perpendicularly to the plane of their translational motion. This geometry allows the minimization of inelastic losses due to chemical reactions

  8. Effect of dipole polarizability on positron binding by strongly polar molecules

    International Nuclear Information System (INIS)

    Gribakin, G F; Swann, A R

    2015-01-01

    A model for positron binding to polar molecules is considered by combining the dipole potential outside the molecule with a strongly repulsive core of a given radius. Using existing experimental data on binding energies leads to unphysically small core radii for all of the molecules studied. This suggests that electron–positron correlations neglected in the simple model play a large role in determining the binding energy. We account for these by including the polarization potential via perturbation theory and non-perturbatively. The perturbative model makes reliable predictions of binding energies for a range of polar organic molecules and hydrogen cyanide. The model also agrees with the linear dependence of the binding energies on the polarizability inferred from the experimental data (Danielson et al 2009 J. Phys. B: At. Mol. Opt. Phys. 42 235203). The effective core radii, however, remain unphysically small for most molecules. Treating molecular polarization non-perturbatively leads to physically meaningful core radii for all of the molecules studied and enables even more accurate predictions of binding energies to be made for nearly all of the molecules considered. (paper)

  9. Molecular simulation of polar molecules interaction with MOFs family materials

    International Nuclear Information System (INIS)

    De Toni, M.

    2012-01-01

    The topic of this thesis is the adsorption of simple molecular fluids in nano-porous materials. Many industrial processes are based on this phenomenon, including ionic exchange, selective separation and heterogeneous catalysis. I used molecular simulation to study the adsorption properties of polar molecules of industrial interest (CO 2 and H 2 O) in a new class of crystalline microporous hybrid organic-inorganic materials called Metal-Organic Frameworks (MOFs). They have exceptional adsorption properties due to their topological variety and their versatility, allowed by the large range of possibilities offered by organic and coordination chemistry and functionalizations. I first studied the adsorption of CO 2 in a family of materials called IRMOFs, which share the same topology but have different porous volume, in order to characterize the effect of confinement on their adsorption performance. In particular, a general behavior has been highlighted: the critical temperature decreases when the confinement increases. Then, I looked at a recently synthesized cationic MOF called Zn2(CBTACN). After having localized the extra-framework halogen anions in the unit cell of the material, something which was not possible experimentally, I characterized CO 2 adsorption in this system first as a pure gas and then as a component of different mixtures. Finally, I was interested in the hydrothermal stability of MOFs, a crucial issue for their use in industrial applications. I observed the hydration mechanism of system that is analogous to the MOF-5 (IRMOF-0h) and shed light on some collaborative effects of the attack of water that were unknown to in the literature. (author)

  10. Polarization response of clathrate hydrates capsulated with guest molecules

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Qun; Li, Jinshan, E-mail: ljs915@263.net, E-mail: myang@scu.edu.cn; Huang, Hui [Institute of Chemical Materials, China Academy of Engineering Physics (CAEP), Mianyang 621900 (China); Wang, Xinqin; Yang, Mingli, E-mail: ljs915@263.net, E-mail: myang@scu.edu.cn [Institute of Atomic and Molecular Physics, Key Laboratory of High Energy Density Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610065 (China)

    2016-05-28

    Clathrate hydrates are characterized by their water cages encapsulating various guest atoms or molecules. The polarization effect of these guest-cage complexes was studied with combined density functional theory and finite-field calculations. An addition rule was noted for these systems whose total polarizability is approximately equal to the polarizability sum of the guest and the cage. However, their distributional polarizability computed with Hirshfeld partitioning scheme indicates that the guest–cage interaction has considerable influence on their polarization response. The polarization of encapsulated guest is reduced while the polarization of water cage is enhanced. The counteraction of these two opposite effects leads to the almost unchanged total polarizability. Further analysis reveals that the reduced polarizability of encapsulated guest results from the shielding effect of water cage against the external field and the enhanced polarizability of water cage from the enhanced bonding of hydrogen bonds among water molecules. Although the charge transfer through the hydrogen bonds is rather small in the water cage, the polarization response of clathrate hydrates is sensitive to the changes of hydrogen bonding strength. The guest encapsulation strengthens the hydrogen bonding network and leads to enhanced polarizability.

  11. Simulating electric field interactions with polar molecules using spectroscopic databases.

    Science.gov (United States)

    Owens, Alec; Zak, Emil J; Chubb, Katy L; Yurchenko, Sergei N; Tennyson, Jonathan; Yachmenev, Andrey

    2017-03-24

    Ro-vibrational Stark-associated phenomena of small polyatomic molecules are modelled using extensive spectroscopic data generated as part of the ExoMol project. The external field Hamiltonian is built from the computed ro-vibrational line list of the molecule in question. The Hamiltonian we propose is general and suitable for any polar molecule in the presence of an electric field. By exploiting precomputed data, the often prohibitively expensive computations associated with high accuracy simulations of molecule-field interactions are avoided. Applications to strong terahertz field-induced ro-vibrational dynamics of PH 3 and NH 3 , and spontaneous emission data for optoelectrical Sisyphus cooling of H 2 CO and CH 3 Cl are discussed.

  12. Three dimensional alignment of molecules using elliptically polarized laser fields

    DEFF Research Database (Denmark)

    Larsen, J.J.; Bjerre, N.; Hald, K.

    2000-01-01

    We demonstrate, theoretically and experimentally, that an intense, elliptically polarized, nonresonant laser field can simultaneously force all three axes of a molecule to align along given axes fixed in space, thus inhibiting the free rotation in all three Euler angles. Theoretically, the effect...... is illustrated through time dependent quantum mechanical calculations. Experimentally, 3, 4-dibromothiophene molecules are aligned with a nanosecond laser pulse. The alignment is probed by 2D ion imaging of the fragments from a 20 fs laser pulse induced Coulomb explosion....

  13. High-order harmonic generation from polar molecules

    DEFF Research Database (Denmark)

    Etches, Adam

    When a molecule is submitted to a very intense laser pulse it emits coherent bursts of light in each optical half-cycle of the laser field. This process is known as high-order harmonic generation because the spectrum consists of many peaks at energies corresponding to an integer amount of laser...... generation is extended to polar molecules by including the laser-induced Stark shift of each molecular orbitals. The Stark shift is shown to have a major influence on the relative strength of harmonic bursts in neighbouring half-cycles, as well as leaving an imprint on the phase of the harmonics...

  14. Dielectric relaxation phenomena of rigid polar liquid molecules ...

    Indian Academy of Sciences (India)

    Abstract. The dielectric relaxation phenomena of rigid polar liquid molecules chloral and ethyl- trichloroacetate (j) in benzene, n-hexane and n-heptane (i) under 4.2, 9.8 and 24.6 GHz electric fields at 30ÆC are studied to show the possible existence of double relaxation times τ2 and τ1 for rotations of the whole and the ...

  15. Chip-based microtrap arrays for cold polar molecules

    Science.gov (United States)

    Hou, Shunyong; Wei, Bin; Deng, Lianzhong; Yin, Jianping

    2017-12-01

    Compared to the atomic chip, which has been a powerful platform to perform an astonishing range of applications from rapid Bose-Einstein condensate (BEC) production to the atomic clock, the molecular chip is only in its infant stages. Recently a one-dimensional electric lattice was demonstrated to trap polar molecules on a chip. This excellent work opens up the way to building a molecular chip laboratory. Here we propose a two-dimensional (2D) electric lattice on a chip with concise and robust structure, which is formed by arrays of squared gold wires. Arrays of microtraps that originate in the microsize electrodes offer a steep gradient and thus allow for confining both light and heavy polar molecules. Theoretical analysis and numerical calculations are performed using two types of sample molecules, N D3 and SrF, to justify the possibility of our proposal. The height of the minima of the potential wells is about 10 μm above the surface of the chip and can be easily adjusted in a wide range by changing the voltages applied on the electrodes. These microtraps offer intriguing perspectives for investigating cold molecules in periodic potentials, such as quantum computing science, low-dimensional physics, and some other possible applications amenable to magnetic or optical lattice. The 2D adjustable electric lattice is expected to act as a building block for a future gas-phase molecular chip laboratory.

  16. Far-from-Equilibrium Quantum Magnetism with Ultracold Polar Molecules

    Science.gov (United States)

    Hazzard, Kaden R. A.; Manmana, Salvatore R.; Foss-Feig, Michael; Rey, Ana Maria

    2013-02-01

    Recent theory has indicated how to emulate tunable models of quantum magnetism with ultracold polar molecules. Here we show that present molecule optical lattice experiments can accomplish three crucial goals for quantum emulation, despite currently being well below unit filling and not quantum degenerate. The first is to verify and benchmark the models proposed to describe these systems. The second is to prepare correlated and possibly useful states in well-understood regimes. The third is to explore many-body physics inaccessible to existing theoretical techniques. Our proposal relies on a nonequilibrium protocol that can be viewed either as Ramsey spectroscopy or an interaction quench. The proposal uses only routine experimental tools available in any ultracold molecule experiment. To obtain a global understanding of the behavior, we treat short times pertubatively, develop analytic techniques to treat the Ising interaction limit, and apply a time-dependent density matrix renormalization group to disordered systems with long range interactions.

  17. POLAR ORGANIC CHEMICAL INTEGRATIVE SAMPLING ...

    Science.gov (United States)

    The purpose of the research presented in this paper is two-fold: (1) to demonstrate the 4 coupling of two state-of-the-art techniques: a time-weighted polar organic integrative sampler (POCIS) and micro-liquid chromatography-electrospray/ion trap mass spectrometry (u-LC-6 ES/ITMS); and (2) the assessment of these methodologies in a real-world environment -wastewater effluent - for detecting six drugs (four prescription and two illicit). In the effluent from three wastewater treatment plants (WWTP), azithromycin was detected at concentrations ranging from 15ng/L to 66ng/L, equivalent to the total annual release of 0.4 -4 kg into the receiving waters. Detected and confirmed in the effluent from two WWTPs were two illicit drugs methamphetamine and methylenedioxymethamphetamine (MDMA), at 2ng/L and 0.5ng/L, respectively. While the ecotoxicological significance of drugs in environmental matrices, particularly water, has not been closely examined, it can only be surmised that these substances have the potential to adversely affect biota that are continuously exposed to them even at very low levels. The potential for chronic affects on human health is also unknown, but of increasing concern due to the multi use character of water, particularly in densely populated arid areas. The research focused on in the subtasks is the development and application of state-of the-art technologies to meet the needs of the public, Office of Water, and ORD in the area of Water Quality

  18. Characterization of Interstellar Organic Molecules

    Data.gov (United States)

    National Aeronautics and Space Administration — Understanding the origins of life has been one of the greatest dreams throughout history. It is now known that star-forming regions contain complex organic...

  19. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    IAS Admin

    books on organic pigments and dyes and retains its popularity as a blue dye. ... Blue is a popular colour as it is cool and calming. During the 16th century, Germany banned the import of indigo to protect the dye locally produced from woad. .... This pigment, variously known as Tyrian purple, Royal purple,. Imperial purple ...

  20. Fascinating Organic Molecules from Nature

    Indian Academy of Sciences (India)

    IAS Admin

    The story of curare has elements of social and cultural history of the indigenous people of the Orinoco and Amazon river basins of. South America as well as strands from classical organic chemis- try and physiology. Eminent scientists including Sir Henry Dale,. Paul Karrer and H Wieland have made significant contributions.

  1. Tunable disorder in a crystal of cold polar molecules

    International Nuclear Information System (INIS)

    Herrera, Felipe; Krems, Roman V.; Litinskaya, Marina

    2010-01-01

    We show that a two-species mixture of polar molecules trapped on an optical lattice gives rise to a system of rotational excitons in the presence of tunable impurities. The exciton-impurity interactions can be controlled by an external electric field, which can be exploited for quantum simulation of localization phenomena in disordered media. We demonstrate that an external electric field can be used to induce resonant enhancement of the exciton-impurity scattering cross sections and delocalization of excitonic states in a correlated one-dimensional disorder potential.

  2. Polarization and ellipticity of high-order harmonics from aligned molecules generated by linearly polarized intense laser pulses

    International Nuclear Information System (INIS)

    Le, Anh-Thu; Lin, C. D.; Lucchese, R. R.

    2010-01-01

    We present theoretical calculations for polarization and ellipticity of high-order harmonics from aligned N 2 , CO 2 , and O 2 molecules generated by linearly polarized lasers. Within the rescattering model, the two polarization amplitudes of the harmonics are determined by the photo-recombination amplitudes for photons emitted with polarization parallel or perpendicular to the direction of the same returning electron wave packet. Our results show clear species-dependent polarization states, in excellent agreement with experiments. We further note that the measured polarization ellipse of the harmonic furnishes the needed parameters for a 'complete' experiment in molecules.

  3. Inducing elliptically polarized high-order harmonics from aligned molecules with linearly polarized femtosecond pulses

    DEFF Research Database (Denmark)

    Etches, Adam; Madsen, Christian Bruun; Madsen, Lars Bojer

    2010-01-01

    A recent paper reported elliptically polarized high-order harmonics from aligned N2 using a linearly polarized driving field [X. Zhou et al., Phys. Rev. Lett. 102, 073902 (2009)]. This observation cannot be explained in the standard treatment of the Lewenstein model and has been ascribed to many...... of additional contributions, which can be interpreted as quantum orbits in which the active electron is ionized at one atomic center within the molecule and recombines at another. The associated exchange harmonics are responsible for the nonvanishing ellipticity and result from a correlation between...... the ionization site and the recombination site in high-order harmonic generation....

  4. Our Galactic Neighbor Hosts Complex Organic Molecules

    Science.gov (United States)

    Hensley, Kerry

    2018-03-01

    For the first time, data from the Atacama Large Millimeter/submillimeter Array (ALMA) reveal the presence of methyl formate and dimethyl ether in a star-forming region outside our galaxy. This discovery has important implications for the formation and survival of complex organic compounds importantfor the formation of life in low-metallicity galaxies bothyoung and old.No Simple Picture of Complex Molecule FormationALMA, pictured here with the Magellanic Clouds above, has observed organic molecules in our Milky Way Galaxy and beyond. [ESO/C. Malin]Complex organic molecules (those with at least six atoms, one or more of which must be carbon) are the precursors to the building blocks of life. Knowing how and where complex organic molecules can form is a key part of understanding how life came to be on Earth and how it might arise elsewhere in the universe. From exoplanet atmospheres to interstellar space, complex organic molecules are ubiquitous in the Milky Way.In our galaxy, complex organic molecules are often found in the intense environments of hot cores clumps of dense molecular gas surrounding the sites of star formation. However, its not yet fully understood how the complex organic molecules found in hot cores come to be. One possibility is that the compounds condense onto cold dust grains long before the young stars begin heating their natal shrouds. Alternatively, they might assemble themselves from the hot, dense gas surrounding the blazing protostars.Composite infrared and optical image of the N 113 star-forming region in the LMC. The ALMA coverage is indicated by the gray line. Click to enlarge. [Sewio et al. 2018]Detecting Complexity, a Galaxy AwayUsing ALMA, a team of researchers led by Marta Sewio (NASA Goddard Space Flight Center) recently detected two complex organic molecules methyl formate and dimethyl ether for the first time in our neighboring galaxy, the Large Magellanic Cloud (LMC). Previous searches for organic molecules in the LMC detected

  5. 3D-Printed Beam Splitter for Polar Neutral Molecules

    Science.gov (United States)

    Gordon, Sean D. S.; Osterwalder, Andreas

    2017-04-01

    We describe a macroscopic beam splitter for polar neutral molecules. A complex electrode structure is required for the beam splitter which would be very difficult to produce with traditional manufacturing methods. Instead, we make use of a nascent manufacturing technique: 3D printing of a plastic piece, followed by electroplating. This fabrication method opens a plethora of avenues for research, since 3D printing imposes practically no limitations on possible shapes, and the plating produces chemically robust, conductive construction elements with an almost free choice of surface material. It has the added advantage of dramatically reduced production cost and time. Our beam splitter is an electrostatic hexapole guide that smoothly transforms into two bent quadrupoles. We demonstrate the correct functioning of this device by separating a supersonic molecular beam of ND3 into two correlated fractions. It is shown that this device can be used to implement experiments with differential detection wherein one of the fractions serves as a probe and the other as a reference. Reverse operation would allow the merging of two beams of polar neutral molecules.

  6. Organic- and molecule-based magnets

    Indian Academy of Sciences (India)

    The discovery of organic- and molecule-based magnets has led to design and synthesis of several families with magnetic ordering temperatures as high as ∼ 125° C. Examples of soft and hard magnets with coercivities as high as 27 kOe have also been reported. Examples from our laboratory of organic-based magnets ...

  7. Organic-and molecule-based magnets

    Indian Academy of Sciences (India)

    The discovery of organic- and molecule-based magnets has led to design and synthesis of several families with magnetic ordering temperatures as high as ∼ 125° C. Examples of soft and hard magnets with coercivities as high as 27 kOe have also been reported. Examples from our laboratory of organic-based magnets ...

  8. Spectral simulations of polar diatomic molecules immersed in He clusters: application to the ICl (X) molecule

    Energy Technology Data Exchange (ETDEWEB)

    Villarreal, P [Instituto de Matematicas y Fasica Fundamental (CSIC), Serrano 123, E-28006-Madrid (Spain); Lara-Castells, M P de [Instituto de Matematicas y Fasica Fundamental (CSIC), Serrano 123, E-28006-Madrid (Spain); Prosmiti, R [Instituto de Matematicas y Fasica Fundamental (CSIC), Serrano 123, E-28006-Madrid (Spain); Delgado-Barrio, G [Instituto de Matematicas y Fasica Fundamental (CSIC), Serrano 123, E-28006-Madrid (Spain); Lopez-Duran, D [Instituto de Matematicas y Fasica Fundamental (CSIC), Serrano 123, E-28006-Madrid (Spain); Gianturco, F A [Department of Chemistry and INFM, The University of Rome, Citta Universitaria, 00185, Rome (Italy); Jellinek, J [Chemistry Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2007-09-15

    A recently developed quantum-chemistry-like methodology to study molecules solvated in atomic clusters is applied to the ICl (iodine chloride) polar diatomic molecule immersed in clusters of He atoms. The atoms of the solvent clusters are treated as the 'electrons' and the solvated molecule as a structured 'nucleus' of the combined solvent-solute system. The helium-helium and helium-dopant interactions are represented by parametrized two-body and ab initio three-body potentials, respectively. The ground-state wavefunctions are used to compute the infrared (IR) spectra of the solvated molecule. In agreement with the experimental observations, the computed spectra exhibit considerable differences depending on whether the solvent cluster is comprised of bosonic ({sup 4}He) or fermionic ({sup 3}He) atoms. The source of these differences is attributed to the different spin-statistics of the solvent clusters. The bosonic versus fermionic nature of the solvent is reflected in the IR absorption selection rules. Only P and R branches with single state transitions appear in the spectrum when the molecule is solvated in a bosonic cluster. On the other hand, when the solvent represents a fermionic environment, quasi-degenerate multiplets of spin states contribute to each branch and, in addition, the Q-branch becomes also allowed. Combined, these two factors explain the more congested nature of the spectrum in the fermionic case.

  9. Spectral simulations of polar diatomic molecules immersed in He clusters: application to the ICl (X) molecule

    International Nuclear Information System (INIS)

    Villarreal, P; Lara-Castells, M P de; Prosmiti, R; Delgado-Barrio, G; Lopez-Duran, D; Gianturco, F A; Jellinek, J

    2007-01-01

    A recently developed quantum-chemistry-like methodology to study molecules solvated in atomic clusters is applied to the ICl (iodine chloride) polar diatomic molecule immersed in clusters of He atoms. The atoms of the solvent clusters are treated as the 'electrons' and the solvated molecule as a structured 'nucleus' of the combined solvent-solute system. The helium-helium and helium-dopant interactions are represented by parametrized two-body and ab initio three-body potentials, respectively. The ground-state wavefunctions are used to compute the infrared (IR) spectra of the solvated molecule. In agreement with the experimental observations, the computed spectra exhibit considerable differences depending on whether the solvent cluster is comprised of bosonic ( 4 He) or fermionic ( 3 He) atoms. The source of these differences is attributed to the different spin-statistics of the solvent clusters. The bosonic versus fermionic nature of the solvent is reflected in the IR absorption selection rules. Only P and R branches with single state transitions appear in the spectrum when the molecule is solvated in a bosonic cluster. On the other hand, when the solvent represents a fermionic environment, quasi-degenerate multiplets of spin states contribute to each branch and, in addition, the Q-branch becomes also allowed. Combined, these two factors explain the more congested nature of the spectrum in the fermionic case

  10. Beam broadening of polar molecules and clusters in deflection experiments.

    Science.gov (United States)

    Bulthuis, J; Kresin, V V

    2012-01-07

    A beam of rotating dipolar particles (molecules or clusters) will broaden when passed through an electric or magnetic field gradient region. This broadening, which is a common experimental observable, can be expressed in terms of the variance of the distribution of the resulting polarization orientation (the direction cosine). Here, the broadening for symmetric-top and linear rotors is discussed. These two types of rotors have qualitatively different low-field orientation distribution functions, but behave similarly in a strong field. While analytical expressions for the polarization variance can be derived from first-order perturbation theory, for experimental guidance it is important to identify the applicability and limitations of these expressions, and the general dependence of the broadening on the experimental parameters. For this purpose, the analytical results are compared with the full diagonalization of the rotational Stark-effect matrices. Conveniently for experimental estimations, it is found that for symmetric tops, the dependence of the broadening parameter on the rotational constant, the axial ratio, and the field strength remains similar to the analytical expression even outside of the perturbative regime. Also, it is observed that the shape envelope, the centroid, and the width of the orientation distribution function for a symmetric top are quite insensitive to the value of its rotational constant (except at low rotational temperatures).

  11. Spin-orbital dynamics in a system of polar molecules

    Science.gov (United States)

    Syzranov, Sergey V.; Wall, Michael L.; Gurarie, Victor; Rey, Ana Maria

    2014-11-01

    Spin-orbit coupling in solids normally originates from the electron motion in the electric field of the crystal. It is key to understanding a variety of spin-transport and topological phenomena, such as Majorana fermions and recently discovered topological insulators. Implementing and controlling spin-orbit coupling is thus highly desirable and could open untapped opportunities for the exploration of unique quantum physics. Here we show that dipole-dipole interactions can produce an effective spin-orbit coupling in two-dimensional ultracold polar molecule gases. This spin-orbit coupling generates chiral excitations with a non-trivial Berry phase 2π. These excitations, which we call chirons, resemble low-energy quasiparticles in bilayer graphene and emerge regardless of the quantum statistics and for arbitrary ratios of kinetic to interaction energies. Chirons manifest themselves in the dynamics of the spin density profile, spin currents and spin coherences, even for molecules pinned in a deep optical lattice and should be observable in current experiments.

  12. Engineering and control of cold molecules. Making manipulating and exploiting ultra-cold polar molecules

    International Nuclear Information System (INIS)

    Bigelow, N.P.; Haimberger, C.; Kleinert, J.; Tscherneck, M.; Holmes, M.E.

    2005-01-01

    In the last 12 months several groups have demonstrated the use of photo association to create cold heteronuclear (polar) molecules. We report on the formation of translationally cold NaCs molecules starting from a laser-cooled atomic vapor of Na and Cs atoms. Colliding atoms are transferred into bound molecular states in a two-step photoactivated process. We find a translational temperature of T ≅ 260 mK. To increase the density and number of trapped atoms, dark-spot techniques are used on the MOT and a Zeeman slowed sodium beam is used to load the sodium atoms into the trap. Spectroscopy of these molecules is underway using time-of-flight ion detection and trap-loss. Initial REMPI measurements indicate that both singlet and triplet states are being populated by the spontaneous-decay driven process. We measure a rate constant for molecule formation of K NaCs = 7.43 · 10 15 cm 3 s -1 . (author)

  13. Molecule Matters-Metal Organic Frameworks (MOFs)

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 12; Issue 11. Molecule Matters - Metal Organic Frameworks (MOFs). R Sarvanakumar S Sankararaman ... Author Affiliations. R Sarvanakumar1 S Sankararaman1. Department of Chemistry, Indian Institute of Technology, Madras, Chennai 600036, India.

  14. Organic molecules with abnormal geometric parameters

    International Nuclear Information System (INIS)

    Komarov, Igor V

    2001-01-01

    Organic molecules, the structural parameters of which (carbon-carbon bond lengths, bond and torsion angles) differ appreciably from the typical most frequently encountered values, are discussed. Using many examples of 'record-breaking' molecules, the limits of structural distortions in carbon compounds and their unusual chemical properties are demonstrated. Particular attention is devoted to strained compounds not yet synthesised whose properties have been predicted using quantum-chemical calculations. Factors that ensure the stability of such compounds are outlined. The bibliography includes 358 references.

  15. Electron and positron collisions with polar molecules: studies with the benchmark water molecule

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Rui; Tennyson, Jonathan [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Faure, Alexandre [Laboratoire d' Astrophysique, UMR 5571 CNRS, Universite Joseph-Fourier, BP 53, 38041 Grenoble cedex 09 (France)], E-mail: j.tennyson@ucl.ac.uk

    2009-07-15

    It is difficult to measure low-energy cross sections for collisions of charged particles with strongly dipolar systems since the magnitude of such cross sections is completely dominated by collisions in the forward direction. Theoretically, it is possible to account for the strong forward scattering using the Born approximation but the procedure for combining Born 'top-up' with the more sophisticated treatments required to treat the scattering in other directions is not unique. This comment describes recent progress in describing both electron and positron collisions with polar molecules taking the important water molecule as a benchmark. Previous calculations on electron water at collision energies below 7 eV are compared with new experiments. Positron water studies up to 10 eV are re-analysed based on given experimental acceptance profiles, which depend on the details of the apparatus and method used in the measurements. It is suggested that theory is capable of giving reliable results for elastic and rotationally inelastic electron/positron collisions with strongly dipolar species.

  16. Polarization properties of below-threshold harmonics from aligned molecules H2+ in linearly polarized laser fields.

    Science.gov (United States)

    Dong, Fulong; Tian, Yiqun; Yu, Shujuan; Wang, Shang; Yang, Shiping; Chen, Yanjun

    2015-07-13

    We investigate the polarization properties of below-threshold harmonics from aligned molecules in linearly polarized laser fields numerically and analytically. We focus on lower-order harmonics (LOHs). Our simulations show that the ellipticity of below-threshold LOHs depends strongly on the orientation angle and differs significantly for different harmonic orders. Our analysis reveals that this LOH ellipticity is closely associated with resonance effects and the axis symmetry of the molecule. These results shed light on the complex generation mechanism of below-threshold harmonics from aligned molecules.

  17. Organization of central synapses by adhesion molecules.

    Science.gov (United States)

    Tallafuss, Alexandra; Constable, John R L; Washbourne, Philip

    2010-07-01

    Synapses are the primary means for transmitting information from one neuron to the next. They are formed during the development of the nervous system, and the formation of appropriate synapses is crucial for the establishment of neuronal circuits that underlie behavior and cognition. Understanding how synapses form and are maintained will allow us to address developmental disorders such as autism, mental retardation and possibly also psychological disorders. A number of biochemical and proteomic studies have revealed a diverse and vast assortment of molecules that are present at the synapse. It is now important to untangle this large array of proteins and determine how it assembles into a functioning unit. Here we focus on recent reports describing how synaptic cell adhesion molecules interact with and organize the presynaptic and postsynaptic specializations of both excitatory and inhibitory central synapses. © The Authors (2010). Journal Compilation © Federation of European Neuroscience Societies and Blackwell Publishing Ltd.

  18. Evidence for Nuclear Tensor Polarization of Deuterium Molecules in Storage Cells

    International Nuclear Information System (INIS)

    van den Brand, J.; Bulten, H.; Zhou, Z.; Unal, O.; van den Brand, J.; Ferro-Luzzi, M.; Botto, T.; Bouwhuis, M.; Heimberg, P.; de Jager, C.; de Lange, D.; Nooren, G.; Papadakis, N.; Passchier, I.; Poolman, H.; Steijger, J.; Vodinas, N.; de Vries, H.; van den Brand, J.; Ferro-Luzzi, M.; Lang, J.; Alarcon, R.; Dolfini, S.; Ent, R.; Higinbotham, D.

    1997-01-01

    Deuterium molecules were obtained by recombination, on a copper surface, of deuterium atoms prepared in specific hyperfine states. The molecules were stored for about 5ms in an open-ended cylindrical cell, placed in a 23mT magnetic field, and their tensor polarization was measured by elastic scattering of 704MeV electrons. The results of the measurements are consistent with the deuterium molecules retaining the tensor polarization of the initial atoms. copyright 1997 The American Physical Society

  19. Quantum interference experiments with complex organic molecules

    International Nuclear Information System (INIS)

    Eibenberger, S. I.

    2015-01-01

    Matter-wave interference with complex particles is a thriving field in experimental quantum physics. The quest for testing the quantum superposition principle with highly complex molecules has motivated the development of the Kapitza-Dirac-Talbot-Lau interferometer (KDTLI). This interferometer has enabled quantum interference with large organic molecules in an unprecedented mass regime. In this doctoral thesis I describe quantum superposition experiments which we were able to successfully realize with molecules of masses beyond 10 000 amu and consisting of more than 800 atoms. The typical de Broglie wavelengths of all particles in this thesis are in the order of 0.3-5 pm. This is significantly smaller than any molecular extension (nanometers) or the delocalization length in our interferometer (hundreds of nanometers). Many vibrational and rotational states are populated since the molecules are thermally highly excited (300-1000 K). And yet, high-contrast quantum interference patterns could be observed. The visibility and position of these matter-wave interference patterns is highly sensitive to external perturbations. This sensitivity has opened the path to extensive studies of the influence of internal molecular properties on the coherence of their associated matter waves. In addition, it enables a new approach to quantum-assisted metrology. Quantum interference imprints a high-contrast nano-structured density pattern onto the molecular beam which allows us to resolve tiny shifts and dephasing of the molecular beam. I describe how KDTL interferometry can be used to investigate a number of different molecular properties. We have studied vibrationally-induced conformational changes of floppy molecules and permanent electric dipole moments using matter-wave deflectometry in an external electric field. We have developed a new method for optical absorption spectroscopy which uses the recoil of the molecules upon absorption of individual photons. This allows us to

  20. [Progress in sample preparation and analytical methods for trace polar small molecules in complex samples].

    Science.gov (United States)

    Zhang, Qianchun; Luo, Xialin; Li, Gongke; Xiao, Xiaohua

    2015-09-01

    Small polar molecules such as nucleosides, amines, amino acids are important analytes in biological, food, environmental, and other fields. It is necessary to develop efficient sample preparation and sensitive analytical methods for rapid analysis of these polar small molecules in complex matrices. Some typical materials in sample preparation, including silica, polymer, carbon, boric acid and so on, are introduced in this paper. Meanwhile, the applications and developments of analytical methods of polar small molecules, such as reversed-phase liquid chromatography, hydrophilic interaction chromatography, etc., are also reviewed.

  1. Measurement of the nuclear polarization of hydrogen and deuterium molecules using a Lamb-shift polarimeter

    Energy Technology Data Exchange (ETDEWEB)

    Engels, Ralf, E-mail: r.w.engels@fz-juelich.de; Gorski, Robert; Grigoryev, Kiril; Mikirtychyants, Maxim; Rathmann, Frank; Seyfarth, Hellmut; Ströher, Hans; Weiss, Philipp [Institut für Kernphysik, Forschungszentrum Jülich, Wilhelm-Johnen-Str. 1, 52428 Jülich (Germany); Kochenda, Leonid; Kravtsov, Peter; Trofimov, Viktor; Tschernov, Nikolay; Vasilyev, Alexander; Vznuzdaev, Marat [Laboratory of Cryogenic and Superconductive Technique, Petersburg Nuclear Physics Institute, Orlova Roscha 1, 188300 Gatchina (Russian Federation); Schieck, Hans Paetz gen. [Institut für Kernphysik, Universität zu Köln, Zülpicher Str. 77, 50937 Köln (Germany)

    2014-10-15

    Lamb-shift polarimeters are used to measure the nuclear polarization of protons and deuterons at energies of a few keV. In combination with an ionizer, the polarization of hydrogen and deuterium atoms was determined after taking into account the loss of polarization during the ionization process. The present work shows that the nuclear polarization of hydrogen or deuterium molecules can be measured as well, by ionizing the molecules and injecting the H{sub 2}{sup +} (or D{sub 2}{sup +}) ions into the Lamb-shift polarimeter.

  2. Imaging and manipulation of a polar molecule on Ag(111)

    DEFF Research Database (Denmark)

    Lin, R.; Braun, K.F.; Tang, H.

    2001-01-01

    A scanning tunneling microscope (STM) was applied to image and laterally manipulate isolated phosphangulene molecules on Ag(111) at 6 K. Atomic-resolution images clearly revealed three characteristic types of appearances (three-lobed, fish and bump shape) for the adsorbed molecules, which could...... correspond to three distinct binding configurations. From a detailed analysis of the relative distance between neighboring three-lobed molecules we determine the adsorption site. Applying the lateral manipulation technique ws demonstrate that the molecule can be pulled, slid or pushed by the tip...... on the surface. Accompanying with the reposition, molecular rotation and/or changing of binding configurations can also be induced. It is found that the dipole moment of the molecule has minor effects on its lateral movement. The results demonstrate that due to many degrees of freedom for large molecules...

  3. Imaging and manipulation of a polar molecule oil Ag(111)

    DEFF Research Database (Denmark)

    Lin, Rong; Braun, K.F.; Tang, H.

    2001-01-01

    A scanning tunneling microscope (STM) was applied to image and laterally manipulate isolated phosphangulene molecules on Ag(111) at 6 K. Atomic-resolution images clearly revealed three characteristic types of appearances (three-lobed, fish and bump shape) for the adsorbed molecules, which could...... correspond to three distinct binding configurations. From a detailed analysis of the relative distance between neighboring three-lobed molecules we determine the adsorption site. Applying the lateral manipulation technique ws demonstrate that the molecule can be pulled, slid or pushed by the tip...... on the surface. Accompanying with the reposition, molecular rotation and/or changing of binding configurations can also be induced. It is found that the dipole moment of the molecule has minor effects on its lateral movement. The results demonstrate that due to many degrees of freedom for large molecules...

  4. A Density-Dependent Switch Drives Stochastic Clustering and Polarization of Signaling Molecules

    Science.gov (United States)

    Jilkine, Alexandra; Angenent, Sigurd B.; Wu, Lani F.; Altschuler, Steven J.

    2011-01-01

    Positive feedback plays a key role in the ability of signaling molecules to form highly localized clusters in the membrane or cytosol of cells. Such clustering can occur in the absence of localizing mechanisms such as pre-existing spatial cues, diffusional barriers, or molecular cross-linking. What prevents positive feedback from amplifying inevitable biological noise when an un-clustered “off” state is desired? And, what limits the spread of clusters when an “on” state is desired? Here, we show that a minimal positive feedback circuit provides the general principle for both suppressing and amplifying noise: below a critical density of signaling molecules, clustering switches off; above this threshold, highly localized clusters are recurrently generated. Clustering occurs only in the stochastic regime, suggesting that finite sizes of molecular populations cannot be ignored in signal transduction networks. The emergence of a dominant cluster for finite numbers of molecules is partly a phenomenon of random sampling, analogous to the fixation or loss of neutral mutations in finite populations. We refer to our model as the “neutral drift polarity model.” Regulating the density of signaling molecules provides a simple mechanism for a positive feedback circuit to robustly switch between clustered and un-clustered states. The intrinsic ability of positive feedback both to create and suppress clustering is a general mechanism that could operate within diverse biological networks to create dynamic spatial organization. PMID:22102805

  5. A density-dependent switch drives stochastic clustering and polarization of signaling molecules.

    Directory of Open Access Journals (Sweden)

    Alexandra Jilkine

    2011-11-01

    Full Text Available Positive feedback plays a key role in the ability of signaling molecules to form highly localized clusters in the membrane or cytosol of cells. Such clustering can occur in the absence of localizing mechanisms such as pre-existing spatial cues, diffusional barriers, or molecular cross-linking. What prevents positive feedback from amplifying inevitable biological noise when an un-clustered "off" state is desired? And, what limits the spread of clusters when an "on" state is desired? Here, we show that a minimal positive feedback circuit provides the general principle for both suppressing and amplifying noise: below a critical density of signaling molecules, clustering switches off; above this threshold, highly localized clusters are recurrently generated. Clustering occurs only in the stochastic regime, suggesting that finite sizes of molecular populations cannot be ignored in signal transduction networks. The emergence of a dominant cluster for finite numbers of molecules is partly a phenomenon of random sampling, analogous to the fixation or loss of neutral mutations in finite populations. We refer to our model as the "neutral drift polarity model." Regulating the density of signaling molecules provides a simple mechanism for a positive feedback circuit to robustly switch between clustered and un-clustered states. The intrinsic ability of positive feedback both to create and suppress clustering is a general mechanism that could operate within diverse biological networks to create dynamic spatial organization.

  6. Beam dynamics in a storage ring for neutral (polar) molecules

    International Nuclear Information System (INIS)

    Lambertson, Glen R.

    2003-01-01

    The force from a non-uniform electric field on the electric dipole moment of a molecule may be used to circulate and focus molecules in a storage ring. The nature of the forces from multipole electrodes for bending and focusing are described for strong-field-seeking and for weak-field-seeking molecules. Fringe-field forces are analyzed. Examples of storage ring designs are presented; these include long straight sections and provide bunching and acceleration

  7. Imaging and manipulation of a polar molecule oil Ag(111)

    DEFF Research Database (Denmark)

    Lin, Rong; Braun, K.F.; Tang, H.

    2001-01-01

    A scanning tunneling microscope (STM) was applied to image and laterally manipulate isolated phosphangulene molecules on Ag(111) at 6 K. Atomic-resolution images clearly revealed three characteristic types of appearances (three-lobed, fish and bump shape) for the adsorbed molecules, which could...

  8. Triton - Stratospheric molecules and organic sediments

    Science.gov (United States)

    Thompson, W. Reid; Singh, Sushil K.; Khare, B. N.; Sagan, Carl

    1989-01-01

    Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

  9. Mechanochemical synthesis of small organic molecules

    Directory of Open Access Journals (Sweden)

    Tapas Kumar Achar

    2017-09-01

    Full Text Available With the growing interest in renewable energy and global warming, it is important to minimize the usage of hazardous chemicals in both academic and industrial research, elimination of waste, and possibly recycle them to obtain better results in greener fashion. The studies under the area of mechanochemistry which cover the grinding chemistry to ball milling, sonication, etc. are certainly of interest to the researchers working on the development of green methodologies. In this review, a collection of examples on recent developments in organic bond formation reactions like carbon–carbon (C–C, carbon–nitrogen (C–N, carbon–oxygen (C–O, carbon–halogen (C–X, etc. is documented. Mechanochemical syntheses of heterocyclic rings, multicomponent reactions and organometallic molecules including their catalytic applications are also highlighted.

  10. Mechanochemical synthesis of small organic molecules.

    Science.gov (United States)

    Achar, Tapas Kumar; Bose, Anima; Mal, Prasenjit

    2017-01-01

    With the growing interest in renewable energy and global warming, it is important to minimize the usage of hazardous chemicals in both academic and industrial research, elimination of waste, and possibly recycle them to obtain better results in greener fashion. The studies under the area of mechanochemistry which cover the grinding chemistry to ball milling, sonication, etc. are certainly of interest to the researchers working on the development of green methodologies. In this review, a collection of examples on recent developments in organic bond formation reactions like carbon-carbon (C-C), carbon-nitrogen (C-N), carbon-oxygen (C-O), carbon-halogen (C-X), etc. is documented. Mechanochemical syntheses of heterocyclic rings, multicomponent reactions and organometallic molecules including their catalytic applications are also highlighted.

  11. Proposal for the formation of ultracold paramagnetic polar molecules

    Science.gov (United States)

    Dulieu, Olivier; Borsalino, Dimitri; Luc, Eliane; Bouloufa-Maafa, Nadia; Zuchowski, Piotr

    2016-05-01

    Alkali-alkaline-earth dimers, such as RbCa and RbSr, possess (in their ground electronic state) both a permanent magnetic and electric dipole moment in the molecular frame, allowing their manipulation with external fields at ultracold temperatures. Such molecules have been proposed as candidates for quantum simulators. We propose an efficient method combining a photoassociation step and a stimulated Raman process to create ultracold RbSr and RbCa molecules in their absolute ground state, suitable for studying dipolar interactions in quantum gases. Our model is based on new accurate quantum chemistry computations of potential energy surfaces of ground and excited molecular states and of relevant transition dipole moments of these molecules. The results are in good agreement with recent low-resolution spectroscopic data recorded with Helium nanodroplets.

  12. Polarization shaping of high-order harmonics in laser-aligned molecules

    Science.gov (United States)

    Skantzakis, E.; Chatziathanasiou, S.; Carpeggiani, P. A.; Sansone, G.; Nayak, A.; Gray, D.; Tzallas, P.; Charalambidis, D.; Hertz, E.; Faucher, O.

    2016-01-01

    The present work reports on the generation of short-pulse coherent extreme ultraviolet radiation of controlled polarization. The proposed strategy is based on high-order harmonics generated in pre-aligned molecules. Field-free molecular alignment produced by a short linearly-polarized infrared laser pulse is used to break the isotropy of a gas medium. Driving the aligned molecules by a circularly-polarized infrared pulse allows to transfer the anisotropy of the medium to the polarization of the generated harmonic light. The ellipticity of the latter is controlled by adjusting the angular distribution of the molecules at the time they interact with the driving pulse. Extreme ultraviolet radiation produced with high degree of ellipticity (close to circular) is demonstrated. PMID:27995974

  13. Organic small molecule semiconducting chromophores for use in organic electronic devices

    Energy Technology Data Exchange (ETDEWEB)

    Welch, Gregory C.; Hoven, Corey V.; Nguyen, Thuc-Quyen

    2018-02-13

    Small organic molecule semi-conducting chromophores containing a pyridalthiadiazole, pyridaloxadiazole, or pyridaltriazole core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

  14. Manipulation of organic polyradicals in a single-molecule transistor

    NARCIS (Netherlands)

    Fock, J.; Leijnse, M.; Jennum, K.; Zyazin, A.S.; Paaske, J.; Hedegard, P.; Brondsted Nielsen, M.; Van der Zant, H.S.J.

    2012-01-01

    Inspired by cotunneling spectroscopy of spin-states in a single OPE5-based molecule, we investigate the prospects for electric control of magnetism in purely organic molecules contacted in a three-terminal geometry. Using the gate electrode, the molecule is reversibly switched between three

  15. Managing light polarization via plasmon-molecule interactions within an asymmetric metal nanoparticle trimer

    International Nuclear Information System (INIS)

    Shegai, Timur; Li, Zhipeng; Zhang, Zhenyu; Xu, Hongxing; Haran, Gilad

    2008-01-01

    The interaction of light with metal nanoparticles leads to novel phenomena mediated by surface plasmon excitations. In this paper we use single molecules to characterize the interaction of surface plasmons with light, and show that such interaction can strongly modulate the polarization of the emitted light. The simplest nanostructures that enable such polarization modulation are asymmetric silver nanocrystal trimers, where individual Raman scattering molecules are located in the gap between two of the nanoparticles. The third particle breaks the dipolar symmetry of the two-particle junction, generating a wavelength-dependent polarization pattern. Indeed, the scattered light becomes elliptically polarized and its intensity pattern is rotated in the presence of the third particle. We use a combination of spectroscopic observations on single molecules, scanning electron microscope imaging, and generalized Mie theory calculations to provide a full picture of the effect of particles on the polarization of the emitted light. Furthermore, our theoretical analysis allows us to show that the observed phenomenon is very sensitive to the size of the trimer particles and their relative position, suggesting future means for precise control of light polarization on the nanoscale.

  16. Ionization of oriented carbonyl sulfide molecules by intense circularly polarized laser pulses

    DEFF Research Database (Denmark)

    Dimitrovski, Darko; Abu-Samha, Mahmoud; Madsen, Lars Bojer

    2011-01-01

    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction...... of the molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one......-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article [Phys. Rev. A 83, 023406 (2011)] the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron...

  17. X-ray characterization of solid small molecule organic materials

    Science.gov (United States)

    Billinge, Simon; Shankland, Kenneth; Shankland, Norman; Florence, Alastair

    2014-06-10

    The present invention provides, inter alia, methods of characterizing a small molecule organic material, e.g., a drug or a drug product. This method includes subjecting the solid small molecule organic material to x-ray total scattering analysis at a short wavelength, collecting data generated thereby, and mathematically transforming the data to provide a refined set of data.

  18. CHEMICAL TRANSPORT FACILITATED BY COLLOIDAL-SIZED ORGANIC MOLECULES

    Science.gov (United States)

    The fluid passing through the pores of soils and geologic materials is not just water with dissolved inorganic chemicals, but a complex mixture of organic and inorganic molecules. Large organic molecules such as humic and fulvic materials may impact the movement of contaminants. ...

  19. Organic molecules in translucent interstellar clouds.

    Science.gov (United States)

    Krełowski, Jacek

    2014-09-01

    Absorption spectra of translucent interstellar clouds contain many known molecular bands of CN, CH+, CH, OH, OH(+), NH, C2 and C3. Moreover, one can observe more than 400 unidentified absorption features, known as diffuse interstellar bands (DIBs), commonly believed to be carried by complex, carbon-bearing molecules. DIBs have been observed in extragalactic sources as well. High S/N spectra allow to determine precisely the corresponding column densities of the identified molecules, rotational temperatures which differ significantly from object to object in cases of centrosymmetric molecular species, and even the (12)C/(13)C abundance ratio. Despite many laboratory based studies of possible DIB carriers, it has not been possible to unambiguously link these bands to specific species. An identification of DIBs would substantially contribute to our understanding of chemical processes in the diffuse interstellar medium. The presence of substructures inside DIB profiles supports the idea that DIBs are very likely features of gas phase molecules. So far only three out of more than 400 DIBs have been linked to specific molecules but none of these links was confirmed beyond doubt. A DIB identification clearly requires a close cooperation between observers and experimentalists. The review presents the state-of-the-art of the investigations of the chemistry of interstellar translucent clouds i.e. how far our observations are sufficient to allow some hints concerning the chemistry of, the most common in the Galaxy, translucent interstellar clouds, likely situated quite far from the sources of radiation (stars).

  20. Hierarchical organization in aggregates of protein molecules

    DEFF Research Database (Denmark)

    Bohr, Henrik; Kyhle, Anders; Sørensen, Alexis Hammer

    1997-01-01

    of the solution and the density of protein are varied shows the existence of specific growth processes resulting in different branch-like structures. The resulting structures are strongly influenced by the shape of each protein molecule. Lysozyme and ribonuclease are found to form spherical structures...

  1. Method of monitoring photoactive organic molecules in-situ during gas-phase deposition of the photoactive organic molecules

    Science.gov (United States)

    Forrest, Stephen R.; Vartanian, Garen; Rolin, Cedric

    2015-06-23

    A method for in-situ monitoring of gas-phase photoactive organic molecules in real time while depositing a film of the photoactive organic molecules on a substrate in a processing chamber for depositing the film includes irradiating the gas-phase photoactive organic molecules in the processing chamber with a radiation from a radiation source in-situ while depositing the film of the one or more organic materials and measuring the intensity of the resulting photoluminescence emission from the organic material. One or more processing parameters associated with the deposition process can be determined from the photoluminescence intensity data in real time providing useful feedback on the deposition process.

  2. Photofragment angular momentum polarization in the photolysis of symmetric top molecules: Production, detection, and rotational depolarization

    International Nuclear Information System (INIS)

    Shternin, Peter S.; Suits, Arthur G.; Vasyutinskii, Oleg S.

    2012-01-01

    Highlights: ► We describe the product polarization in the photolysis of symmetric top molecules. ► The polarization is written in terms of the anisotropy transforming coefficients. ► We studied the role of the angular momentum depolarization due to molecular rotation. ► We present a compact spherical tensor expression for the 2 + 1 REMPI absorption signal. - Abstract: We present the fully quantum mechanical distribution of the photofragment angular momentum polarization in the photolysis of an isotropic ensemble of symmetric top molecules. The distribution is written in terms of the recently established anisotropy transforming coefficients c k d q k K (P.S. Shternin, O.S. Vasyutinskii, Chem. Phys. 128 (2008) 194314) which contain all dynamical information on the photolysis dynamics and can be either determined from experiment, or calculated from theory. Explicit expressions for the coefficients c k d q k K for the case of photolysis of symmetric top molecules were obtained within the full quantum mechanical approach and then simplified using the quasiclassical approximation in the high-J limit. The role of the photofragment angular momentum depolarization due to molecular rotation was analyzed for three important particular cases: photolysis of diatomic molecules, photolysis of symmetric top molecules when the angular momentum polarization of atomic photofragments are detected, photolysis of symmetric top molecules when the angular momentum polarization of molecular photofragments are detected. The obtained rotation factors were compared with the results of previous studies. The paper also presents a compact spherical tensor expression for the 2 + 1 REMPI absorption signal which can be used for direct determination of the coefficients c k d q k K from experiment. A comparison was made between the anisotropy transforming coefficients c k d q k K and the polarization parameters A q K introduced very recently by (T.P. Rakitzis, A.J. Alexander, J. Chem. Phys

  3. Modeling the adiabatic creation of ultracold polar 23Na40K molecules

    Science.gov (United States)

    Seeßelberg, Frauke; Buchheim, Nikolaus; Lu, Zhen-Kai; Schneider, Tobias; Luo, Xin-Yu; Tiemann, Eberhard; Bloch, Immanuel; Gohle, Christoph

    2018-01-01

    In this work we model and realize stimulated Raman adiabatic passage (STIRAP) in the diatomic 23Na40K molecule from weakly bound Feshbach molecules to the rovibronic ground state via the |vd=5 ,J =Ω =1 〉 excited state in the d3Π electronic potential. We demonstrate how to set up a quantitative model for polar molecule production by taking into account the rich internal structure of the molecules and the coupling laser phase noise. We find excellent agreement between the model predictions and the experiment, demonstrating the applicability of the model in the search for an ideal STIRAP transfer path. In total we produce 5000 fermionic ground-state molecules. The typical phase-space density of the sample is 0.03 and induced dipole moments of up to 0.54 D can be observed.

  4. Prospects for quantum computing with an array of ultracold polar paramagnetic molecules.

    Science.gov (United States)

    Karra, Mallikarjun; Sharma, Ketan; Friedrich, Bretislav; Kais, Sabre; Herschbach, Dudley

    2016-03-07

    Arrays of trapped ultracold molecules represent a promising platform for implementing a universal quantum computer. DeMille [Phys. Rev. Lett. 88, 067901 (2002)] has detailed a prototype design based on Stark states of polar (1)Σ molecules as qubits. Herein, we consider an array of polar (2)Σ molecules which are, in addition, inherently paramagnetic and whose Hund's case (b) free-rotor pair-eigenstates are Bell states. We show that by subjecting the array to combinations of concurrent homogeneous and inhomogeneous electric and magnetic fields, the entanglement of the array's Stark and Zeeman states can be tuned and the qubit sites addressed. Two schemes for implementing an optically controlled CNOT gate are proposed and their feasibility discussed in the face of the broadening of spectral lines due to dipole-dipole coupling and the inhomogeneity of the electric and magnetic fields.

  5. Prospects for quantum computing with an array of ultracold polar paramagnetic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Karra, Mallikarjun; Sharma, Ketan; Friedrich, Bretislav, E-mail: bretislav.friedrich@fhi-berlin.mpg.de [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Kais, Sabre [Departments of Chemistry, Physics and Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907 (United States); Herschbach, Dudley [Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 (United States)

    2016-03-07

    Arrays of trapped ultracold molecules represent a promising platform for implementing a universal quantum computer. DeMille [Phys. Rev. Lett. 88, 067901 (2002)] has detailed a prototype design based on Stark states of polar {sup 1}Σ molecules as qubits. Herein, we consider an array of polar {sup 2}Σ molecules which are, in addition, inherently paramagnetic and whose Hund’s case (b) free-rotor pair-eigenstates are Bell states. We show that by subjecting the array to combinations of concurrent homogeneous and inhomogeneous electric and magnetic fields, the entanglement of the array’s Stark and Zeeman states can be tuned and the qubit sites addressed. Two schemes for implementing an optically controlled CNOT gate are proposed and their feasibility discussed in the face of the broadening of spectral lines due to dipole-dipole coupling and the inhomogeneity of the electric and magnetic fields.

  6. Self-assembly patterning of organic molecules on a surface

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Minghu; Fuentes-Cabrera, Miguel; Maksymovych, Petro; Sumpter, Bobby G.; Li, Qing

    2017-04-04

    The embodiments disclosed herein include all-electron control over a chemical attachment and the subsequent self-assembly of an organic molecule into a well-ordered three-dimensional monolayer on a metal surface. The ordering or assembly of the organic molecule may be through electron excitation. Hot-electron and hot-hole excitation enables tethering of the organic molecule to a metal substrate, such as an alkyne group to a gold surface. All-electron reactions may allow a direct control over the size and shape of the self-assembly, defect structures and the reverse process of molecular disassembly from single molecular level to mesoscopic scale.

  7. Single-molecule probes in organic field-effect transistors

    NARCIS (Netherlands)

    Nicolet, Aurélien Armel Louis

    2007-01-01

    The goal of this thesis is to study charge transport phenomena in organic materials. This is done optically by means of single-molecule spectroscopy in a field-effect transistor based on a molecular crystal. We present (in Chapter 2) a fundamental requirement for single-molecule spectroscopy

  8. Organic- and molecule-based magnets

    Indian Academy of Sciences (India)

    Bulk ferro- and ferrimagnets based on organic/molecular components [5,9,10] with critical temperatures exceeding room temperature [5,6,11]. • Prussian Blue structured, room temperature magnets [12–15]. • Clusters in high spin states with a large magnetic anisotropy and negative zero-field splitting can trap magnetic flux ...

  9. Pulse train induced rotational excitation and orientation of a polar molecule.

    Science.gov (United States)

    Tyagi, Ashish; Arya, Urvashi; Vidhani, Bhavna; Prasad, Vinod

    2014-08-14

    We investigate theoretically the rotational excitation and field free molecular orientation of polar HBr molecule, interacting with train of ultrashort laser pulses. By adjusting the number of pulses, pulse period and the intensity of the pulse, one can suppress a population while simultaneously enhancing the desired population in particular rotational state. We have used train of laser pulses of different shaped pulse envelopes. The dynamics and orientation of molecules in the presence of pulse train of different shapes is studied and explained. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Electrocatalytic hydrogenation of organic molecules on conductive new catalytic material

    Energy Technology Data Exchange (ETDEWEB)

    Tountian, D. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide; Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Brisach-Wittmeyer, A.; Menard, H. [Sherbrooke Univ., Sherbrooke, PQ (Canada). Dept. de Chimie, Centre de Recherche en Electrochimie et Electrocatalyse; Nkeng, P.; Poillerat, G. [Louis Pasteur Univ., Strasbourg (France). Laboratoire d' Electrochimie et de Chimie Physique du Corps Solide

    2008-07-01

    Electrocatalytic hydrogenation (ECH) of organic molecules is a process where chemisorbed hydrogen is produced by electroreduction of water which reacts with the species in bulk. Greater emphasis is being placed on improving the nature of the building material of the electrodes in order to increase ECH efficiency. The effectiveness of the ECH is known to be linked to the nature of electrode materials used and their adsorption properties. This work presented the effect of conductive support material on ECH. The conductive catalysts were obtained from tin dioxide which is chemically stable. Palladium was the catalytic metal used in this study. The production of chemisorbed hydrogen was shown to depend on the quantity of metallic nanoaggregates in electrical contact with the reticulated vitreous carbon use as electrode. The conductive support, F-doped tin dioxide, was obtained by the sol-gel method. The electrocatalysts were characterized by different methods as resistivity measurements, linear sweep voltammetry, XRD, SEM, TGA/DSC, and FTIR analysis. The effects of temperature and time of calcination were also investigated. The study showed that the F-doped SnO2 electrocatalyst appeared to increase the rate of phenol electrohydrogenation. It was concluded that the improved electrocatalytic activity of Pd/F-doped SnO2 can be attributed to the simultaneous polarization of all the metallic Pd nanoaggregates present on the surface as well as in the pores of the matrix by contact with RVC. This results in a better production of chemisorbed atomic hydrogen with a large number of adlienation points. 9 refs., 3 figs.

  11. Short bent-core molecules: X-ray, polarization, dielectricity, texture and electro-optics investigations.

    Science.gov (United States)

    Torgova, S; Sreenilayam, S P; Panarin, Yu P; Francescangeli, O; Vita, F; Vij, J K; Pozhidaev, E; Minchenko, M; Ferrero, C; Strigazzi, A

    2017-08-30

    Bent-core liquid crystals based on 1,2,4-oxadiazole as a central unit have been the first mesogens to exhibit a ferroelectric response in the nematic phase. This behavior has been widely recognized as due to the presence of smectic-like polar cybotactic clusters permeating the nematic phase. Unfortunately, these compounds exhibited rather high melting points, about 120 °C, due to the presence of four benzene rings in the molecules. Here we describe the synthesis and physical characterization of a new series of BC mesogens, featuring the same bent core as the previous compounds but shorter outer substituents. By keeping only two benzene rings, we were able to lower the melting points to about 70 °C. However, while X-ray diffraction and dielectric spectroscopy measurements confirm the cybotactic nature of the nematic phase of these compounds, polarization and electro-optical measurements ascribe their polar response to flexoelectricity rather than to spontaneous polarization. Finally, texture investigation suggests the biaxiality of the nematic phase, which is indicated also by conoscopic measurements. These results are important for recognizing size and rigidity limitations in designing bent-core liquid crystal molecules suitable for applications.

  12. Photophysics of organic molecules at high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, Dean James [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1978-01-01

    The pressure dependence of emission intensities, energies, and lifetimes of several classes of organic compounds in plastic media were investigated over the range 0-140 kilobars. The fluorescence intensity of 9-anthraldehyde, 9-acetylanthracene, and 9-benzoylanthracene increases remarkably with increasing pressure, accompanied by a large red shift in the emission spectrum. For azulene and several derivatives, the efficiency of fluorescence from both the second and first excited singlet states was pressure dependent as was the relative energy of these states. The rate of internal conversion depended strongly on the energy separating the relevant states. The energy and quantum efficiency of fluorescence for fluorenone in crystalline form and in several polymeric matrices was measured as a function of pressure. The quantum yield, ranged from 0.001 at low pressure to a maximum of about 0.1 at high pressure in paraffinic plastics. Fluorescence quantum yields and phosphorescence quantum yields and lifetimes were measured for pyrazine (P) 2,6-dimethylpyrazine and tetramethylpyrazine (TMP) in PMMA over the pessure range 20-120 kbar. An additional emission, which is attributed to excimer fluorescence, was also observed for these samples and for crystalline pyrazine. The phosphorescence radiative lifetime for P and TMP was about 18 ms.

  13. Crystallization of Organic Semiconductor Molecules in Nanosized Cavities

    DEFF Research Database (Denmark)

    Milita, Silvia; Dionigi, Chiara; Borgatti, Francesco

    2008-01-01

    The crystallization of an organic semiconductor, viz., tetrahexil-sexithiophene (H4T6) molecules, confined into nanosized cavities of a self-organized polystyrene beads template, has been investigated by means of in situ grazing incidence X-ray diffraction measurements, during the solvent...

  14. Interface properties of organic molecules on metal surfaces; Grenzflaecheneigenschaften organischer Molekuele auf Metalloberflaechen

    Energy Technology Data Exchange (ETDEWEB)

    Karacuban, Hatice

    2010-01-28

    In this work, the growth of the archetype molecules CuPc and PTCDA was investigated on Cu(111). PTCDA was also studied on NaCl/Cu(111). The main experiments were carried out with a scanning tunneling microscope. Structural analysis of CuPc on Cu (111) is only possible at low temperatures, since at room temperature the molecules exhibit a high surface mobility. For the investigation of these structures and especially to enable scanning tunneling spectroscopy, a low-temperature scanning tunneling microscope was developed. Using this home built STM the experiments could be carried out at about 10 K. After the adsorption of CuPc on Cu (111) a substrate-induced symmetry reduction of the molecules can be observed in scanning tunneling microscopy. When the occupied states of the molecules are imaged, a switching between two distinct levels is found. These modifications are determined by the adsorption geometry of the molecules. Based on high resolution STM data, an on-top adsorption geometry of the CuPc-molecules on Cu (111)-substrate can be deducted. At low temperatures, two new superstructures of PTCDA on Cu(111) are observed. The molecules within these superstructures are tilted with respect to the substrate. Intermolecular interactions may be the crucial factor for the realignment of the molecules. If PTCDA molecules are adsorbed on a NaCl/Cu (111) substrate, at room temperature, also two new superstructures on the copper substrate were found. They indicate the formation of a metall-organic-complex. On top of the NaCl layer the molecules exclusively grow at polar NaCl step edges. This is an indication for electrostatic interaction between the PTCDA molecules and the NaCl layer. When the molecule density is further increased, a Vollmer-Weber growth sets in. If both molecules PTCDA and CuPc are present on the sample at the same time, local spectroscopy provides information on the metal-organic interface in direct comparison. The STS-results of CuPc/PTCDA on Cu (111

  15. Classical study of the rovibrational dynamics of a polar diatomic molecule in static electric fields

    Energy Technology Data Exchange (ETDEWEB)

    Inarrea, Manuel, E-mail: manuel.inarrea@unirioja.e [Area de Fisica, Universidad de la Rioja, E-26006 Logrono (Spain); Salas, J. Pablo [Area de Fisica, Universidad de la Rioja, E-26006 Logrono (Spain); Gonzalez-Ferez, Rosario [Instituto ' Carlos I' de Fisica Teorica y Computacional, Universidad de Granada, E-18071 Granada (Spain); Departamento de Fisica Atomica, Molecular y Nuclear, Universidad de Granada, E-18071 Granada (Spain); Schmelcher, Peter [Theoretische Chemie, Physikalisch-Chemisches Institut, D-69120 Heidelberg (Germany); Physikalisches Institut, Universitaet Heidelberg, D-69120 Heidelberg (Germany)

    2010-01-04

    We study the classical dynamics of a polar diatomic molecule in the presence of a strong static homogeneous electric field. Our full rovibrational investigation includes the interaction with the field due to the permanent electric dipole moment and the polarizability of the molecule. Using the LiCs molecule as a prototype, we explore the stability of the equilibrium points and their bifurcations as the field strength is increased. The phase space structure and its dependence on the energy and field strength are analyzed in detail. We demonstrate that depending on the field strength and on the energy, the phase space is characterized either by regular features or by small stochastic layers of chaotic motion.

  16. Electrospray deposition of organic molecules on bulk insulator surfaces.

    Science.gov (United States)

    Hinaut, Antoine; Pawlak, Rémy; Meyer, Ernst; Glatzel, Thilo

    2015-01-01

    Large organic molecules are of important interest for organic-based devices such as hybrid photovoltaics or molecular electronics. Knowing their adsorption geometries and electronic structures allows to design and predict macroscopic device properties. Fundamental investigations in ultra-high vacuum (UHV) are thus mandatory to analyze and engineer processes in this prospects. With increasing size, complexity or chemical reactivity, depositing molecules by thermal evaporation becomes challenging. A recent way to deposit molecules in clean conditions is Electrospray Ionization (ESI). ESI keeps the possibility to work with large molecules, to introduce them in vacuum, and to deposit them on a large variety of surfaces. Here, ESI has been successfully applied to deposit triply fused porphyrin molecules on an insulating KBr(001) surface in UHV environment. Different deposition coverages have been obtained and characterization of the surface by in-situ atomic force microscopy working in the non-contact mode shows details of the molecular structures adsorbed on the surface. We show that UHV-ESI, can be performed on insulating surfaces in the sub-monolayer regime and to single molecules which opens the possibility to study a variety of complex molecules.

  17. Spectroscopic imaging studies of nanoscale polarity and mass transport phenomena in self-assembled organic nanotubes.

    Science.gov (United States)

    Xu, Hao; Nagasaka, Shinobu; Kameta, Naohiro; Masuda, Mitsutoshi; Ito, Takashi; Higgins, Daniel A

    2017-08-02

    Synthetic organic nanotubes self-assembled from bolaamphiphile surfactants are now being explored for use as drug delivery vehicles. In this work, several factors important to their implementation in drug delivery are explored. All experiments are performed with the nanotubes immersed in ethanol. First, Nile Red (NR) and a hydroxylated Nile Red derivative (NR-OH) are loaded into the nanotubes and spectroscopic fluorescence imaging methods are used to determine the apparent dielectric constant of their local environment. Both are found in relatively nonpolar environments, with the NR-OH molecules preferring regions of relatively higher dielectric constant compared to NR. Unique two-color imaging fluorescence correlation spectroscopy (imaging FCS) measurements are then used along with the spectroscopic imaging results to deduce the dielectric properties of the environments sensed by mobile and immobile populations of probe molecules. The results reveal that mobile NR molecules pass through less polar regions, likely within the nanotube walls, while immobile NR molecules are found in more polar regions, possibly near the nanotube surfaces. In contrast, mobile and immobile NR-OH molecules are found to locate in environments of similar polarity. The imaging FCS results also provide quantitative data on the apparent diffusion coefficient for each dye. The mean diffusion coefficient for the NR dye was approximately two-fold larger than that of NR-OH. Slower diffusion by the latter could result from its additional hydrogen bonding interactions with polar triglycine, amine, and glucose moieties near the nanotube surfaces. The knowledge gained in these studies will allow for the development of nanotubes that are better engineered for applications in the controlled transport and release of uncharged, dipolar drug molecules.

  18. Characterization of polar organics in airborne particulate matter

    Science.gov (United States)

    Yokouchi, Y.; Ambe, Y.

    The methanol-extractable highly polar organics in atmospheric aerosol were characterized using GC-MS. Dicarboxylic acids having 2-16 carbon numbers were detected with a total concentration of 172 ng m -3. Azelaic acid ( C9) was the most abundant diacid and it possibly originated from the ozonolysis of unsaturated carboxylic acids such as oleic acid and linoleic acid, which mainly originate from terrestrial plants. A compound, which was tentatively identified as tetrahydrofuroic acid, contributed to about 10% of the highly polar organics. Other polyfunctional compounds found in the samples included some ketocarboxylic acids and aromatic acids such as phthalic acids, anisic acid and vanillic acid.

  19. Possible sequestration of polar gas molecules by superhalogen supported aluminum nitride nanoflakes.

    Science.gov (United States)

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar

    2016-11-01

    The feasibility of having MF 3 (where M = Rh, Ir, Pd, Pt, Ag, Au) supported AlN nanoflakes (AlNF) was investigated through density functional theory based calculations. The thermodynamic analysis reveals that the superhalogen MF 3 molecules can bind with the host AlNF in a thermodynamically favorable way. The nature of interaction in between the metal centers and the host is of partly covalent type whereas the F centers bind with the host in a non-covalent fashion as vindicated by natural bond orbital and atoms-in a-molecule analyses. An ab initio molecular dynamics study carried out at 298 K temperature confirms the stability of the MF 3 @AlNF moieties in a dynamical context. The MF 3 guests can reduce the HOMO-LUMO gaps of the host nanoflakes. In general, the MF 3 @AlNF complexes can sequestrate polar adsorbates such as CO, NO, and H 2 O in a thermodynamically favorable way in most of the cases. An ab initio molecular dynamics calculation illustrates that the MF 3 @AlNF can adsorb the chosen representative polar molecules in a more favorable way as compared to the corresponding adsorption scenario in the case of pristine AlNF.

  20. Controlling the magnetism of adsorbed metal-organic molecules.

    Science.gov (United States)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  1. Two-center minima in harmonic spectra from aligned polar molecules

    International Nuclear Information System (INIS)

    Etches, Adam; Gaarde, Mette B.; Madsen, Lars Bojer

    2011-01-01

    We extend a model of two-center interference to include the superposition of opposite orientations in aligned polar molecules. We show that the position of the minimum in the harmonic spectrum from both aligned and oriented CO depends strongly on the relative recombination strength at different atoms, not just the relative phase. We reinterpret the minimum in aligned CO as an interference between opposite orientations, and obtain good agreement with numerical calculations. Inclusion of the first-order Stark effect shifts the position of the interference minimum in aligned CO even though aligned molecules do not posses total permanent dipoles. We explain the shift in terms of the phase that the electron of oriented CO accumulates due to the Stark effect.

  2. Two-center minima in harmonic spectra from aligned polar molecules

    DEFF Research Database (Denmark)

    Etches, Adam; Gaarde, Mette B.; Madsen, Lars Bojer

    2011-01-01

    We extend a model of two-center interference to include the superposition of opposite orientations in aligned polar molecules. We show that the position of the minimum in the harmonic spectrum from both aligned and oriented CO depends strongly on the relative recombination strength at different...... atoms, not just the relative phase. We reinterpret the minimum in aligned CO as an interference between opposite orientations, and obtain good agreement with numerical calculations. Inclusion of the first-order Stark effect shifts the position of the interference minimum in aligned CO even though...... aligned molecules do not posses total permanent dipoles. We explain the shift in terms of the phase that the electron of oriented CO accumulates due to the Stark effect....

  3. Organic Molecules On the Surfaces of Iapetus and Phoebe

    Science.gov (United States)

    Pendleton, Yvonne J.; Dalle Ore, Cristina M.; Clark, Roger N.; Cruikshank, Dale P.

    2017-01-01

    Absorption bands of both aliphatic and aromatic organic molecules are found in the reflectance spectra of Saturn satellites Iapetus, Phoebe, and Hyperion obtained with the Cassini Visible-Infrared Mapping Spectrometer (VIMS). The VIMS data do not fully resolve the individual bands of C-H functional groups specific to particular molecules, but instead show absorption envelopes representing blended clusters of the bands of aromatic (approximately 3.28 microns) and aliphatic (approximately 3.4 microns) hydrocarbons known in spectra of interstellar dust. In Cruikshank et al. (2014), we matched components of the unresolved hydrocarbon band envelopes with clusters of bands of a range of functional groups in specific types of organic compounds (e.g., normal and N-substituted polycyclic aromatic hydrocarbons, olefins, cycloalkanes, and molecules with lone-pair interactions of N and O with CH3+). In the work reported here, we revisit the spectra of Iapetus and Phoebe using VIMS data processed with improved radiometric and wavelength calibration (denoted RC19). The band envelopes of both aromatic and aliphatic hydrocarbons are now more clearly defined, corroborating the provisional assignment of specific classes of molecules in Cruikshank et al. 2014, but permitting a more reliable quantitative assessment of the relative contributions of those classes, and a revision to the earlier estimate of the ratio of the abundances of aromatic to aliphatic molecules.

  4. Tuning Interfacial States Using Organic Molecules as Spin Filters

    Science.gov (United States)

    Deloach, Andrew; Wang, Jingying; Papa, Christopher M.; Myahkostupov, Mykhaylo; Castellano, Felix N.; Dougherty, Daniel B.; Jiang, Wei; Liu, Feng

    Organic semiconductors are known to have long spin relaxation times which makes them a good candidate for spintronics. However, an issue with these materials is that at metal-organic interfaces there is a conductivity mismatch problem that suppresses spin injection. To overcome this, orbital mixing at the interface can be tuned with an organic spacer layer to promote the formation of spin polarized interface states. These states act as a ``spin filters'' and have been proposed as an explanation for the large tunneling magnetoresistance seen in devices using tris-(8-hydroxyquinolate)-aluminum(Alq3). Here, we show that the spin polarized interface states can be tuned from metallic to resistive by subtle changes in molecular orbitals. This is done using spin polarized scanning tunneling microscopy with three different tris-(8-hydroxyquinolate) compounds: aluminum, chromium, and iron. Differences in d-orbital mixing results in different mechanisms of interfacial coupling, giving rise to metallic or resistive interface states. Supported by the U.S. DoE award No. DE-SC0010324.

  5. Optically stimulated slowing of polar heavy-atom molecules with a constant beat phase

    Science.gov (United States)

    Yin, Yanning; Xu, Supeng; Xia, Meng; Xia, Yong; Yin, Jianping

    2018-04-01

    Polar heavy-atom molecules have been well recognized as promising candidates for precision measurements and tests of fundamental physics. A much slower molecular beam to increase the interaction time should lead to a more sensitive measurement. Here we theoretically demonstrate the possibility of the stimulated longitudinal slowing of heavy-atom molecules by the coherent optical bichromatic force with a constant beat phase. Taking the YbF meolecule as an example, we show that a rapid and short-distance deceleration of heavy molecules by a phase-compensation method is feasible with moderate conditions. A molecular beam of YbF with a forward velocity of 120 m/s can be decelerated below 10 m/s within a distance of 3.5 cm and with a laser irradiance for each traveling wave of 107.2 W/cm 2 . Our proposed slowing method could be a promising approach to break through the space constraint or the limited capture efficiency of molecules loadable into a magneto-optical trap in traditional deceleration schemes, opening the possibility for a significant improvement of the precision measurement sensitivity.

  6. In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

    Science.gov (United States)

    Li, Xiang; Brinckerhoff, William B.; Pinnick, Veronica T; van Amerom, Friso H. W.; Danell, Ryan M.; Arevalo, Ricardo D., Jr.; Getty, Stephanie; Mahaffy, Paul R.

    2015-01-01

    The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds.

  7. Signal regulatory proteins (SIRPS) are secreted presynaptic organizing molecules.

    Science.gov (United States)

    Umemori, Hisashi; Sanes, Joshua R

    2008-12-05

    Formation of chemical synapses requires exchange of organizing signals between the synaptic partners. Using synaptic vesicle aggregation in cultured neurons as a marker of presynaptic differentiation, we purified candidate presynaptic organizers from mouse brain. A major bioactive species was the extracellular domain of signal regulatory protein alpha (SIRP-alpha), a transmembrane immunoglobulin superfamily member concentrated at synapses. The extracellular domain of SIRP-alpha is cleaved and shed in a developmentally regulated manner. The presynaptic organizing activity of SIRP-alpha is mediated in part by CD47. SIRP-alpha homologues, SIRP-beta and -gamma also have synaptic vesicle clustering activity. The effects of SIRP-alpha are distinct from those of another presynaptic organizer, FGF22: the two proteins induced vesicle clusters of different sizes, differed in their ability to promote neurite branching, and acted through different receptors and signaling pathways. SIRP family proteins may act together with other organizing molecules to pattern synapses.

  8. Surface functionalization of aluminosilicate nanotubes with organic molecules

    Directory of Open Access Journals (Sweden)

    Wei Ma

    2012-02-01

    Full Text Available The surface functionalization of inorganic nanostructures is an effective approach for enriching the potential applications of existing nanomaterials. Inorganic nanotubes attract great research interest due to their one-dimensional structure and reactive surfaces. In this review paper, recent developments in surface functionalization of an aluminosilicate nanotube, “imogolite”, are introduced. The functionalization processes are based on the robust affinity between phosphate groups of organic molecules and the aluminol (AlOH surface of imogolite nanotubes. An aqueous modification process employing a water soluble ammonium salt of alkyl phosphate led to chemisorption of molecules on imogolite at the nanotube level. Polymer-chain-grafted imogolite nanotubes were prepared through surface-initiated polymerization. In addition, the assembly of conjugated molecules, 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-ylethylphosphonic acid (HT3P and 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-ylethylphosphonic acid 1,1-dioxide (HT3OP, on the imogolite nanotube surface was achieved by introducing a phosphonic acid group to the corresponding molecules. The optical and photophysical properties of these conjugated-molecule-decorated imogolite nanotubes were characterized. Moreover, poly(3-hexylthiophene (P3HT chains were further hybridized with HT3P modified imogolite to form a nanofiber hybrid.

  9. Luminescence stability of porous Si terminated by hydrophilic organic molecules

    Science.gov (United States)

    Matsumoto, Kimihisa; Kamiguchi, Masao; Kamiya, Kazuhide; Nomura, Takashi; Suzuki, Shinya

    2016-02-01

    The effects of the surface termination of a porous Si surface by propionic acid and by undecylenic acid on their hydrophilicity and luminescence stability were studied. In the measurements of the contact angle of water droplets on porous Si films, the hydrophilicity of porous Si is improved by the surface termination each types of organic molecule. The PL intensity of as-prepared porous Si decreased with increasing aging time in ambient air. As PL quenching involves PL blue shift and increasing Si-O bonds density, nonradiative recombination centers are formed in the surface oxide. After the hydrosilylation process of propionic acid and undecylenic acid, PL intensity decreased and became 30% that of as-prepared porous Si film. However, the PL intensity was stable and exceeded that of the as-prepared film after 1000 min of aging in the ambient air. The PL stabilities are contributed to the termination by organic molecules that inhibits surface oxidation.

  10. The tritium labelling of organic molecules by heterogeneous catalytic exchange

    International Nuclear Information System (INIS)

    Angoso Marina, M.; Kaiser Ruiz del Olmo, F.

    1977-01-01

    The influence of the temperature at 65 degree centigree and 120 degree centigree on the labelling of three organic molecules with tritium was studied. The compounds were: benzoic acid, de phenyl glyoxal and 2,3-tetramethylene-4-pantothenyl-7-oxo diacetin.The method employed was the heterogeneous catalytic exchange between tritiated water and the organic compound. The purification was made by thin-layer chromatography and the concentration, purity and specific activity of the products were determined by counting and ultraviolet techniques. The thermal stability and the radiolytic effects on labelled benzoic acid were also considered. (Author) 9 refs

  11. The tritium labelling of organic molecules by heterogeneous catalytic exchange

    International Nuclear Information System (INIS)

    Angoso, M.; Kaiser, F.

    1977-01-01

    The influence of the temperature at 65degC and 120degC on the labelling of three organic molecules with tritium was studied. The compounds were: benzoic acid, diphenyl glioxal and 2,3-tetramethylene-4-phenylthien-7-oxodiacetin. The method employed was the heterogeneous catalytic exchange between tritiaded water and the organic compound. The purification was made by thin-layer chromatography and the concentration, purity and specific activity of the products were determined by counting and ultraviolet techniques. The thermal stability and the radiolitic effects on labelled benzoic acid were also considered. (author) [es

  12. Complex organic molecules in organic-poor massive young stellar objects

    DEFF Research Database (Denmark)

    Fayolle, Edith C.; Öberg, Karin I.; Garrod, Robin T.

    2015-01-01

    Context. Massive young stellar objects (MYSOs) with hot cores are classic sources of complex organic molecules. The origins of these molecules in such sources, as well as the small-and large-scale differentiation between nitrogen-and oxygen-bearing complex species, are poorly understood. Aims. We...

  13. Design of magnetic system to produce intense beam of polarized molecules of H2 and D2

    Science.gov (United States)

    Yurchenko, A. V.; Nikolenko, D. M.; Rachek, I. A.; Shestakov, Yu V.; Toporkov, D. K.; Zorin, A. V.

    2017-12-01

    A magnetic-separating system is designed to produce polarized molecular high-density beams of H2/D2. The distribution of the magnetic field inside the aperture of the multipole magnet was calculated using the Mermaid software package. The calculation showed that the characteristic value of the magnetic field is 40 kGs, the field gradient is about 60 kGs/cm. A numerical calculation of the trajectories of the motion of molecules with different spin projections in this magnetic system is performed. The article discusses the possibility of using the magnetic system designed for the creation of a high-intensity source of polarized molecules. The expected intensity of this source is calculated. The expected flux of molecules focused in the receiver tube is 3.5·1016 mol/s for the hydrogen molecule and 2.0·1015 mol/s for the deuterium molecule.

  14. In Situ Analysis of Organic Compounds on Mars by Gas Chromatography : Application to the Mars Organic Molecule Analyzer (MOMA) Experiment

    Science.gov (United States)

    Buch, Arnaud; Sternberg, R.; Freissinet, C.; Szopa, C.; Coll, P.; Garnier, C.; Rodier, C.; Phillipon, C.; El bekri, J.; Stambouli, M.; Goesmann, F.; Raulin, F.; MOMA GC-team

    2009-09-01

    The search for signs of past or present life is one of the primary goals of the future Mars exploratory missions. With this aim the Mars Organic Molecule Analyzer (MOMA) experiment of the ExoMars 2016 next coming European Space Agency mission is designed to the in situ analysis of organic molecules of exobiological interest in the Martian soil such as amino acids, carboxylic acids, nucleobases or polycyclic aromatic hydrocarbons (PAHs). With the aim to extract from the soil, separate and detect organic compounds we have developed a sample processing system allowing the Gas Chromatographic analysis, within space compatible operating conditions, of the refractory organic compounds able to be contained at trace level in the Martian soil. The sample processing is performed in the oven dedicated to the MOMA experiment containing the solid sample ( 200mg). The internal temperature can be ranged from 20 to 1000 °C. The extraction step is achieved by using thermodesorption in the range of 100 to 300°C for 5 to 20 min. Then, the chemical derivatization or thermochemolysis of the extracted compounds is achieved directly on the soil with a mixture of MTBSTFA-DMF, TMAH or DMF-DMA solution when enantiomeric separation is required. By decreasing the polarity of the target molecules, this step allows their volatilization at a temperature below 250°C without any chemical degradation. Once derivatized, the target volatile molecules are trapped in a cold or chemical trap and promptly desorbed in the gas chromatograph coupled with a mass spectrometer. Organic compounds such as amino and carboxylic acids contained in Martian analogue soil (Atacama) have been detected by using our sample processing system.

  15. Self-Assembly of Small Molecules for Organic Photovoltaic Applications

    Science.gov (United States)

    Aytun, Taner

    Organic photovoltaic (OPV) solar cells aim to provide efficient, flexible and lightweight photovoltaics (PV) with simple processing and low-cost. Advances in device optimization, structural and molecular design, as well as mechanistic understanding have helped increase device efficiency and performance. Within the framework of active layer optimization, systematically improving bulk heterojunction (BHJ) morphology could improve the power conversion efficiency of OPVs. However, most strategies aimed at improving morphology focus on annealing methods or the use of solvent additives. Rational approaches in supramolecular self-assembly can potentially offer additional control over the morphology of BHJ active layers and lead to improved power conversion efficiencies. In Chapter 2, the author explores the effect of molecular shape on the assembly of electron donating small molecules, and its ensuing effect on OPV performance. Two tripodal 'star-shaped' donor molecules with diketopyrrolopyrrole (DPP) side chains were used to generate solution-processed BHJ OPVs. It was found that the tripod molecules neither aggregate in solution nor form crystalline domains in thin films when a branched alkyl solubilizing group is used. On the other hand, linear alkyl chains promote the formation of one-dimensional (1D) nanowires and crystalline domains as well. This work demonstrated that the one-dimensional assembly of donor molecules enhances the performance of the corresponding solution-processed OPVs by 50%. This is attributed to the reduction of trap states in the 1D nanowires, resulting in a significant increase in the fill factor of the devices. In Chapter 3, experiments are described in which the electron donor is a hairpin-shaped molecule containing a trans-1,2-diamidocyclohexane core and two DPP conjugated segments, and a fullerene derivative as the electron acceptor. Self-assembly of the donor molecule is driven by the synergistic interaction between hydrogen bonds and pi

  16. Modeling adsorption and reactions of organic molecules at metal surfaces.

    Science.gov (United States)

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias

    2014-11-18

    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  17. Preservation of organic molecules at Mars' near-surface

    Science.gov (United States)

    Freissinet, Caroline

    2016-07-01

    One of the biggest concerns for the in situ detection of organics on extraterrestrial environment is the preservation potential of the molecules at the surface and subsurface given the harsh radiation conditions and oxidants they are exposed to. The Mars Science Laboratory (MSL) search for hydrocarbons is designed to understand taphonomic windows of organic preservation in the Mars' near-surface. The Sample Analysis at Mars (SAM) instrument on the MSL Curiosity rover discovered chlorohydrocarbon indigenous to a mudstone drilled sample, Cumberland (CB). The discovery of chlorohydrocarbons in the martian surface means that reduced material with covalent bonds has survived despite the severe degrading conditions. However, the precursors of the chlorohydrocarbons detected by pyrolysis at CB remain unknown. Organic compounds in this ancient sedimentary rock on Mars could include polycyclic aromatic hydrocarbons and refractory organic material, either formed on Mars from igneous, hydrothermal, atmospheric, or biological processes or, alternatively, delivered directly to Mars via meteorites, comets, or interplanetary dust particles. It has been postulated that organic compounds in near-surface rocks may undergo successive oxidation reactions that eventually form metastable benzenecarboxylates, including phthalic and mellitic acids. These benzenecarboxylates are good candidates as the precursors of the chlorohydrocarbons detected in SAM pyrolysis at CB. Indeed, recently, SAM performed a derivatization experiments on a CB sample, using the residual vapor of N-methyl-N-tertbutylsilyltrifluoroacetamide (MTBSTFA) leaking into the system. The preliminary interpretations are compatible with the presence of benzocarboxylates, coincidently with long chain carboxylic acids and alcohols. The analysis of this interesting data set to identify these derivatization products, as well as future SAM measurements on Mt Sharp, should shed additional light on the chemical nature and the

  18. Dark states in spin-polarized transport through triple quantum dot molecules

    Science.gov (United States)

    Wrześniewski, K.; Weymann, I.

    2018-02-01

    We study the spin-polarized transport through a triple-quantum-dot molecule weakly coupled to ferromagnetic leads. The analysis is performed by means of the real-time diagrammatic technique, including up to the second order of perturbation expansion with respect to the tunnel coupling. The emphasis is put on the impact of dark states on spin-resolved transport characteristics. It is shown that the interplay of coherent population trapping and cotunneling processes results in a highly nontrivial behavior of the tunnel magnetoresistance, which can take negative values. Moreover, a super-Poissonian shot noise is found in transport regimes where the current is blocked by the formation of dark states, which can be additionally enhanced by spin dependence of tunneling processes, depending on the magnetic configuration of the device. The mechanisms leading to those effects are thoroughly discussed.

  19. Precise Molecular Sieving Architectures with Janus Pathways for Both Polar and Nonpolar Molecules.

    Science.gov (United States)

    Liu, Jiangtao; Hua, Dan; Zhang, Yu; Japip, Susilo; Chung, Tai-Shung

    2018-03-01

    Precise molecular sieving architectures with Janus superhighways are constructed via a molecularly engineered interfacial reaction between cyclodextrin (CD) and trimesoyl chloride (TMC). Interestingly, the CD/TMC nanofilms constructed with both hydrophobic inner cavities and hydrophilic channels exhibit exceptionally high permeances for both polar and nonpolar solvents. The precise molecular sieving functions are determined by the type of CD building blocks and the inner cavities of intrinsic 3D hollow bowls. Positron annihilation spectroscopy (PAS) confirms that a larger inner CD cavity tends to generate a larger free volume and higher microporosity. Based on the rejection ratio of various dyes, the estimated molecular weight cutoff of CD/TMC nanofilms follows the trend of α-CD/TMC (320 Da) sieving membrane with intrinsic microporosity containing tunable pore size and sharp pore-size distribution can effectively discriminate molecules with different 3D sizes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Single-molecule fluorescence polarization study of conformational change in archaeal group II chaperonin.

    Directory of Open Access Journals (Sweden)

    Ryo Iizuka

    Full Text Available Group II chaperonins found in archaea and in eukaryotic cytosol mediate protein folding without a GroES-like cofactor. The function of the cofactor is substituted by the helical protrusion at the tip of the apical domain, which forms a built-in lid on the central cavity. Although many studies on the change in lid conformation coupled to the binding and hydrolysis of nucleotides have been conducted, the molecular mechanism of lid closure remains poorly understood. Here, we performed a single-molecule polarization modulation to probe the rotation of the helical protrusion of a chaperonin from a hyperthermophilic archaeum, Thermococcus sp. strain KS-1. We detected approximately 35° rotation of the helical protrusion immediately after photorelease of ATP. The result suggests that the conformational change from the open lid to the closed lid state is responsible for the approximately 35° rotation of the helical protrusion.

  1. Permeability of uncharged organic molecules in reverse osmosis desalination membranes.

    Science.gov (United States)

    Dražević, Emil; Košutić, Krešimir; Svalina, Marin; Catalano, Jacopo

    2017-06-01

    Reverse osmosis (RO) membranes are primarily designed for removal of salts i.e. for desalination of brackish and seawater, but they have also found applications in removal of organic molecules. While it is clear that steric exclusion is the dominant removal mechanism, the fundamental explanation for how and why the separation occurs remains elusive. Until recently there was no strong microscopic evidences elucidating the structure of the active polyamide layers of RO membranes, and thus they have been conceived as "black boxes"; or as an array of straight capillaries with a distribution of radii; or as polymers with a small amount of polymer free domains. The knowledge of diffusion and sorption coefficients is a prerequisite for understanding the intrinsic permeability of any organic solute in any polymer. At the same time, it is technically challenging to accurately measure these two fundamental parameters in very thin (20-300 nm) water-swollen active layers. In this work we have measured partition and diffusion coefficients and RO permeabilities of ten organic solutes in water-swollen active layers of two types of RO membranes, low (SWC4+) and high flux (XLE). We deduced from our results and recent microscopic studies that the solute flux of organic molecules in polyamide layer of RO membranes occurs in two domains, dense polymer (the key barrier layer) and the water filled domains. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Genetic control of organ shape and tissue polarity.

    Directory of Open Access Journals (Sweden)

    Amelia A Green

    2010-11-01

    Full Text Available The mechanisms by which genes control organ shape are poorly understood. In principle, genes may control shape by modifying local rates and/or orientations of deformation. Distinguishing between these possibilities has been difficult because of interactions between patterns, orientations, and mechanical constraints during growth. Here we show how a combination of growth analysis, molecular genetics, and modelling can be used to dissect the factors contributing to shape. Using the Snapdragon (Antirrhinum flower as an example, we show how shape development reflects local rates and orientations of tissue growth that vary spatially and temporally to form a dynamic growth field. This growth field is under the control of several dorsoventral genes that influence flower shape. The action of these genes can be modelled by assuming they modulate specified growth rates parallel or perpendicular to local orientations, established by a few key organisers of tissue polarity. Models in which dorsoventral genes only influence specified growth rates do not fully account for the observed growth fields and shapes. However, the data can be readily explained by a model in which dorsoventral genes also modify organisers of tissue polarity. In particular, genetic control of tissue polarity organisers at ventral petal junctions and distal boundaries allows both the shape and growth field of the flower to be accounted for in wild type and mutants. The results suggest that genetic control of tissue polarity organisers has played a key role in the development and evolution of shape.

  3. Photoinduced electric currents in ring-shaped molecules by circularly polarized laser pulses

    International Nuclear Information System (INIS)

    Nobusada, Katsuyuki; Yabana, Kazuhiro

    2007-01-01

    We have theoretically demonstrated that circularly polarized laser pulses induce electric currents and magnetic moments in ring-shaped molecules Na 10 and benzene. The time-dependent adiabatic local density approximation is employed for this purpose, solving the time-dependent Kohn-Sham equation in real space and real time. It has been found that the electric currents are induced efficiently and persist continuously even after the laser pulses were switched off provided the frequency of the applied laser pulse is in tune with the excitation energy of the electronic excited state with the dipole strength for each molecular system. The electric currents are definitely revealed to be a second-order nonlinear optical response to the magnitude of the electric field. The magnetic dipole moments inevitably accompany the ring currents, so that the molecules are magnetized. The production of the electric currents and the magnetic moments in the present procedure is found to be much more efficient than that utilizing static magnetic fields

  4. Tilting and Wobble of Myosin V by High-Speed Single-Molecule Polarized Fluorescence Microscopy

    Science.gov (United States)

    Beausang, John F.; Shroder, Deborah Y.; Nelson, Philip C.; Goldman, Yale E.

    2013-01-01

    Myosin V is biomolecular motor with two actin-binding domains (heads) that take multiple steps along actin by a hand-over-hand mechanism. We used high-speed polarized total internal reflection fluorescence (polTIRF) microscopy to study the structural dynamics of single myosin V molecules that had been labeled with bifunctional rhodamine linked to one of the calmodulins along the lever arm. With the use of time-correlated single-photon counting technology, the temporal resolution of the polTIRF microscope was improved ∼50-fold relative to earlier studies, and a maximum-likelihood, multitrace change-point algorithm was used to objectively determine the times when structural changes occurred. Short-lived substeps that displayed an abrupt increase in rotational mobility were detected during stepping, likely corresponding to random thermal fluctuations of the stepping head while it searched for its next actin-binding site. Thus, myosin V harnesses its fluctuating environment to extend its reach. Additional, less frequent angle changes, probably not directly associated with steps, were detected in both leading and trailing heads. The high-speed polTIRF method and change-point analysis may be applicable to single-molecule studies of other biological systems. PMID:23528086

  5. Spin-polarized transport through single-molecule magnet Mn6 complexes

    KAUST Repository

    Cremades, Eduard

    2013-01-01

    The coherent transport properties of a device, constructed by sandwiching a Mn6 single-molecule magnet between two gold surfaces, are studied theoretically by using the non-equilibrium Green\\'s function approach combined with density functional theory. Two spin states of such Mn6 complexes are explored, namely the ferromagnetically coupled configuration of the six MnIII cations, leading to the S = 12 ground state, and the low S = 4 spin state. For voltages up to 1 volt the S = 12 ground state shows a current one order of magnitude larger than that of the S = 4 state. Furthermore this is almost completely spin-polarized, since the Mn6 frontier molecular orbitals for S = 12 belong to the same spin manifold. As such the high-anisotropy Mn6 molecule appears as a promising candidate for implementing, at the single molecular level, both spin-switches and low-temperature spin-valves. © 2013 The Royal Society of Chemistry.

  6. Transferable Atomic Multipole Machine Learning Models for Small Organic Molecules.

    Science.gov (United States)

    Bereau, Tristan; Andrienko, Denis; von Lilienfeld, O Anatole

    2015-07-14

    Accurate representation of the molecular electrostatic potential, which is often expanded in distributed multipole moments, is crucial for an efficient evaluation of intermolecular interactions. Here we introduce a machine learning model for multipole coefficients of atom types H, C, O, N, S, F, and Cl in any molecular conformation. The model is trained on quantum-chemical results for atoms in varying chemical environments drawn from thousands of organic molecules. Multipoles in systems with neutral, cationic, and anionic molecular charge states are treated with individual models. The models' predictive accuracy and applicability are illustrated by evaluating intermolecular interaction energies of nearly 1,000 dimers and the cohesive energy of the benzene crystal.

  7. On structure of some laminated crystals with organic molecules

    International Nuclear Information System (INIS)

    Volodina, G.F.; Ivanova, V.Ya.; Malinovskij, T.I.

    1982-01-01

    A survey is made of papers dealing with intercalation of organic molecules into crystals of dihalcogenides of some transition metals (TaS 2 , TiS 2 , NbS 2 , ZrS 2 , TaSe 2 ), variation of their structure and physical properties. Among the used intercalates ammonia, pyridine, aniline and other aromatic amines proved to be most satisfactory from the viewpoint of reaction rate and product stability. A possibility is discussed of intercalation into PbI 2 and CdI 2 crystals that are of the same structural type as dihalcogenides

  8. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    Science.gov (United States)

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Core Level Spectra of Organic Molecules Adsorbed on Graphene

    Directory of Open Access Journals (Sweden)

    Abhilash Ravikumar

    2018-03-01

    Full Text Available We perform first principle calculations based on density functional theory to investigate the effect of the adsorption of core-excited organic molecules on graphene. We simulate Near Edge X-ray absorption Fine Structure (NEXAFS and X-ray Photoemission Spectroscopy (XPS at the N and C edges for two moieties: pyridine and the pyridine radical on graphene, which exemplify two different adsorption characters. The modifications of molecular and graphene energy levels due to their interplay with the core-level excitation are discussed. We find that upon physisorption of pyridine, the binding energies of graphene close to the adsorption site reduce mildly, and the NEXAFS spectra of the molecule and graphene resemble those of gas phase pyridine and pristine graphene, respectively. However, the chemisorption of the pyridine radical is found to significantly alter these core excited spectra. The C 1s binding energy of the C atom of graphene participating in chemisorption increases by ∼1 eV, and the C atoms of graphene alternate to the adsorption site show a reduction in the binding energy. Analogously, these C atoms also show strong modifications in the NEXAFS spectra. The NEXAFS spectrum of the chemisorbed molecule is also modified as a result of hybridization with and screening by graphene. We eventually explore the electronic properties and magnetism of the system as a core-level excitation is adiabatically switched on.

  10. Nanoscale contacts to organic molecules based on layered semiconductor substrates

    Energy Technology Data Exchange (ETDEWEB)

    Strobel, Sebastian

    2009-06-15

    This work reports on the integration of organic molecules as nanoelectronic device units on semiconductor substrates. Two novel preparation methods for sub-10-nm separated metal electrodes are presented using current microelectronics process technology. The first method utilises AlGaAs/GaAs heterostructures grown by molecular beam epitaxy (MBE) as mold to create planar metal electrodes employing a newly developed, high resolution nanotransfer printing (nTP) process. The second method uses commercially available Silicon-on-Insulator (SOI) substrates as base material for the fabrication of nanogap electrode devices. This sandwich-like material stack consists of a silicon substrate, a thin silicon oxide layer, and a capping silicon layer on top. Electronic transport measurements verified their excellent electrical properties at liquid helium temperatures. Specifically tailored nanogap devices featured an electrode insulation in the GW range even up to room temperature as well as within aqueous electrolyte solution. Finally, the well defined layer architecture facilitated the fabrication of electrodes with gap separations below-10-nm to be directly bridged by molecules. Approximately 12-nm-long conjugated molecules with extended -electron system were assembled onto the devices from solution. A large conductance gap was observed with a steep increase in current at a bias voltage of V{sub T}{approx}{+-}1.5 V. Theoretical calculations based on density functional theory and non-equilibrium Green's function formalism confirmed the measured non-linear IV-characteristics qualitatively and lead to the conclusion that the conductance gap mainly originates from the oxygen containing linker. Temperature dependent investigations of the conductance indicated a hopping charge transport mechanism through the central part of the molecule for bias voltages near but below V{sub T}. (orig.)

  11. Complex Organic Molecules in Taurus Molecular Cloud-1

    Science.gov (United States)

    Soma, Tatsuya; Sakai, Nami; Watanabe, Yoshimasa; Yamamoto, Satoshi

    2018-02-01

    We have observed the millimeter-wave rotational spectral lines of CH3CHO, H2CCO, cyclopropenone, and H2CO toward the cyanoployyne peak of Taurus Molecular Cloud-1 (TMC-1 CP). The spectral line profile of CH3CHO is found to reveal a well-separated double peak. It is similar to the line profile of CH3OH, but is much different from those of carbon-chain molecules and C34S. The different line profiles mean different distributions along the line of sight. The similarity of the spectral line profiles between CH3CHO and CH3OH suggests that CH3CHO is mainly formed on dust grains as CH3OH or through gas-phase reactions starting from CH3OH. On the other hand, the spectral line profiles of H2CCO and cyclopropenone are rather similar to those of carbon-chain molecules and C34S, implying their gas-phase productions. H2CO shows a composite spectral line profile reflecting the contributions of both gas-phase and grain-surface productions. In addition, we have detected the spectral lines of CH3CHO and HCOOCH3 toward the methanol peak near TMC-1 CP. We have also tentatively detected one line of (CH3)2O. Considering the chemical youth of TMC-1, the present results indicate that fairly complex organic species have already been formed in the early evolutionary phase of starless cores. TMC-1 is thus recognized as a novel source where formation processes of complex organic molecules can be studied on the basis of the line profiles.

  12. Optical and Transport Properties of Organic Molecules: Methods and Applications

    Science.gov (United States)

    Strubbe, David Alan

    Organic molecules are versatile and tunable building blocks for technology, in nanoscale and bulk devices. In this dissertation, I will consider some important applications for organic molecules involving optical and transport properties, and develop methods and software appropriate for theoretical calculations of these properties. Specifically, we will consider second-harmonic generation, a nonlinear optical process; photoisomerization, in which absorption of light leads to mechanical motion; charge transport in junctions formed of single molecules; and optical excitations in pentacene, an organic semiconductor with applications in photovoltaics, optoelectronics, and flexible electronics. In the Introduction (Chapter 1), I will give an overview of some phenomenology about organic molecules and these application areas, and discuss the basics of the theoretical methodology I will use: density-functional theory (DFT), time-dependent density-functional theory (TDDFT), and many-body perturbation theory based on the GW approximation. In the subsequent chapters, I will further discuss, develop, and apply this methodology. 2. I will give a pedagogical derivation of the methods for calculating response properties in TDDFT, with particular focus on the Sternheimer equation, as will be used in subsequent chapters. I will review the many different response properties that can be calculated (dynamic and static) and the appropriate perturbations used to calculate them. 3. Standard techniques for calculating response use either integer occupations (as appropriate for a system with an energy gap) or fractional occupations due to a smearing function, used to improve convergence for metallic systems. I will present a generalization which can be used to compute response for a system with arbitrary fractional occupations. 4. Chloroform (CHCl3) is a small molecule commonly used as a solvent in measurements of nonlinear optics. I computed its hyperpolarizability for second

  13. Challenges for single molecule electronic devices with nanographene and organic molecules. Do single molecules offer potential as elements of electronic devices in the next generation?

    Science.gov (United States)

    Enoki, Toshiaki; Kiguchi, Manabu

    2018-03-01

    Interest in utilizing organic molecules to fabricate electronic materials has existed ever since organic (molecular) semiconductors were first discovered in the 1950s. Since then, scientists have devoted serious effort to the creation of various molecule-based electronic systems, such as molecular metals and molecular superconductors. Single-molecule electronics and the associated basic science have emerged over the past two decades and provided hope for the development of highly integrated molecule-based electronic devices in the future (after the Si-based technology era has ended). Here, nanographenes (nano-sized graphene) with atomically precise structures are among the most promising molecules that can be utilized for electronic/spintronic devices. To manipulate single small molecules for an electronic device, a single molecular junction has been developed. It is a powerful tool that allows even small molecules to be utilized. External electric, magnetic, chemical, and mechanical perturbations can change the physical and chemical properties of molecules in a way that is different from bulk materials. Therefore, the various functionalities of molecules, along with changes induced by external perturbations, allows us to create electronic devices that we cannot create using current top-down Si-based technology. Future challenges that involve the incorporation of condensed matter physics, quantum chemistry calculations, organic synthetic chemistry, and electronic device engineering are expected to open a new era in single-molecule device electronic technology.

  14. Spin-polarized light-emitting diodes based on organic bipolar spin valves

    Energy Technology Data Exchange (ETDEWEB)

    Vardeny, Zeev Valentine; Nguyen, Tho Duc; Ehrenfreund, Eitan Avraham

    2017-10-25

    Spin-polarized organic light-emitting diodes are provided. Such spin-polarized organic light-emitting diodes incorporate ferromagnetic electrodes and show considerable spin-valve magneto-electroluminescence and magneto-conductivity responses, with voltage and temperature dependencies that originate from the bipolar spin-polarized space charge limited current.

  15. Polar Organizing Protein PopZ Is Required for Chromosome Segregation in Agrobacterium tumefaciens.

    Science.gov (United States)

    Ehrle, Haley M; Guidry, Jacob T; Iacovetto, Rebecca; Salisbury, Anne K; Sandidge, D J; Bowman, Grant R

    2017-09-01

    Despite being perceived as relatively simple organisms, many bacteria exhibit an impressive degree of subcellular organization. In Caulobacter crescentus , the evolutionarily conserved polar organizing protein PopZ facilitates cytoplasmic organization by recruiting chromosome centromeres and regulatory proteins to the cell poles. Here, we characterize the localization and function of PopZ in Agrobacterium tumefaciens , a genetically related species with distinct anatomy. In this species, we find that PopZ molecules are relocated from the old pole to the new pole in the minutes following cell division. PopZ is not required for the localization of the histidine kinases DivJ and PdhS1, which become localized to the old pole after PopZ relocation is complete. The histidine kinase PdhS2 is temporally and spatially related to PopZ in that it localizes to transitional poles just before they begin to shed PopZ and disappears from the old pole after PopZ relocalization. At the new pole, PopZ is required for tethering the centromere of at least one of multiple replicons (chromosome I), and the loss of popZ results in a severe chromosome segregation defect, aberrant cell division, and cell mortality. After cell division, the daughter that inherits polar PopZ is shorter in length and delayed in chromosome I segregation compared to its sibling. In this cell type, PopZ completes polar relocation well before the onset of chromosome segregation. While A. tumefaciens PopZ resembles its C. crescentus homolog in chromosome tethering activity, other aspects of its localization and function indicate distinct properties related to differences in cell organization. IMPORTANCE Members of the Alphaproteobacteria exhibit a wide range of phenotypic diversity despite sharing many conserved genes. In recent years, the extent to which this diversity is reflected at the level of subcellular organization has become increasingly apparent. However, which factors control such organization and how

  16. Field-free orientation of diatomic molecule via the linearly polarized resonant pulses

    Science.gov (United States)

    Li, Su-Yu; Guo, Fu-Ming; Wang, Jun; Yang, Yu-Jun; Jin, Ming-Xing

    2015-10-01

    We propose a scheme to coherently control the field-free orientation of NO molecule whose rotational temperature is above 0 K. It is found that the maximum molecular orientation is affected by two factors: one is the sum of the population of M = 0 rotational states and the other is their distribution, however, their distribution plays a much more significant role in molecular orientation than the sum of their population. By adopting a series of linearly polarized pulses resonant with the rotational states, the distribution of M = 0 rotational states is well rearranged. Though the number of pulses used is small, a relatively high orientation degree can be obtained. This scheme provides a promising approach to the achievement of a good orientation effect. Project supported by the National Basic Research Program of China (Grant No. 2013CB922200), the National Natural Science Foundation of China (Grant Nos. 11034003, 11474129, 11274141, and 11304116), the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20130061110021), and the Graduate Innovation Fund of Jilin University (Grant No. 2015091).

  17. Multiorbital effects in strong-field ionization and dissociation of aligned polar molecules CH3I and CH3Br

    Science.gov (United States)

    Luo, Sizuo; Zhou, Shushan; Hu, Wenhui; Li, Xiaokai; Ma, Pan; Yu, Jiaqi; Zhu, Ruihan; Wang, Chuncheng; Liu, Fuchun; Yan, Bing; Liu, Aihua; Yang, Yujun; Guo, Fuming; Ding, Dajun

    2017-12-01

    Controlling the molecular axis offers additional ways to study molecular ionization and dissociation in strong laser fields. We measure the ionization and dissociation yields of aligned polar CH3X (X =I , Br) molecules in a linearly polarized femtosecond laser field. The current data show that maximum ionization occurs when the laser polarization is perpendicular to the molecular C -X axis, and dissociation prefers to occur at the laser polarization parallel to the C -X axis. The observed angular distributions suggest that the parent ions are generated by ionization from the HOMO. The angular distribution of fragment ions indicates that dissociation occurs mainly from an ionic excited state produced by ionization from the HOMO-1.

  18. Photodegradation and polarization properties of vertical external surface-emitting organic laser

    International Nuclear Information System (INIS)

    Leang, Tatiana

    2014-01-01

    Although organic solid-state dye lasers can provide wavelength tunability in the whole visible spectrum and offers perspectives of low-cost compact lasers, they are still limited by several drawbacks, especially photodegradation. The geometry of a Vertical External Cavity Surface-emitting Organic Laser (VECSOL) enables organic lasers to reach high energies, excellent conversion efficiencies and good beam quality, it also enables an external control on many parameters, a feature that we have used here to study the photodegradation phenomenon as well as some polarization properties of organic solid-state lasers. In the first part of this thesis, we studied the lifetime of the laser upon varying several parameters (pump pulse-width, repetition rate, output coupling,...) and we found that the intracavity laser intensity, independently of the pump intensity, had a major on photodegradation rate. Moreover, we observed that the profile of the laser beam was also degrading with time: while it is Gaussian in the beginning it gradually shifts to an annular shape. In the second part, we investigated the polarization properties of VECSOLs, with a special emphasis on fluorescence properties of some typical dyes used in lasers. The crucial role played by resonant non-radiative energy transfers between dye molecules (HOMO-FRET) is evidenced and enables explaining the observed fluorescence depolarization, compared to the expected limiting fluorescence anisotropy. Energy transfers happen to play a negligible role above laser threshold, as the organic laser beam is shown to be linearly polarized in a wide range of experimental conditions when excitation occurs in the first singlet state. (author) [fr

  19. Fluorescence detection of organic molecules in the Jovian atmosphere.

    Science.gov (United States)

    Levine, J S; Rogowski, R S

    1975-07-01

    A search for fluorescent emission due to the presence of possible organic molecules in the Jovian atmosphere is described. We first consider natural Jovian fluorescent emission excited by precipitating auroral particles. Due to our lack of knowledge of the Jovian precipitation particle energies and fluxes we next consider fluorescent emission excited by a laser system aboard a Jupiter spacecraft. Laser-induced fluorescence is routinely used to monitor trace constituents and pollutants in the terrestrial atmosphere. Several spacecraft laser systems are currently under development. Our calculations indicate that laser-induced fluorescent detection is approximately two orders of magnitude more sensitive than rocket ultraviolet measurements of possible Jovian absorption features at 2600 A that have been attributed to the presence of adenine or benzene.

  20. Optimization of the polar organic chemical integrative sampler for the sampling of acidic and polar herbicides.

    Science.gov (United States)

    Fauvelle, Vincent; Mazzella, Nicolas; Belles, Angel; Moreira, Aurélie; Allan, Ian J; Budzinski, Hélène

    2014-05-01

    This paper presents an optimization of the pharmaceutical Polar Organic Chemical Integrative Sampler (POCIS-200) under controlled laboratory conditions for the sampling of acidic (2,4-dichlorophenoxyacetic acid (2,4-D), acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid, bentazon, dicamba, mesotrione, and metsulfuron) and polar (atrazine, diuron, and desisopropylatrazine) herbicides in water. Indeed, the conventional configuration of the POCIS-200 (46 cm(2) exposure window, 200 mg of Oasis® hydrophilic lipophilic balance (HLB) receiving phase) is not appropriate for the sampling of very polar and acidic compounds because they rapidly reach a thermodynamic equilibrium with the Oasis HLB receiving phase. Thus, we investigated several ways to extend the initial linear accumulation. On the one hand, increasing the mass of sorbent to 600 mg resulted in sampling rates (R s s) twice as high as those observed with 200 mg (e.g., 287 vs. 157 mL day(-1) for acetochlor ESA). Although detection limits could thereby be reduced, most acidic analytes followed a biphasic uptake, proscribing the use of the conventional first-order model and preventing us from estimating time-weighted average concentrations. On the other hand, reducing the exposure window (3.1 vs. 46 cm(2)) allowed linear accumulations of all analytes over 35 days, but R s s were dramatically reduced (e.g., 157 vs. 11 mL day(-1) for acetochlor ESA). Otherwise, the observation of biphasic releases of performance reference compounds (PRC), though mirroring acidic herbicide biphasic uptake, might complicate the implementation of the PRC approach to correct for environmental exposure conditions.

  1. Fgf8-related secondary organizers exert different polarizing planar instructions along the mouse anterior neural tube.

    Directory of Open Access Journals (Sweden)

    Ivan Crespo-Enriquez

    Full Text Available Early brain patterning depends on proper arrangement of positional information. This information is given by gradients of secreted signaling molecules (morphogens detected by individual cells within the responding tissue, leading to specific fate decisions. Here we report that the morphogen FGF8 exerts initially a differential signal activity along the E9.5 mouse neural tube. We demonstrate that this polarizing activity codes by RAS-regulated ERK1/2 signaling and depends on the topographical location of the secondary organizers: the isthmic organizer (IsO and the anterior neural ridge (anr but not on zona limitans intrathalamica (zli. Our results suggest that Sprouty2, a negative modulator of RAS/ERK pathway, is important for regulating Fgf8 morphogenetic signal activity by controlling Fgf8-induced signaling pathways and positional information during early brain development.

  2. Chemical and electrochemical oxidation of small organic molecules

    Science.gov (United States)

    Smart, Marshall C.

    Direct oxidation fuel cells using proton-exchange membrane electrolytes have long been recognized as being an attractive mode of power generation. The current work addresses the electro-oxidation characteristics of a number of potential fuels on Pt-based electrodes which can be used in direct oxidation fuel cells, including hydrocarbons and oxygenated molecules, such as alcohols, formates, ethers, and acetals. Promising alternative fuels which were identified, such as trimethoxymethane and dimethoxymethane, were then investigated in liquid-feed PEM-based fuel cells. In addition to investigating the nature of the anodic electro-oxidation of organic fuels, effort was also devoted to developing novel polymer electrolyte membranes which have low permeability to organic molecules, such as methanol. This research was initiated with the expectation of reducing the extent of fuel crossover from the anode to the cathode in the liquid-feed design fuel cell which results in lower fuel efficiency and performance. Other work involving efforts to improve the performance of direct oxidation fuel cell includes research focused upon improving the kinetics of oxygen reduction. There is continued interest in the identification of new, safe, non-toxic, and inexpensive reagents which can be used in the oxidation of organic compounds. Urea-hydrogen peroxide (UHP), a hydrogen bonded adduct, has been shown to serve as a valuable source of hydrogen peroxide in a range of reactions. UHP has been shown to be ideal for the monohydroxylation of aromatics, including toluene, ethylbenzene, p-xylene, m-xylene, and mesitylene, as well as benzene, in the presence of trifluoromethanesulfonic acid. It was also found that aniline was converted to a mixture containing primarily azobenzene, azoxybenzene and nitrobenzene when reacted with UHP in glacial acetic acid. A number of aniline derivatives have been investigated and it was observed that the corresponding azoxybenzene derivatives could be

  3. Enantiomeric separation of complex organic molecules produced from irradiation of interstellar/circumstellar ice analogs

    Science.gov (United States)

    Nuevo, M.; Meierhenrich, U. J.; D'Hendecourt, L.; Muñoz Caro, G. M.; Dartois, E.; Deboffle, D.; Thiemann, W. H.-P.; Bredehöft, J.-H.; Nahon, L.

    Irradiation of interstellar/circumstellar ice analogs by ultraviolet (UV) light followed by warm up in the laboratory leads to the formation of complex organic molecules, stable at room temperature. Hydrolysis of the room temperature residue releases amino acids, the building blocks of proteins. These amino acids exist in two different forms (L and D), but proteins encountered in living beings consist exclusively of L enantiomers. The origin of this property, called homochirality, is still unknown. Amino acids can be detected and quantified by chemical techniques such as chiral gas chromatography coupled with mass spectrometry (GC-MS). Enantiomers of chiral organics are also known to interact selectively with circularly polarized light (CPL), leading to a selective production or destruction of the final compounds. This paper describes how we settled an experiment where amino acids are formed by irradiation of interstellar/circumstellar ice analogs with ultraviolet (UV) CPL, produced by a synchrotron radiation beamline, which allowed us to quantify the effect of such polarized light on the production of amino acids. These results can be compared to the enantiomeric excesses measured in primitive meteorites such as Murchison.

  4. Optimization of thermochemolysis analysis conditions for the in situ detection of organic compounds in Martian soil with the Mars Organic Molecule Analyzer (MOMA) experiment

    Science.gov (United States)

    Morisson, Marietta; Buch, Arnaud; Szopa, Cyril; Raulin, François; Stambouli, Moncef

    2017-04-01

    Martian surface is exposed to harsh radiative and oxidative conditions which are destructive for organic molecules. That is why the future ExoMars rover will examine the molecular composition of samples acquired from depths down to two meters below the Martian surface, where organics may have been protected from radiative and oxidative degradation. The samples will then be analyzed by the Pyrolysis-Gas Chromatography-Mass Spectrometry (Pyr-GC-MS) operational mode of the Mars Organic Molecule Analyzer (MOMA) instrument. To prevent thermal alteration of organic molecules during pyrolysis, thermochemolysis with tetramethylammonium hydroxide (TMAH) will extract the organics from the mineral matrix and methylate the polar functional groups, allowing the volatilization of molecules at lower temperatures and protecting the most labile chemical groups from thermal degradation. This study has been carried out on a Martian regolith analogue (JSC-Mars-1) with a high organic content with the aim of optimizing the thermochemolysis temperature within operating conditions similar to the MOMA experiment ones. We also performed Pyrolysis-GC-MS analysis as a comparison. The results show that, unlike pyrolysis alone - which mainly produces aromatics, namely thermally altered molecules - thermochemolysis allows the extraction and identification of numerous organic molecules of astrobiological interest. They also show that the main compounds start to be detectable at low thermochemolysis temperatures ranging from 400°C to 600°C. However, we noticed that the more the temperature increases, the more the chromatograms are saturated with thermally evolved molecules leading to many coelutions and making identification difficult.

  5. Linear Ion Trap for the Mars Organic Molecule Analyzer

    Science.gov (United States)

    Brinckerhoff, William; Arevalo, Ricardo; Danell, Ryan; van Amerom, Friso; Pinnick, Veronica; Li, Xiang; Hovmand, Lars; Getty, Stephanie; Mahaffy, Paul; Goesmann, Fred; Steininger, Harald

    2014-05-01

    The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. MOMA includes a linear, or 2D, ion trap mass spectrometer (ITMS) that is designed to analyze molecular composition of (i) gas evolved from pyrolyzed powder samples and separated on a gas chromatograph and (ii) ions directly desorbed from solid samples at Mars ambient pressure using a pulsed laser and a fast-valve capillary ion inlet system. This "dual source" approach gives MOMA unprecedented breadth of detection over a wide range of molecular weights and volatilities. Analysis of nonvolatile, higher-molecular weight organics such as carboxylic acids and peptides even in the presence of significant perchlorate concentrations is enabled by the extremely short (~1 ns) pulses of the desorption laser. Use of the ion trap's tandem mass spectrometry mode permits selective focus on key species for isolation and controlled fragmentation, providing structural analysis capabilities. The flight-like engineering test unit (ETU) of the ITMS, now under construction, will be used to verify breadboard performance with high fidelity, while simultaneously supporting the development of analytical scripts and spectral libraries using synthetic and natural Mars analog samples guided by current results from MSL. ETU campaign data will strongly advise the specifics of the calibration applied to the MOMA flight model as well as the science operational procedures during the mission.

  6. Conjugated donor-acceptor-acceptor (D-A-A) molecule for organic nonvolatile resistor memory.

    Science.gov (United States)

    Dong, Lei; Li, Guangwu; Yu, An-Dih; Bo, Zhishan; Liu, Cheng-Liang; Chen, Wen-Chang

    2014-12-01

    A new donor-acceptor-acceptor (D-A-A) type of conjugated molecule, N-(4-(N',N'-diphenyl)phenylamine)-4-(4'-(2,2-dicyanovinyl)phenyl) naphthalene-1,8-dicarboxylic monoimide (TPA-NI-DCN), consisting of triphenylamine (TPA) donors and naphthalimide (NI)/dicyanovinylene (DCN) acceptors was synthesized and characterized. In conjunction with previously reported D-A based materials, the additional DCN moiety attached as end group in the D-A-A configuration can result in a stable charge transfer (CT) and charge-separated state to maintain the ON state current. The vacuum-deposited TPA-NI-DCN device fabricated as an active memory layer was demonstrated to exhibit write-once-read-many (WORM) switching characteristics of organic nonvolatile memory due to the strong polarity of the TPA-NI-DCN moiety. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The Mars Organic Molecule Analyser : in situ analysis of organic compounds on Mars by Gas Chromatography-Mass Spectrometry.

    Science.gov (United States)

    Buch, Arnaud; Sternberg, Robert; Freissinet, Caroline; Pinnick, Veronika; Szopa, Cyril; Coll, Patrice; Geffroy-Rodier, Claude; Raulin, Francois; Goesmann, Fred

    The search for signs of past or present life is one of the primary goals of the future Mars exploratory missions. With this aim the Mars Organic Molecule Analyzer (MOMA) experiment of the ExoMars 2016-2018 next coming joint ESA/NASA mission is designed to perform the in situ analysis of exobiological organic molecules of exobiological interest in the Martian soil such as amino acids, carboxylic acids, nucleobases or polycyclic aromatic hydrocarbons (PAHs). With the aim to separate and detect organic compounds from Martian soil, US and European teams have respectively built an ion trap mass spectrometer and a gas chromatograph. The mass spectrometer prototype has been coupled with the gas chromatograph prototype which is able to work in standalone mode by using a TCD detector. A GC-MS compatible sample processing system (SPS) allowing the extraction and the chemical transformation of the organic compounds from the soil, within space compatible operating conditions, has also been devel-oped. The sample processing is performed in an oven, dedicated to the MOMA experiment containing the solid sample (50-100mg). The internal temperature of which can be ranged from 20 to 1000 C. The extraction step is achieved by using thermodesorption in the range of 100 to 300C for 5 to 20 min. Then, the chemical derivatization and/or thermochemolysis of the extracted compounds is performed directly on the soil with a mixture of MTBSTFA-DMF, TMAH or DMF-DMA solution when enantiomeric separation is required. By decreasing the polarity of the target molecules, this step allows their volatilization at a temperature below 250C without any chemical degradation. Once derivatized, the volatile target molecules are trapped in a cold and chemical trap and promptly desorbed into the gas chromatograph coupled with a mass spectrometer. Preliminary tests, performed on Martian analogue soils (Atacama), with the MOMA SPS-GC/MS experiment, allowed the detection of organic compounds such as amino and

  8. Formation of highly oxygenated organic molecules from aromatic compounds

    Directory of Open Access Journals (Sweden)

    U. Molteni

    2018-02-01

    Full Text Available Anthropogenic volatile organic compounds (AVOCs often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs, such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene and ethylbenzene, as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl. We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

  9. Developing powerful tritide technique: Organic and biological molecule labeling

    International Nuclear Information System (INIS)

    Anon.

    1991-01-01

    Complex hydrides are very important reagents in organic synthesis due to the range of reducing powers and selectivities available from different agents. Unfortunately, the availability of these compounds for radiosynthesis has been extremely limited due to the difficulty of making them with adequate levels of tritium. Investigators at the Lawrence Berkeley Laboratory (LBL) National Tritium Labeling Facility have developed a new addition to the repertoire of the tritium-labeling chemist. The new method allows site-specific incorporation of tritium into organic and biological molecules by efficient reduction processes. Exceptionally reactive and selective reducing agents are prepared and used for labeling in a on-pot process. Three new tritide reagents - supertritide (lithium triethyl borotritide), LiAlT 4 (lithium aluminum tritide), and L-Selectride (sterically hindered lithium tri-sec-butyl borotritide) - have been synthesized at carrier-free levels, and have been demonstrated to be fully reactive. The availability of these versatile and reactive reagents gives the tritium radiochemist great control over chemoselectivity and stereoselectivity. The LBL tritide reagents can drive numerous conventional chemical reactions, and have been used to reduce p-toluene sulfonates, amides, lactones, esters, and aldehydes. These reactions produce good yields and result in products with maximum specific activities. The reagents clearly exhibit superior reactivity and may be used in many more synthetic processes than sodium borohydride, which is the currently used reagent. In addition, tritide reagents such as L-selectride have been shown to give greater control over stereochemistry and selectivity than sodium borohydride

  10. Formation of highly oxygenated organic molecules from aromatic compounds

    Science.gov (United States)

    Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs

    2018-02-01

    Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

  11. Self-organized spatiotemporal patterns of PIP3 and PTEN during spontaneous cell polarization

    Science.gov (United States)

    Knoch, Fabian; Tarantola, Marco; Rappel, Wouter-Jan; Bodenschatz, Eberhard

    2014-03-01

    During spontaneous cell polarization of Dictyostelium discoideum cells, PIP3 (phosphatidylinositol (3,4,5)-triphoshpate) and PTEN (phosphatase tensin homolog) have been identified as key signaling molecules, which govern the process of polarization in a self-organized manner. Gerisch et al. have shown that randomly triggered excitable PIP3 waves regulate the anti-correlated PTEN concentration. Here we show that this requires a switch-like dynamics of the overall membrane bound PTEN concentration in combination with two species of PTEN differing in their dephosphorylation rates. A quantitative modeling with a coupled reaction-diffusion system shows excellent agreement with experimental results and predicts a ratio σ of dephosphorylation rates acting on PIP3 of σ ~ 80 - 100. Our quantitative analysis suggests that surface-attached cell membrane spanning PIP3 waves are necessary for resetting the global actin network. This is evidenced by the experimentally observed delay between polarization-cycles also quantitatively captured by our analysis. Max Planck Society and Center for Theoretical Biological Physics.

  12. Electrochemical behavior of uranyl in anhydrous polar organic media

    Energy Technology Data Exchange (ETDEWEB)

    Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

    2017-09-01

    Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

  13. Functional fixedness and functional reduction as common sense reasonings in chemical equilibrium and in geometry and polarity of molecules

    Science.gov (United States)

    Furió, C.; Calatayud, M. L.; Bárcenas, S. L.; Padilla, O. M.

    2000-09-01

    Many of the learning difficulties in the specific domain of chemistry are found not only in the ideas already possessed by students but in the strategic and procedural knowledge that is characteristic of everyday thinking. These defects in procedural knowledge have been described as functional fixedness and functional reduction. This article assesses the procedural difficulties of students (grade 12 and first and third year of university) based on common sense reasoning in two areas of chemistry: chemical equilibrium and geometry and polarity of molecules. In the first area, the theme of external factors affecting equilibria (temperature and concentration change) was selected because the explanations given by the students could be analyzed easily. The existence of a functional fixedness where Le Chatelier's principle was almost exclusively applied by rote could be observed, with this being the cause of the incorrect responses given to the proposed items. Functional fixedness of the Lewis structure also led to an incorrect prediction of molecular geometry. When molecular geometry was correctly determined by the students, it seemed that other methodological or procedural difficulties appeared when the task was to determine molecular polarity. The students showed a tendency, in many cases, to reduce the factors affecting molecular polarity in two possible ways: (a) assuming that polarity depends only on shape (geometric functional reduction) or (b) assuming that molecular polarity depends only on the polarity of bonds (bonding functional reduction).

  14. M-CARS and EFISHG study of the influence of a static electric field on a non-polar molecule

    Science.gov (United States)

    Capitaine, E.; Louot, C.; Ould-Moussa, N.; Lefort, C.; Kaneyasu, J. F.; Kano, H.; Pagnoux, D.; Couderc, V.; Leproux, P.

    2016-03-01

    The influence of a static electric field on a non-polar molecule has been studied by means of multiplex coherent anti-Stokes Raman scattering (M-CARS). A parallel measurement of electric field induced second harmonic generation (EFISHG) has also been led. Both techniques suggest a reorientation of the molecule due to the presence of an electric field. This phenomenon can be used to increase the chemical selectivity and the signal to non-resonant background ratio, namely, the sensitivity of the M-CARS spectroscopy.

  15. Ionization of one- and three-dimensionally-oriented asymmetric-top molecules by intense circularly polarized femtosecond laser pulses

    DEFF Research Database (Denmark)

    Hansen, Jonas Lerche; Holmegaard, Lotte; Kalhøj, Line

    2011-01-01

    are quantum-state selected using a deflector and three-dimensionally (3D) aligned and oriented adiabatically using an elliptically polarized laser pulse in combination with a static electric field. A characteristic splitting in the molecular frame photoelectron momentum distribution reveals the position......We present a combined experimental and theoretical study on strong-field ionization of a three-dimensionally-oriented asymmetric top molecule, benzonitrile (C7H5N), by circularly polarized, nonresonant femtosecond laser pulses. Prior to the interaction with the strong field, the molecules...... of the nodal planes of the molecular orbitals from which ionization occurs. The experimental results are supported by a theoretical tunneling model that includes and quantifies the splitting in the momentum distribution. The focus of the present article is to understand strong-field ionization from 3D...

  16. Small molecules as tracers in atmospheric secondary organic aerosol

    Science.gov (United States)

    Yu, Ge

    Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and

  17. Single Molecule Study of DNA Organization and Recombination

    Science.gov (United States)

    Xiao, Botao

    We have studied five projects related to DNA organization and recombination using mainly single molecule force-spectroscopy and statistical tools. First, HU is one of the most abundant DNA-organizing proteins in bacterial chromosomes and participates in gene regulation. We report experiments that study the dependence of DNA condensation by HU on force, salt and HU concentration. A first important result is that at physiological salt levels, HU only bends DNA, resolving a previous paradox of why a chromosome-compacting protein should have a DNA-stiffening function. A second major result is quantitative demonstration of strong dependencies of HU-DNA dissociation on both salt concentration and force. Second, we have used a thermodynamic Maxwell relation to count proteins driven off large DNAs by tension, an effect important to understanding DNA organization. Our results compare well with estimates of numbers of proteins HU and Fis in previous studies. We have also shown that a semi-flexible polymer model describes our HU experimental data well. The force-dependent binding suggests mechano-chemical mechanisms for gene regulation. Third, the elusive role of protein H1 in chromatin has been clarified with purified H1 and Xenopus extracts. We find that H1 compacts DNA by both bending and looping. Addition of H1 enhances chromatin formation and maintains the plasticity of the chromatin. Fourth, the topology and mechanics of DNA twisting are critical to DNA organization and recombination. We have systematically measured DNA extension as a function of linking number density from 0.08 to -2 with holding forces from 0.2 to 2.4 pN. Unlike previous proposals, the DNA extension decreases with negative linking number. Finally, DNA recombination is a dynamic process starting from enzyme-DNA binding. We report that the Int-DBD domain of lambda integrase binds to DNA without compaction at low Int-DBD concentration. High concentration of Int-DBD loops DNA below a threshold force

  18. Probing the origin of elliptical high-order harmonic generation from aligned molecules in linearly polarized laser fields

    International Nuclear Information System (INIS)

    Son, Sang-Kil; Telnov, Dmitry A.; Chu, Shih-I.

    2010-01-01

    A recent experiment [Phys. Rev. Lett. 102, 073902 (2009)] has demonstrated that elliptically polarized high-order harmonic generation can be produced from linearly polarized driving fields for aligned molecular systems. In order to reveal the underlying physical mechanisms of elliptical harmonics, we present fully ab initio and high-precision calculations and analyses of the amplitude, phase, and polarization state of the harmonic radiation from molecular hydrogen ions with arbitrary orientation. We find that high ellipticity arises from molecular orbital symmetry and two-center interference effects. Our ab initio exploration and findings lead to a general rule that the ellipticity becomes high for molecular orbitals represented by a symmetric combination of atomic orbitals, whereas it becomes low for molecular orbitals represented by an antisymmetric combination. This finding also applies to the general case of aligned linear molecules.

  19. Singlet oxygen: photosensitized generation, detection and reaction with organic molecules

    International Nuclear Information System (INIS)

    Barik, Atanu; Indira Priyadarsini, K.; Hari Mohan; Bajaj, P.N.; Sapre, A.V.; Mittal, J.P.; Mukherjee, T.

    2006-10-01

    Singlet molecular oxygen ( 1 O 2 ) is an excited state of molecular oxygen, having antiparallel spin in the same π antibonding orbital. The study of singlet oxygen production and reactivity has emerged as a rich and diverse area, with implication in diverse fields, such as synthetic chemistry, polymer chemistry, photodynamic therapy, etc. There are several known methods to produce singlet oxygen, and also various techniques employed to detect it. Out of these, photosensitization method is the most popular one. In this article, photosensitized production of singlet oxygen from triplet oxygen and photosensitizers in presence of light, and its detection by the infrared luminescence at 1270 nm have been presented. Further, some results using different types of photosensitizers, effect of solvent on singlet oxygen quantum yields and lifetime have been discussed. The quenching rate constants of singlet oxygen have been determined with different types of organic molecules such as derivatives of thiourea and its analogues, hydroxy indoles and antioxidants and the results have been presented. (author)

  20. Aperture Valve for the Mars Organic Molecule Analyzer (MOMA)

    Science.gov (United States)

    Hakun, Claef F.; Engler, Charles D.; Barber, Willie E.; Canham, John S.

    2014-01-01

    NASA's participation in the multi-nation ExoMars 2018 Rover mission includes a critical astrobiology Mass Spectrometer Instrument on the Rover called the Mars Organic Molecule Analyzer (MOMA). The Aperture Valve is a critical electromechanical valve used by the Mass Spectrometer to facilitate the transfer of ions from Martian soil to the Mass Spectrometer for analysis. The MOMA Aperture Valve development program will be discussed in terms of the Initial valve design and subsequent improvements that resulted from prototype testing. The Initial Aperture Valve concept seemed promising, based on calculations and perceived merits. However, performance results of this design were disappointing, due to delamination of TiN and DLC coatings applied to the Titanium base metals, causing debris from the coatings to seize the valve. While peer reviews and design trade studies are important forums to vet a concept design, results from testing should not be underestimated.Despite the lack of development progress to meet requirements, valuable information from weakness discovered in the Initial Valve design was used to develop a second, more robust Aperture valve. Based on a check-ball design, the ETU flight valve design resulted in significantly less surface area to create the seal. Moreover, PVD coatings were eliminated in favor of hardened, nonmagnetic corrosion resistant alloys. Test results were impressive, with the valve achieving five orders of magnitude better sealing leak rate over end of life requirements. Cycle life was equally impressive, achieving 280,000 cycles without failure.

  1. Diester Molecules for Organic-Based Electrical and Photoelectrical Devices

    Science.gov (United States)

    Topal, Giray; Tombak, Ahmet; Yigitalp, Esref; Batibay, Derya; Kilicoglu, Tahsin; Ocak, Yusuf Selim

    2017-07-01

    Diester derivatives of terephthalic acid molecules were synthesized according to the literature. Au/Diester derivatives/ n-Si organic-inorganic (OI) heterojunction-type devices were fabricated, and the current-voltage ( I- V) characteristics of the devices have been investigated at room temperature. I- V characteristics demonstrated that all diodes had excellent rectification properties. Primary diode parameters such as series resistance and barrier height were extracted by using semi-log I- V plots and Norde methods, and were compared. It was seen that there was a substantial agreement between results obtained from two methods. Calculated barrier height values were about the same with 0.02-eV differences that were attributed to the series resistance. Ideality factors, which show how the diode closes to ideal diodes, were also extracted from semi-log I- V plots. Thus, the modification of the Au/ n-Si diode potential barrier was accomplished using diester derivatives as an interlayer. The I- V measurements were repeated to characterize the devices at 100 mW/cm2 illumination intensity with the help of a solar simulator with an AM1.5G filter.

  2. Modeling self-organized spatio-temporal patterns of PIP₃ and PTEN during spontaneous cell polarization.

    Science.gov (United States)

    Knoch, Fabian; Tarantola, Marco; Bodenschatz, Eberhard; Rappel, Wouter-Jan

    2014-08-01

    During spontaneous cell polarization of Dictyostelium discoideum cells, phosphatidylinositol (3,4,5)-triphoshpate (PIP3) and PTEN (phosphatase tensin homolog) have been identified as key signaling molecules which govern the process of polarization in a self-organized manner. Recent experiments have quantified the spatio-temporal dynamics of these signaling components. Surprisingly, it was found that membrane-bound PTEN can be either in a high or low state, that PIP3 waves were initiated in areas lacking PTEN through an excitable mechanism, and that PIP3 was degraded even though the PTEN concentration remained low. Here we develop a reaction-diffusion model that aims to explain these experimental findings. Our model contains bistable dynamics for PTEN, excitable dynamics for PIP3, and postulates the existence of two species of PTEN with different dephosphorylation rates. We show that our model is able to produce results that are in good qualitative agreement with the experiments, suggesting that our reaction-diffusion model underlies the self-organized spatio-temporal patterns observed in experiments.

  3. CO2 Binding Organic Liquids Gas Capture with Polarity Swing Assisted Regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Heldebrant, David [Battelle Memorial Institute, Columbus, OH (United States)

    2014-05-31

    This report outlines the comprehensive bench-scale testing of the CO2-binding organic liquids (CO2BOLs) solvent platform and its unique Polarity Swing Assisted Regeneration (PSAR). This study outlines all efforts on a candidate CO2BOL solvent molecule, including solvent synthesis, material characterization, preliminary toxicology studies, and measurement of all physical, thermodynamic and kinetic data, including bench-scale testing. Equilibrium and kinetic models and analysis were made using Aspen Plus™. Preliminary process configurations, a technoeconomic assessment and solvent performance projections for separating CO2 from a subcritical coal-fired power plant are compared to the U.S. Department of Energy's Case 10 monoethanolamine baseline.

  4. Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors

    KAUST Repository

    Ryno, Sean

    2016-05-16

    The polarizable environment surrounding charge carriers in organic semiconductors impacts the efficiency of the charge transport process. Here, we consider two representative organic semiconductors, tetracene and rubrene, and evaluate their polarization energies in the bulk and at the organic-vacuum interface using a polarizable force field that accounts for induced-dipole and quadrupole interactions. Though both oligoacenes pack in a herringbone motif, the tetraphenyl substituents on the tetracene backbone of rubrene alter greatly the nature of the packing. The resulting change in relative orientations of neighboring molecules is found to reduce the bulk polarization energy of holes in rubrene by some 0.3 eV when compared to tetracene. The consideration of model organic-vacuum interfaces highlights the significant variation in the electrostatic environment for a charge carrier at a surface although the net change in polarization energy is small; interestingly, the environment of a charge even just one layer removed from the surface can be viewed already as representative of the bulk. Overall, it is found that in these herringbone-type layered crystals the polarization energy has a much stronger dependence on the intralayer packing density than interlayer packing density.

  5. Luminescent systems based on the isolation of conjugated PI systems and edge charge compensation with polar molecules on a charged nanostructured surface

    Science.gov (United States)

    Ivanov, Ilia N.; Puretzky, Alexander A.; Zhao, Bin; Geohegan, David B.; Styers-Barnett, David J.; Hu, Hui

    2014-07-15

    A photoluminescent or electroluminescent system and method of making a non-luminescent nanostructured material into such a luminescent system is presented. The method of preparing the luminescent system, generally, comprises the steps of modifying the surface of a nanostructured material to create isolated regions to act as luminescent centers and to create a charge imbalance on the surface; applying more than one polar molecule to the charged surface of the nanostructured material; and orienting the polar molecules to compensate for the charge imbalance on the surface of the nanostructured material. The compensation of the surface charge imbalance by the polar molecules allows the isolated regions to exhibit luminescence.

  6. Evolution of organic molecules under Mars-like UV radiation conditions in space and laboratory

    Science.gov (United States)

    Rouquette, L.; Stalport, F.; Cottin, H.; Coll, P.; Szopa, C.; Saiagh, K.; Poch, O.; Khalaf, D.; Chaput, D.; Grira, K.; Dequaire, T.

    2017-09-01

    The detection and identification of organic molecules at Mars are of prime importance, as some of these molecules are life precursors and components. While in situ planetary missions are searching for them, it is essential to understand how organic molecules evolve and are preserved at the surface of Mars. Indeed the harsh conditions of the environment of Mars such as ultraviolet (UV) radiation or oxidative processes could explain the low abundance and diversity of organic molecules detected by now [1]. In order to get a better understanding of the evolution of organic matter at the surface of Mars, we exposed organic molecules under a Mars-like UV radiation environment. Similar organic samples were exposed to the Sun radiation, outside the International Space Station (ISS), and under a UV lamp (martian pressure and temperature conditions) in the laboratory. In both experiments, organic molecules tend to photodegrade under Mars-like UV radiation. Minerals, depending on their nature, can protect or accelerate the degradation of organic molecules. For some molecules, new products, possibly photoresistant, seem to be produced. Finally, experimenting in space allow us to get close to in situ conditions and to validate our laboratory experiment while the laboratory experiment is essential to study the evolution of a large amount and diversity of organic molecules.

  7. Molecules with multiple switching units on a Au(111) surface: self-organization and single-molecule manipulation

    Science.gov (United States)

    Mielke, Johannes; Selvanathan, Sofia; Peters, Maike; Schwarz, Jutta; Hecht, Stefan; Grill, Leonhard

    2012-10-01

    Three different molecules, each containing two azobenzene switching units, were synthesized, successfully deposited onto a Au(111) surface by sublimation and studied by scanning tunneling microscopy at low temperatures. To investigate the influence of electronic coupling between the switching units as well as to the surface, the two azo moieties were connected either via π-conjugated para-phenylene or decoupling meta-phenylene bridges, and the number of tert-butyl groups was varied in the meta-phenylene-linked derivatives. Single molecules were found to be intact after deposition as identified by their characteristic appearance in STM images. Due to their mobility on the Au(111) surface at room temperature, the molecules spontaneously formed self-organized molecular arrangements that reflected their chemical structure. While lateral displacement of the molecules was accomplished by manipulation, trans-cis isomerization processes, typical for azobenzene switches, could not be induced.

  8. Relationship between infrared and Raman intensities in molecules with polarized π electrons

    Science.gov (United States)

    Tommasini, M.; Castiglioni, C.; Del Zoppo, M.; Zerbi, G.

    1999-05-01

    A model is presented which allows to obtain a linear relationship between infrared and Raman intensity parameters of the strongest vibrational bands of push-pull conjugated molecules. The results obtained clarify the origin of the exceptionally large values of the vibrational first hyperpolarizability shown by these molecules.

  9. Deceleration and trapping of polar molecules using time-varying electric fields

    NARCIS (Netherlands)

    Bethlem, Hendrick Lucas

    2002-01-01

    What we experience as an agreeable temperature is in fact due to a constant bombardment of our skin by very fast molecules. At room temperature the average velocity of air molecules around us is about 500 m/s, corresponding to about 2000 km/hour. Only at very low temperatures, close to the absolute

  10. The influence of non polar and polar molecules in mouse motile cells membranes and pure lipid bilayers.

    Directory of Open Access Journals (Sweden)

    Francisco J Sierra-Valdez

    Full Text Available We report an experimental study of mouse sperm motility that shows chief aspects characteristic of neurons: the anesthetic (produced by tetracaine and excitatory (produced by either caffeine or calcium effects and their antagonic action. While tetracaine inhibits sperm motility and caffeine has an excitatory action, the combination of these two substances balance the effects, producing a motility quite similar to that of control cells. We also study the effects of these agents (anesthetic and excitatory on the melting points of pure lipid liposomes constituted by 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC and dipalmitoyl phosphatidic acid (DPPA. Tetracaine induces a large fluidization of the membrane, shifting the liposomes melting transition temperature to much lower values. The effect of caffeine is null, but its addition to tetracaine-doped liposomes greatly screen the fluidization effect. A high calcium concentration stiffens pure lipid membranes and strongly reduces the effect of tetracaine. Molecular Dynamics Simulations are performed to further understand our experimental findings at the molecular level. We find a strong correlation between the effect of antagonic molecules that could explain how the mechanical properties suitable for normal cell functioning are affected and recovered.

  11. Controlling electron-electron correlation in frustrated double ionization of triatomic molecules with orthogonally polarized two-color laser fields

    Science.gov (United States)

    Chen, A.; Kling, M. F.; Emmanouilidou, A.

    2017-09-01

    We demonstrate the control of electron-electron correlation in frustrated double ionization (FDI) of the two-electron triatomic molecule D3 + when driven by two orthogonally polarized two-color laser fields. We employ a three-dimensional semiclassical model that fully accounts for the electron and nuclear motion in strong fields. We analyze the FDI probability and the distribution of the momentum of the escaping electron along the polarization direction of the longer wavelength and more intense laser field. These observables, when considered in conjunction, bear clear signatures of the prevalence or absence of electron-electron correlation in FDI, depending on the time delay between the two laser pulses. We find that D3 + is a better candidate than H2 for demonstrating also experimentally that electron-electron correlation indeed underlies FDI.

  12. Formation of intermediate products during the resonance stepwise polarization of dibenzyl ketone and benzil molecules

    International Nuclear Information System (INIS)

    Polevoi, A.V.; Matyuk, V.M.; Grigor'eva, G.A.; Potapov, V.K.

    1987-01-01

    The processes resulting in the intramolecular redistribution of energy in electronically excited S/sub ππ*/ states of dibenzyl ketone and benzil molecules have been investigated by laser mass spectrometry. The decisive role of dissociation under the conditions of the resonance stepwise photoionization of these molecules upon excitation by radiation with λ = 266 nm has been demonstrated. The ionization potentials of the molecules and the appearance potentials of fragment ions from dibenzyl ketone and benzil have been determined on the basis of an analysis of photoionization efficiency curves

  13. Evolution of organic molecules under Mars-like UV radiation conditions in space and laboratory

    OpenAIRE

    Rouquette, Laura; Stalport, Fabien; Cottin, Hervé; Coll, Patrice; Szopa, Cyril; Saiagh, Kafila; Poch, Olivier; Khalaf, Diana; Chaput, Didier; Grira, Katia; Dequaire, Tristan

    2017-01-01

    International audience; The detection and identification of organic molecules at Mars are of prime importance, as some of these molecules are life precursors and components. While in situ planetary missions are searching for them, it is essential to understand how organic molecules evolve and are preserved at the surface of Mars. Indeed the harsh conditions of the environment of Mars such as ultraviolet (UV) radiation or oxidative processes could explain the low abundance and diversity of org...

  14. Organic Materials in the Undergraduate Laboratory: Microscale Synthesis and Investigation of a Donor-Acceptor Molecule

    Science.gov (United States)

    Pappenfus, Ted M.; Schliep, Karl B.; Dissanayake, Anudaththa; Ludden, Trevor; Nieto-Ortega, Belen; Lopez Navarrete, Juan T.; Ruiz Delgado, M. Carmen; Casado, Juan

    2012-01-01

    A series of experiments for undergraduate courses (e.g., organic, physical) have been developed in the area of small molecule organic materials. These experiments focus on understanding the electronic and redox properties of a donor-acceptor molecule that is prepared in a convenient one-step microscale reaction. The resulting intensely colored…

  15. How many molecular layers of polar solvent molecules control chemistry? The concept of compensating dipoles.

    Science.gov (United States)

    Langhals, Heinz; Braun, Patricia; Dietl, Christian; Mayer, Peter

    2013-09-27

    The extension of the solvent influence of the shell into the volume of a polar medium was examined by means of anti-collinear dipoles on the basis of the E(T)(30) solvent polarity scale (i.e., the molar energy of excitation of a pyridinium-N-phenolatebetaine dye; generally: E(T) =28,591 nm kcal mol(-1)/λmax) where no compensation effects were found. As a consequence, solvent polarity effects are concentrated to a very thin layer of a few thousand picometres around the solute where extensions into the bulk solvent become unimportant. A parallelism to the thin surface layer of water to the gas phase is discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. High resolution SPM imaging of organic molecules with functionalized tips

    Czech Academy of Sciences Publication Activity Database

    Jelínek, Pavel

    2017-01-01

    Roč. 29, č. 34 (2017), 1-18, č. článku 343002. ISSN 0953-8984 R&D Projects: GA MŠk LM2015087; GA MŠk 8E15B010; GA ČR(CZ) GC14-16963J Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : atomic-force microscopy * scanning tunneling microscope * on-surface synthesis * single- molecule * AFM * STM * high resolution * molecule s * surfaces Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.649, year: 2016

  17. Prospects for reconstructing paleoenvironmental conditions from organic compounds in polar snow and ice

    Science.gov (United States)

    Giorio, Chiara; Kehrwald, Natalie; Barbante, Carlo; Kalberer, Markus; King, Amy C. F.; Thomas, Elizabeth R.; Wolff, Eric W.; Zennaro, Piero

    2018-03-01

    Polar ice cores provide information about past climate and environmental changes over periods ranging from a few years up to 800,000 years. The majority of chemical studies have focused on determining inorganic components, such as major ions and trace elements as well as on their isotopic fingerprint. In this paper, we review the different classes of organic compounds that might yield environmental information, discussing existing research and what is needed to improve knowledge. We also discuss the problems of sampling, analysis and interpretation of organic molecules in ice. This review highlights the great potential for organic compounds to be used as proxies for anthropogenic activities, past fire events from different types of biomass, terrestrial biogenic emissions and marine biological activity, along with the possibility of inferring past temperature fluctuations and even large-scale climate variability. In parallel, comprehensive research needs to be done to assess the atmospheric stability of these compounds, their ability to be transported long distances in the atmosphere, and their stability in the archive in order to better interpret their fluxes in ice cores. In addition, specific decontamination procedures, analytical methods with low detection limits (ng/L or lower), fast analysis time and low sample requests need to be developed in order to ensure a good time resolution in the archive.

  18. Prospects for reconstructing paleoenvironmental conditions from organic compounds in polar snow and ice

    Science.gov (United States)

    Giorio, Chiara; Kehrwald, Natalie; Barbante, Carlo; Kalberer, Markus; King, Amy C.F.; Thomas, Elizabeth R.; Wolff, Eric W.; Zennaro, Piero

    2018-01-01

    Polar ice cores provide information about past climate and environmental changes over periods ranging from a few years up to 800,000 years. The majority of chemical studies have focused on determining inorganic components, such as major ions and trace elements as well as on their isotopic fingerprint. In this paper, we review the different classes of organic compounds that might yield environmental information, discussing existing research and what is needed to improve knowledge. We also discuss the problems of sampling, analysis and interpretation of organic molecules in ice. This review highlights the great potential for organic compounds to be used as proxies for anthropogenic activities, past fire events from different types of biomass, terrestrial biogenic emissions and marine biological activity, along with the possibility of inferring past temperature fluctuations and even large-scale climate variability. In parallel, comprehensive research needs to be done to assess the atmospheric stability of these compounds, their ability to be transported long distances in the atmosphere, and their stability in the archive in order to better interpret their fluxes in ice cores. In addition, specific decontamination procedures, analytical methods with low detection limits (ng/L or lower), fast analysis time and low sample requests need to be developed in order to ensure a good time resolution in the archive.

  19. Distilling two-center-interference information during tunneling of aligned molecules with orthogonally polarized two-color laser fields

    Science.gov (United States)

    Gao, F.; Chen, Y. J.; Xin, G. G.; Liu, J.; Fu, L. B.

    2017-12-01

    When electrons tunnel through a barrier formed by the strong laser field and the two-center potential of a diatomic molecule, a double-slit-like interference can occur. However, this interference effect can not be probed directly right now, as it is strongly coupled with other dynamical processes during tunneling. Here, we show numerically and analytically that orthogonally polarized two-color (OTC) laser fields are capable of resolving the interference effect in tunneling, while leaving clear footprints of this effect in photoelectron momentum distributions. Moreover, this effect can be manipulated by changing the relative field strength of OTC fields.

  20. Expanding signaling-molecule wavefront model of cell polarization in the Drosophila wing primordium.

    Science.gov (United States)

    Wortman, Juliana C; Nahmad, Marcos; Zhang, Peng Cheng; Lander, Arthur D; Yu, Clare C

    2017-07-01

    In developing tissues, cell polarization and proliferation are regulated by morphogens and signaling pathways. Cells throughout the Drosophila wing primordium typically show subcellular localization of the unconventional myosin Dachs on the distal side of cells (nearest the center of the disc). Dachs localization depends on the spatial distribution of bonds between the protocadherins Fat (Ft) and Dachsous (Ds), which form heterodimers between adjacent cells; and the Golgi kinase Four-jointed (Fj), which affects the binding affinities of Ft and Ds. The Fj concentration forms a linear gradient while the Ds concentration is roughly uniform throughout most of the wing pouch with a steep transition region that propagates from the center to the edge of the pouch during the third larval instar. Although the Fj gradient is an important cue for polarization, it is unclear how the polarization is affected by cell division and the expanding Ds transition region, both of which can alter the distribution of Ft-Ds heterodimers around the cell periphery. We have developed a computational model to address these questions. In our model, the binding affinity of Ft and Ds depends on phosphorylation by Fj. We assume that the asymmetry of the Ft-Ds bond distribution around the cell periphery defines the polarization, with greater asymmetry promoting cell proliferation. Our model predicts that this asymmetry is greatest in the radially-expanding transition region that leaves polarized cells in its wake. These cells naturally retain their bond distribution asymmetry after division by rapidly replenishing Ft-Ds bonds at new cell-cell interfaces. Thus we predict that the distal localization of Dachs in cells throughout the pouch requires the movement of the Ds transition region and the simple presence, rather than any specific spatial pattern, of Fj.

  1. Organic Field Effect Transistors with Dipole-Polarized Polymer Gate Dielectrics for Control of Threshold Voltage

    OpenAIRE

    Sakai, Heisuke; Takahashi, Yoshikazu; Murata, Hideyuki

    2007-01-01

    The authors demonstrate organic field effect transistors (OFETs) with a dipole-polarized polyurea for the gate dielectrics. In the dielectrics, the internal electric field induces the mobile charge carrier in the semiconductor layer to the semiconductor-dielectric interface. OFETs with dipole-polarized gate dielectrics exhibit lower threshold voltage. With nonpolarized gate dielectrics, the threshold voltage was -11.4 V, whereas that decreased to -5.3 V with polarized gate dielectrics. In a...

  2. Electronic absorption spectra and geometry of organic molecules an application of molecular orbital theory

    CERN Document Server

    Suzuki, Hiroshi

    1967-01-01

    Electronic Absorption Spectra and Geometry of Organic Molecules: An Application of Molecular Orbital Theory focuses on electronic absorption spectra of organic compounds and molecules. The book begins with the discussions on molecular spectra, electronic absorption spectra of organic compounds, and practical measures of absorption intensity. The text also focuses on molecular orbital theory and group theory. Molecular state functions; fundamental postulates of quantum theory; representation of symmetry groups; and symmetry operations and symmetry groups are described. The book also dis

  3. A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

    OpenAIRE

    Kallenbach, Mario; Baldwin, Ian T; Bonaventure, Gustavo

    2009-01-01

    Abstract Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI) compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enri...

  4. Single-molecule tracking of small GTPase Rac1 uncovers spatial regulation of membrane translocation and mechanism for polarized signaling

    Science.gov (United States)

    Das, Sulagna; Yin, Taofei; Yang, Qingfen; Zhang, Jingqiao; Wu, Yi I.; Yu, Ji

    2015-01-01

    Polarized Rac1 signaling is a hallmark of many cellular functions, including cell adhesion, motility, and cell division. The two steps of Rac1 activation are its translocation to the plasma membrane and the exchange of nucleotide from GDP to GTP. It is, however, unclear whether these two processes are regulated independent of each other and what their respective roles are in polarization of Rac1 signaling. We designed a single-particle tracking (SPT) method to quantitatively analyze the kinetics of Rac1 membrane translocation in living cells. We found that the rate of Rac1 translocation was significantly elevated in protrusions during cell spreading on collagen. Furthermore, combining FRET sensor imaging with SPT measurements in the same cell, the recruitment of Rac1 was found to be polarized to an extent similar to that of the nucleotide exchange process. Statistical analysis of single-molecule trajectories and optogenetic manipulation of membrane lipids revealed that Rac1 membrane translocation precedes nucleotide exchange, and is governed primarily by interactions with phospholipids, particularly PI(3,4,5)P3, instead of protein factors. Overall, the study highlights the significance of membrane translocation in spatial Rac1 signaling, which is in addition to the traditional view focusing primarily on GEF distribution and exchange reaction. PMID:25561548

  5. Photoelectron angular distributions from polar molecules probed by intense femtosecond lasers

    DEFF Research Database (Denmark)

    Abu-Samha, Mahmoud; Madsen, Lars Bojer

    2010-01-01

    -active-electron and frozen-nuclei approximations. Our analysis shows that for the HF and LiF molecules, anisotropies in the molecular potential and the probed orbital lead to enhanced ionization during laser half cycles with the field pointing antiparallel to the permanent dipole of the dipole term in a multipolar expansion...

  6. Students' Use of Three Different Visual Representations to Interpret Whether Molecules Are Polar or Nonpolar

    Science.gov (United States)

    Host, Gunnar E.; Schonborn, Konrad J.; Palmerius, Karljohan E. Lundin

    2012-01-01

    Visualizing molecular properties is often crucial for constructing conceptual understanding in chemistry. However, research has revealed numerous challenges surrounding students' meaningful interpretation of the relationship between the geometry and electrostatic properties of molecules. This study explored students' (n = 18) use of three visual…

  7. Elliptically polarized high-order harmonics from aligned molecules within the strong-field approximation

    DEFF Research Database (Denmark)

    Etches, Adam; Madsen, Christian Bruun; Madsen, Lars Bojer

    A correction term is introduced in the stationary-point analysis on high-order harmonic generation (HHG) from aligned molecules. Arising from a multi-centre expansion of the electron wave function, this term brings our numerical calculations of the Lewenstein model into qualitative agreement...

  8. Small organic molecules on surfaces fundamentals and applications

    CERN Document Server

    Draxl, Claudia; Ramsey, Michael

    2013-01-01

    This book deals with basic aspects of polymer electronics and optoelectronics. There is an enormous world-wide effort both in basic scientific research as well as in industrial development in the area of organic electronics. It is becoming increasingly clear that, if devices based on organic materials are ever going to have a significant relevance beyond being a cheap replacement for inorganic semiconductors, there will be a need to understand interface formation, film growth and functionality. A control of these aspects will allow the realisation of totally new device concepts exploiting the enormous flexibility inherent in organic chemistry. In this book we focus on oligomeric/molecular films as we believe that the control of molecular structures and interfaces provides highly defined systems which allow, on the one hand the study of the basic physics and on the other hand to find the important parameters necessary to improve organic devices.

  9. Chemical analysis of organic molecules in carbonaceous meteorites

    OpenAIRE

    Torrao Pinto Martins, Zita Carla

    2007-01-01

    Meteorites are extraterrestrial objects that survive the passage through the Earth’s atmosphere and impact the Earth's surface. They can be divided into several classes, the carbonaceous chondrites being one of them. Carbonaceous chondrites are the oldest and best preserved meteorites and contain a record of the birth of the solar system. They are rich in carbon, containing up to 3 wt% of organic carbon. Carbonaceous chondrites have a rich organic inventory that includes, among others, amino ...

  10. Inorganic-Organic Molecules and Solids with Nanometer-Sized Pores

    Energy Technology Data Exchange (ETDEWEB)

    Maverick, Andrew W

    2011-12-17

    We are constructing porous inorganic-organic hybrid molecules and solids, many of which contain coordinatively unsaturated metal centers. In this work, we use multifunctional ²-diketone ligands as building blocks to prepare extended-solid and molecular porous materials that are capable of reacting with a variety of guest molecules.

  11. Spin thermoelectric effects in organic single-molecule devices

    Energy Technology Data Exchange (ETDEWEB)

    Wang, H.L.; Wang, M.X.; Qian, C.; Hong, X.K.; Zhang, D.B.; Liu, Y.S.; Yang, X.F., E-mail: xfyang@cslg.edu.cn

    2017-05-25

    Highlights: • A stronger spin thermoelectric performance in a polyacetylene device is observed. • For the antiferromagnetic (AFM) ordering, a transport gap is opened. Thus the thermoelectric effects are largely enhanced. - Abstract: The spin thermoelectric performance of a polyacetylene chain bridging two zigzag graphene nanoribbons (ZGNRs) is investigated based on first principles method. Two different edge spin arrangements in ZGNRs are considered. For ferromagnetic (FM) ordering, transmission eigenstates with different spin indices distributed below and above Fermi level are observed, leading directly to a strong spin thermoelectric effect in a wide temperature range. With the edge spins arranged in the antiferromagnetic (AFM) ordering, an obvious transport gap appears in the system, which greatly enhances the thermoelectric effects. The presence of a small spin splitting also induces a spin thermoelectric effect greater than the charge thermoelectric effect in certain temperature range. In general, the single-molecule junction exhibits the potential to be used for the design of perfect thermospin devices.

  12. Molecular complex formation between positronium and organic molecules in solutions

    International Nuclear Information System (INIS)

    Madia, W.J.; Nichols, A.L.; Ache, H.J.

    1975-01-01

    Evidence is presented which supports the reversible formation of molecular complexes between Ps atoms and a series of nitrobenzene derivatives and p-benzoquinone in solution. The activation energy for the forward reaction step I (Ps + M (II) reversible PsM (I)) is generally very small; E/sub A/ approximately 1 kcal/mol. ΔH/sub EQ/, the enthalpy of the overall process, ranges from almost zero, in the case of very unreactive substrates, such as toluene or heptane, to -8 kcal/mol for dinitrobenzene or p-benzoquinone. The reactivities of the various substrate molecules toward Ps follow trends as observed in conventional molecular complex formation. Furthermore an attempt was made to assess the role of the solvent upon the stability of the molecular complexes

  13. Novel High-Activity Organic Piezoelectric Materials - From Single-Molecule Response to Energy Harvesting Films

    Science.gov (United States)

    2015-08-24

    flexible devices and applications from touch sensors to medical implants have not been matched with solutions for energy storage, conversion and generation...the backbone significantly distort the helical shape and do not allow favorable alignment of the donor (amine) and acceptor ( nitro ) groups. Adding...originates from the switch of an asymmetrical polar unit cell in inorganic crystals, mobile hydrogens or ions in organic crystals, or from the polar

  14. Probing non polar interstellar molecules through their protonated form: Detection of protonated cyanogen (NCCNH+).

    Science.gov (United States)

    Agúndez, M; Cernicharo, J; de Vicente, P; Marcelino, N; Roueff, E; Fuente, A; Gerin, M; Guélin, M; Albo, C; Barcia, A; Barbas, L; Bolaño, R; Colomer, F; Diez, M C; Gallego, J D; Gómez-González, J; López-Fernández, I; López-Fernández, J A; López-Pérez, J A; Malo, I; Serna, J M; Tercero, F

    2015-07-01

    Cyanogen (NCCN) is the simplest member of the series of dicyanopolyynes. It has been hypothesized that this family of molecules can be important constituents of interstellar and circumstellar media, although the lack of a permanent electric dipole moment prevents its detection through radioastronomical techniques. Here we present the first solid evidence of the presence of cyanogen in interstellar clouds through the detection of its protonated form toward the cold dark clouds TMC-1 and L483. Protonated cyanogen (NCCNH + ) has been identified through the J = 5 - 4 and J = 10 - 9 rotational transitions using the 40m radiotelescope of Yebes and the IRAM 30m telescope. We derive beam averaged column densities for NCCNH + of (8.6 ± 4.4) × 10 10 cm -2 in TMC-1 and (3.9 ± 1.8) × 10 10 cm -2 in L483, which translate to fairly low fractional abundances relative to H 2 , in the range (1-10) × 10 -12 . The chemistry of protonated molecules in dark clouds is discussed, and it is found that, in general terms, the abundance ratio between the protonated and non protonated forms of a molecule increases with increasing proton affinity. Our chemical model predicts an abundance ratio NCCNH + /NCCN of ~ 10 -4 , which implies that the abundance of cyanogen in dark clouds could be as high as (1-10) × 10 -8 relative to H 2 , i.e., comparable to that of other abundant nitriles such as HCN, HNC, and HC 3 N.

  15. Induction of unidirectional π-electron rotations in low-symmetry aromatic ring molecules using two linearly polarized stationary lasers.

    Science.gov (United States)

    Mineo, Hirobumi; Yamaki, Masahiro; Kim, Gap-Sue; Teranishi, Yoshiaki; Lin, Sheng Hsien; Fujimura, Yuichi

    2016-09-29

    A new laser-control scenario of unidirectional π-electron rotations in a low-symmetry aromatic ring molecule having no degenerate excited states is proposed. This scenario is based on dynamic Stark shifts of two relevant excited states using two linearly polarized stationary lasers. Each laser is set to selectively interact with one of the two electronic states, the lower and higher excited states are shifted up and down with the same rate, respectively, and the two excited states become degenerate at their midpoint. One of the four control parameters of the two lasers, i.e. two frequencies and two intensities, determines the values of all the other parameters. The direction of π-electron rotations, clockwise or counter-clockwise rotation, depends on the sign of the relative phase of the two lasers at the initial time. An analytical expression for the time-dependent expectation value of the rotational angular momentum operator is derived using the rotating wave approximation (RWA). The control scenario depends on the initial condition of the electronic states. The control scenario with the ground state as the initial condition was applied to toluene molecules. The derived time-dependent angular momentum consists of a train of unidirectional angular momentum pulses. The validity of the RWA was checked by numerically solving the time-dependent Schrödinger equation. The simulation results suggest an experimental realization of the induction of unidirectional π-electron rotations in low-symmetry aromatic ring molecules without using any intricate quantum-optimal control procedure. This may open up an effective generation method of ring currents and current-induced magnetic fields in biomolecules such as amino acids having aromatic ring molecules for searching their interactions.

  16. Water adsorption on non polar ZnO surfaces: from single molecules to multilayers

    Science.gov (United States)

    Kenmoe, Stephane; Biedermann, P. Ulrich

    2015-03-01

    The interface between water and ZnO plays an important role in many domains of technological relevance. Following the vital role of adsorbed water on substrate properties and the fascinating properties of interfacial water, there is a great interest in characterizing this interface. We use DFT to study the possible aggregation regimes that can form on the ZnO non-polar low-index (1010) and (1120) surfaces. We study the adsorption of water monomers, small water clusters like water dimers, water chains, ladder-like water structures, water thin films and water multilayers. Based on this, trends in binding energy as well as the binding mechanisms are analyzed to understand the driving forces and the nature of the fundamental interactions that stabilize the adsorbed layers.

  17. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

  18. A-D-A small molecules for solution-processed organic photovoltaic cells.

    Science.gov (United States)

    Ni, Wang; Wan, Xiangjian; Li, Miaomiao; Wang, Yunchuang; Chen, Yongsheng

    2015-03-25

    A-D-A small molecules have drawn more and more attention in solution-processed organic solar cells due to the advantages of a diversity of structures, easy control of energy levels, etc. Recently, a power conversion efficiency of nearly 10% has been achieved through careful material design and device optimization. This feature article reviews recent representative progress in the design and application of A-D-A small molecules in organic photovoltaic cells.

  19. The Distribution of Complex Organic Molecules in the Orion KL Molecular Core

    Science.gov (United States)

    Kuan, Yi-Jehng; Hsu, Yu-Sen; Charnley, Steven B.; Wang, Kuo-Song

    2011-01-01

    We conducted high angular-resolution observations toward the massive star-forming region Orion KL at 1.3 mm using the Submillimeter Array (SMA). Spectral emission from twelve complex organic molecules was simultaneously imaged. We discuss the distinct chemical characteristics among four sub- regions in Orion KL by comparing the spatial distributions and fractional abundances of these complex molecules. These observations will allow us to test and constrain chemical models of interstellar organic synthesis.

  20. Sugar-Based Polyamides: Self-Organization in Strong Polar Organic Solvents.

    Science.gov (United States)

    Rosu, Cornelia; Russo, Paul S; Daly, William H; Cueto, Rafael; Pople, John A; Laine, Roger A; Negulescu, Ioan I

    2015-09-14

    Periodic patterns resembling spirals were observed to form spontaneously upon unassisted cooling of d-glucaric acid- and d-galactaric acid-based polyamide solutions in N-methyl-N-morpholine oxide (NMMO) monohydrate. Similar observations were made in d-galactaric acid-based polyamide/ionic liquid (IL) solutions. The morphologies were investigated by optical, polarized light and confocal microscopy assays to reveal pattern details. Differential scanning calorimetry was used to monitor solution thermal behavior. Small- and wide-angle X-ray scattering data reflected the complex and heterogeneous nature of the self-organized patterns. Factors such as concentration and temperature were found to influence spiral dimensions and geometry. The distance between rings followed a first-order exponential decay as a function of polymer concentration. Fourier-Transform Infrared Microspectroscopy analysis of spirals pointed to H-bonding between the solvent and the pendant hydroxyl groups of the glucose units from the polymer backbone. Tests on self-organization into spirals of ketal-protected d-galactaric acid polyamides in NMMO monohydrate confirmed the importance of the monosaccharide's pendant free hydroxyl groups on the formation of these patterns. Rheology performed on d-galactaric-based polyamides at high concentration in NMMO monohydrate solution revealed the optimum conditions necessary to process these materials as fibers by spinning. The self-organization of these sugar-based polyamides mimics certain biological materials.

  1. Mixing times of organic molecules within secondary organic aerosol particles: a global planetary boundary layer perspective

    Science.gov (United States)

    Maclean, Adrian M.; Butenhoff, Christopher L.; Grayson, James W.; Barsanti, Kelley; Jimenez, Jose L.; Bertram, Allan K.

    2017-11-01

    When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1 h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are SOA in the planetary boundary layer (PBL), the region of the atmosphere where SOA concentrations are on average the highest. First, a parameterization for viscosity as a function of temperature and RH was developed for α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of ˜ 1000 µg m-3. Based on this parameterization, the mixing times within α-pinene SOA are 0.5 µg m-3 at the surface). Next, as a starting point to quantify how often mixing times of organic molecules are SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature-independent parameterization for viscosity using the room-temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of ˜ 70 µg m-3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose-water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83 % of the mixing times within anthropogenic SOA in the PBL are < 1 h for January and July, respectively, when concentrations are significant. These percentages are likely lower

  2. Organic Molecules in the Sheepbed Mudstone, Gale Crater, Mars

    Science.gov (United States)

    Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Miller, K. E.; Eigenbrode, J. L.; Summons, R. E.; Brunner, A. E.; Buch, A.; Szopa, C.; Archer, P. D.; hide

    2014-01-01

    The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally released from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. Here we report on various chlorinated hydrocarbons (chloromethanes, chlorobenzene and dichloroalkanes) detected at elevated levels above instrument background at the Cumberland (CB) drill site, and discuss their possible sources.

  3. Single-molecule detection of chaperonin dynamics through polarization rotation modulation of CdSe QD luminescence imaging

    International Nuclear Information System (INIS)

    Tani, Toshiro; Oda, Masaru; Araki, Daisuke; Miyashita, Tatsuki; Nakajima, Koudai; Arita, Mayuno; Yohda, Masafumi

    2014-01-01

    We report our recent trials examining the single-molecule three-dimensional (3D) detection of protein conformational dynamics at room temperature. Using molecular chaperones as model proteins and cadmium selenide (CdSe) semiconductor quantum dots (QDs) as nanometer-scale probes, we monitored the temporal evolution of ATP-induced conformation changes with a total internal reflection fluorescence (TIRF) microscopy imaging technique in buffer solutions. The two-dimensional (2D) degenerate nature of the emission dipoles of the QDs, due to the uniaxial wurtzite crystal structure, made it possible to capture the 3D orientation using a polarization modulation technique in real time. The temporal resolution was half the period of analyzer rotation. Although still insufficient, the obtained signals suggest possible 3D detection of specific motions, which supports the two-step conformational changes triggered by ATP attachment. - Highlights: • We report our recent trials examining the single-molecule three-dimensional (3D) detection of protein conformational dynamics at room temperature. • Using molecular chaperones as model proteins and cadmium selenide (CdSe) semiconductor quantum dots (QDs) as nanometer-scale probes, we monitored the temporal evolution of ATP-induced conformation changes with a total internal reflection fluorescence (TIRF) microscopy imaging technique in buffer solutions. • The two-dimensional (2D) degenerate nature of the emission dipoles of the QDs, due to the uniaxial wurtzite crystal structure, made it possible to capture the 3D orientation using a polarization modulation technique in real time. • The temporal resolution was half the period of analyzer rotation. • Although still insufficient, the obtained signals suggest possible 3D detection of specific motions, which supports the two-step conformational changes triggered by ATP attachment

  4. Direct visualization of polarization reversal of organic ferroelectric memory transistor by using charge modulated reflectance imaging

    Science.gov (United States)

    Otsuka, Takako; Taguchi, Dai; Manaka, Takaaki; Iwamoto, Mitsumasa

    2017-11-01

    By using the charge modulated reflectance (CMR) imaging technique, charge distribution in the pentacene organic field-effect transistor (OFET) with a ferroelectric gate insulator [P(VDF-TrFE)] was investigated in terms of polarization reversal of the P(VDF-TrFE) layer. We studied the polarization reversal process and the carrier spreading process in the OFET channel. The I-V measurement showed a hysteresis behavior caused by the spontaneous polarization of P(VDF-TrFE), but the hysteresis I-V curve changes depending on the applied drain bias, possibly due to the gradual shift of the polarization reversal position in the OFET channel. CMR imaging visualized the gradual shift of the polarization reversal position and showed that the electrostatic field formed by the polarization of P(VDF-TrFE) contributes to hole and electron injection into the pentacene layer and the carrier distribution is significantly dependent on the direction of the polarization. The polarization reversal position in the channel region is governed by the electrostatic potential, and it happens where the potential reaches the coercive voltage of P(VDF-TrFE). The transmission line model developed on the basis of the Maxwell-Wagner effect element analysis well accounts for this polarization reversal process in the OFET channel.

  5. Small molecule host materials for solution processed phosphorescent organic light-emitting diodes.

    Science.gov (United States)

    Yook, Kyoung Soo; Lee, Jun Yeob

    2014-07-02

    Solution processed phosphorescent organic light-emitting diodes (OLEDs) have been actively developed due to merits of high quantum efficiency of phosphorescent materials and simple fabrication processes of solution processed OLEDs. The device performances of the solution processed phosphorescent OLEDs have been greatly improved in the last 10 years and the progress of the device performances was made by the development of small molecule host materials for solution processes. A hybrid host of polymer and small molecules, a single small molecule host and a mixed host of small molecule hosts have effectively enhanced the quantum efficiency of the solution processed phosphorescent OLEDs. Therefore, this paper reviews recent developments in small molecule host materials for solution processed phosphorescent OLEDs and provides future directions for the development of the small molecule host materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis

    Science.gov (United States)

    Francois, P.; Szopa, C.; Buch, A.; Coll, P.; McAdam, A. C.; Mahaffy, P. R.; Freissinet, C.; Glavin, D. P.; Navarro-Gonzalez, R.; Cabane, M.

    2016-01-01

    Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

  7. The impact of coulombic interactions among polar molecules and metal substrates on flow and lubrication properties

    Science.gov (United States)

    Gkagkas, K.; Ponnuchamy, V.

    2017-09-01

    In the current work we present an extensive study on the impact of short- and long-range interactions between solids and liquids on the hydrodynamic and lubrication behaviour of a tribological system. We have implemented a coarse grain molecular dynamics description of two ionic liquids (ILs) as lubricants which are confined by two infinitely long flat iron solids and which are subjected to a shearing flow. The impact of surface polarizability and molecule geometry on the ion arrangement under shearing has been studied in detail. The results have revealed two regimes of lubrication, with a liquid phase being present under low normal loads, while solidification of the ILs, accompanied by a steep rise of normal forces and significant wall slip is observed at small plate-to-plate distances.

  8. PLACENTAL STEREOLOGY: SPANNING THE LEVELS FROM MOLECULE TO WHOLE ORGAN

    Directory of Open Access Journals (Sweden)

    Terry M Mayhew

    2011-05-01

    Full Text Available Stereology can provide hard (functionally-relevant quantitative information at different levels of 3D structural organization. My researches have applied established methods to study organ function and developed novel methods to study subcellular localization of marker probes. We have studied whole-organ function (passive diffusion in the human placenta and quantified various processes at tissue and subcellular levels and in normal and complicated pregnancies. Fetoplacental angiogenesis and villous growth and maturation involve phased changes particularly around mid-gestation. Growth is associated with increased numbers of cells or nuclei and counts have shown that villous trophoblast continuously renews itself via cytotrophoblast (CT proliferation and recruitment and syncytiotrophoblast (ST differentiation and extrusion. Integration of these processes results in changes in total oxygen (O2 diffusive conductance which match the growing fetal mass. Similar processes occur during development of the mouse placenta and at least some are compromised in human pregnancies. For example: [a] in pure pre-eclampsia (PE, villous and fetoplacental vascular volumes and surfaces are similar to those seen in uncomplicated pregnancies but reduced in pure intrauterine growth restriction (IUGR and in PE+IUGR; [b] trophoblast extrusion is accelerated in PE and IUGR but the latter exhibits reduced CT proliferation and this perturbed steady state leads to smaller trophoblast volumes and surfaces; [c] O2 diffusive conductances alter in various pregnancy complications, including IUGR and PE+IUGR; [d] fetal weight is diminished, but diffusive transport increases, in placentas from mice exposed to urban air pollution. Finally, innovations in quantitative immunoelectron microscopy (immunoEM have produced a portfolio of methods for revealing non-random distributions of marker gold particles in different cellular compartments and for testing whether patterns shift following

  9. Characterisation of aggregation of tributylphosphate molecules in organic solvent

    International Nuclear Information System (INIS)

    Mandin, C.; Martinet, L.; Zemb, Th.; Berthon, L.; Madic, Ch.

    2000-01-01

    This report presents a structural study of the aggregates formed with the organic phases of the extractant tri-n-butyl phosphate, used in the industrial PUREX process (Plutonium and Uranium Extraction; liquid-liquid solvent extraction) for the treatment of high radioactive waste. Combined Small Angle X-ray Scattering and Small Angle Neutron Scattering show that organic TBP solutions (in equilibrium with acid solutions) are organised in oligomeric aggregates. The influence of various parameters such as HNO 3 or TBP concentrations, diluent or acid natures, does not seem to modify the aggregate shape and size, whereas the interactions are modified. Moreover the aggregates disappear under high temperatures, whereas the attractive interactions between them increase at low temperatures. The 'drop weight' method gives the critical micellar concentration values of TBP in case of H 2 O or HNO 3 extractions (H 2 O: 0.48 M; HNO 3 2M: 0.65 M; at 21 deg C). Furthermore, the measures at different acid concentrations show that the c.m.c. varies with the acidity. The more acid the aqueous phase is, the smaller is the entropy in the system because of the numerous negative charges, i.e. the harder the micellization occurs, so the higher the c.m.c. value is. The sticky sphere model proposed by Baxter, can be used to model successfully small reverse micelles of the organic TBP phases. The aggregation number would be 4±1 (water extraction) and 5±1(HNO 3 2M extraction). These values are also given by vapor pressure measurements. (authors)

  10. Effects of humic acid and heavy metals on the sorption of polar and apolar organic pollutants onto biochars.

    Science.gov (United States)

    Wang, Fei; Sun, Hongwen; Ren, Xinhao; Liu, Yarui; Zhu, Hongkai; Zhang, Peng; Ren, Chao

    2017-12-01

    The effects of humic acid (HA) and heavy metals (Cu 2+ and Ag + ) on the sorption of polar and apolar organic pollutants onto biochars that were produced at temperatures of 200 °C (BC200) and 700 °C (BC700) were studied. Due to the plentiful polar functional groups on BC200, cationic propranolol exhibited higher levels of sorption than naphthalene on BC200 while naphthalene and propranolol showed similar sorption capacities on BC700. HA changed the characteristics of biochars and generally inhibited the sorption of target organic pollutants on biochars; however, enhancement occurred in some cases depending on the pollutants involved and their concentrations, biochars used and the addition sequences and concentrations of HA. On BC200, HA modifications mainly influenced sorption by decreasing its polarity and increasing its aromaticity, while on BC700, the surface area and pore volume greatly decreased due to the pore-blocking effects of HA. Residue dissolved HA in solution may also contribute to sorption inhibition. Complexation between polar functional groups on BC200 and heavy metals slightly enhanced the sorption of neutral naphthalene and significantly enhanced that of anionic 4-nitro-1-naphtol, while limited the sorption of cationic propranolol. Heavy metals together with their associated water molecules decreased the sorption of target chemicals on BC700 via pore-filling or pore-mouth-covering. Inhibition of heavy metals for 4-nitro-1-naphthol was found to be the weakest due to the bridge effects of heavy metals between 4-nitro-1-naphtol and BC700. The higher polarizability of Ag + led to the increase of its sorption on biochars in the presence of organic aromatic pollutants. The results of the present study shed light on the sorption mechanisms of bi-solute systems and enable us to select suitable biochar sorbents when chemicals co-exist. Copyright © 2017. Published by Elsevier Ltd.

  11. Organic polar pollutants in surface waters of inland seas.

    Science.gov (United States)

    Orlikowska, Anna; Fisch, Kathrin; Schulz-Bull, Detlef E

    2015-12-30

    Available data about contamination by polar substances are mostly reported for rivers and near-shore waters and only limited studies exists about their occurrence in marine waters. We present concentrations and distribution of several polar pesticides and UV-filters in surface waters of three inland seas, the Baltic, Black and Mediterranean Sea. Many of the investigated compounds were below detection limits, however, those found in off-shore waters raise a concern about their persistence and possible adverse effect on the ecosystem. Despite a longstanding EU-wide ban we were able to detect atrazine in the Mediterranean and the Baltic Sea. Concentrations in the Black Sea were substantially higher. Runoff from agricultural and urban areas was the main transport route to marine ecosystems for investigated compounds, though irgarol in Mediterranean waters was attributed to intense maritime traffic. 2-Phenylbenzimidazole-5-sulfonic acid was the only UV-filter detected in marine waters, while benzophenone-4 was observed in the estuaries. Occurrence of UV-filters was seasonal. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions

    Science.gov (United States)

    Compernolle, S.; Ceulemans, K.; Müller, J.-F.

    2011-09-01

    We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects), a method to predict (subcooled) liquid pure compound vapour pressure p0 of organic molecules that requires only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T) is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: aldehydes, ketones, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA).

  13. Power losses in bilayer inverted small molecule organic solar cells

    KAUST Repository

    Trinh, Cong

    2012-01-01

    Inverted bilayer organic solar cells using copper phthalocyanine (CuPc) as a donor and C60 as an acceptor with the structure: glass/indium tin oxide (ITO)/ZnO/C60/CuPc/MoO3/Al, in which the zinc oxide (ZnO) was deposited by atomic layer deposition, are compared with a conventional device: glass/ITO/CuPc/C60/bathocuproine/Al. These inverted and conventional devices give short circuit currents of 3.7 and 4.8 mA/cm 2, respectively. However, the inverted device gives a reduced photoresponse from the CuPc donor compared to that of the conventional device. Optical field models show that the arrangement of organic layers in the inverted devices leads to lower absorption of long wavelengths by the CuPc donor; the low energy portion of the spectrum is concentrated near the metal oxide electrode in both devices. © 2012 American Institute of Physics.

  14. Microtubules in legume root hairs: cell polarity and response to rhizobial signal molecules

    NARCIS (Netherlands)

    Sieberer, B.

    2005-01-01

    Microtubules, which occur as hollow protein tubes with a diameter of 25 nanometers, are an important compound of the cytoskeleton and occur in plant cells as a highly organized and dynamic array, which actual arrangement will depend on its tasks during the cell cycle. Microtubules play a key-role in

  15. Organic molecules in the atmosphere of Jupiter. Final report

    International Nuclear Information System (INIS)

    Ponnamperuma, C.A.

    1978-01-01

    Organic synthesis in the primitive solar system was simulated by Fischer Tropsch type experiments. Particular attention was given to the formation of lower molecular weight hydrocarbons. In a gas flow experiment, a gas mixture of H 2 and CO was introduced into a heated reaction tube at a constant flow rate and passed through a catalyst (powdered Canyon Diablo). The products that emerged were directly analyzed by gas chromatography. The results of 21 runs under various gas mixing rations, reaction temperatures, and gas-catalyst contact times showed the predominance of the saturated hydrocarbon formation at C 4 and C 5 over the unsaturated ones. Saturate/unsaturate ratios were mostly less than 0.4 and none showed over 0.7

  16. Ultrafast photoelectron spectroscopy of small molecule organic films

    Science.gov (United States)

    Read, Kendall Laine

    As research in the field of ultrafast optics has produced shorter and shorter pulses, at an ever-widening range of frequencies, ultrafast spectroscopy has grown correspondingly. In particular, ultrafast photoelectron spectroscopy allows direct observation of electrons in transient or excited states, regardless of the eventual relaxation mechanisms. High-harmonic conversion of 800nm, femtosecond, Ti:sapphire laser pulses allows excite/probe spectroscopy down into atomic core level states. To this end, an ultrafast, X-UV photoelectron spectroscopic system is described, including design considerations for the high-harmonic generation line, the time of flight detector, and the subsequent data collection electronics. Using a similar experimental setup, I have performed several ultrafast, photoelectron excited state decay studies at the IBM, T. J. Watson Research Center. All of the observed materials were electroluminescent thin film organics, which have applications as the emitter layer in organic light emitting devices. The specific materials discussed are: Alq, BAlq, DPVBi, and Alq doped with DCM or DMQA. Alq:DCM is also known to lase at low photoexcitation thresholds. A detailed understanding of the involved relaxation mechanisms is beneficial to both applications. Using 3.14 eV excite, and 26.7 eV probe, 90 fs laser pulses, we have observed the lowest unoccupied molecular orbital (LUMO) decay rate over the first 200 picoseconds. During this time, diffusion is insignificant, and all dynamics occur in the absence of electron transport. With excitation intensities in the range of 100μJ/cm2, we have modeled the Alq, BAlq, and DPVBi decays via bimolecular singlet-singlet annihilation. At similar excitations, we have modeled the Alq:DCM decay via Förster transfer, stimulated emission, and excimeric formation. Furthermore, the Alq:DCM occupied to unoccupied molecular orbital energy gap was seen to shrink as a function of excite-to-probe delay, in accordance with the

  17. A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

    Directory of Open Access Journals (Sweden)

    Bonaventure Gustavo

    2009-11-01

    Full Text Available Abstract Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. Results A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA and small polar molecules (e.g., jasmonic acid (JA, salicylic acid (SA containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. Conclusion The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the

  18. A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS.

    Science.gov (United States)

    Kallenbach, Mario; Baldwin, Ian T; Bonaventure, Gustavo

    2009-11-25

    Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI) compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA)) and small polar molecules (e.g., jasmonic acid (JA), salicylic acid (SA)) containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the molecules must contain at least one free carboxyl group.

  19. Structure of the Buried Metal-Molecule Interface in Organic Thin Film Devices

    DEFF Research Database (Denmark)

    Hansen, Christian Rein; Sørensen, Thomas Just; Glyvradal, Magni

    2009-01-01

    . By comparison of XR data for the five-layer Pb2+ arachidate LB film before and after vapor deposition of the Ti/Al top electrode, a detailed account of the structural damage to the organic film at the buried metal-molecule interface is obtained. We find that the organized structure of the two topmost LB layers...

  20. Adsorption of organic molecules may explain growth of newly nucleated clusters and new particle formation

    Science.gov (United States)

    Wang, Jian; Wexler, Anthony S.

    2013-05-01

    New particle formation consists of formation of thermodynamically stable clusters from trace gas molecules (homogeneous nucleation) followed by growth of these clusters to a detectable size. Because of the large coagulation rate of clusters smaller than 3 nm with the preexisting aerosol population, for new particle formation to take place, these clusters need to grow sufficiently fast to escape removal by coagulation. Previous studies have indicated that condensation of low-volatility organic vapor may play an important role in the initial growth of the clusters. However, due to the relatively high vapor pressure and partial molar volume of even highly oxidized organic compounds, the strong Kelvin effect may prevent typical ambient organics from condensing on these small clusters. Earlier studies did not consider that adsorption of organic molecules on the cluster surface, due to the intermolecular forces between the organic molecule and cluster, may occur and substantially alter the growth process under sub-saturated conditions. Using the Brunauer-Emmett-Teller (BET) isotherm, we show that the adsorption of organic molecules onto the surface of clusters may significantly reduce the saturation ratio required for condensation of organics to occur, and therefore may provide a physico-chemical explanation for the enhanced initial growth by condensation of organics despite the strong Kelvin effect.

  1. Stability of dispersions in polar organic media. I. Electrostatic stabilization

    NARCIS (Netherlands)

    Rooy, N. de; Bruyn, P.L. de; Overbeek, J.Th.G.

    Electrostatically stabilized sols of silver, silver iodide, α-goethite, and copper phthalocyanine in methanol, ethanol, isopropanol, and acetone have been prepared and characterized. Coagulation concentrations with electrolytes of various charge numbers have been determined in water, in organic

  2. Partitioning of polar and non-polar neutral organic chemicals into human and cow milk.

    Science.gov (United States)

    Geisler, Anett; Endo, Satoshi; Goss, Kai-Uwe

    2011-10-01

    The aim of this work was to develop a predictive model for milk/water partition coefficients of neutral organic compounds. Batch experiments were performed for 119 diverse organic chemicals in human milk and raw and processed cow milk at 37°C. No differences (milk were observed. The polyparameter linear free energy relationship model fit the calibration data well (SD=0.22 log units). An experimental validation data set including hormones and hormone active compounds was predicted satisfactorily by the model. An alternative modelling approach based on log K(ow) revealed a poorer performance. The model presented here provides a significant improvement in predicting enrichment of potentially hazardous chemicals in milk. In combination with physiologically based pharmacokinetic modelling this improvement in the estimation of milk/water partitioning coefficients may allow a better risk assessment for a wide range of neutral organic chemicals. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. Xenoendocrine pollutants may reduce size of sexual organs in East Greenland polar bears (Ursus maritimus)

    DEFF Research Database (Denmark)

    Sonne, Christian; Leifsson, Páll Skuli; Dietz, Rune

    2006-01-01

    Reproductive organs from 55 male and 44 female East Greenland polar bears were examined to investigate the potential negative impact from organohalogen pollutants (OHCs). Multiple regressions normalizing for age showed a significant inverse relationship between OHCs and testis length and baculum.......01) and uterine horn length and HCB (p = 0.02). The study suggests thatthere is an impact from xenoendocrine pollutants on the size of East Greenland polar bear genitalia. This may pose a riskto this polar bear subpopulation in the future because of reduced sperm and egg quality/quantity and uterus and penis size...

  4. Self-organizing ontology of biochemically relevant small molecules.

    Science.gov (United States)

    Chepelev, Leonid L; Hastings, Janna; Ennis, Marcus; Steinbeck, Christoph; Dumontier, Michel

    2012-01-06

    The advent of high-throughput experimentation in biochemistry has led to the generation of vast amounts of chemical data, necessitating the development of novel analysis, characterization, and cataloguing techniques and tools. Recently, a movement to publically release such data has advanced biochemical structure-activity relationship research, while providing new challenges, the biggest being the curation, annotation, and classification of this information to facilitate useful biochemical pattern analysis. Unfortunately, the human resources currently employed by the organizations supporting these efforts (e.g. ChEBI) are expanding linearly, while new useful scientific information is being released in a seemingly exponential fashion. Compounding this, currently existing chemical classification and annotation systems are not amenable to automated classification, formal and transparent chemical class definition axiomatization, facile class redefinition, or novel class integration, thus further limiting chemical ontology growth by necessitating human involvement in curation. Clearly, there is a need for the automation of this process, especially for novel chemical entities of biological interest. To address this, we present a formal framework based on Semantic Web technologies for the automatic design of chemical ontology which can be used for automated classification of novel entities. We demonstrate the automatic self-assembly of a structure-based chemical ontology based on 60 MeSH and 40 ChEBI chemical classes. This ontology is then used to classify 200 compounds with an accuracy of 92.7%. We extend these structure-based classes with molecular feature information and demonstrate the utility of our framework for classification of functionally relevant chemicals. Finally, we discuss an iterative approach that we envision for future biochemical ontology development. We conclude that the proposed methodology can ease the burden of chemical data annotators and

  5. Self-organizing ontology of biochemically relevant small molecules

    Directory of Open Access Journals (Sweden)

    Chepelev Leonid L

    2012-01-01

    Full Text Available Abstract Background The advent of high-throughput experimentation in biochemistry has led to the generation of vast amounts of chemical data, necessitating the development of novel analysis, characterization, and cataloguing techniques and tools. Recently, a movement to publically release such data has advanced biochemical structure-activity relationship research, while providing new challenges, the biggest being the curation, annotation, and classification of this information to facilitate useful biochemical pattern analysis. Unfortunately, the human resources currently employed by the organizations supporting these efforts (e.g. ChEBI are expanding linearly, while new useful scientific information is being released in a seemingly exponential fashion. Compounding this, currently existing chemical classification and annotation systems are not amenable to automated classification, formal and transparent chemical class definition axiomatization, facile class redefinition, or novel class integration, thus further limiting chemical ontology growth by necessitating human involvement in curation. Clearly, there is a need for the automation of this process, especially for novel chemical entities of biological interest. Results To address this, we present a formal framework based on Semantic Web technologies for the automatic design of chemical ontology which can be used for automated classification of novel entities. We demonstrate the automatic self-assembly of a structure-based chemical ontology based on 60 MeSH and 40 ChEBI chemical classes. This ontology is then used to classify 200 compounds with an accuracy of 92.7%. We extend these structure-based classes with molecular feature information and demonstrate the utility of our framework for classification of functionally relevant chemicals. Finally, we discuss an iterative approach that we envision for future biochemical ontology development. Conclusions We conclude that the proposed methodology

  6. Organic molecule fluorescence as an experimental test-bed for quantum jumps in thermodynamics.

    Science.gov (United States)

    Browne, Cormac; Farrow, Tristan; Dahlsten, Oscar C O; Taylor, Robert A; Vlatko, Vedral

    2017-08-01

    We demonstrate with an experiment how molecules are a natural test bed for probing fundamental quantum thermodynamics. Single-molecule spectroscopy has undergone transformative change in the past decade with the advent of techniques permitting individual molecules to be distinguished and probed. We demonstrate that the quantum Jarzynski equality for heat is satisfied in this set-up by considering the time-resolved emission spectrum of organic molecules as arising from quantum jumps between states. This relates the heat dissipated into the environment to the free energy difference between the initial and final state. We demonstrate also how utilizing the quantum Jarzynski equality allows for the detection of energy shifts within a molecule, beyond the relative shift.

  7. Di(ethylene glycol) methyl ether methacrylate (DEGMEMA)-derived gels align small organic molecules in methanol.

    Science.gov (United States)

    García, Manuela E; Woodruff, Shannon R; Hellemann, Erich; Tsarevsky, Nicolay V; Gil, Roberto R

    2017-03-01

    Residual dipolar couplings (RDCs) constitute an important NMR parameter for structural elucidation in all areas of chemistry. In this study, di(ethylene glycol) methyl ether methacrylate (DEGMEMA)-based gels are introduced as alignment media for the measurement of RDCs of small organic molecules in polar solvents such as methanol. The low viscosity of methanol permits the execution of J-scaled BIRD HSQC experiments that yield very sharp lines in anisotropic conditions. The gels have excellent mechanical properties, and their compression and expansion in the swollen state can be reversed and performed multiple times. This process enables the easy loading and release of analytes. The excellent performance of these new aligning gels is demonstrated by analyzing the structure of the alkaloid retrorsine. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  8. Fgf8-Related Secondary Organizers Exert Different Polarizing Planar Instructions along the Mouse Anterior Neural Tube

    OpenAIRE

    Crespo-Enriquez, Ivan; Partanen, Juha; Martinez, Salvador; Echevarria, Diego

    2012-01-01

    Early brain patterning depends on proper arrangement of positional information. This information is given by gradients of secreted signaling molecules (morphogens) detected by individual cells within the responding tissue, leading to specific fate decisions. Here we report that the morphogen FGF8 exerts initially a differential signal activity along the E9.5 mouse neural tube. We demonstrate that this polarizing activity codes by RAS-regulated ERK1/2 signaling and depends on the topographical...

  9. A Self-Perpetuating Catalyst for the Production of Complex Organic Molecules in Protostellar Nebulae

    Science.gov (United States)

    Nuth, Joseph A.; Johnson, N. M.

    2010-01-01

    The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. Many mechanisms may contribute to the total organic content in protostellar nebulae, ranging from organics formed via ion-molecule and atom-molecule reactions in the cold dark clouds from which such nebulae collapse, to similar ion-molecule and atom-molecule reactions in the dark regions of the nebula far from the proto star, to gas phase reactions in sub-nebulae around growing giant planets and in the nebulae themselves. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. The Haber-Bosch catalytic reduction of N2 by hydrogen was thought to produce the reduced nitrogen found in meteorites. However, the clean iron metal surfaces that catalyze these reactions are easily poisoned via reaction with any number of molecules, including the very same complex organics that they produce and both reactions work more efficiently in the hot regions of the nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Although none work as well as pure iron grains, and all produce a wide range of organic products rather than just pure methane, these materials are not truly catalysts.

  10. Phase-coherent electron transport through metallic atomic-sized contacts and organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Pauly, F.

    2007-02-02

    This work is concerned with the theoretical description of systems at the nanoscale, in particular the electric current through atomic-sized metallic contacts and organic molecules. In the first part, the characteristic peak structure in conductance histograms of different metals is analyzed within a tight-binding model. In the second part, an ab-initio method for quantum transport is developed and applied to single-atom and single-molecule contacts. (orig.)

  11. Nanocoating of titanium implant surfaces with organic molecules. Polysaccharides including glycosaminoglycans

    DEFF Research Database (Denmark)

    Gurzawska, Katarzyna Aleksandra; Svava, Rikke; Jørgensen, Niklas Rye

    2012-01-01

    Long-term stability of titanium implants are dependent on a variety of factors. Nanocoating with organic molecules is one of the method used to improve osseointegration. Nanoscale modification of titanium implants affects surface properties, such as hydrophilicity, biochemical bonding capacity...... with focus on polysaccharides including glycosaminoglycans, and how these molecules change surface properties, cell reactions and affect on osseointegartion. The included in vitro studies demonstrated increased cell adhesion, proliferation and mineralization of a number of the tested polysaccharide...

  12. Isotope substitution extends the lifetime of organic molecules in transmission electron microscopy.

    Science.gov (United States)

    Chamberlain, Thomas W; Biskupek, Johannes; Skowron, Stephen T; Bayliss, Peter A; Bichoutskaia, Elena; Kaiser, Ute; Khlobystov, Andrei N

    2015-02-04

    Structural characterisation of individual molecules by high-resolution transmission electron microscopy (HRTEM) is fundamentally limited by the element and electron energy-specific interactions of the material with the high energy electron beam. Here, the key mechanisms controlling the interactions between the e-beam and C-H bonds, present in all organic molecules, are examined, and the low atomic weight of hydrogen-resulting in its facile atomic displacement by the e-beam-is identified as the principal cause of the instability of individual organic molecules. It is demonstrated theoretically and proven experimentally that exchanging all hydrogen atoms within molecules with the deuterium isotope, and therefore doubling the atomic weight of the lightest atoms in the structure, leads to a more than two-fold increase in the stability of organic molecules in the e-beam. Substitution of H for D significantly reduces the amount of kinetic energy transferred from the e-beam to the atom (main factor contributing to stability) and also increases the barrier for bond dissociation, primarily due to the changes in the zero-point energy of the C-D vibration (minor factor). The extended lifetime of coronene-d12 , used as a model molecule, enables more precise analysis of the inter-molecular spacing and more accurate measurement of the molecular orientations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Quantum Drude oscillator model of atoms and molecules: Many-body polarization and dispersion interactions for atomistic simulation

    Science.gov (United States)

    Jones, Andrew P.; Crain, Jason; Sokhan, Vlad P.; Whitfield, Troy W.; Martyna, Glenn J.

    2013-04-01

    Treating both many-body polarization and dispersion interactions is now recognized as a key element in achieving the level of atomistic modeling required to reveal novel physics in complex systems. The quantum Drude oscillator (QDO), a Gaussian-based, coarse grained electronic structure model, captures both many-body polarization and dispersion and has linear scale computational complexity with system size, hence it is a leading candidate next-generation simulation method. Here, we investigate the extent to which the QDO treatment reproduces the desired long-range atomic and molecular properties. We present closed form expressions for leading order polarizabilities and dispersion coefficients and derive invariant (parameter-free) scaling relationships among multipole polarizability and many-body dispersion coefficients that arise due to the Gaussian nature of the model. We show that these “combining rules” hold to within a few percent for noble gas atoms, alkali metals, and simple (first-row hydride) molecules such as water; this is consistent with the surprising success that models with underlying Gaussian statistics often exhibit in physics. We present a diagrammatic Jastrow-type perturbation theory tailored to the QDO model that serves to illustrate the rich types of responses that the QDO approach engenders. QDO models for neon, argon, krypton, and xenon, designed to reproduce gas phase properties, are constructed and their condensed phase properties explored via linear scale diffusion Monte Carlo (DMC) and path integral molecular dynamics (PIMD) simulations. Good agreement with experimental data for structure, cohesive energy, and bulk modulus is found, demonstrating a degree of transferability that cannot be achieved using current empirical models or fully ab initio descriptions.

  14. The Kinesin Adaptor Calsyntenin-1 Organizes Microtubule Polarity and Regulates Dynamics during Sensory Axon Arbor Development

    Directory of Open Access Journals (Sweden)

    Mary C. Halloran

    2017-04-01

    Full Text Available Axon growth and branching, and development of neuronal polarity are critically dependent on proper organization and dynamics of the microtubule (MT cytoskeleton. MTs must organize with correct polarity for delivery of diverse cargos to appropriate subcellular locations, yet the molecular mechanisms regulating MT polarity remain poorly understood. Moreover, how an actively branching axon reorganizes MTs to direct their plus ends distally at branch points is unknown. We used high-speed, in vivo imaging of polymerizing MT plus ends to characterize MT dynamics in developing sensory axon arbors in zebrafish embryos. We find that axonal MTs are highly dynamic throughout development, and that the peripheral and central axons of sensory neurons show differences in MT behaviors. Furthermore, we show that Calsyntenin-1 (Clstn-1, a kinesin adaptor required for sensory axon branching, also regulates MT polarity in developing axon arbors. In wild type neurons the vast majority of MTs are directed in the correct plus-end-distal orientation from early stages of development. Loss of Clstn-1 causes an increase in MTs polymerizing in the retrograde direction. These misoriented MTs most often are found near growth cones and branch points, suggesting Clstn-1 is particularly important for organizing MT polarity at these locations. Together, our results suggest that Clstn-1, in addition to regulating kinesin-mediated cargo transport, also organizes the underlying MT highway during axon arbor development.

  15. Polarization splay as the origin of the modulation in the B1 and B7 smectic phases of bent-core molecules

    Czech Academy of Sciences Publication Activity Database

    Coleman, D.A.; Jones, C.D.; Nakata, M.; Clark, N.A.; Walba, D.M.; Weissflog, W.; Fodor-Csorba, K.; Watanabe, J.; Novotná, Vladimíra; Hamplová, Věra

    2008-01-01

    Roč. 77, č. 2 (2008), 021703/1-021703/6 ISSN 1539-3755 Grant - others:NSF MRSEC(US) DMR-0213918; NSF(US) DMR-0072989 Institutional research plan: CEZ:AV0Z10100520 Keywords : liquid crystals * bent-core molecules * polarization splay Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.508, year: 2008

  16. The effect of organic molecules adsorption on hydrogen absorption in relation to the hydrogen evolution reaction

    Directory of Open Access Journals (Sweden)

    LJILJANA VRACAR

    2001-12-01

    Full Text Available The competitive adsorption of organic molecules (2,7-naphthalenedisulfonic acid and adsorbed H is of interest in relation to its influence on H absorption into a Pd-Ni electrodeposited alloy. The experimental results, in acid solution, show an enhancement of the coverage of the electrode surface with adosrbed H due to the competitive adsorption of organic molecules that interfere with H atoms, through lateral attractive interactions between the adsorbed species and communal electronic effects, leading supposedly to a decreased probability of H entry into the alloy. Chemisorbed H is, on the other hand, an intermediate in the HER, so the enhancement of the electrode coverage in the presence of co-adsorbed organic molecules promotes the hydrogen evolution reaction.

  17. Development of a Sample Processing System (SPS) for the in situ search of organic compounds on Mars : application to the Mars Organic Molecule Analyzer (MOMA) experiment

    Science.gov (United States)

    Buch, A.; Sternberg, R.; Garnier, C.; Fressinet, C.; Szopa, C.; El Bekri, J.; Coll, P.; Rodier, C.; Raulin, F.; Goesmann, F.

    2008-09-01

    The search for past or present life signs is one of the primary goals of the future Mars exploratory missions. With this aim the Mars Organic Molecule Analyzer (MOMA) module of the ExoMars 2013 next coming European space mission is designed to the in situ analysis, in the Martian soil, of organic molecules of exobiological interest such as amino acids, carboxylic acids, nucleobases or polycyclic aromatic hydrocarbons (PAHs). In the frame of the MOMA experiment we have been developing a Sample Processing System (SPS) compatible with gas chromatography (GC) analysis. The main goal of SPS is to allow the extraction and the gas chromatography separation of the refractory organic compounds from a solid matrix at trace level within space compatible operating conditions. The SPS is a mini-reactor, containing the solid sample (~500mg), able to increase (or decrease) the internal temperature from 20 to 500 °C within 13 sec. The extraction step is therefore performed by using thermodesorption, the best yield of extraction being obtained at 300°C for 10 to 20 min. It has to be noticed that the temperature could be increased up to 500°C without a significant lost of efficiency if the heating run time is kept below 3 min. After the thermodesorption the chemical derivatization of the extracted compounds is performed directly on the soil with a mixture of MTBSTFA and DMF [buch et al.]. By decreasing the polarity of the target molecules, this step allows their volatilization at a temperature below 250°C without any chemical degradation. Once derivatized, the targeted volatile molecules are transferred through a heated transfer line in the gas chromatograph coupled with a mass spectrometer for the detection. The SPS is a "one step/one pot" sample preparation system which should allow the MOMA experiment to detect the refractory molecules absorbed in the Martian soil at a detection limit below the ppb level. A. Buch, R. Sternberg, C. Szopa, C. Freissinet, C. Garnier, J. El Bekri

  18. Toxicity of natural mixtures of organic pollutants in temperate and polar marine phytoplankton

    KAUST Repository

    Echeveste, Pedro

    2016-07-26

    Semivolatile and persistent organic pollutants (POPs) undergo atmospheric transport before being deposited to the oceans, where they partition to phytoplankton organic matter. The goal of this study was to determine the toxicity of naturally occurring complex mixtures of organic pollutants to temperate and polar phytoplankton communities from the Mediterranean Sea, the North East (NE) Atlantic, and Southern Oceans. The cell abundance of the different phytoplankton groups, chlorophyll a concentrations, viability of the cells, and growth and decay constants were monitored in response to addition of a range of concentrations of mixtures of organic pollutants obtained from seawater extracts. Almost all of the phytoplankton groups were significantly affected by the complex mixtures of non-polar and polar organic pollutants, with toxicity being greater for these mixtures than for single POPs or simple POP mixtures. Cocktails\\' toxicity arose at concentrations as low as tenfold the field oceanic levels, probably due to a higher chemical activity of the mixture than of simple POPs mixtures. Overall, smaller cells were the most affected, although Mediterranean picophytoplankton was significantly more tolerant to non-polar POPs than picophytoplankton from the Atlantic Ocean or the Bellingshausen Sea microphytoplankton. © 2016 Elsevier B.V.

  19. Dipole polarizability of alkali-metal (Na, K, Rb)-alkaline-earth-metal (Ca, Sr) polar molecules: Prospects for alignment

    Science.gov (United States)

    Gopakumar, Geetha; Abe, Minori; Hada, Masahiko; Kajita, Masatoshi

    2014-06-01

    Electronic open-shell ground-state properties of selected alkali-metal-alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the 2Σ+ ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes (23Na, 39K, 85Rb)-(40Ca, 88Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  20. Solution processable organic polymers and small molecules for bulk-heterojunction solar cells: A review

    International Nuclear Information System (INIS)

    Sharma, G. D.

    2011-01-01

    Solution processed bulk heterojunction (BHJ) organic solar cells (OSCs) have gained wide interest in past few years and are established as one of the leading next generation photovoltaic technologies for low cost power production. Power conversion efficiencies up to 6% and 6.5% have been reported in the literature for single layer and tandem solar cells, respectively using conjugated polymers. A recent record efficiency about 8.13% with active area of 1.13 cm 2 has been reported. However Solution processable small molecules have been widely applied for photovoltaic (PV) devices in recent years because they show strong absorption properties, and they can be easily purified and deposited onto flexible substrates at low cost. Introducing different donor and acceptor groups to construct donor--acceptor (D--A) structure small molecules has proved to be an efficient way to improve the properties of organic solar cells (OSCs). The power conversion efficiency about 4.4 % has been reported for OSCs based on the small molecules. This review deals with the recent progress of solution processable D--A structure small molecules and discusses the key factors affecting the properties of OSCs based on D--A structure small molecules: sunlight absorption, charge transport and the energy level of the molecules.

  1. Modeling self-organized spatio-temporal patterns of PIP3 and PTEN during spontaneous cell polarization

    International Nuclear Information System (INIS)

    Knoch, Fabian; Tarantola, Marco; Bodenschatz, Eberhard; Rappel, Wouter-Jan

    2014-01-01

    During spontaneous cell polarization of Dictyostelium discoideum cells, phosphatidylinositol (3,4,5)-triphoshpate (PIP 3 ) and PTEN (phosphatase tensin homolog) have been identified as key signaling molecules which govern the process of polarization in a self-organized manner. Recent experiments have quantified the spatio-temporal dynamics of these signaling components. Surprisingly, it was found that membrane-bound PTEN can be either in a high or low state, that PIP 3 waves were initiated in areas lacking PTEN through an excitable mechanism, and that PIP 3 was degraded even though the PTEN concentration remained low. Here we develop a reaction-diffusion model that aims to explain these experimental findings. Our model contains bistable dynamics for PTEN, excitable dynamics for PIP 3 , and postulates the existence of two species of PTEN with different dephosphorylation rates. We show that our model is able to produce results that are in good qualitative agreement with the experiments, suggesting that our reaction-diffusion model underlies the self-organized spatio-temporal patterns observed in experiments. (paper)

  2. Modeling self-organized spatio-temporal patterns of PIP3 and PTEN during spontaneous cell polarization

    Science.gov (United States)

    Knoch, Fabian; Tarantola, Marco; Bodenschatz, Eberhard; Rappel, Wouter-Jan

    2014-08-01

    During spontaneous cell polarization of Dictyostelium discoideum cells, phosphatidylinositol (3,4,5)-triphoshpate (PIP3) and PTEN (phosphatase tensin homolog) have been identified as key signaling molecules which govern the process of polarization in a self-organized manner. Recent experiments have quantified the spatio-temporal dynamics of these signaling components. Surprisingly, it was found that membrane-bound PTEN can be either in a high or low state, that PIP3 waves were initiated in areas lacking PTEN through an excitable mechanism, and that PIP3 was degraded even though the PTEN concentration remained low. Here we develop a reaction-diffusion model that aims to explain these experimental findings. Our model contains bistable dynamics for PTEN, excitable dynamics for PIP3, and postulates the existence of two species of PTEN with different dephosphorylation rates. We show that our model is able to produce results that are in good qualitative agreement with the experiments, suggesting that our reaction-diffusion model underlies the self-organized spatio-temporal patterns observed in experiments.

  3. Chemical selectivity in the dissociative ionization of organic molecules by low-energy positrons

    International Nuclear Information System (INIS)

    Xu, J.; Hulett, L.D. Jr.; Lewis, T.A.; McLuckey, S.A.

    1995-01-01

    The ionization and dissociation, induced by positrons having kinetic energies in the range 0.3--3 eV, of a large number of organic molecules have been studied. The required energies for ionization and dissociation are supplied through the annihilation of electrons by the positrons. Cross sections for these interactions are strong functions of molecular size, molecular structure, and bond type. Fragmentation usually occurs between atoms linked by σ bonds. Multiple bonds tend to stabilize the molecules against fragmentation. Fragmentation induced under the low-energy process occurs preferably in the linear groups of molecules rather than in ring structures. Ionization and dissociation cross sections of large alkane molecules are higher than those of smaller molecules. A possible explanation of the fragmentation phenomena is that positrons annihilate electrons in energy levels below the highest occupied molecular orbital (HOMO), leaving the molecules in excited states. Multiple bonds in molecules tend to promote higher populations near the HOMO state; annihilation of electrons near the HOMO state does not result in fragmentation

  4. Development of new methods in modern selective organic synthesis: preparation of functionalized molecules with atomic precision

    International Nuclear Information System (INIS)

    Ananikov, V P; Khemchyan, L L; Ivanova, Yu V; Dilman, A D; Levin, V V; Bukhtiyarov, V I; Sorokin, A M; Prosvirin, I P; Romanenko, A V; Simonov, P A; Vatsadze, S Z; Medved'ko, A V; Nuriev, V N; Nenajdenko, V G; Shmatova, O I; Muzalevskiy, V M; Koptyug, I V; Kovtunov, K V; Zhivonitko, V V; Likholobov, V A

    2014-01-01

    The challenges of the modern society and the growing demand of high-technology sectors of industrial production bring about a new phase in the development of organic synthesis. A cutting edge of modern synthetic methods is introduction of functional groups and more complex structural units into organic molecules with unprecedented control over the course of chemical transformation. Analysis of the state-of-the-art achievements in selective organic synthesis indicates the appearance of a new trend — the synthesis of organic molecules, biologically active compounds, pharmaceutical substances and smart materials with absolute selectivity. Most advanced approaches to organic synthesis anticipated in the near future can be defined as 'atomic precision' in chemical reactions. The present review considers selective methods of organic synthesis suitable for transformation of complex functionalized molecules under mild conditions. Selected key trends in the modern organic synthesis are considered including the preparation of organofluorine compounds, catalytic cross-coupling and oxidative cross-coupling reactions, atom-economic addition reactions, methathesis processes, oxidation and reduction reactions, synthesis of heterocyclic compounds, design of new homogeneous and heterogeneous catalytic systems, application of photocatalysis, scaling up synthetic procedures to industrial level and development of new approaches to investigation of mechanisms of catalytic reactions. The bibliography includes 840 references

  5. Transport properties of graphene nanoribbons with side-attached organic molecules

    International Nuclear Information System (INIS)

    Rosales, L; Pacheco, M; Barticevic, Z; Latge, A; Orellana, P A

    2008-01-01

    In this work we address the effects on the conductance of graphene nanoribbons (GNRs) of organic molecules adsorbed at the ribbon edge. We studied the case of armchair and zigzag GNRs with quasi-one-dimensional side-attached molecules, such as linear poly-aromatic hydrocarbons and poly(para-phenylene). These nanostructures are described using a single-band tight-binding Hamiltonian and their electronic conductance and density of states are calculated within the Green's function formalism based on real-space renormalization techniques. We found that the conductance exhibits an even-odd parity effect as a function of the length of the attached molecules. Furthermore, the corresponding energy spectrum of the molecules can be obtained as a series of Fano antiresonances in the conductance of the system. The latter result suggests that GNRs can be used as a spectrograph sensor device

  6. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

    Science.gov (United States)

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-10-22

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

  7. Sorption of polar and nonpolar organic contaminants by oil-contaminated soil.

    Science.gov (United States)

    Chen, Hong; Chen, Shuo; Quan, Xie; Zhao, Huimin; Zhang, Yaobin

    2008-12-01

    Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil-water distribution coefficients (K(oil)). The resulting oil-contaminated soil-water distribution coefficients (K(d)) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C(oil)) but sorption-reducing (competitive) effects at intermediate C(oil) (approximately 1 g kg(-1)). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K(d) at C(oil) above approximately 1 g kg(-1) were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.

  8. Generation of circularly polarized XUV and soft-x-ray high-order harmonics by homonuclear and heteronuclear diatomic molecules subject to bichromatic counter-rotating circularly polarized intense laser fields

    Science.gov (United States)

    Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

    2017-12-01

    Recently, studies of bright circularly polarized high-harmonic beams from atoms in the soft-x-ray region as a source for x-ray magnetic circular dichroism measurement in a tabletop-scale setup have received considerable attention. In this paper, we address the problem with molecular targets and perform a detailed quantum study of H2 +, CO, and N2 molecules in bichromatic counter-rotating circularly polarized laser fields where we adopt wavelengths (1300 and 790 nm) and intensities (2 ×1014W /cm2 ) reported in a recent experiment [Proc. Natl. Acad. Sci. USA 112, 14206 (2015), 10.1073/pnas.1519666112]. Our treatment of multiphoton processes in homonuclear and heteronuclear diatomic molecules is nonperturbative and based on the time-dependent density-functional theory for multielectron systems. The calculated radiation spectrum contains doublets of left and right circularly polarized harmonics with high-energy photons in the XUV and soft-x-ray ranges. Our results reveal intriguing and substantially different nonlinear optical responses for homonuclear and heteronuclear diatomic molecules subject to circularly polarized intense laser fields. We study in detail the below- and above-threshold harmonic regions and analyze the ellipticity and phase of the generated harmonic peaks.

  9. Removal of sulfur-containing organic molecules adsorbed on inorganic supports by Rhodococcus Rhodochrous spp.

    Science.gov (United States)

    Carvajal, P; Dinamarca, M Alejandro; Baeza, P; Camú, E; Ojeda, J

    2017-02-01

    To remove dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) adsorbed on alumina, silica and sepiolite through biodesulfurization (BDS) using Rhodococcus Rhodochrous spp., that selectively reduce sulfur molecules without generating of gaseous pollutants. The adsorption of DBT and 4,6-DMDBT was affected by the properties of the supports, including particle size and the presence of surface acidic groups. The highest adsorption of both sulfur-containing organic molecules used particle sizes of 0.43-0.063 mm. The highest percentage removal was with sepiolite (80 % for DBT and 56 % for 4,6-DMDBT) and silica (71 % for DBT and 37 % for 4,6-DMDBT). This is attributed to the close interaction between these supports and the bacteria. Biodesulfurization is effective for removing the sulfur-containing organic molecules adsorbed on inorganic materials and avoids the generation of gaseous pollutants.

  10. Separation of polar compounds using a flexible metal-organic framework

    NARCIS (Netherlands)

    Motkuri, R.K.; Thallapally, P.K.; Annapureddy, H.V.R.; Dang, L.X.; Krishna, R.; Nune, S.K.; Fernandez, C.A.; Liu, J.; McGrail, B.P.

    2015-01-01

    A flexible metal-organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds (propanol isomers) by exploiting the differences in the saturation capacities of the constituents. Transient breakthrough simulations show that these

  11. Diffusion as a function of guest molecule length and functionalization in flexible metal–organic frameworks

    KAUST Repository

    Zheng, B.

    2016-05-11

    Understanding guest diffusion in nanoporous host-guest systems is crucial in the efficient design of metal-organic frameworks (MOFs) for chemical separation and drug delivery applications. In this work, we investigated the effect of molecule length on the diffusion rate in the zeolitic imidazolate framework 8 (ZIF-8), trying to find a simple and straightforward variable to characterize the complicated guest diffusion. We found that, counter-intuitively, long guest molecules can diffuse as quickly as short molecules; the diffusion coefficient of ethyl acetate for example is of the same order of magnitude as ethane and ethanol, as excludes the existence of a simple relationship between molecule length and diffusion rate. This phenomenon is explained by a study of the contributions of intra- and inter-cage movement to overall transport. Steric confinement limits the degrees of freedom of long guest molecules, shortening their residence time and increasing the efficiency of radial diffusion. In contrast, shorter molecules meander within MOF cages, reducing transport. Furthermore, the energy barrier of inter-cage transport also does not exhibit a simple dependence on a guest molecule length, attributing to the effect of the type of functional group on diffusion. Guests over varying lengths were investigated by using theoretical methods, revealing that the guest diffusion in ZIF-8 depends on the number of contiguous carbon atoms in a molecule, rather than its overall length. Thus, we proposed simple criteria to predict arbitrary guest molecule diffusivity in ZIF-8 without time-consuming experimentation. © 2016 The Royal Society of Chemistry.

  12. Water and oxygen induced degradation of small molecule organic solar cells

    DEFF Research Database (Denmark)

    Hermenau, Martin; Riede, Moritz; Leo, Karl

    2011-01-01

    Small molecule organic solar cells were studied with respect to water and oxygen induced degradation by mapping the spatial distribution of reaction products in order to elucidate the degradation patterns and failure mechanisms. The active layers consist of a 30 nm bulk heterojunction formed...

  13. Directed self-organization of single DNA molecules in a nanoslit via embedded nanopit arrays

    DEFF Research Database (Denmark)

    Reisner, Walter; Larsen, Niels Bent; Flyvbjerg, Henrik K.

    2009-01-01

    We show that arrays of nanopit structures etched in a nanoslit can control the positioning and conformation of single DNA molecules in nanofluidic devices. By adjusting the spacing, organization and placement of the nanopits it is possible to immobilize DNA at predetermined regions of a device...

  14. Plasma-polymerized films providing selective affinity to the polarity of vaporized organic solvents

    International Nuclear Information System (INIS)

    Akimoto, Takuo; Ikeshita, Yusuke; Terashima, Ryo; Karube, Isao

    2009-01-01

    Plasma-polymerized films (PPFs) were fabricated as recognition membranes for a vapor-sensing device, and their affinity to vaporized organic solvents was evaluated with surface plasmon resonance. The affinity we intended to create is the selective sorption of the vaporized organic solvents depending on their polarity. For this purpose, acetonitrile, ethylenediamine (EDA), styrene, hexamethyldisiloxane (HMDSO), and hexamethyldisilazane were used to fabricate PPFs. Vaporized methanol, ethanol, and 1-propanol were used as high-polar solvents to be analyzed. Hexane, toluene, and p-xylene were used as low-polar solvents. As a result, the HMDSO-PPF with 97.3 o of contact angle was found to provide affinity to the low-polar solvents. In contrast, the EDA-PPF with 7.1 o of contact angle provided affinity to the high-polar solvents. Observations of the surface morphology of the HMDSO- and EDA-PPFs with a scanning electron microscope revealed that they are composed of nano-scale islands.

  15. Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing

    KAUST Repository

    Rancatore, Benjamin J.

    2016-01-21

    © 2016 American Chemical Society. Small molecules (SMs) with unique optical or electronic properties provide an opportunity to incorporate functionality into block copolymer (BCP)-based supramolecules. However, the assembly of supramolecules based on these highly crystalline molecules differs from their less crystalline counterparts. Here, two families of organic semiconductor SMs are investigated, where the composition of the crystalline core, the location (side- vs end-functionalization) of the alkyl solubilizing groups, and the constitution (branched vs linear) of the alkyl groups are varied. With these SMs, we present a systematic study of how the phase behavior of the SMs affects the overall assembly of these organic semiconductor-based supramolecules. The incorporation of SMs has a large effect on the interfacial curvature, the supramolecular periodicity, and the overall supramolecular morphology. The crystal packing of the SM within the supramolecule does not necessarily lead to the assembly of the comb block within the BCP microdomains, as is normally observed for alkyl-containing supramolecules. An unusual lamellar morphology with a wavy interface between the microdomains is observed due to changes in the packing structure of the small molecule within BCP microdomains. Since the supramolecular approach is modular and small molecules can be readily switched out, present studies provide useful guidance toward access supramolecular assemblies over several length scales using optically active and semiconducting small molecules.

  16. Generation of wavelength-tunable soliton molecules in a 2-μm ultrafast all-fiber laser based on nonlinear polarization evolution.

    Science.gov (United States)

    Wang, Pan; Bao, Chengying; Fu, Bo; Xiao, Xiaosheng; Grelu, Philippe; Yang, Changxi

    2016-05-15

    We report on the experimental observation of stable single solitons and soliton molecules in a 2-μm thulium-holmium-doped fiber laser mode-locked through the nonlinear polarization evolution technique within an anomalously dispersive cavity. Single 0.65 nJ solitons feature a 7.3 nm spectral FWHM and 540 fs temporal duration, yielding a time-bandwidth product close to the Fourier-transform limitation. Under the same pumping power of 740 mW, stable out-of-phase twin-soliton molecules, featuring a temporal separation of 2.5 ps between the two ∼700  fs pulses, are generated in a deterministic way, while the central wavelength of the soliton molecules can be tuned from 1920 to 1940 nm. Finally, we present strong experimental evidence of vibrating soliton molecules.

  17. Acenes, Heteroacenes and Analogous Molecules for Organic Photovoltaic and Field Effect Transistor Applications

    Science.gov (United States)

    Granger, Devin Benjamin

    Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have likewise been investigated. Functionalization of acene compounds by placement of groups around the molecule affects the way in which molecules interact in the solid state, in addition to the energetics of the molecule. The use of electron donating or electron withdrawing groups affects the frontier molecular orbitals and thus affects the optical and electronic gaps of the molecules. The use of bulky side groups such as alkylsilylethynyl groups allows for crystal engineering of molecular aggregates, and changing the volume and dimensions of the alkylsilyl groups affects the intermolecular interactions and thus changes the packing motif. In chapter 2, a series of tetracene and pentacene molecules with strongly electron withdrawing groups is described. The investigation focuses on the change in energetics of the frontier molecular orbitals between the base acene and the nitrile and dicyanovinyl derivatives as well as the differences between the pentacene and tetracene molecules. The differences in close packing motifs through use of bulky alkylsilylethynyl groups is also discussed in relation to electron acceptor material design and bulk heterojunction organic photovoltaic characteristics. Chapter 3 focuses on molecular acceptor and

  18. Effect of the dynamic core-electron polarization of CO molecules on high-order harmonic generation

    Science.gov (United States)

    Le, Cam-Tu; Hoang, Van-Hung; Tran, Lan-Phuong; Le, Van-Hoang

    2018-04-01

    We theoretically investigate the influence of dynamic core-electron polarization (DCeP) of CO molecules on high-order harmonic generation (HHG) by solving the time-dependent Schrödinger equation (TDSE) within the single-active-electron (SAE) approximation. The effect of DCeP is shown to depend strongly on the molecular orientation angle θ . Particularly, compared to the calculations without DCeP, the inclusion of this effect gives rise to an enhancement of harmonic intensity at θ =0° when the electric field aligns along the O-C direction and to a suppression at θ =180° when the field heads in the opposite direction. Meanwhile, when the electric field is perpendicular to the molecular axis, the effect is almost insignificant. The phenomenon is thought to be linked to the ionization process. However, this picture is not completed yet. By solving the TDSE within the SAE approximation and conducting a classical simulation, we are able to obtain the ionization probability as well as the ionization rate and prove that HHG, in fact, receives a major contribution from electrons ionized at only a certain time interval, rather than throughout the whole pulse propagation. Including DCeP, the variation of the ionization rate in this interval highly correlates to that of the HHG intensity. To better demonstrate the origin of this manifestation, we also show the alternation DCeP makes on the effective potential that corresponds to the observed change in the ionization rate and consequently the HHG intensity. Our results confirm previous studies' observations and, more importantly, provide the missing physical explanation. With the role of DCeP now better understood for the entire range of the orientation angle, this effect can be handled more conveniently for calculating the HHG of other targets.

  19. Organization of extracting molecules of the diamide type: link with the extracting properties?

    International Nuclear Information System (INIS)

    Meridiano, Y.

    2009-02-01

    The aim of these studies is to establish a link between the different organizations of diamide extractants (used in the DIAMEX process) and their extracting properties. The effects of the key parameters leading the liquid-liquid extraction (concentration of extractant, nature of solute, activity of the aqueous phase, nature of the diluent and temperature) are studied: 1) at the supramolecular scale, with the characterization of the extractant organizations by vapor-pressure osmometry (VPO) and small angle neutron and X-ray scattering (SANS/SAXS) experiments; 2) at the molecular scale, with the quantification of the extracted solutes (water, nitric acid, metal nitrate) and the determination of extracted complexes stoichiometries by electro-spray mass spectrometry (ESI-MS) experiments. The DMDOHEMA molecule acts as a classical surfactant and forms aggregates of the reverse micelle type. Taking into account the established supramolecular diagrams, a quantitative link between the extractants structures and their extracting properties has been brought to light. To model the europium nitrate extraction, two approaches have been developed: - an approach based on mass action laws. Extractions equilibria have been proposed taking into account the supramolecular speciation; - an innovative approach considering the extracted ions as adsorbed on a specific surface of the extractant molecule which depends on the extractant organization state. The ion extraction can be considered as a sum of isotherms corresponding to the different states of organization. This approach allows to compare the extraction efficiency of an extracting molecule as a function of its organization state. (author)

  20. Correlating Molecular Structures with Transport Dynamics in High-Efficiency Small-Molecule Organic Photovoltaics.

    Science.gov (United States)

    Peng, Jiajun; Chen, Yani; Wu, Xiaohan; Zhang, Qian; Kan, Bin; Chen, Xiaoqing; Chen, Yongsheng; Huang, Jia; Liang, Ziqi

    2015-06-24

    Efficient charge transport is a key step toward high efficiency in small-molecule organic photovoltaics. Here we applied time-of-flight and organic field-effect transistor to complementarily study the influences of molecular structure, trap states, and molecular orientation on charge transport of small-molecule DRCN7T (D1) and its analogue DERHD7T (D2). It is revealed that, despite the subtle difference of the chemical structures, D1 exhibits higher charge mobility, the absence of shallow traps, and better photosensitivity than D2. Moreover, charge transport is favored in the out-of-plane structure within D1-based organic solar cells, while D2 prefers in-plane charge transport.

  1. CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

    Energy Technology Data Exchange (ETDEWEB)

    Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H. [LISA Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris Est Créteil (UPEC), Université Paris Diderot (UPD), Institut Pierre Simon Laplace, Labex ESEP, Paris (France); Duvernay, F.; Chiavassa, T., E-mail: vvinogradoff@mnhn.fr [PIIM, Laboratoire de Physique des Interactions Ioniques et Moléculaires, Université Aix-Marseille, UMR CNRS 7345, Marseille (France)

    2015-08-20

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H{sub 2}O, NH{sub 3}, CO{sub 2}, H{sub 2}CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

  2. CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

    International Nuclear Information System (INIS)

    Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H.; Duvernay, F.; Chiavassa, T.

    2015-01-01

    Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H 2 O, NH 3 , CO 2 , H 2 CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites

  3. EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions

    Directory of Open Access Journals (Sweden)

    S. Compernolle

    2011-09-01

    Full Text Available We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects, a method to predict (subcooled liquid pure compound vapour pressure p0 of organic molecules that requires only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: aldehydes, ketones, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA.

  4. Intercalation of organic molecules in 2D copper (II) nitroprusside: Intermolecular interactions and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Osiry, H.; Cano, A.; Lemus-Santana, A.A.; Rodríguez, A. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico); Carbonio, R.E. [INFIQC-CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, X5000HUA Córdoba (Argentina); Reguera, E., E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico)

    2015-10-15

    This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π–π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which was actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting. - Highlights: • Intercalation of organic molecules in 2D copper (II) nitroprusside. • Molecular properties of intercalation compounds of 2D copper (II) nitroprusside. • Magnetic properties of hybrid inorganic–organic solids. • Hybrid inorganic–organic 3D framework.

  5. UP-scaling of inverted small molecule based organic solar cells

    DEFF Research Database (Denmark)

    Patil, Bhushan Ramesh; Madsen, Morten

    Organic solar cells (OSC), in spite of being a promising technology, still face challenges regarding large-scale fabrication. Although efficiencies of up to 12 % has been reached for small molecule OSC, their performance, both in terms of device efficiency and stability, is significantly reduced...... during up-scaling processes. The work presented here is focused on an approach towards up-scaling of small molecule based OSC with inverted device configuration. Bilayer OSC from Tetraphenyldibenzoperiflanthene (DBP) and Fullerenes (C70), as electron donor and acceptor respectively, with cell area...

  6. Thermal Reactivity Of Organic Molecules With Perchlorates And The Detection Of Organics In Mars Samples With SAM Onboard Curiosity Rover

    Science.gov (United States)

    Szopa, C.; Millan, M.; Buch, A.; Freissinet, C.; Guzman, M.; Glavin, D. P.; Mahaffy, P. R.; Navarro-Gonzalez, R.

    2017-12-01

    The search for organic molecules at the Mars surface is a key objective to assess the potential for habitability of the planet and to find biomarkers. Both the past Viking landers and the Curiosity rover of today carry onboard instruments based on gas chromatography coupled to mass spectrometry with the aim to analyze the content of organics present in soil or rock samples. These instruments analyze the volatile compounds released from the samples submitted to thermal or chemical treatments. Even though these sample preparation processes are commonly used on Earth for their efficient extraction of organic materials from mineral matrixes, the presence of oxychlorines recently discovered in the Mars soil [1, 2] makes the process for space applications more complex and the results more difficult to interpret. Indeed, the release of volatile inorganic reactive molecules from oxychlorines during the sample heating process induces reactions of chlorination and oxidation of the organic molecules. For this reason, in an effort to contribute to the interpretation of the results obtained with the Viking/GCMS, and the MSL/SAM experiment our team currently operates on Mars, we started to study systematically the thermal reactivity of a series of organic molecules, of interest for Mars and life purposes, mixed with oxychlorines either detected or potentially present in the soil of Mars [3]. In this presentation, we will mainly focus on two sets of results that were obtained while studying the reactivity of calcium perchlorates with polyaromatic hydrocarbons, amino acids and carboxylic acids under pyrolytic conditions similar to those used in the SAM experiment. First of all, we will show the dependence of reactivity on the temperature of sublimation and decomposition of the individual components in the mixture and, secondly, we will discuss the detection of aromatic chlorinated species by SAM in samples collected at the Cumberland site from the results obtained in this study

  7. Extending the strong-field approximation of high-order harmonic generation to polar molecules: gating mechanisms and extension of the harmonic cutoff

    DEFF Research Database (Denmark)

    Etches, Adam; Madsen, Lars Bojer

    2010-01-01

    Polar molecules such as CO are interesting target systems for high-order harmonic generation (HHG) as they can be oriented with current laser techniques, thus allowing the study of systems without inversion symmetry. However, the asymmetry of the molecule also means that the molecular orbitals...... (enhanced) every other half-cycle. We show that the Stark shift weakens the strength of system-induced gating and also determines the relative contribution from opposite orientations in field-induced gating. Finally, we propose a novel scheme for extending the high-order harmonic cutoff by letting the two...

  8. Xenoendocrine pollutants May Reduce Size of Sexual Organs in East Greenland Polar Bears (Ursus Maritimus)

    DEFF Research Database (Denmark)

    Sonne, Christian; Leifsson, Pall S.; Dietz, Rune

    2006-01-01

    .01) and uterine horn length and HCB (p = 0.02). The study suggests thatthere is an impact from xenoendocrine pollutants on the size of East Greenland polar bear genitalia. This may pose a riskto this polar bear subpopulation in the future because of reduced sperm and egg quality/quantity and uterus and penis size......Reproductive organs from 55 male and 44 female East Greenland polar bears were examined to investigate the potential negative impact from organohalogen pollutants (OHCs). Multiple regressions normalizing for age showed a significant inverse relationship between OHCs and testis length and baculum...... length and weight, respectively, and was found in both subadults (dichlorodiphenyl trichloroethanes, dieldrin, chlordanes, hexacyclohexanes, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs)) and adults (hexachlorobenzene [HCB]) (all p

  9. Searching for Bio-Precursors and Complex Organic Molecules in Space using the GBT

    Science.gov (United States)

    Cordiner, M.; Charnley, S.; Kisiel, Z.

    2012-01-01

    Using the latest microwave receiver technology, large organic molecules with abundances as low as approx. 10(exp -11) times that of molecular hydrogen are detectable in cold interstellar clouds via their rotational emission line spectra. We report new observations to search for complex molecules, including molecules of possible pre-biotic importance, using the newly-commissioned Kband focal plane array (KFPA) of the NRAO Robert C. Byrd Green Bank Telescope. Spectra are presented of the dense molecular cloud TMC-1, showing strict upper limits on the level of emission from nitrogen-bearing rings pyrimidine, quinoline and iso-quinoline, carbon-chain oxides C60, C70, HC60 and HC70, and the carbon-chain anion C4H-. The typical RMS brightness temperature noise levels we achieved are approx. 1 mK at around 20 GHz.

  10. Electrochemical assembly of organic molecules by the reduction of iodonium salts

    Science.gov (United States)

    Dirk, Shawn M [Albuquerque, NM; Howell, Stephen W [Albuquerque, NM; Wheeler, David R [Albuquerque, NM

    2009-06-23

    Methods are described for the electrochemical assembly of organic molecules on silicon, or other conducting or semiconducting substrates, using iodonium salt precursors. Iodonium molecules do not assemble on conducting surfaces without a negative bias. Accordingly, the iodonium salts are preferred for patterning applications that rely on direct writing with negative bias. The stability of the iodonium molecule to acidic conditions allows them to be used with standard silicon processing. As a directed assembly process, the use of iodonium salts provides for small features while maintaining the ability to work on a surface and create structures on a wafer level. Therefore, the process is amenable for mass production. Furthermore, the assembled monolayer (or multilayer) is chemically robust, allowing for subsequent chemical manipulations and the introduction of various molecular functionalities for various chemical and biological applications.

  11. Microtubule-organizing center polarity and the immunological synapse: protein kinase C and beyond

    Directory of Open Access Journals (Sweden)

    Morgan eHuse

    2012-07-01

    Full Text Available Cytoskeletal polarization is crucial for many aspects of immune function, ranging from neutrophil migration to the sampling of gut flora by intestinal dendritic cells. It also plays a key role during lymphocyte cell-cell interactions, the most conspicuous of which is perhaps the immunological synapse (IS formed between a T cell and an antigen-presenting cell (APC. IS formation is associated with the reorientation of the T cell’s microtubule-organizing center (MTOC to a position just beneath the cell-cell interface. This cytoskeletal remodeling event aligns secretory organelles inside the T cell with the IS, enabling the directional release of cytokines and cytolytic factors toward the APC. MTOC polarization is therefore crucial for maintaining the specificity of a T cell’s secretory and cytotoxic responses. It has been known for some time that T cell receptor (TCR stimulation activates the MTOC polarization response. It has been difficult, however, to identify the machinery that couples early TCR signaling to cytoskeletal remodeling. Over the past few years, considerable progress has been made in this area. This review will present an overview of recent advances, touching on both the mechanisms that drive MTOC polarization and the effector responses that require it. Particular attention will be paid to both novel and atypical members of the protein kinase C family, which are now known to play important roles in both the establishment and the maintenance of the polarized state.

  12. Microtubule-organizing center polarity and the immunological synapse: protein kinase C and beyond.

    Science.gov (United States)

    Huse, Morgan

    2012-01-01

    Cytoskeletal polarization is crucial for many aspects of immune function, ranging from neutrophil migration to the sampling of gut flora by intestinal dendritic cells. It also plays a key role during lymphocyte cell-cell interactions, the most conspicuous of which is perhaps the immunological synapse (IS) formed between a T cell and an antigen-presenting cell (APC). IS formation is associated with the reorientation of the T cell's microtubule-organizing center (MTOC) to a position just beneath the cell-cell interface. This cytoskeletal remodeling event aligns secretory organelles inside the T cell with the IS, enabling the directional release of cytokines and cytolytic factors toward the APC. MTOC polarization is therefore crucial for maintaining the specificity of a T cell's secretory and cytotoxic responses. It has been known for some time that T cell receptor (TCR) stimulation activates the MTOC polarization response. It has been difficult, however, to identify the machinery that couples early TCR signaling to cytoskeletal remodeling. Over the past few years, considerable progress has been made in this area. This review will present an overview of recent advances, touching on both the mechanisms that drive MTOC polarization and the effector responses that require it. Particular attention will be paid to both novel and atypical members of the protein kinase C family, which are now known to play important roles in both the establishment and the maintenance of the polarized state.

  13. Investigating organic molecules responsible of auxin-like activity of humic acid fraction extracted from vermicompost

    International Nuclear Information System (INIS)

    Scaglia, Barbara; Nunes, Ramom Rachide; Rezende, Maria Olímpia Oliveira; Tambone, Fulvia; Adani, Fabrizio

    2016-01-01

    This work studied the auxin-like activity of humic acids (HA) obtained from vermicomposts produced using leather wastes plus cattle dung at different maturation stages (fresh, stable and mature). Bioassays were performed by testing HA concentrations in the range of 100–6000 mg carbon L −1 . 13 C CPMAS-NMR and GC–MS instrumental methods were used to assess the effect of biological processes and starting organic mixtures on HA composition. Not all HAs showed IAA-like activity and in general, IAA-like activity increased with the length of the vermicomposting process. The presence of leather wastes was not necessary to produce the auxin-like activity of HA, since HA extracted from a mix of cattle manure and sawdust, where no leather waste was added, showed IAA-like activity as well. CPMAS 13 CNMR revealed that HAs were similar independently of the mix used and that the humification process involved the increasing concentration of pre-existing alkali soluble fractions in the biomass. GC/MS allowed the identification of the molecules involved in IAA-like effects: carboxylic acids and amino acids. The concentration of active molecules, rather than their simple presence in HA, determined the bio-stimulating effect, and a good linear regression between auxin-like activity and active stimulating molecules concentration was found (R 2 = − 0.85; p < 0.01, n = 6). - Highlights: • Vermicomposting converts waste into organic fertilizer. • Vermicomposts can have biostimulating effect for the presence of hormone-like molecules. • Auxine-like activity was associated to the vermicompost humic acid fraction (HA). • HA carboxylic acids and amino acids, were reported to act as auxin-like molecules. • A linear regression was found between molecules and auxin-like activity.

  14. Investigating organic molecules responsible of auxin-like activity of humic acid fraction extracted from vermicompost

    Energy Technology Data Exchange (ETDEWEB)

    Scaglia, Barbara, E-mail: barbara.scaglia@unimi.it [Gruppo Ricicla Labs – DiSAA, Università degli Studi di Milano, Via Celoria 2 (Italy); Nunes, Ramom Rachide; Rezende, Maria Olímpia Oliveira [Laboratório de Química Ambiental, Universidade de São Paulo, Instituto de Química de São Carlos, Avenida Trabalhador São Carlense, 400, São Carlos (Brazil); Tambone, Fulvia [Gruppo Ricicla Labs – DiSAA, Università degli Studi di Milano, Via Celoria 2 (Italy); Adani, Fabrizio, E-mail: fabrizio.adani@unimi.it [Gruppo Ricicla Labs – DiSAA, Università degli Studi di Milano, Via Celoria 2 (Italy)

    2016-08-15

    This work studied the auxin-like activity of humic acids (HA) obtained from vermicomposts produced using leather wastes plus cattle dung at different maturation stages (fresh, stable and mature). Bioassays were performed by testing HA concentrations in the range of 100–6000 mg carbon L{sup −1}. {sup 13}C CPMAS-NMR and GC–MS instrumental methods were used to assess the effect of biological processes and starting organic mixtures on HA composition. Not all HAs showed IAA-like activity and in general, IAA-like activity increased with the length of the vermicomposting process. The presence of leather wastes was not necessary to produce the auxin-like activity of HA, since HA extracted from a mix of cattle manure and sawdust, where no leather waste was added, showed IAA-like activity as well. CPMAS {sup 13}CNMR revealed that HAs were similar independently of the mix used and that the humification process involved the increasing concentration of pre-existing alkali soluble fractions in the biomass. GC/MS allowed the identification of the molecules involved in IAA-like effects: carboxylic acids and amino acids. The concentration of active molecules, rather than their simple presence in HA, determined the bio-stimulating effect, and a good linear regression between auxin-like activity and active stimulating molecules concentration was found (R{sup 2} = − 0.85; p < 0.01, n = 6). - Highlights: • Vermicomposting converts waste into organic fertilizer. • Vermicomposts can have biostimulating effect for the presence of hormone-like molecules. • Auxine-like activity was associated to the vermicompost humic acid fraction (HA). • HA carboxylic acids and amino acids, were reported to act as auxin-like molecules. • A linear regression was found between molecules and auxin-like activity.

  15. Resource recovery from waste LCD panel by hydrothermal transformation of polarizer into organic acids.

    Science.gov (United States)

    Li, Feng; Bai, Lan; He, Wenzhi; Li, Guangming; Huang, Juwen

    2015-12-15

    Based on the significant advantages of hydrothermal technology, it was applied to treat polarizer from the waste LCD panel with the aim of transforming it into organic acids (mainly acetic acid and lactic acid). Investigation was done to evaluate the effects of different factors on yields of organic acids, including the reaction temperature, reaction time and H2O2 supply, and the degradation process of polarizer was analyzed. Liquid samples were analyzed by GC/MS and HPLC, and solid-phase products were characterized by SEM and FTIR. Results showed that at the condition of temperature 300 °C and reaction time 5 min, the organic materials reached its highest conversion rate of 71.47% by adding 0.2 mL H2O2 and acetic acid was dominant in the products of organic acids with the yield of 6.78%. When not adding H2O2 to the system, the yields of lactic and acetic acid were respectively 4.24% and 3.80% at a nearly equal degree, they are suitable for esterification to form ethyl lactate instead of separating them for this case. In the hydrothermal process, polarizer was first decomposed to monosaccharides, alkane, etc., and then furfural and acids are produced with further decomposition. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Manipulating Magnetism at Organic/Ferromagnetic Interfaces by Molecule-Induced Surface Reconstruction.

    Science.gov (United States)

    Pang, Rui; Shi, Xingqiang; Van Hove, Michel A

    2016-03-30

    Fullerenes have several advantages as potential materials for organic spintronics. Through a theoretical first-principles study, we report that fullerene C60 adsorption can induce a magnetic reconstruction in a Ni(111) surface and expose the merits of the reconstructed C60/Ni(111) spinterface for molecular spintronics applications. Surface reconstruction drastically modifies the magnetic properties at both sides of the C60/Ni interface. Three outstanding properties of the reconstructed structure are revealed, which originate from reconstruction enhanced spin-split π-d coupling between C60 and Ni(111): (1) the C60 spin polarization and conductance around the Fermi level are enhanced simultaneously, which can be important for read-head sensor miniaturization; (2) localized spin-polarized states appear in C60 with a spin-filter functionality; and (3) magnetocrystalline anisotropic energy and exchange coupling in the outermost Ni layer are reduced enormously. Surface reconstruction can be realized simply by controlling the annealing temperature in experiments.

  17. Laser-induced desorption of organic molecules from front- and back-irradiated metal foils

    International Nuclear Information System (INIS)

    Zinovev, Alexander V.; Veryovkin, Igor V.; Pellin, Michael J.

    2009-01-01

    Laser-Induced Acoustic Desorption (LIAD) from thin metal foils is a promising technique for gentle and efficient volatilization of intact organic molecules from surfaces of solid substrates. Using the Single Photon Ionization (SPI) method combined with time-of-flight mass-spectrometry (TOF MS), desorbed flux in LIAD was examined and compared to that from direct laser desorption (LD). Molecules of various organic dyes were used in experiments. Translational velocities of the desorbed intact molecules did not depend on the desorbing laser intensity, which implies the presence of more sophisticated mechanism of energy transfer than the direct mechanical or thermal coupling between the laser pulse and the adsorbed molecules. The results of our experiments indicate that the LIAD phenomenon cannot be described in terms of a simple mechanical shake-off nor the direct laser desorption. Rather, they suggest that multi-step energy transfer processes are involved. Possible qualitative mechanism of LIAD that are based on formation of non-equilibrium energy states in the adsorbate-substrate system are proposed and discussed.

  18. The cell adhesion molecule Fasciclin2 regulates brush border length and organization in Drosophila renal tubules.

    Science.gov (United States)

    Halberg, Kenneth A; Rainey, Stephanie M; Veland, Iben R; Neuert, Helen; Dornan, Anthony J; Klämbt, Christian; Davies, Shireen-Anne; Dow, Julian A T

    2016-04-13

    Multicellular organisms rely on cell adhesion molecules to coordinate cell-cell interactions, and to provide navigational cues during tissue formation. In Drosophila, Fasciclin 2 (Fas2) has been intensively studied due to its role in nervous system development and maintenance; yet, Fas2 is most abundantly expressed in the adult renal (Malpighian) tubule rather than in neuronal tissues. The role Fas2 serves in this epithelium is unknown. Here we show that Fas2 is essential to brush border maintenance in renal tubules of Drosophila. Fas2 is dynamically expressed during tubule morphogenesis, localizing to the brush border whenever the tissue is transport competent. Genetic manipulations of Fas2 expression levels impact on both microvilli length and organization, which in turn dramatically affect stimulated rates of fluid secretion by the tissue. Consequently, we demonstrate a radically different role for this well-known cell adhesion molecule, and propose that Fas2-mediated intermicrovillar homophilic adhesion complexes help stabilize the brush border.

  19. Organic crystals: properties, devices, functionalization and bridges to bio-molecules.

    Science.gov (United States)

    Brooks, James S

    2010-07-01

    The purpose of this critical review is twofold: first, to review organic "small molecule" crystalline materials in terms of structure and function; and second, to consider if and how such materials might eventually enter the realm of device applicability. This area, one of the most interdisciplinary fields of research in contemporary materials science, embraces chemistry, physics, engineering, biology, theory and computation. The review therefore attempts to treat a relatively large number of examples including fundamental physical and electronic structure, single component and charge transfer complexes, physical properties of single crystalline materials, thin film and single crystal electronic and photonic devices, functional materials, and bio-inspired structures. The point of view is that of an experimental physicist, and in this context, challenges and possible routes to further advances in the development and utilization of organic small molecule materials are discussed for both fundamental and applied purposes (153 references).

  20. Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules

    DEFF Research Database (Denmark)

    Hubert, Mickaël; Hedegård, Erik D.; Jensen, Hans Jørgen Aa

    2016-01-01

    inadequate when the molecule has near-degeneracies and/or low-lying double-excited states. To address these issues we have recently proposed multiconfiguration short-range density-functional theory-MC-srDFT-as a new tool in the toolbox. While initial applications for systems with multireference character......Computational methods that can accurately and effectively predict all types of electronic excitations for any molecular system are missing in the toolbox of the computational chemist. Although various Kohn-Sham density-functional methods (KS-DFT) fulfill this aim in some cases, they become......-srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2...

  1. Charge-Transfer States in Organic Solar Cells: Understanding the Impact of Polarization, Delocalization, and Disorder

    KAUST Repository

    Zheng, Zilong

    2017-05-08

    We investigate the impact of electronic polarization, charge delocalization, and energetic disorder on the charge-transfer (CT) states formed at a planar C60/pentacene interface. The ability to examine large complexes containing up to seven pentacene molecules and three C60 molecules allows us to take explicitly into account the electronic polarization effects. These complexes are extracted from a bilayer architecture modeled by molecular dynamics simulations and evaluated by means of electronic-structure calculations based on long-range-separated functionals (ωB97XD and BNL) with optimized range-separation parameters. The energies of the lowest charge-transfer states derived for the large complexes are in very good agreement with the experimentally reported values. The average singlet-triplet energy splittings of the lowest CT states are calculated not to exceed 10 meV. The rates of geminate recombination as well as of dissociation of the triplet excitons are also evaluated. In line with experiment, our results indicate that the pentacene triplet excitons generated through singlet fission can dissociate into separated charges on a picosecond time scale, despite the fact that their energy in C60/pentacene heterojunctions is slightly lower than the energies of the lowest CT triplet states.

  2. Boost up carrier mobility for ferroelectric organic transistor memory via buffering interfacial polarization fluctuation.

    Science.gov (United States)

    Sun, Huabin; Wang, Qijing; Li, Yun; Lin, Yen-Fu; Wang, Yu; Yin, Yao; Xu, Yong; Liu, Chuan; Tsukagoshi, Kazuhito; Pan, Lijia; Wang, Xizhang; Hu, Zheng; Shi, Yi

    2014-11-27

    Ferroelectric organic field-effect transistors (Fe-OFETs) have been attractive for a variety of non-volatile memory device applications. One of the critical issues of Fe-OFETs is the improvement of carrier mobility in semiconducting channels. In this article, we propose a novel interfacial buffering method that inserts an ultrathin poly(methyl methacrylate) (PMMA) between ferroelectric polymer and organic semiconductor layers. A high field-effect mobility (μFET) up to 4.6 cm(2) V(-1) s(-1) is obtained. Subsequently, the programming process in our Fe-OFETs is mainly dominated by the switching between two ferroelectric polarizations rather than by the mobility-determined charge accumulation at the channel. Thus, the "reading" and "programming" speeds are significantly improved. Investigations show that the polarization fluctuation at semiconductor/insulator interfaces, which affect the charge transport in conducting channels, can be suppressed effectively using our method.

  3. Passive sampling of selected endocrine disrupting compounds using polar organic chemical integrative samplers

    International Nuclear Information System (INIS)

    Arditsoglou, Anastasia; Voutsa, Dimitra

    2008-01-01

    Two types of polar organic chemical integrative samplers (pharmaceutical POCIS and pesticide POCIS) were examined for their sampling efficiency of selected endocrine disrupting compounds (EDCs). Laboratory-based calibration of POCISs was conducted by exposing them at high and low concentrations of 14 EDCs (4-alkyl-phenols, their ethoxylate oligomers, bisphenol A, selected estrogens and synthetic steroids) for different time periods. The kinetic studies showed an integrative uptake up to 28 days. The sampling rates for the individual compounds were obtained. The use of POCISs could result in an integrative approach to the quality status of the aquatic systems especially in the case of high variation of water concentrations of EDCs. The sampling efficiency of POCISs under various field conditions was assessed after their deployment in different aquatic environments. - Calibration and field performance of polar organic integrative samplers for monitoring EDCs in aquatic environments

  4. Boost Up Carrier Mobility for Ferroelectric Organic Transistor Memory via Buffering Interfacial Polarization Fluctuation

    Science.gov (United States)

    Sun, Huabin; Wang, Qijing; Li, Yun; Lin, Yen-Fu; Wang, Yu; Yin, Yao; Xu, Yong; Liu, Chuan; Tsukagoshi, Kazuhito; Pan, Lijia; Wang, Xizhang; Hu, Zheng; Shi, Yi

    2014-11-01

    Ferroelectric organic field-effect transistors (Fe-OFETs) have been attractive for a variety of non-volatile memory device applications. One of the critical issues of Fe-OFETs is the improvement of carrier mobility in semiconducting channels. In this article, we propose a novel interfacial buffering method that inserts an ultrathin poly(methyl methacrylate) (PMMA) between ferroelectric polymer and organic semiconductor layers. A high field-effect mobility (μFET) up to 4.6 cm2 V-1 s-1 is obtained. Subsequently, the programming process in our Fe-OFETs is mainly dominated by the switching between two ferroelectric polarizations rather than by the mobility-determined charge accumulation at the channel. Thus, the ``reading'' and ``programming'' speeds are significantly improved. Investigations show that the polarization fluctuation at semiconductor/insulator interfaces, which affect the charge transport in conducting channels, can be suppressed effectively using our method.

  5. Nature of chalcogen hor ellipsis chalcogen contact interactions in organic donor-molecule salts

    Energy Technology Data Exchange (ETDEWEB)

    Novoa, J.J.; Whangbo, Myung-Hwan (North Carolina State Univ., Raleigh, NC (USA). Dept. of Chemistry); Williams, J.M. (Argonne National Lab., IL (USA))

    1990-01-01

    The nature of chalcogen{hor ellipsis}chalcogen contact interactions in organic donor-molecule salts was examined by performing ab initio SCF-MO/MP2 calculations on H{sub 2}X{hor ellipsis}XH{sub 2}(X = O, S, SE, Te) and MM2 calculations on donor dimers (TXF){sub 2} (X = S, SE, Te) and (BEDX-TTF){sub 2} (X = O, S). 14 refs., 4 figs., 4 tabs.

  6. Diffusivity of dicarboxylic acids molecules to secondary organic material governed by particle phase state

    Science.gov (United States)

    Han, Y.; Gong, Z.; Liu, P.; de Sá, S. S.; McKinney, K. A.; Martin, S. T.

    2017-12-01

    Atmospheric secondary organic material (SOM) from oxidation of volatile organic compounds can exist in amorphous solid, semisolid, and liquid states depending on a range of factors such as relative humidity (RH), temperature, and reaction history. The phase state of SOM affects the dynamic exchange and reactivity between particles and gas-phase molecules. Dicarboxylic acids are ubiquitous in ambient atmosphere and the uptake of which may lead to substantial changes in hygroscopicity, absorption property, and light scattering of aerosol particles. This study investigates the diffusivity of dicarboxylic acids to the matrix of SOM particles. SOM was generated from dark ozonolysis of a-pinene in Harvard Environmental Chamber. The produced SOM particles were passed through an ozone scrubber to remove gas-phase chemistry before being led into a flask reactor, where gas-phase dicarboxylic acid was injected continuously and RH was varied from 5% to 85%. The probe dicarboxylic acids molecules including malonic acid and a-ketoglutaric acid have been investigated for the uptake to SOM particles. Organic composition in the outflow of the flask was measured with a high-resolution time-of-flight aerosol mass spectrometer. The mass fractions of tracer ions in total organic mass for both malonic acid and a-ketoglutaric acid increased substantially with the increase of RH values. The tracer ions of malonic acid were also more abundant in a-pinene SOM particles with increased gas-phase concentrations. These results suggest that the diffusion of the studied dicarboxylic acids molecules to a-pinene SOM particles was enhanced at increased RH values, which is possibly due to the phase transition of a-pinene SOM particles from non-liquid to liquid states. Therefore, particle phase state may be an important factor governing the diffusivity of dicarboxylic acids molecules to a-pinene SOM. Further dicarboxylic acids with various functional groups will be investigated to understand the

  7. Expert systems for structure elucidation of organic molecules by spectral methods

    International Nuclear Information System (INIS)

    Elyashberg, Mikhail E

    1999-01-01

    The state-of-the-art of the investigations aimed at creating expert systems for establishing the structure of organic molecules from IR, 1 H and 13 C NMR spectra is analysed. Computer methods used for identification of molecular fragments, generation of their structure and spectra prediction are considered. Principles of the creation of modern expert systems and general strategy of solving structural problems are discussed. The bibliography includes 174 references.

  8. Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2014-03-15

    Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

  9. Evaluation of performance reference compounds (PRCs) to monitor emerging polar contaminants by polar organic chemical integrative samplers (POCIS) in rivers.

    Science.gov (United States)

    Carpinteiro, Inmaculada; Schopfer, Adrien; Estoppey, Nicolas; Fong, Camille; Grandjean, Dominique; de Alencastro, Luiz F

    2016-02-01

    In this work, a method combining polar organic chemical integrative samplers (POCIS) and ultraperformance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was assessed for the determination of two corrosion inhibitors (benzotriazole and methylbenzotriazole), seven pesticides (atrazine, diuron, isoproturon, linuron, metolachlor, penconazole, terbuthylazine), and four pharmaceuticals (carbamazepine, diclofenac, metformin, sulfamethoxazole) in river water. As a first step, two POCIS sorbents, hydrophilic-lipophilic balance (HLB) and Strata X-CW, were compared. The comparison of the uptake profiles of the studied compounds showed that the HLB sorbent provides better uptake (higher sampled amount and better linearity) than Strata X-CW except for the basic compound metformin. Since the sampling rate (R s) of POCIS depends on environmental factors, seven compounds were evaluated as potential performance reference compounds (PRCs) through kinetic experiments. Deisopropylatrazine-d5 (DIA-d5) and, as far as we know, for the first time 4-methylbenzotriazole-d3 showed suitable desorption. The efficiency of both compounds to correct for the effect of water velocity was shown using a channel system in which POCIS were exposed to 2 and 50 cm s(-1). Finally, POCIS were deployed upstream and downstream of agricultural wine-growing and tree-growing areas in the Lienne River and the Uvrier Canal (Switzerland). The impact of the studied areas on both streams could be demonstrated.

  10. Calamitic Smectic A-Polar Smectic APA Transition Observed in Bent Molecules with Large Bent-Angle Central Core of 4,6-Dichlorobenzene and Alkylthio Terminal Tail

    Science.gov (United States)

    Nguyen, Ha; Kang, Sungmin; Tokita, Masatoshi; Watanabe, Junji

    2011-07-01

    New homologs of bent molecules with a large bent-angle central core of 4,6-dichloro benzene and an alkylthio terminal tail have been synthesized. Although the corresponding alkoxy-tail homologs show only the calamitic phases because of its large bent angles around 160°, the new homologs with an alkylthio tail exhibit the antiferroelectric smectic APA (SmAPA) banana phase that is transformed on cooling from the calamitic smectic A (SmA) phase. The biaxial polar packing of bent molecules in the SmAPA phase is considered to arise from the hindered rotation around the molecular long axis due to the expansion of the mesophase temperatures to a lower temperature region. This study indicates that the bent molecules, even with a large bent angle, have the potential to form a switchable banana phase with a remarkable decrease in its phase temperature range to around 60 °C.

  11. Quantum control of molecular vibrational and rotational excitations in a homonuclear diatomic molecule: A full three-dimensional treatment with polarization forces

    Science.gov (United States)

    Ren, Qinghua; Balint-Kurti, Gabriel G.; Manby, Frederick R.; Artamonov, Maxim; Ho, Tak-San; Rabitz, Herschel

    2006-01-01

    The optimal control of the vibrational excitation of the hydrogen molecule [Balint-Kurti et al., J. Chem. Phys. 122, 084110 (2005)] utilizing polarization forces is extended to three dimensions. The polarizability of the molecule, to first and higher orders, is accounted for using explicit ab initio calculations of the molecular electronic energy in the presence of an electric field. Optimal control theory is then used to design infrared laser pulses that selectively excite the molecule to preselected vibrational-rotational states. The amplitude of the electric field of the optimized pulses is restricted so that there is no significant ionization during the process, and a new frequency sifting method is used to simplify the frequency spectrum of the pulse. The frequency spectra of the optimized laser pulses for processes involving rotational excitation are more complex than those relating to processes involving only vibrational excitation.

  12. Investigating roles of organic and inorganic soil components in sorption of polar and nonpolar aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Shi Xin; Ji Liangliang [State Key Laboratory of Pollution Control and Resource Reuse/School of the Environment, Nanjing University, Jiangsu 210093 (China); Zhu Dongqiang, E-mail: zhud@nju.edu.c [State Key Laboratory of Pollution Control and Resource Reuse/School of the Environment, Nanjing University, Jiangsu 210093 (China)

    2010-01-15

    The main objective of the present study was to assess the roles of various soil components in sorption of organic compounds differing in polarity. Removal of the whole soil organic matter decreased sorption by approximately 86% for nonpolar 1,3,5-trichlorobenzene (TCB), but only 34-54% for highly polar 1,3,5-trinitrobenzene (TNB); however, removal of the extractable humic/fulvic acids did not much affect sorption of the two sorbates. With normalization of solute hydrophobicity, TNB exhibits several orders of magnitude stronger sorption compared with TCB to maize burn residue (black carbon), extracted humic acid and Na{sup +}-saturated montmorillonite clay, suggesting specific sorptive interactions for TNB with the individual model soil components. It was proposed that sorption of TCB to the bulk soil was dominated by hydrophobic partition to the condensed, non-extractable fraction of organic matters (humin/kerogen and black carbon), while interactions with soil clay minerals were an important additional factor for sorption of TNB. - Soil humin and black carbon play a predominant role in sorption of 1,3,5-trichlorobenzene, while polar interactions with soil clay minerals are an important additional factor for sorption of 1,3,5-trinitrobenzene.

  13. Near-unity mass accommodation coefficient of organic molecules of varying structure.

    Science.gov (United States)

    Julin, Jan; Winkler, Paul M; Donahue, Neil M; Wagner, Paul E; Riipinen, Ilona

    2014-10-21

    Atmospheric aerosol particles have a significant effect on global climate, air quality, and consequently human health. Condensation of organic vapors is a key process in the growth of nanometer-sized particles to climate relevant sizes. This growth is very sensitive to the mass accommodation coefficient α, a quantity describing the vapor uptake ability of the particles, but knowledge on α of atmospheric organics is lacking. In this work, we have determined α for four organic molecules with diverse structural properties: adipic acid, succinic acid, naphthalene, and nonane. The coefficients are studied using molecular dynamics simulations, complemented with expansion chamber measurements. Our results are consistent with α = 1 (indicating nearly perfect accommodation), regardless of the molecular structural properties, the phase state of the bulk condensed phase, or surface curvature. The results highlight the need for experimental techniques capable of resolving the internal structure of nanoparticles to better constrain the accommodation of atmospheric organics.

  14. Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Shanlin [Univ. of Alabama, Tuscaloosa, AL (United States)

    2014-11-16

    Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest that the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an

  15. Endothelial Adhesion Molecules and Multiple Organ Failure in Patients With Severe Sepsis

    Science.gov (United States)

    Amalakuhan, Bravein; Habib, Sheila A.; Mangat, Mandeep; Reyes, Luis F.; Rodriguez, Alejandro H.; Hinojosa, Cecilia A.; Soni, Nilam J.; Gilley, Ryan P.; Bustamante, Carlos A.; Anzueto, Antonio; Levine, Stephanie M.; Peters, Jay I.; Aliberti, Stefano; Sibila, Oriol; Chalmers, James D.; Torres, Antoni; Waterer, Grant W.; Martin-Loeches, Ignacio; Bordon, Jose; Blanquer, Jose; Sanz, Francisco; Marcos, Pedro J.; Rello, Jordi; Ramirez, Julio; Solé-Violán, Jordi; Luna, Carlos M.; Feldman, Charles; Witzenrath, Martin; Wunderink, Richard G.; Stolz, Daiana; Wiemken, Tim L.; Shindo, Yuichiro; Dela Cruz, Charles S.; Orihuela, Carlos J.; Restrepo, Marcos I.

    2016-01-01

    Objective To determine if serum levels of endothelial adhesion molecules were associated with the development of multiple organ failure (MOF) and in-hospital mortality in adult patients with severe sepsis. Design This study was a secondary data analysis of a prospective cohort study. Setting Patients were admitted to two tertiary intensive care units in San Antonio, TX, between 2007 and 2012. Patients Patients with severe sepsis at the time of intensive care unit (ICU) admission were enrolled. Inclusion criteria were consistent with previously published criteria for severe sepsis or septic shock in adults. Exclusion criteria included immunosuppressive medications or conditions. Interventions None. Measurements Baseline serum levels of the following endothelial cell adhesion molecules were measured within the first 72 hours of ICU admission: Intracellular Adhesion Molecule 1 (ICAM-1), Vascular Cell Adhesion Molecule-1 (VCAM-1), and Vascular Endothelial Growth Factor (VEGF). The primary and secondary outcomes were development of MOF (≥2 organ dysfunction) and in-hospital mortality, respectively. Main results Forty-eight patients were enrolled in this study, of which 29 (60%) developed MOF. Patients that developed MOF had higher levels of VCAM-1 (p=0.01) and ICAM-1 (p=0.01), but not VEGF (p=0.70) compared with patients without MOF (single organ failure only). The area under the curve (AUC) to predict MOF according to VCAM-1, ICAM-1 and VEGF was 0.71, 0.73, and 0.54, respectively. Only increased VCAM-1 levels were associated with in-hospital mortality (p=0.03). These associations were maintained even after adjusting for APACHE and SOFA scores using logistic regression. Conclusions High levels of serum ICAM-1 was associated with the development of MOF. High levels of VCAM-1 was associated with both MOF and in-hospital mortality. PMID:27701021

  16. Polarization and bonding of the intrinsic characteristic contours of hydrogen and fluorine atoms of forming a hydrogen fluoride molecule based on an ab initio study

    Science.gov (United States)

    Yang, Zhong-Zhi; Zhao, Dong-Xia; Wu, Yang

    2004-08-01

    The spatial changing feature of the shapes and sizes of the system consisted of one hydrogen atom and one fluorine atom of forming a hydrogen fluoride molecule is investigated. We give formalism of the potential acting on an electron in a molecule and derive its concrete expression in Hartree-Fock self-consistent molecular orbital theory including configuration interaction. The program of calculating the potential acting on an electron in a molecule is programmed and compiled in the framework of the MELD program package. We formulate briefly the approach of the molecular intrinsic characteristic contour (MICC) which is defined in terms of the classical turning points of electronic motion. The MICC for a molecular system is intrinsic and can be calculated by means of an ab initio CI method. Then, the polarization and bonding features of the intrinsic characteristic contours of hydrogen and fluorine atoms forming a hydrogen fluoride molecule are presented and discussed from ab initio calculations. Furthermore, electron density distribution as an added dimension has been demonstrated on the changing MICC and thus the vivid polarization and bonding features for a chemical process have been shown. It seems that at the early stage (internuclear distance Ind=5.0-20.0 a.u.) the fluorine atom gives more enthusiastic with the sensitive and expanded polarization to welcome coupling with the hydrogen atom while the latter has little response even "shy" with shrinking a bit its size at the beginning of putting the two atoms into a system and it is only around the critical point, the contact point (Ind=4.73 a.u.), that both of them stretch their hands and arms to meet and then fuse together.

  17. The polarity protein Par1b/EMK/MARK2 regulates T cell receptor-induced microtubule-organizing center polarization.

    Science.gov (United States)

    Lin, Joseph; Hou, Kirk K; Piwnica-Worms, Helen; Shaw, Andrey S

    2009-07-15

    Engagement of a T cell to an APC induces the formation of an immunological synapse as well as reorientation of the microtubule-organizing center (MTOC) toward the APC. How signals emanating from the TCR induce MTOC polarization is not known. One group of proteins known to play a critical role in asymmetric cell division and cell polarization is the partitioning defective (Par) family of proteins. In this study we found that Par1b, a member of the Par family of proteins, was inducibly phosphorylated following TCR stimulation. This phosphorylation resulted in 14-3-3 protein binding and caused the relocalization of Par1b from the membrane into the cytoplasm. Because a dominant-negative form of Par1b blocked TCR-induced MTOC polarization, our data suggest that Par1b functions in the establishment of T cell polarity following engagement to an APC.

  18. Signatures of dynamics in charge transport through organic molecules; Dynamisches Verhalten beim Ladungstransport durch organische Molekuele

    Energy Technology Data Exchange (ETDEWEB)

    Secker, Daniel

    2008-06-03

    The aim of the thesis at hand was to investigate dynamical behaviour in charge transport through organic molecules experimentally with the help of the mechanically controlled break junction (MCBJ) technique. the thesis concentrates on the complex interaction between the molecular contact configuration and the electronic structure. it is shown that by variation of the electrode distance and so by a manipulation of the molecule and contact configuration the electronic structure as well as the coupling between the molecule and the electrodes is affected. The latter statement is an additional hint how closely I-V-characteristics depend on the molecular contact configuration. Depending on the applied voltage and so the electric field there are two different configurations preferred by the molecular contact. A potential barrier between these two states is the origin of the hysteresis. A central part of the thesis is dealing with measurements of the current noise. Finally it can be concluded that the detailed discussion reveals the strong effect of dynamical interactions between the atomic configuration of the molecular contact and the electronic structure on the charge transport in single molecule junctions. (orig.)

  19. Organohalogen concentrations and a gross and histologic assessment of multiple organ systems in East Greenland polar bears (Ursus maritimus)

    DEFF Research Database (Denmark)

    Sonne, C.

    To investigate the relation between biological parameters, not earlier investigated in the polar bear, and organohalogen pollution in East Greenland polar bears, we initiated a sampling of adipose tissue, internal organs and skulls from more than 100 free-ranging polar bears killed by local...... in the adipose tissue and pathological changes in skulls and internal organs. Our results suggested a decrease in adipose tissue concentrations of organohalogens in East Greenland polar bears from 1990 to 1999-2001. Two of the biological effect parameters (FA and enlarged clitoris) did not indicate a link......, infectious agents, season and meaby chronic exposure to organohalogens. These result fill out an existing knowledge gap in potential effects of environmental, organic contaminants on fluctuating asymmetry, bone mineral density and functional anatomy (histology) in the polar bear. In addition, the results may...

  20. Retention of U(VI) onto silica in presence of model organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Pham, T.T.H.; Mercier-Bion, F.; Drot, R.; Lagarde, G.; Simoni, E. [Groupe de Radiochimie, IPNO, Universite Paris 11, Orsay, 91406 (France); Lambert, J. [LCPME, 405 rue de Vandoeuvre, Villers-les-Nancy, 54600 (France)

    2008-07-01

    It is well-known that the organic matter influences the retention of ions onto mineral surfaces. However, the major part of concerned studies implies humic substances and complex solids. Another approach for identifying the sorption mechanisms is possible by studying simpler solids than those present in natural medium. So, silica is chosen as mineral surface because of its abundance in soils and of the presence of Si-O groups in clayey minerals. Uranium (VI) is selected as cation. Simple organic molecules like acetic (one carboxylic group) and oxalic (two carboxylic functions) acids are considered as models of the natural organic matter for understanding their role in the retention of U(VI) onto powders and slides of silica. Binary (organics/silica, U(VI)/silica) and ternary systems (organics/silica/U(VI)) are studied by complementary approaches. Sorption edges as function of pH are obtained by liquid scintillation methods and capillary electrophoresis. Different spectroscopic techniques are used to deduce the interactions between the organic matter and U(VI) sorbed onto the silica whose: Time-Resolved Laser induced Fluorescence Spectroscopy (TRLFS), X-ray Photoelectron Spectroscopy (XPS), Nuclear Microprobe Analysis (NMA). The results of the effect of these model organic molecules onto the U(VI) retention showed a good agreement between the different techniques. Concerning the acetic acid, there are not differences in the sorption percentages of uranyl (see the figure). All these results indicate that the uranyl-acetate complexes stay in the aqueous solution rather than sorbing onto the silica. On the contrary, oxalic acid influences the sorption of U(VI) onto the silica surface. The sorption percentage of U(VI) in the ternary system (oxalic acid/silica/U(VI)) is lower than the binary system (U(VI)/silica) (see the figure). So, the presence of oxalic acid decreases the sorption of U(VI) onto the silica surface. (authors)

  1. Simple organic molecules as catalysts for enantioselective synthesis of amines and alcohols.

    Science.gov (United States)

    Silverio, Daniel L; Torker, Sebastian; Pilyugina, Tatiana; Vieira, Erika M; Snapper, Marc L; Haeffner, Fredrik; Hoveyda, Amir H

    2013-02-14

    The discovery of catalysts that can be used to synthesize complex organic compounds by enantioselective transformations is central to advances in the life sciences; for this reason, many chemists aim to discover catalysts that allow for preparation of chiral molecules as predominantly one mirror-image isomer. The ideal catalyst should not contain precious elements and should bring reactions to completion in a few hours through operationally simple procedures. Here we introduce a set of small organic molecules that can catalyse reactions of unsaturated organoboron reagents with imines and carbonyls; the products of the reactions are enantiomerically pure amines and alcohols, which might serve as intermediates in the preparation of biologically active molecules. A distinguishing feature of this catalyst class is the presence of a 'key' proton embedded within their structure. Catalysts are derived from the abundant amino acid valine and are prepared in large quantities in four steps with inexpensive reagents. Reactions are scalable, do not demand stringent conditions, and can be performed with as little as 0.25 mole per cent catalyst in less than six hours at room temperature to generate products in more than 85 per cent yield and ≥97:3 enantiomeric ratio. The efficiency, selectivity and operational simplicity of the transformations and the range of boron-based reagents are expected to render this advance important for future progress in syntheses of amines and alcohols, which are useful in chemistry, biology and medicine.

  2. In Situ Assembly of Nanoparticles into Hierarchical Beta Zeolite with Tailored Simple Organic Molecule.

    Science.gov (United States)

    Zhang, Kai; Liu, Zewei; Yan, Xin; Hao, Xuelong; Wang, Min; Li, Chao; Xi, Hongxia

    2017-12-19

    A hierarchically structured beta zeolite with intercrystalline mesopores was successfully synthesized via in situ assembly of nanoparticles by employing a simple organic molecule N 2 -p-N 2 , tailored from polyquaternium surfactant, with no hydrophobic long chain. The generated samples were studied by using powder X-ray diffraction (XRD) and nitrogen adsorption/desorption isotherms. Computer simulation, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) technologies were also used. The characterized results show that the tailored template molecule N 2 -p-N 2 without hydrophobic long-chain tail still can direct the zeolite crystallization, while the hydrophobic long-chain tail is not necessary during the mesoporous Beta zeolite formation. The catalytic performances of the sample were studied using alkylation of benzene with propene reaction to evaluate the relationship between the structure and property. The results apparently suggested an overall improved resistance against deactivation as compared to conventional beta zeolite in reactions. Furthermore, this tailored simple organic molecule strategy from dual-functional surfactant for making mesoporous zeolite would offer a new method of synthesizing other hierarchically structured zeolites.

  3. Solution-grown small-molecule organic semiconductor with enhanced crystal alignment and areal coverage for organic thin film transistors

    Directory of Open Access Journals (Sweden)

    Sheng Bi

    2015-07-01

    Full Text Available Drop casting of small-molecule organic semiconductors typically forms crystals with random orientation and poor areal coverage, which leads to significant performance variations of organic thin-film transistors (OTFTs. In this study, we utilize the controlled evaporative self-assembly (CESA method combined with binary solvent system to control the crystal growth. A small-molecule organic semiconductor,2,5-Di-(2-ethylhexyl-3,6-bis(5″-n-hexyl-2,2′,5′,2″]terthiophen-5-yl-pyrrolo[3,4-c]pyrrole-1,4-dione (SMDPPEH, is used as an example to demonstrate the effectiveness of our approach. By optimizing the double solvent ratios, well-aligned SMDPPEH crystals with significantly improved areal coverage were achieved. As a result, the SMDPPEH based OTFTs exhibit a mobility of 1.6 × 10−2 cm2/V s, which is the highest mobility from SMDPPEH ever reported.

  4. Metal–Organic Frameworks as Platforms for the Controlled Nanostructuring of Single-Molecule Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Aulakh, Darpandeep; Pyser, Joshua B.; Zhang, Xuan; Yakovenko, Andrey A.; Dunbar, Kim R.; Wriedt, Mario

    2015-07-29

    The prototypical SMM molecule [Mn12O12(O2CCH3)16(OH2)4] was incorporated under mild conditions into a highly porous metal-organic framework (MOF) matrix as a proof of principle for controlled nanostructuring of SMMs. Four independent experiments revealed that the SMM clusters were successfully loaded in the MOF pores, namely synchrotron-based powder diffraction, physisorption analysis, and in-depth magnetic and thermal analyses. The results provide incontrovertible evidence that the magnetic composite, SMM@MOF, combines key SMM properties with the functional properties of MOFs. Most importantly, the incorporated SMMs exhibit a significant enhanced thermal stability with SMM loading advantageously occurring at the periphery of the bulk MOF crystals with only a single SMM molecule isolated in the transverse direction of the pores.

  5. Biotin conjugated organic molecules and proteins for cancer therapy: A review.

    Science.gov (United States)

    Maiti, Santanu; Paira, Priyankar

    2018-02-10

    The main transporter for biotin is sodium dependent multivitamin transporter (SMVT), which is overexpressed in various aggressive cancer cell lines such as ovarian (OV 2008, ID8), leukemia (L1210FR), mastocytoma (P815), colon (Colo-26), breast (4T1, JC, MMT06056), renal (RENCA, RD0995), and lung (M109) cancer cell lines. Furthermore, its overexpression was found higher to that of folate receptor. Therefore, biotin demand in the rapidly growing tumors is higher than normal tissues. Several biotin conjugated organic molecules has been reported here for selective delivery of the drug in cancer cell. Biotin conjugated molecules are showing higher fold of cytotoxicity in biotin positive cancer cell lines than the normal cell. Nanoparticles and polymer surface modified drugs and biotin mediated cancer theranostic strategy was highlighted in this review. The cytotoxicity and selectivity of the drug in cancer cells has enhanced after biotin conjugation. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  6. Leucine-rich repeat-containing synaptic adhesion molecules as organizers of synaptic specificity and diversity.

    Science.gov (United States)

    Schroeder, Anna; de Wit, Joris

    2018-04-09

    The brain harbors billions of neurons that form distinct neural circuits with exquisite specificity. Specific patterns of connectivity between distinct neuronal cell types permit the transfer and computation of information. The molecular correlates that give rise to synaptic specificity are incompletely understood. Recent studies indicate that cell-surface molecules are important determinants of cell type identity and suggest that these are essential players in the specification of synaptic connectivity. Leucine-rich repeat (LRR)-containing adhesion molecules in particular have emerged as key organizers of excitatory and inhibitory synapses. Here, we discuss emerging evidence that LRR proteins regulate the assembly of specific connectivity patterns across neural circuits, and contribute to the diverse structural and functional properties of synapses, two key features that are critical for the proper formation and function of neural circuits.

  7. Systematic Investigation of Controlled Nanostructuring of Mn 12 Single-Molecule Magnets Templated by Metal–Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Aulakh, Darpandeep [Department of Chemistry; amp, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States; Xie, Haomiao [Department of Chemistry, Texas A& amp,M University, College Station, Texas 77845, United States; Shen, Zhe [Department of Chemistry, Texas A& amp,M University, College Station, Texas 77845, United States; Harley, Alexander [Department of Chemistry; amp, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States; Zhang, Xuan [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Yakovenko, Andrey A. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States; Dunbar, Kim R. [Department of Chemistry, Texas A& amp,M University, College Station, Texas 77845, United States; Wriedt, Mario [Department of Chemistry; amp, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States

    2017-05-25

    This is the first systematic study exploring metal–organic frameworks (MOFs) as platforms for the controlled nanostructuring of molecular magnets. We report the incorporation of seven single-molecule magnets (SMMs) of general composition [Mn12O12(O2CR)16(OH2)4], with R = CF3 (1), (CH3)CCH2 (2), CH2Cl (3), CH2Br (4), CHCl2 (5), CH2But (6), and C6H5 (7), into the hexagonal channel pores of a mesoporous MOF host. The resulting nanostructured composites combine the key SMM properties with the functional properties of the MOF. Synchrotron-based powder diffraction with difference envelope density analysis, physisorption analysis (surface area and pore size distribution), and thermal analyses reveal that the well-ordered hexagonal structure of the host framework is preserved, and magnetic measurements indicate that slow relaxation of the magnetization, characteristic of the corresponding Mn12 derivative guests, occurs inside the MOF pores. Structural host–guest correlations including the bulkiness and polarity of peripheral SMM ligands are discussed as fundamental parameters influencing the global SMM@MOF loading capacities. These results demonstrate that employing MOFs as platforms for the nanostructuration of SMMs is not limited to a particular host–guest system but potentially applicable to a multitude of other molecular magnets. Such fundamental findings will assist in paving the way for the development of novel advanced spintronic devices.

  8. Novel small molecules for organic field-effect transistors: towards processability and high performance.

    Science.gov (United States)

    Mas-Torrent, Marta; Rovira, Concepció

    2008-04-01

    The processing characteristics of organic semiconductors make them potentially useful for electronic applications where low-cost, large area coverage and structural flexibility are required. This critical review gives a general introduction about the current standing in the area of OFETs focusing on the new processable small molecules that have been recently reported for their use as organic semiconductors. A general description of the OFETs device operation and the transport mechanisms that dominate organic semiconductors is provided, followed by an overview of the strategies and materials employed to fabricate p-type, n-type and ambipolar OFETs. Some new tendencies and applications that are currently being developed employing OFETs are also described, such as the preparation of electronic paper, sensors or light emitting transistors (85 references).

  9. A Research Module for the Organic Chemistry Laboratory: Multistep Synthesis of a Fluorous Dye Molecule.

    Science.gov (United States)

    Slade, Michael C; Raker, Jeffrey R; Kobilka, Brandon; Pohl, Nicola L B

    2014-01-14

    A multi-session research-like module has been developed for use in the undergraduate organic teaching laboratory curriculum. Students are tasked with planning and executing the synthesis of a novel fluorous dye molecule and using it to explore a fluorous affinity chromatography separation technique, which is the first implementation of this technique in a teaching laboratory. Key elements of the project include gradually introducing students to the use of the chemical literature to facilitate their searching, as well as deliberate constraints designed to force them to think critically about reaction design and optimization in organic chemistry. The project also introduces students to some advanced laboratory practices such as Schlenk techniques, degassing of reaction mixtures, affinity chromatography, and microwave-assisted chemistry. This provides students a teaching laboratory experience that closely mirrors authentic synthetic organic chemistry practice in laboratories throughout the world.

  10. Sorptive capacities of lipids determined by passive dosing of non-polar organic chemicals

    DEFF Research Database (Denmark)

    Jahnke, Annika; Kierkegaard, Amelie; Bolinius, Damien

    Lipids often are considered the major partitioning phase for non-polar organic chemicals. What is referred to as “lipid”, however, is a complex matrix consisting of a highly variable mixture of neutral (‘storage’) and polar (‘membrane’) lipids that usually is operationally defined by the extraction......VMS), chlorobenzenes and polychlorinated biphenyls via a common headspace over an olive oil donor phase to transfer the same chemical activity into the samples; iii) sampling of EOM and olive oil controls at different time points; iv) purge-and-trap extraction of the model chemicals onto ENV+ SPE cartridges, elution...... and GC/MS analysis; v) characterization of the lipid composition in all samples via NMR. Our experiments demonstrate that the sorptive capacities of the EOM samples do not differ significantly from the olive oil controls if the EOM consists of neutral lipids only. However, the EOM samples show small...

  11. Regulation of vascular endothelial cell polarization and migration by Hsp70/Hsp90-organizing protein.

    Science.gov (United States)

    Li, Jingyu; Sun, Xiaodong; Wang, Zaizhu; Chen, Li; Li, Dengwen; Zhou, Jun; Liu, Min

    2012-01-01

    Hsp70/Hsp90-organizing protein (HOP) is a member of the co-chaperone family, which directly binds to chaperones to regulate their activities. The participation of HOP in cell motility and endothelial cell functions remains largely unknown. In this study, we demonstrate that HOP is critically involved in endothelial cell migration and angiogenesis. Tube formation and capillary sprouting experiments reveal that depletion of HOP expression significantly inhibits vessel formation from endothelial cells. Wound healing and transwell migration assays show that HOP is important for endothelial cell migration. By examination of centrosome reorientation and membrane ruffle dynamics, we find that HOP plays a crucial role in the establishment of cell polarity in response to migratory stimulus. Furthermore, our data show that HOP interacts with tubulin and colocalizes with microtubules in endothelial cells. These findings indicate HOP as a novel regulator of angiogenesis that functions through promoting vascular endothelial cell polarization and migration.

  12. Self-organized pattern formation upon femtosecond laser ablation by circularly polarized light

    International Nuclear Information System (INIS)

    Varlamova, Olga; Costache, Florenta; Reif, Juergen; Bestehorn, Michael

    2006-01-01

    Surface ripples generation upon femtosecond laser ablation is attributed to self-organized structure formation from instability. We report that linear arrangements are observed not only for linearly polarized light but also for ablation with circularly polarized light. Long ordered chains of spherical nanoparticles, reminding of bead-strings are almost parallel but exhibit typical non-linear dynamics features such as bifurcations. In a first attempt to understand the self-assembly, we rely on models recently developed for the description of similar structures upon ion beam erosion and for the simulation of instabilities in thin liquid films. Our picture describes an unstable surface layer, non-uniformly eroded through Coulomb repulsion between individual positive charges

  13. Photoionization of water molecules by a train of attosecond pulses assisted by a near-infrared laser: delay and polarization control

    Science.gov (United States)

    Martini, Lara; Boll, Diego I. R.; Fojón, Omar A.

    2017-08-01

    Basic reactions involving water molecules are essential to understand the interaction between radiation and the biological tissue because living cells are composed mostly by water. Therefore, the knowledge of ionization of the latter is crucial in many domains of Biology and Physics. So, we study theoretically the photoionization of water molecules by extreme ultraviolet attopulse trains assisted by lasers in the near-infrared range. We use a separable Coulomb-Volkov model in which the temporal evolution of the system can be divided into three stages allowing spatial and temporal separation for the Coulomb and Volkov final state wavefunctions. First, we analyze photoelectron angular distributions for different delays between the attopulse train and the assistant laser field. We compare our results for water and Ne atoms as they belong to the same isoelectronic series. Moreover, we contrast our calculations with previous theoretical and experimental work for Ar atoms due to the similarities of the orbitals involved in the reaction. Second, we study the effect of varying the relative orientations of the attopulse and laser field polarizations and we compare our predictions with other theories and experiments. We expect these studies contribute to the improvement of polarization experiments and the development of the attopulse trains and assistant laser fields technologies. Finally, we hope our work promote progress on the control of the chemical reactivity of water molecules since this could be useful in different fields such as radiobiology and medical physics.

  14. Designing small molecule polyaromatic p- and n-type semiconductor materials for organic electronics

    KAUST Repository

    Collis, Gavin E.

    2015-12-22

    By combining computational aided design with synthetic chemistry, we are able to identify core 2D polyaromatic small molecule templates with the necessary optoelectronic properties for p- and n-type materials. By judicious selection of the functional groups, we can tune the physical properties of the material making them amenable to solution and vacuum deposition. In addition to solubility, we observe that the functional group can influence the thin film molecular packing. By developing structure-property relationships (SPRs) for these families of compounds we observe that some compounds are better suited for use in organic solar cells, while others, varying only slightly in structure, are favoured in organic field effect transistor devices. We also find that the processing conditions can have a dramatic impact on molecular packing (i.e. 1D vs 2D polymorphism) and charge mobility; this has implications for material and device long term stability. We have developed small molecule p- and n-type materials for organic solar cells with efficiencies exceeding 2%. Subtle variations in the functional groups of these materials produces p- and ntype materials with mobilities higher than 0.3 cm2/Vs. We are also interested in using our SPR approach to develop materials for sensor and bioelectronic applications.

  15. Density Functional Investigation of Graphene Doped with Amine-Based Organic Molecules

    Directory of Open Access Journals (Sweden)

    Yeun Hee Hwang

    2015-01-01

    Full Text Available To improve the electronic properties of graphene, many doping techniques have been studied. Herein, we investigate the electronic and molecular structure of doped graphene using density functional theory, and we report the effects of amine-based benzene dopants adsorbed on graphene. Density functional theory (DFT calculations were performed to determine the role of amine-based aromatic compounds in graphene doping. These organic molecules bind to graphene through long-range interactions such as π-π interactions and C-H⋯π hydrogen bonding. We compared the electronic structures of pristine graphene and doped graphene to understand the electronic structure of doped graphene at the molecular level. Also, work functions of doped graphene were obtained from electrostatic potential calculations. A decrease in the work function was observed when the amine-based organic compounds were adsorbed onto graphene. Because these systems are based on physisorption, there was no obvious band structure change at point K at the Fermi level after doping. However, the amine-based organic dopants did change the absolute Fermi energy levels. In this study, we showed that the Fermi levels of the doped graphene were affected by the HOMO energy level of the dopants and by the intermolecular charge transfer between the adsorbed molecules and graphene.

  16. Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Manidipa; Pal, Nabanita; Bhaumik, Asim, E-mail: msab@iacs.res.in

    2012-08-01

    Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6-7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate-adsorbent interaction at the surfaces. - Graphical abstract: Highly ordered 2D-hexagonal mesoporous borosilicate materials have been synthesized by using Pluronic P123 as template. The materials show very good adsorption and release of organic cationic dye molecules under physiological conditions. Highlights: Black-Right-Pointing-Pointer Highly ordered 2D-hexagonal mesoporous borosilicate. Black-Right-Pointing-Pointer Nonionic Pluoronic P123 templated mesoporous material. Black-Right-Pointing-Pointer Adsorption of organic dyes at the mesopore surface. Black-Right-Pointing-Pointer Controlled release of dyes under physiological pH and temperature. Black-Right-Pointing-Pointer Release of safranine T (ST) and malachite green (MG) dyes in simulated body fluids.

  17. Hydrophilicity and Microsolvation of an Organic Molecule Resolved on the Sub-molecular Level by Scanning Tunneling Microscopy.

    Science.gov (United States)

    Lucht, Karsten; Loose, Dirk; Ruschmeier, Maximilian; Strotkötter, Valerie; Dyker, Gerald; Morgenstern, Karina

    2018-01-26

    Low-temperature scanning tunneling microscopy was used to follow the formation of a solvation shell around an adsorbed functionalized azo dye from the attachment of the first water molecule to a fully solvated molecule. Specific functional groups bind initially one water molecule each, which act as anchor points for additional water molecules. Further water attachment occurs in areas close to these functional groups even when the functional groups themselves are already saturated. In contrast, water molecules surround the hydrophobic parts of the molecule only when the two-dimensional solvation shell closes around them. This study thus traces hydrophilic and hydrophobic properties of an organic molecule down to a sub-molecular length scale. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model.

    Science.gov (United States)

    Silva, Arnaldo F; Richter, Wagner E; Meneses, Helen G C; Bruns, Roy E

    2014-11-14

    Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

  19. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... bifunctional requirement, which demands both adsorption and water oxidation sites. In this contribution, we explore the possibility of using Pt-Si alloys to fulfill this bifunctional requirement. Silicon, a highly oxophillic element, is alloyed into Pt as a site for water oxidation, while Pt serves as a CO...

  20. Dual Function Additives: A Small Molecule Crosslinker for Enhanced Efficiency and Stability in Organic Solar Cells

    KAUST Repository

    Rumer, Joseph W.

    2015-02-01

    A bis-azide-based small molecule crosslinker is synthesized and evaluated as both a stabilizing and efficiency-boosting additive in bulk heterojunction organic photovoltaic cells. Activated by a noninvasive and scalable solution processing technique, polymer:fullerene blends exhibit improved thermal stability with suppressed polymer skin formation at the cathode and frustrated fullerene aggregation on ageing, with initial efficiency increased from 6% to 7%. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Mars Organic Molecule Analyzer : The Search For Biosignatures And Biohints On Mars

    Science.gov (United States)

    Buch, Arnaud; Freissinet, C.; Brault, A.; Sternberg, R.; Rodier, C.; Szopa, C.; Coll, P.; Pinnick, V.; MOMA Team

    2012-10-01

    The joint ESA-Roscosmos Exo-Mars-2018 rover mission seeks the signs of past or present life on Mars. The Mars Organic Molecule Analyzer (MOMA) aboard the ExoMars rover will be a key analytical tool in providing chemical (molecular) information from the solid samples, with particular focus on the characterization of organic content. One of the instruments aboard MOMA is a gas chromatography-mass spectrometry (GC-MS) which provides a unique ability to characterize a broad range of compounds allowing chemical analyses on volatile and non-volatile species. The key challenge with the analysis of refractory organic compounds contained in soil is their extraction and subsequent analysis by GC-MS. Since the extraction of organic matter is not possible by liquid solvent extraction, thermodesoprtion followed by derivatization has been developed. The goal of the thermodesorption is to quickly extract the organic matter before degradation. One of the main focus is to determine the chirality of amino acids. Indeed, on earth homochirality (especially the L-form) is an indicator for the presence of life. However, other refractory compounds can be analyzed: nucleobases, carbox-ylic acids, PAHs, etc. Thermodesorption occurs within a range of temperatures from 150 °C to 300 °C over a period of 30 s to 10 min, depending on the chemical compound. Under these conditions, we have shown that amino acids are not degraded and that their chirality is preserved. Once extracted, refractory molecules with labile hydrogens (e.g. amino acids, nucleobases, carboxylic acids, etc.) were derivatized. General and sensitive derivatization occurs with a sillylated compounds N,N-methyl-tert-butyl-dimethylsilyl-trifluoroacetamide (MTBSTFA). Derivative compounds were separated on an RTX-5 (Restek) column. If a chiral separation was targeted, then dimethylformamide dimethylacetale derivatization (DMF-DMA) was utilized. With DMF-DMA 11 of the 19 proteinic amino acids were separated on the Chirasil

  2. Full-Stokes polarization imaging method based on the self-organized grating array in fused silica.

    Science.gov (United States)

    Xu, Canhua; Ke, Chaozhen; Ma, Jing; Huang, Yantang; Zeng, Zhiping

    2018-02-05

    A full-Stokes polarization imaging method based on the self-organized grating array was presented. By focusing the ultra-fast laser with moderate fluence into fused silica, the self-organized grating array was fabricated, featuring the optical properties similar to wave plates. A set of four independent polarization measurements were simultaneously acquired with designed grating array mounted in the focal plane of an imaging detector. Experimental results including the device fabrication, calibration and optimization were presented. Finally, a principle verification experiment was implemented for our polarization imaging method.

  3. Electronic excited states of Si(100) and organic molecules adsorbed on Si(100).

    Science.gov (United States)

    Besley, Nicholas A; Blundy, Adam J

    2006-02-02

    The electronically excited states of the Si(100) surface and acetylene, benzene, and 9,10-phenanthrenequinone adsorbed on Si(100) are studied with time-dependent density functional theory. The computational cost of these calculations can be reduced through truncation of the single excitation space. This allows larger cluster models of the surface in conjunction with large adsorbates to be studied. On clean Si(100), the low-lying excitations correspond to transitions between the pi orbitals of the silicon-silicon dimers. These excitations are predicted to occur in the range 0.4-2 eV. When organic molecules are adsorbed on the surface, surface --> molecule, molecule --> surface, and electronic excitations localized within the adsorbate are also observed at higher energies. For acetylene and benzene, the remaining pipi* excitations are found to lie at lower energies than in the corresponding gas-phase species. Even though the aromaticity of 9,10-phenanthrenequinone is retained, significant shifts in the pipi* excitations of the aromatic rings are predicted. This is in part due to structural changes that occur upon adsorption.

  4. Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules.

    Science.gov (United States)

    Ásgeirsson, Vilhjálmur; Bauer, Christoph A; Grimme, Stefan

    2017-07-01

    We introduce a fully stand-alone version of the Quantum Chemistry Electron Ionization Mass Spectra (QCEIMS) program [S. Grimme, Angew. Chem. Int. Ed. , 2013, 52 , 6306] allowing efficient simulations for molecules composed of elements with atomic numbers up to Z = 86. The recently developed extended tight-binding semi-empirical method GFN-xTB has been combined with QCEIMS, thereby eliminating dependencies on third-party electronic structure software. Furthermore, for reasonable calculations of ionization potentials, as required by the method, a second tight-binding variant, IPEA-xTB, is introduced here. This novel combination of methods allows the automatic, fast and reasonably accurate computation of electron ionization mass spectra for structurally different molecules across the periodic table. In order to validate and inspect the transferability of the method, we perform large-scale simulations for some representative organic, organometallic, and main-group inorganic systems. Theoretical spectra for 23 molecules are compared directly to experimental data taken from standard databases. For the first time, realistic quantum chemistry based EI-MS for organometallic systems like ferrocene or copper(ii)acetylacetonate are presented. Compared to previously used semiempirical methods, GFN-xTB is faster, more robust, and yields overall higher quality spectra. The partially analysed theoretical reaction and fragmentation mechanisms are chemically reasonable and reveal in unprecedented detail the extreme complexity of high energy gas phase ion chemistry including complicated rearrangement reactions prior to dissociation.

  5. Investigating roles of organic and inorganic soil components in sorption of polar and nonpolar aromatic compounds.

    Science.gov (United States)

    Shi, Xin; Ji, Liangliang; Zhu, Dongqiang

    2010-01-01

    The main objective of the present study was to assess the roles of various soil components in sorption of organic compounds differing in polarity. Removal of the whole soil organic matter decreased sorption by approximately 86% for nonpolar 1,3,5-trichlorobenzene (TCB), but only 34-54% for highly polar 1,3,5-trinitrobenzene (TNB); however, removal of the extractable humic/fulvic acids did not much affect sorption of the two sorbates. With normalization of solute hydrophobicity, TNB exhibits several orders of magnitude stronger sorption compared with TCB to maize burn residue (black carbon), extracted humic acid and Na(+)-saturated montmorillonite clay, suggesting specific sorptive interactions for TNB with the individual model soil components. It was proposed that sorption of TCB to the bulk soil was dominated by hydrophobic partition to the condensed, non-extractable fraction of organic matters (humin/kerogen and black carbon), while interactions with soil clay minerals were an important additional factor for sorption of TNB.

  6. Asymmetric Microtubule Function Is an Essential Requirement for Polarized Organization of the Drosophila Bristle▿ †

    OpenAIRE

    Bitan, Amir; Guild, Gregory M.; Bar-Dubin, Dikla; Abdu, Uri

    2009-01-01

    While previous studies have shown that microtubules (MTs) are essential for maintaining the highly biased axial growth of the Drosophila bristle, the mechanism for this process has remained vague. We report that the MT minus-end marker, Nod-KHC, accumulates at the bristle tip, suggesting that the MT network in the bristle is organized minus end out. Potential markers for studying the importance of properly polarized MTs to bristle axial growth are Ik2 and Spindle-F (Spn-F), since mutations in...

  7. Emissions of carbon species, organic polar compounds, potassium, and mercury from prescribed burning activities

    Science.gov (United States)

    Zhang, Y.; Obrist, D.; Zielinska, B.; Gerler, A.

    2012-04-01

    Biomass burning is an important emission source of pollutants to the atmosphere, but few studies have focused on the chemical composition of emissions from prescribed burning activities. Here we present results from a sampling campaign to quantify particulate-phase emissions from various types of prescribed fires including carbon species (Elemental Carbon: EC; Organic Carbon: OC; and Total Carbon: TC); polar organic compounds (12 different compounds and four functional classes); water-soluble potassium (K+); and mercury (Hg). We measured emissions from the following types of prescribed biomass burning in the Lake Tahoe basin located on the California/Nevada border: (i) log piles stacked and dried in the field; (ii) log piles along with green understory vegetation; and (iii) understory green vegetation and surface litter; further emissions were collected from burns conducted in a wood stove: (iv) dried wooden logs; (v) green foliage of understory vegetation collected from the field; and (vi) surface organic litter collected from the field; finally, samples were also taken from (vii) ambient air in residential areas during peak domestic wood combustion season. Results show that OC/EC ratios of prescribed burns in the field ranged from 4 to 10, but lower values (around 1) were observed in controlled stove fires. These results are consistent with an excess of OC emissions over EC found in wildfires. OC/EC ratios, however, showed clear separations between controlled wood stove combustion (higher EC) and prescribed burns in the field (lower EC). We attribute this difference to a higher combustion temperatures and dominance of flaming combustion in wood stove fires. OC positively and linearly correlated to the sum of polar organic compounds across all burn types (r2 of 0.82). The most prevalent group of polar compounds emitted during prescribed fires was resin acids (dehydroabietic, pimaric, and abietic acids), followed by levoglucosan plus mannositol. Negligible

  8. A fluorescence polarization based screening assay for identification of small molecule inhibitors of the PICK1 PDZ domain

    DEFF Research Database (Denmark)

    Thorsen, Thor S; Madsen, Kenneth L; Dyhring, Tino

    2011-01-01

    PDZ (PSD-95/Discs-large/ZO-1 homology) domains represent putative targets in several diseases including cancer, stroke, addiction and neuropathic pain. Here we describe the application of a simple and fast screening assay based on fluorescence polarization (FP) to identify inhibitors of the PDZ...

  9. Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks.

    Science.gov (United States)

    Zhang, Xinran; da Silva, Ivan; Godfrey, Harry G W; Callear, Samantha K; Sapchenko, Sergey A; Cheng, Yongqiang; Vitórica-Yrezábal, Inigo; Frogley, Mark D; Cinque, Gianfelice; Tang, Chiu C; Giacobbe, Carlotta; Dejoie, Catherine; Rudić, Svemir; Ramirez-Cuesta, Anibal J; Denecke, Melissa A; Yang, Sihai; Schröder, Martin

    2017-11-15

    During nuclear waste disposal process, radioactive iodine as a fission product can be released. The widespread implementation of sustainable nuclear energy thus requires the development of efficient iodine stores that have simultaneously high capacity, stability and more importantly, storage density (and hence minimized system volume). Here, we report high I 2 adsorption in a series of robust porous metal-organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I 2 uptake of 1.54 g g -1 , and its structure remains completely unperturbed upon inclusion/removal of I 2 . Direct observation and quantification of the adsorption, binding domains and dynamics of guest I 2 molecules within these hosts have been achieved using XPS, TGA-MS, high resolution synchrotron X-ray diffraction, pair distribution function analysis, Raman, terahertz and neutron spectroscopy, coupled with density functional theory modeling. These complementary techniques reveal a comprehensive understanding of the host-I 2 and I 2 -I 2 binding interactions at a molecular level. The initial binding site of I 2 in MFM-300(Sc), I 2 I , is located near the bridging hydroxyl group of the [ScO 4 (OH) 2 ] moiety [I 2 I ···H-O = 2.263(9) Å] with an occupancy of 0.268. I 2 II is located interstitially between two phenyl rings of neighboring ligand molecules [I 2 II ···phenyl ring = 3.378(9) and 4.228(5) Å]. I 2 II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I 2 loading an unprecedented self-aggregation of I 2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I 2 molecules with an exceptional I 2 storage density of 3.08 g cm -3 in MFM-300(Sc).

  10. A new weapon for the interstellar complex organic molecule hunt: the minimum energy principle

    Science.gov (United States)

    Lattelais, M.; Pauzat, F.; Ellinger, Y.; Ceccarelli, C.

    2010-09-01

    Context. The hunt for the interstellar complex organic molecules (COMs) supposed to be the building blocks of the molecules at the origin of life is a challenging but very expensive task. It starts with laboratory experiments, associated with theoretical calculations, that give the line frequencies and strengths of the relevant molecules to be identified and finishes with observations at the telescopes. Aims: The present study aims to suggest possible guidelines to optimize this hunt. Levering on the minimum energy principle (MEP) presented in a previous study, we discuss the link between thermodynamic stability and detectability of a number of structures in the important families of amides, sugars and aminonitriles. Methods: The question of the relative stability of these different species is addressed by means of quantum density functional theory simulations. The hybrid B3LYP formalism was used throughout. All 72 molecules part of this survey were treated on an equal footing. Each structure, fully optimized, was verified to be a stationary point by vibrational analysis. Results: A comprehensive screening of 72 isomers of CH3NO, C2H5NO, C3H7NO, C2H4O2, C3H6O3 and C2H4N2 chemical formula has been carried out. We found that formamide, acetamide and propanamide (the first two identified in the Inter-Stellar Medium) are the most stable compounds in their families demonstrating at the same time that the peptide bond >N-C=O at the origin of life is the most stable bond that can be formed. Dihydroxyacetone, whose detection awaits for confirmation, is far from being the most stable isomer of its family while aminoacetonitrile, that has been recently identified, is effectively the most stable species. Conclusions: The MEP appears to be a useful tool for optimizing the hunt for new species by identifying the potentially more abundant isomers of a given chemical formula.

  11. Focused Role of an Organic Small-Molecule PBD on Performance of the Bistable Resistive Switching.

    Science.gov (United States)

    Li, Lei; Sun, Yanmei; Ai, Chunpeng; Lu, Junguo; Wen, Dianzhong; Bai, Xuduo

    2015-12-01

    An undoped organic small-molecule 2-(4-tert-butylphenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole (PBD) and a kind of nanocomposite blending poly(methyl methacrylate) (PMMA) into PBD are employed to implement bistable resistive switching. For the bistable resistive switching indium tin oxide (ITO)/PBD/Al, its ON/OFF current ratio can touch 6. What is more, the ON/OFF current ratio, approaching to 10(4), is available due to the storage layer PBD:PMMA with the chemical composition 1:1 in the bistable resistive switching ITO/PBD:PMMA/Al. The capacity, data retention of more than 1 year and endurance performance (>10(4) cycles) of ITO/PBD:PMMA(1:1)/Al, exhibits better stability and reliability of the samples, which underpins the technique and application of organic nonvolatile memory.

  12. Van Der Waals Heterostructures between Small Organic Molecules and Layered Substrates

    Directory of Open Access Journals (Sweden)

    Han Huang

    2016-09-01

    Full Text Available Two dimensional atomic crystals, like grapheme (G and molybdenum disulfide (MoS2, exhibit great interest in electronic and optoelectronic applications. The excellent physical properties, such as transparency, semiconductivity, and flexibility, make them compatible with current organic electronics. Here, we review recent progress in the understanding of the interfaces of van der Waals (vdW heterostructures between small organic molecules (pentacene, copper phthalocyanine (CuPc, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA, and dioctylbenzothienobenzothiophene (C8-BTBT and layered substrates (G, MoS2 and hexagonal boron nitride (h-BN. The influences of the underlying layered substrates on the molecular arrangement, electronic and vibrational properties will be addressed.

  13. Ambipolar Small-Molecule:Polymer Blend Semiconductors for Solution-Processable Organic Field-Effect Transistors.

    Science.gov (United States)

    Kang, Minji; Hwang, Hansu; Park, Won-Tae; Khim, Dongyoon; Yeo, Jun-Seok; Kim, Yunseul; Kim, Yeon-Ju; Noh, Yong-Young; Kim, Dong-Yu

    2017-01-25

    We report on the fabrication of an organic thin-film semiconductor formed using a blend solution of soluble ambipolar small molecules and an insulating polymer binder that exhibits vertical phase separation and uniform film formation. The semiconductor thin films are produced in a single step from a mixture containing a small molecular semiconductor, namely, quinoidal biselenophene (QBS), and a binder polymer, namely, poly(2-vinylnaphthalene) (PVN). Organic field-effect transistors (OFETs) based on QBS/PVN blend semiconductor are then assembled using top-gate/bottom-contact device configuration, which achieve almost four times higher mobility than the neat QBS semiconductor. Depth profile via secondary ion mass spectrometry and atomic force microscopy images indicate that the QBS domains in the films made from the blend are evenly distributed with a smooth morphology at the bottom of the PVN layer. Bias stress test and variable-temperature measurements on QBS-based OFETs reveal that the QBS/PVN blend semiconductor remarkably reduces the number of trap sites at the gate dielectric/semiconductor interface and the activation energy in the transistor channel. This work provides a one-step solution processing technique, which makes use of soluble ambipolar small molecules to form a thin-film semiconductor for application in high-performance OFETs.

  14. Dynamic Control of Synaptic Adhesion and Organizing Molecules in Synaptic Plasticity

    Energy Technology Data Exchange (ETDEWEB)

    Rudenko, Gabby (Texas-MED)

    2017-01-01

    Synapses play a critical role in establishing and maintaining neural circuits, permitting targeted information transfer throughout the brain. A large portfolio of synaptic adhesion/organizing molecules (SAMs) exists in the mammalian brain involved in synapse development and maintenance. SAMs bind protein partners, formingtrans-complexes spanning the synaptic cleft orcis-complexes attached to the same synaptic membrane. SAMs play key roles in cell adhesion and in organizing protein interaction networks; they can also provide mechanisms of recognition, generate scaffolds onto which partners can dock, and likely take part in signaling processes as well. SAMs are regulated through a portfolio of different mechanisms that affect their protein levels, precise localization, stability, and the availability of their partners at synapses. Interaction of SAMs with their partners can further be strengthened or weakened through alternative splicing, competing protein partners, ectodomain shedding, or astrocytically secreted factors. Given that numerous SAMs appear altered by synaptic activity, in vivo, these molecules may be used to dynamically scale up or scale down synaptic communication. Many SAMs, including neurexins, neuroligins, cadherins, and contactins, are now implicated in neuropsychiatric and neurodevelopmental diseases, such as autism spectrum disorder, schizophrenia, and bipolar disorder and studying their molecular mechanisms holds promise for developing novel therapeutics.

  15. Biological response of HeLa cells to gold nanoparticles coated with organic molecules.

    Science.gov (United States)

    Cardoso Avila, P E; Rangel Mendoza, A; Pichardo Molina, J L; Flores Villavicencio, L L; Castruita Dominguez, J P; Chilakapati, M K; Sabanero Lopez, M

    2017-08-01

    In this work, gold nanospheres functionalized with low weight organic molecules (4-aminothiphenol and cysteamine) were synthesized in a one-step method for their in vitro cytotoxic evaluation on HeLa cells. To enhance the biocompatibility of the cysteamine-capped GNPs, BSA was used due to its broad PH stability and high binding affinity to gold nanoparticles. Besides, the widely reported silica coated gold nanorods were tested here to contrast their toxic response against our nanoparticles coated with organic molecules. Our results shown, the viability measured at 1.9×10 -5 M did not show significant differences against negative controls for all the samples; however, the metabolic activity of HeLa cells dropped when they were exposed to silica gold nanorods in the range of concentrations from 2.9×10 -7 M to 3.0×10 -4 M, while in the cases of gold nanospheres, we found that only at concentrations below 1.9×10 -5 M metabolic activity was normal. Our preliminary results did not indicate any perceivable harmful toxicity to cell membrane, cytoskeleton or nucleus due to our nanospheres at 1.9×10 -5 M. Additional test should be conducted in order to ensure a safe use of them for biological applications, and to determine the extent of possible damage. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Isotope-selective high-order interferometry with large organic molecules in free fall

    Science.gov (United States)

    Rodewald, Jonas; Dörre, Nadine; Grimaldi, Andrea; Geyer, Philipp; Felix, Lukas; Mayor, Marcel; Shayeghi, Armin; Arndt, Markus

    2018-03-01

    Interferometry in the time domain has proven valuable for matter-wave based measurements. This concept has recently been generalized to cold molecular clusters using short-pulse standing light waves which realized photo-depletion gratings, arranged in a time-domain Talbot–Lau interferometer (OTIMA). Here we extend this idea further to large organic molecules and demonstrate a new scheme to scan the emerging molecular interferogram in position space. The capability of analyzing different isotopes of the same monomer under identical conditions opens perspectives for studying the interference fringe shift as a function of time in gravitational free fall. The universality of OTIMA interferometry allows one to handle a large variety of particles. In our present work, quasi-continuous laser evaporation allows transferring fragile organic molecules into the gas phase, covering more than an order of magnitude in mass between 614 amu and 6509 amu, i.e. 300% more massive than in previous OTIMA experiments. For all masses, we find about 30% fringe visibility.

  17. Probing Zeolite Crystal Architecture and Structural Imperfections using Differently Sized Fluorescent Organic Probe Molecules.

    Science.gov (United States)

    Hendriks, Frank C; Schmidt, Joel E; Rombouts, Jeroen A; Lammertsma, Koop; Bruijnincx, Pieter C A; Weckhuysen, Bert M

    2017-05-05

    A micro-spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4-(4-diethylaminostyryl)-1-methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM-5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization-dependent measurements provide evidence for the probe molecule's alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture-dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X-ray diffraction. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  18. Regulation of cell polarity by cell adhesion receptors.

    Science.gov (United States)

    Ebnet, Klaus; Kummer, Daniel; Steinbacher, Tim; Singh, Amrita; Nakayama, Masanori; Matis, Maja

    2017-07-22

    The ability of cells to polarize is an intrinsic property of almost all cells and is required for the devlopment of most multicellular organisms. To develop cell polarity, cells integrate various signals derived from intrinsic as well as extrinsic sources. In the recent years, cell-cell adhesion receptors have turned out as important regulators of cellular polarization. By interacting with conserved cell polarity proteins, they regulate the recruitment of polarity complexes to specific sites of cell-cell adhesion. By initiating intracellular signaling cascades at those sites, they trigger their specific subcellular activation. Not surprisingly, cell-cell adhesion receptors regulate diverse aspects of cell polarity, including apico-basal polarity in epithelial and endothelial cells, front-to-rear polarity in collectively migrating cells, and planar cell polarity during organ development. Here, we review the recent developments highlighting the central roles of cell-cell adhesion molecules in the development of cell polarity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Functionalization of nanoparticle titanium dioxide with different bifunctional organic molecules and trimers of transition compounds for obtaining new materials

    International Nuclear Information System (INIS)

    Rivera Martinez, Maria Cinthya

    2012-01-01

    Functionalization of titanium dioxide in nanoporous anatase phase is investigated for obtaining new nanomaterials. Functionalizations were performed using two heating methods: the conventional of refluxing heating method and microwave irradiation with bifunctional organic molecules is used to study how to anchor molecules and the change in the wettability of the material. Besides, reactions with organic molecules were performed as the derived from nanoproxene. The growth layer by layer is performed using the bifunctional molecules previous for the immobilization of cobalt trimers. Functionalized molecules were characterized by infrared spectroscopy, X-ray diffraction, contact angle, scanning electron microscopy, x-ray elemental analysis, plasma atomic emission spectroscopy coupled inductively, x-ray photoelectron spectroscopy and thermogravimetric analysis. This type of functionalizations on nanoporous titanium dioxide could potentially improve optical sensitivity and activity of this nanomaterial in the visible region. (author) [es

  20. Lifetimes of organic photovoltaics: Design and synthesis of single oligomer molecules in order to study chemical degradation mechanisms

    DEFF Research Database (Denmark)

    Alstrup, J.; Norrman, K.; Jørgensen, M.

    2006-01-01

    Degradation mechanisms in organic and polymer photovoltaics are addressed through the study of an organic photovoltaic molecule based on a single phenylene-vinylene-type oligomer molecule. The synthesis of such a model compound with different end-groups is presented that allows for assignment...... of degradation products from different parts of the molecule. Photovoltaic devices with and without C(60) have been prepared and their characteristics under AM1.5 conditions are reported. The degradation of the active phenylene-vinylene compound in darkness and after 20h of illumination were investigated using...

  1. Simultaneously improving optical absorption of both transverse-electric polarized and transverse-magnetic polarized light for organic solar cells with Ag grating used as transparent electrode

    Directory of Open Access Journals (Sweden)

    Yongbing Long

    2014-08-01

    Full Text Available Theoretical simulations are performed to investigate optical performance of organic solar cells with Ag grating electrode. It is demonstrated that optical absorption for both transverse-electric (TE polarized and transverse-magnetic(TM polarized light is simultaneously improved when compared with that for the device without the Ag grating. The improvement is respectively attributed to the resonance and the surface plasmon polaritons within the device. After an additional WO3 layer is capped on the Ag grating, absorption of TE-polarized light is further improved due to resonance of double microcavities within the device, and absorption of TM-polarized light is improved by the combined effects of the microcavity resonance and the surface plasmon polaritons. Correspondingly, the short current density for randomly polarized light is improved by 18.1% from that of the device without the Ag grating. Finally, it is demonstrated that high transmission may not be an essential prerequisite for metallic gratings when they are used as transparent electrode since absorption loss caused by low transmission can be compensated by using a capping layer to optimize optical resonance of the WMC structure within the device.

  2. EU-wide survey of polar organic persistent pollutants in European river waters

    Energy Technology Data Exchange (ETDEWEB)

    Loos, Robert [European Commission, Joint Research Centre, Institute for Environment and Sustainability, Via Enrico Fermi, 21020 Ispra (Italy)], E-mail: robert.loos@jrc.it; Gawlik, Bernd Manfred; Locoro, Giovanni; Rimaviciute, Erika; Contini, Serafino; Bidoglio, Giovanni [European Commission, Joint Research Centre, Institute for Environment and Sustainability, Via Enrico Fermi, 21020 Ispra (Italy)

    2009-02-15

    This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. More than 100 individual water samples from over 100 European rivers from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals, pesticides, PFOS, PFOA, benzotriazoles, hormones, and endocrine disrupters. Around 40 laboratories participated in this sampling exercise. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE{sub 1}C). Only about 10% of the river water samples analysed could be classified as 'very clean' in terms of chemical pollution. The rivers responsible for the major aqueous emissions of PFOS and PFOA from the European Continent could be identified. For the target compounds chosen, we are proposing 'indicative warning levels' in surface waters, which are (for most compounds) close to the 90th percentile of all water samples analysed. - More than 100 river water samples from 27 European Countries were analysed for 35 selected polar organic contaminants.

  3. Role of polarity fractions of effluent organic matter in binding and toxicity of silver and copper.

    Science.gov (United States)

    Yoo, Jisu; Shim, Taeyong; Hur, Jin; Jung, Jinho

    2016-11-05

    This study evaluates the effect of the physicochemical properties of effluent organic matter (EfOM) from industrial and sewage wastewater treatment plants (WWTPs) on the binding and toxicity of Ag and Cu. EfOM was isolated into hydrophobic, transphilic, and hydrophilic fractions depending on its polarity, and was characterized by elemental, specific ultraviolet absorbance, and fluorescence excitation-emission matrix analyses. Our results suggest that the EfOM consists of microbially derived non-humic substances that have lower aromaticity than the Suwannee River natural organic matter (SR-NOM). The Freundlich model was better at explaining the binding of Ag and Cu onto both SR-NOM and EfOM than the Langmuir model. In particular, the hydrophilic fractions of sewage EfOM showed higher binding capacities and affinities for Ag and Cu than the corresponding hydrophobic fractions, resulting in better reduction of the acute toxicity of Ag and Cu towards Daphnia magna. However, in the case of both SR-NOM and industrial EfOM, the hydrophobic fractions were more efficient at reducing metal toxicity. These findings suggest that the EfOM has different physicochemical properties compared with NOM and that the binding and toxicity of heavy metals are largely dependent on the polarity fractions of EfOM. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Enhancing the Activity of Pd on Carbon Nanofibers for Deoxygenation of Amphiphilic Fatty Acid Molecules through Support Polarity

    NARCIS (Netherlands)

    Gosselink, R.W.; Xia, W.; Muhler, M.; Jong, de K.P.; Bitter, J.H.

    2013-01-01

    The influence of support polarity on Pd/CNF for the deoxygenation of fatty acids was studied. Catalysts with a low (O/C = 3.5 × 10–2 at/at from X-ray photoelectron spectroscopy (XPS)) and a high (O/C = 5.9 × 10–2 at/at from XPS) amount of oxygen containing groups on the support were prepared. The

  5. Metal-organic and supramolecular architectures based on mechanically interlocked molecules

    Science.gov (United States)

    Fernando, Isurika Rosini

    The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials. Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, are predicted to be unprecedentedly strong while being lightweight and flexible. With the ultimate goal of achieving control over the functioning of molecular devices in the solid state, a variety of pseudorotaxane building blocks were prepared and characterized, including a novel, rare blue-colored motif. The temperature-dependent assembly/disassembly of pseudorotaxanes was exploited for the construction of single-wavelength colorimetric temperature sensors over a 100 °C window. Pseudorotaxanes based on aromatic crown ether wheels and disubstituted 4,4'-bipyridinium axles were converted into rotaxanes upon binding to metal complexes (zinc, cadmium, mercury, copper, cobalt), and the formation of ordered crystalline arrays was studied in the solid state. The columnar organization of pseudorotaxanes by Hg2X6 2-- complexes (X = Cl, Br, I), leading to unprecedented dichroic (blue/red) rotaxane crystals, was demonstrated for the first time. From the crystal structures studied it became apparent that negatively charged metal complexes are needed for successful assembly with the positively charged pseudorotaxane units. To be able to use the more common, positively charged metal ions for rotaxane framework construction, neutral and negatively charged pseudorotaxanes were synthesized

  6. A-π-D-π-A Electron-Donating Small Molecules for Solution-Processed Organic Solar Cells: A Review.

    Science.gov (United States)

    Wang, Zhen; Zhu, Lingyun; Shuai, Zhigang; Wei, Zhixiang

    2017-11-01

    Organic solar cells based on semiconducting polymers and small molecules have attracted considerable attention in the last two decades. Moreover, the power conversion efficiencies for solution-processed solar cells containing A-π-D-π-A-type small molecules and fullerenes have reached 11%. However, the method for designing high-performance, photovoltaic small molecules still remains unclear. In this review, recent studies on A-π-D-π-A electron-donating small molecules for organic solar cells are introduced. Moreover, the relationships between molecular properties and device performances are summarized, from which inspiration for the future design of high performance organic solar cells may be obtained. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. EVAPORATION: a new vapor pressure estimation method for organic molecules including non-additivity and intramolecular interactions

    Science.gov (United States)

    Compernolle, S.; Ceulemans, K.; Müller, J.-F.

    2011-04-01

    We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects), a method to predict vapour pressure p0 of organic molecules needing only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T) is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: carbonyls, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA).

  8. Novel Design Strategies for Platinum-Containing Conjugated Polymers and Small Molecules for Organic Solar Cells

    Science.gov (United States)

    He, Wenhan

    Current state-of-the-art organic solar cells (OSCs) adopt the strategy of using conjugated polymers or small molecules as donors and fullerene derivatives as acceptors in their active layers. Regarding to the donors of interest, the conjugated polymers and small molecules coupled with heavy metals have been less explored compared to their counterparts. Among various transition metal complexes applied, Pt(II) complexes are unique because of their intrinsic square planar geometries and ability to serve as building blocks for conjugated systems. Furthermore, the heavy metal Pt facilitates the formation of triplet excitons with longer life times through spin-orbital coupling which are of benefit for the OSCs application. However, in order to obtain low bandgap polymers, people are intended to use chromophores with long conjugated length, nevertheless such design will inevitably dilute the spin-orbital coupling effect and finally influence the formation of triplet excitons. Furthermore, the majority of Pt-containing conjugated systems reported so far shared a common feature-- they all possessed "dumbbell" shaped structures and were amorphous, leading to poor device performance. In addition, there were few examples reporting the capture of the triplet excitons by the fullerene acceptors in the OSCs since there is a mismatch between the triplet energy state (T1) of the Pt-containing compounds and the LUMO level of fullerene acceptors. As a result, these three intrinsic problems will impede the further development of such a field. In order to solve these problems, I originally designed and synthesized three novel compounds with unique proprieties named as Bodipy-Pt, Pt-SM and C60+SDS-. Specifically, Bodipy has the advantages of compact size, easy to synthesis and high fluorescence quantum yield which can effectively solve the problem of long conjugated length. While in terms of second problem, the new Pt-SM possessed a "roller-wheel" structural design with increased

  9. Elucidating turnover pathways of bioactive small molecules by isotopomer analysis: the persistent organic pollutant DDT.

    Directory of Open Access Journals (Sweden)

    Ina Ehlers

    Full Text Available The persistent organic pollutant DDT (1,1,1-trichloro-2,2-bis(4-chlorophenylethane is still indispensable in the fight against malaria, although DDT and related compounds pose toxicological hazards. Technical DDT contains the dichloro congener DDD (1-chloro-4-[2,2-dichloro-1-(4-chlorophenylethyl]benzene as by-product, but DDD is also formed by reductive degradation of DDT in the environment. To differentiate between DDD formation pathways, we applied deuterium NMR spectroscopy to measure intramolecular deuterium distributions (2H isotopomer abundances of DDT and DDD. DDD formed in the technical DDT synthesis was strongly deuterium-enriched at one intramolecular position, which we traced back to 2H/1H fractionation of a chlorination step in the technical synthesis. In contrast, DDD formed by reductive degradation was strongly depleted at the same position, which was due to the incorporation of 2H-depleted hydride equivalents during reductive degradation. Thus, intramolecular isotope distributions give mechanistic information on reaction pathways, and explain a puzzling difference in the whole-molecule 2H/1H ratio between DDT and DDD. In general, our results highlight that intramolecular isotope distributions are essential to interpret whole-molecule isotope ratios. Intramolecular isotope information allows distinguishing pathways of DDD formation, which is important to identify polluters or to assess DDT turnover in the environment. Because intramolecular isotope data directly reflect isotope fractionation of individual chemical reactions, they are broadly applicable to elucidate transformation pathways of small bioactive molecules in chemistry, physiology and environmental science.

  10. Three dimensional extrusion printing induces polymer molecule alignment and cell organization within engineered cartilage.

    Science.gov (United States)

    Guo, Ting; Ringel, Julia P; Lim, Casey G; Bracaglia, Laura G; Noshin, Maeesha; Baker, Hannah B; Powell, Douglas A; Fisher, John P

    2018-04-16

    Proper cell-material interactions are critical to remain cell function and thus successful tissue regeneration. Many fabrication processes have been developed to create microenvironments to control cell attachment and organization on a three-dimensional (3D) scaffold. However, these approaches often involve heavy engineering and only the surface layer can be patterned. We found that 3D extrusion based printing at high temperature and pressure will result an aligned effect on the polymer molecules, and this molecular arrangement will further induce the cell alignment and different differentiation capacities. In particular, articular cartilage tissue is known to have zonal collagen fiber and cell orientation to support different functions, where collagen fibers and chondrocytes align parallel, randomly, and perpendicular, respectively, to the surface of the joint. Therefore, cell alignment was evaluated in a cartilage model in this study. We used small angle X-ray scattering analysis to substantiate the polymer molecule alignment phenomenon. The cellular response was evaluated both in vitro and in vivo. Seeded mesenchymal stem cells (MSCs) showed different morphology and orientation on scaffolds, as a combined result of polymer molecule alignment and printed scaffold patterns. Gene expression results showed improved superficial zonal chondrogenic marker expression in parallel-aligned group. The cell alignment was successfully maintained in the animal model after 7 days with distinct MSC morphology between the casted and parallel printed scaffolds. This 3D printing induced polymer and cell alignment will have a significant impact on developing scaffold with controlled cell-material interactions for complex tissue engineering while avoiding complicated surface treatment, and therefore provides new concept for effective tissue repairing in future clinical applications. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2018. © 2018 Wiley Periodicals, Inc.

  11. Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

    Energy Technology Data Exchange (ETDEWEB)

    Desai, R. T.; Coates, A. J.; Wellbrock, A.; González-Caniulef, D.; Jones, G. H.; Lewis, G. R.; Taylor, S. A.; Kataria, D. O. [Mullard Space Science Laboratory, University College London, Holmbury St. Mary, Surrey RH5 6NT (United Kingdom); Vuitton, V. [Université Grenoble Alpes, CNRS, IPAG, F-38000 Grenoble (France); Crary, F. J. [Laboratory for Atmospheric and Space Physics, University of Colorado, Innovation Drive, Boulder, CO 80303 (United States); Shebanits, O.; Wahlund, J.-E. [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden); Waite, J. H. [Space Science and Engineering Division, Southwest Research Institute (SWRI), 6220 Culebra Road, San Antonio, TX 78238 (United States); Cordiner, M.; Sittler, E. C. [NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Edberg, N. J. T., E-mail: r.t.desai@ucl.ac.uk [Swedish Institute of Space Physics, Box 537, SE-751 21 Uppsala (Sweden)

    2017-08-01

    Cassini discovered a plethora of neutral and ionized molecules in Titan’s ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q{sup −1}. In this Letter, we forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950–1300 km. We report on detections consistently centered between 25.8 and 26.0 u q{sup −1} and between 49.0–50.1 u q{sup −1} which are identified as belonging to the carbon chain anions, CN{sup −}/C{sub 3}N{sup −} and/or C{sub 2}H{sup −}/C{sub 4}H{sup −}, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73–74 u q{sup −1} could be attributed to the further carbon chain anions C{sub 5}N{sup −}/C{sub 6}H{sup −} but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below <1100 km, the low-mass anions (<150 u q{sup −1}) were found to deplete at a rate proportional to the growth of the larger molecules, a correlation that indicates the anions are tightly coupled to the growth process. This study adds Titan to an increasing list of astrophysical environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.

  12. Doping effects of surface functionalization on graphene with aromatic molecule and organic solvents

    Science.gov (United States)

    Wu, Guangfu; Tang, Xin; Meyyappan, M.; Lai, King Wai Chiu

    2017-12-01

    Aromatic molecule functionalization plays a key role in the development of graphene field-effect transistors (G-FETs) for bio-detection. We have investigated the doping effects of surface functionalization and its influence on the carrier mobility of graphene. The aromatic molecule (1-pyrenebutanoic acid succinimidyl ester, PBASE), which is widely used as a linker to anchor bio-probes, was employed here to functionalize graphene. Dimethyl formamide (DMF) and methanol (CH3OH) were used as two solvents to dissolve PBASE. Raman spectra showed that both PBASE and these two solvents imposed doping effects on graphene. The PBASE was stably immobilized on the graphene surface, which was confirmed by the new peak at around 1623.5 cm-1 and the disordered D peak at 1350 cm-1. Electrical measurements and Fermi level shift analysis further revealed that PBASE imposes a p-doping effect while DMF and CH3OH impose an n-doping effect. More importantly, CH3OH causes a smaller reduction in the carrier mobility of G-FETs (from 1095.6 cm2/V s to 802.4 cm2/V s) than DMF (from 1640.4 cm2/V s to 5.0 cm2/V s). Therefore, CH3OH can be regarded as a better solvent for the PBASE functionalization. This careful study on the influence of organic solvents on graphene during PBASE functionalization process provides an effective approach to monitor the surface functionalization of graphene.

  13. Interplay between efficiency and device architecture for small molecule organic solar cells.

    Science.gov (United States)

    Williams, Graeme; Sutty, Sibi; Aziz, Hany

    2014-06-21

    Small molecule organic solar cells (OSCs) have experienced a resurgence of interest over their polymer solar cell counterparts, owing to their improved batch-to-batch (thus, cell-to-cell) reliability. In this systematic study on OSC device architecture, we investigate five different small molecule OSC structures, including the simple planar heterojunction (PHJ) and bulk heterojunction (BHJ), as well as several planar-mixed structures. The different OSC structures are studied over a wide range of donor:acceptor mixing concentrations to gain a comprehensive understanding of their charge transport behavior. Transient photocurrent decay measurements provide crucial information regarding the interplay between charge sweep-out and charge recombination, and ultimately hint toward space charge effects in planar-mixed structures. Results show that the BHJ/acceptor architecture, comprising a BHJ layer with high C60 acceptor content, generates OSCs with the highest performance by balancing charge generation with charge collection. The performance of other device architectures is largely limited by hole transport, with associated hole accumulation and space charge effects.

  14. Universal structure conversion method for organic molecules: From atomic connectivity to three-dimensional geometry

    International Nuclear Information System (INIS)

    Kim, Yeon Joon; Kim, Woo Youn

    2015-01-01

    We present a powerful method for the conversion of molecular structures from atomic connectivity to bond orders to three-dimensional (3D) geometries. There are a number of bond orders and 3D geometries corresponding to a given atomic connectivity. To uniquely determine an energetically more favorable one among them, we use general chemical rules without invoking any empirical parameter, which makes our method valid for any organic molecule. Specifically, we first assign a proper bond order to each atomic pair in the atomic connectivity so as to maximize their sum and the result is converted to a SMILES notation using graph theory. The corresponding 3D geometry is then obtained using force field or ab initio calculations. This method successfully reproduced the bond order matrices and 3D geometries of 10 000 molecules randomly sampled from the PubChem database with high success rates of near 100% except a few exceptional cases. As an application, we demonstrate that it can be used to search for molecular isomers efficiently

  15. First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Mann, Gregory W., E-mail: gmann@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Mesosphere, Inc., San Francisco, California 94105 (United States); Lee, Kyuho, E-mail: kyuholee@lbl.gov [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Synopsys, Inc., Mountain View, California 94043 (United States); Cococcioni, Matteo, E-mail: matteo.cococcioni@epfl.ch [Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Smit, Berend, E-mail: Berend-Smit@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion (Switzerland); Neaton, Jeffrey B., E-mail: jbneaton@lbl.gov [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2016-05-07

    We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO{sub 2}-MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO{sub 2} binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.

  16. Observations of some oxygen-containing and sulfur-containing organic molecules in cold dark clouds

    Science.gov (United States)

    Irvine, W. M.; Friberg, P.; Kaifu, N.; Kitamura, Y.; Kawaguchi, K.

    1989-01-01

    Observations of nine oxygen- and sulfur-containing organic molecules have been made toward the cold dark clouds TMC-1 and L134N. The presence of paraketene (H2C2O) in TMC-1 is confirmed for orthoketene, and has been observed for the first time and a total ketene column density of about 10 to the 13th/sq cm is found. Thioformaldehyde (H2CS) is easily detectable in both TMC-1 and L134N, with a column density about five times larger in the former source. The fractional abundance of ketene is comparable to the predictions of ion-molecule chemistry, while that of thioformaldehyde in TMC-1 is one to two orders of magnitude greater than that expected from such models at steady state. Interstellar sulfur chemistry thus continues to be poorly understood. Upper limits are set for the column densities of formic acid (HCOOH), vinyl alcohol (CH2CHOH), methyl formate (HCO2CH3), formamide (NH2CHO), methyl mercaptan (CH3SH), isothiocyanic acid (HNCS), and thioketene (H2C2S) in both sources.

  17. Sequential photochemical and microbial degradation of organic molecules bound to humic acid

    International Nuclear Information System (INIS)

    Amador, J.A.; Zika, R.G.; Alexander, M.

    1989-01-01

    We studied the effects of photochemical processes on the mineralization by soil microorganisms of [2- 14 C]glycine bound to soil humic acid. Microbial mineralization of these complexes in the dark increased inversely with the molecular weight of the complex molecules. Sunlight irradiation of glycine-humic acid complexes resulted in loss of absorbance in the UV range and an increase in the amount of 14 C-labeled low-molecular-weight photoproducts and the rate and extent of mineralization. More than half of the radioactivity in the low-molecular-weight photoproducts appears to be associated with carboxylic acids. Microbial mineralization of the organic carbon increased with solar flux and was proportional to the loss of A 330 . Mineralization was proportional to the percentage of the original complex that was converted to low-molecular-weight photoproducts. Only light at wavelengths below 380 nm had an effect on the molecular weight distribution of the products formed from the glycine-humic acid complexes and on the subsequent microbial mineralization. Our results indicate that photochemical processes generate low-molecular-weight, readily biodegradable molecules from high-molecular-weight complexes of glycine with humic acid

  18. Solution-Processed Organic Solar Cells from Dye Molecules: An Investigation of Diketopyrrolopyrrole:Vinazene Heterojunctions

    KAUST Repository

    Walker, Bright

    2012-01-25

    Although one of the most attractive aspects of organic solar cells is their low cost and ease of fabrication, the active materials incorporated into the vast majority of reported bulk heterojunction (BHJ) solar cells include a semiconducting polymer and a fullerene derivative, classes of materials which are both typically difficult and expensive to prepare. In this study, we demonstrate that effective BHJs can be fabricated from two easily synthesized dye molecules. Solar cells incorporating a diketopyrrolopyrrole (DPP)-based molecule as a donor and a dicyanoimidazole (Vinazene) acceptor function as an active layer in BHJ solar cells, producing relatively high open circuit voltages and power conversion efficiencies (PCEs) up to 1.1%. Atomic force microscope images of the films show that active layers are rough and apparently have large donor and acceptor domains on the surface, whereas photoluminescence of the blends is incompletely quenched, suggesting that higher PCEs might be obtained if the morphology could be improved to yield smaller domain sizes and a larger interfacial area between donor and acceptor phases. © 2011 American Chemical Society.

  19. Modifying the thermal conductivity of small molecule organic semiconductor thin films with metal nanoparticles.

    Science.gov (United States)

    Wang, Xinyu; Parrish, Kevin D; Malen, Jonathan A; Chan, Paddy K L

    2015-11-04

    Thermal properties of organic semiconductors play a significant role in the performance and lifetime of organic electronic devices, especially for scaled-up large area applications. Here we employ silver nanoparticles (Ag NPs) to modify the thermal conductivity of the small molecule organic semiconductor, dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT). The differential 3-ω method was used to measure the thermal conductivity of Ag-DNTT hybrid thin films. We find that the thermal conductivity of pure DNTT thin films do not vary with the deposition temperature over a range spanning 24 °C to 80 °C. The thermal conductivity of the Ag-DNTT hybrid thin film initially decreases and then increases when the Ag volume fraction increases from 0% to 32%. By applying the effective medium approximation to fit the experimental results of thermal conductivity, the extracted thermal boundary resistance of the Ag-DNTT interface is 1.14 ± 0.98 × 10(-7) m(2)-K/W. Finite element simulations of thermal conductivity for realistic film morphologies show good agreement with experimental results and effective medium approximations.

  20. Charge-Dipole Acceleration of Polar Gas Molecules towards Charged Nanoparticles: Involvement in Powerful Charge-Induced Catalysis of Heterophase Chemical Reactions and Ball Lightning Phenomenon

    Directory of Open Access Journals (Sweden)

    Oleg Meshcheryakov

    2010-01-01

    Full Text Available In humid air, the substantial charge-dipole attraction and electrostatic acceleration of surrounding water vapour molecules towards charged combustible nanoparticles cause intense electrostatic hydration and preferential oxidation of these nanoparticles by electrostatically accelerated polar water vapour molecules rather than nonaccelerated nonpolar oxygen gas molecules. Intense electrostatic hydration of charged combustible nanoparticles converts the nanoparticle's oxide-based shells into the hydroxide-based electrolyte shells, transforming these nanoparticles into reductant/air core-shell nanobatteries, periodically short-circuited by intraparticle field and thermionic emission. Partially synchronized electron emission breakdowns within trillions of nanoparticles-nanobatteries turn a cloud of charged nanoparticles-nanobatteries into a powerful radiofrequency aerosol generator. Electrostatic oxidative hydration and charge-catalyzed oxidation of charged combustible nanoparticles also contribute to a self-oscillating thermocycling process of evolution and periodic autoignition of inflammable gases near to the nanoparticle's surface. The described effects might be of interest for the improvement of certain nanotechnological heterophase processes and to better understand ball lightning phenomenon.

  1. Accurate on-chip measurement of the Seebeck coefficient of high mobility small molecule organic semiconductors

    Directory of Open Access Journals (Sweden)

    C. N. Warwick

    2015-09-01

    Full Text Available We present measurements of the Seebeck coefficient in two high mobility organic small molecules, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT and 2,9-didecyl-dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C10-DNTT. The measurements are performed in a field effect transistor structure with high field effect mobilities of approximately 3 cm2/V s. This allows us to observe both the charge concentration and temperature dependence of the Seebeck coefficient. We find a strong logarithmic dependence upon charge concentration and a temperature dependence within the measurement uncertainty. Despite performing the measurements on highly polycrystalline evaporated films, we see an agreement in the Seebeck coefficient with modelled values from Shi et al. [Chem. Mater. 26, 2669 (2014] at high charge concentrations. We attribute deviations from the model at lower charge concentrations to charge trapping.

  2. Inducing magnetism in pure organic molecules by single magnetic atom doping.

    Science.gov (United States)

    Iancu, Violeta; Braun, Kai-Felix; Schouteden, Koen; Van Haesendonck, Chris

    2014-09-05

    We report on in situ chemical reactions between an organic trimesic acid (TMA) ligand and a Co atom center. By varying the substrate temperature, we are able to explore the Co-TMA interactions and create novel magnetic complexes that preserve the chemical structure of the ligands. Using scanning tunneling microscopy and spectroscopy combined with density functional theory calculations, we elucidate the structure and the properties of the newly synthesized complex at atomic or molecular size level. Hybridization between the atomic orbitals of the Co and the π orbitals of the ligand results in a delocalized spin distribution onto the TMA. The here demonstrated possibility to conveniently magnetize such versatile molecules opens up new potential applications for TMAs in molecular spintronics.

  3. Formation of ethylene glycol and other complex organic molecules in star-forming regions

    Science.gov (United States)

    Rivilla, V. M.; Beltrán, M. T.; Cesaroni, R.; Fontani, F.; Codella, C.; Zhang, Q.

    2017-02-01

    Context. The detection of complex organic molecules related with prebiotic chemistry in star-forming regions allows us to investigate how the basic building blocks of life are formed. Aims: Ethylene glycol (CH2OH)2 is the simplest sugar alcohol and the reduced alcohol of the simplest sugar glycoladehyde (CH2OHCHO). We study the molecular abundance and spatial distribution of (CH2OH)2, CH2OHCHO and other chemically related complex organic species (CH3OCHO, CH3OCH3, and C2H5OH) towards the chemically rich massive star-forming region G31.41+0.31. Methods: We analyzed multiple single-dish (Green Bank Telescope and IRAM 30 m) and interferometric (Submillimeter Array) spectra towards G31.41+0.31, covering a range of frequencies from 45 to 258 GHz. We fitted the observed spectra with a local thermodynamic equilibrium (LTE) synthetic spectra, and obtained excitation temperatures and column densities. We compared our findings in G31.41+0.31 with the results found in other environments, including low- and high-mass star-forming regions, quiescent clouds and comets. Results: We report for the first time the presence of the aGg' conformer of (CH2OH)2 towards G31.41+0.31, detecting more than 30 unblended lines. We also detected multiple transitions of other complex organic molecules such as CH2OHCHO, CH3OCHO, CH3OCH3, and C2H5OH. The high angular resolution images show that the (CH2OH)2 emission is very compact, peaking towards the maximum of the 1.3 mm continuum. These observations suggest that low abundance complex organic molecules, like (CH2OH)2 or CH2OHCHO, are good probes of the gas located closer to the forming stars. Our analysis confirms that (CH2OH)2 is more abundant than CH2OHCHO in G31.41+0.31, as previously observed in other interstellar regions. Comparing different star-forming regions we find evidence of an increase of the (CH2OH)2/CH2OHCHO abundance ratio with the luminosity of the source. The CH3OCH3/CH3OCHO and (CH2OH)2/C2H5OH ratios are nearly constant with

  4. High mass-resolution electron-ion-ion coincidence measurements on core-excited organic molecules

    CERN Document Server

    Tokushima, T; Senba, Y; Yoshida, H; Hiraya, A

    2001-01-01

    Total electron-ion-ion coincidence measurements on core excited organic molecules have been carried out with high mass resolution by using multimode (reflectron/linear) time-of-flight mass analyzer. From the ion correlation spectra of core excited CH sub 3 OH and CD sub 3 OH, the reaction pathway to form H sub 3 sup + (D sub 3 sup +) is identified as the elimination of three H (D) atoms from the methyl group, not as the inter-group (-CH sub 3 and -OH) interactions. In a PEPIPICO spectrum of acetylacetone (CH sub 3 COCH sub 2 COCH sub 3) measured by using a reflectron TOF, correlations between ions up to mass number 70 with one-mass resolution was recorded.

  5. Ion chemistry of some organic molecules studied by field ionization and field desorption mass spectrometry

    International Nuclear Information System (INIS)

    Greef, J. van der.

    1980-01-01

    The chemistry of isolated ions in the gas phase is strongly dependent on the internal energy which they have required upon formation. Since also the average lifetime of an ion depends on its internal energy, ion lifetime studies have been employed for many years to obtain a better insight in the relation between the chemistry and internal energy of gas phase ions. A very powerful tool for such studies is the field ionization kinetic (FIK) method, because it can provide a time-resolved picture of decompositions of ions with lifetimes varying from 10 -11 to 10 -5 s. The FIK method has been used in combination with 2 H, 13 C and 15 N labelling for mechanistic studies on the fragmentation of some selected ionised organic molecules. (Auth.)

  6. Strategies For Immobilization Of Bioactive Organic Molecules On Titanium Implant Surfaces – A Review

    Directory of Open Access Journals (Sweden)

    Panayotov Ivan V.

    2015-03-01

    Full Text Available Numerous approaches have been used to improve the tissue-implant interface of titanium (Ti and titanium alloy (Ti6Al4V. They all aim at increasing cell migration and attachment to the metal, preventing unspecific protein adsorption and improving post-implantation healing process. Promising methods for titanium and titanium alloy surface modification are based on the immobilization of biologically active organic molecules. New and interesting biochemical approaches to such surface modification include layer-by-layer deposition of polyelectrolyte films, phage display-selected surface binding peptides and self-assembled DNA monolayer systems. The present review summarizes the scientific information about these methods, which are at in vitro or in vivo development stages, and hopes to promote their future application in dental implantology and in oral and maxillofacial surgery.

  7. NEXAFS: a unique tool to follow the photochemistry of small organic molecules in condensed water

    Energy Technology Data Exchange (ETDEWEB)

    Parent, Ph; Laffon, C; Bournel, F; Lasne, J [Laboratoire de Chimie-Physique, Matiere et Rayonnement, Universite Pierre et Marie Curie (UPMC-Univ Paris 06) and CNRS (UMR 7614), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); Lacombe, S, E-mail: philippe.parent@upmc.fr [Institut des Sciences Moleculaires d' Orsay, ISMO (FRE 3363), 91405 Orsay Cedex (France) and Universite Paris Sud 11, CNRS-Bat 351, 91405 Orsay Cedex (France)

    2011-01-01

    Soft X-ray induced chemistry of simple organic molecules as carbon monoxide (CO), methanol (CH{sub 3}OH) and glycine (NH{sub 3}CH{sub 2}COOH) in water and nitric acid hydrate has been investigated with NEXAFS spectroscopy. In the pure species, extremely high survival rates are observed, a consequence of the back reactions allowed in the condensed phase. When mixed with water, the survival rates are considerably reduced by reaction with the hydroxyl radical (OH). The formation of CO{sub 2} is also enhanced at the expense of CO, the main byproduct in the photolysis of the pure species. Finally, it is shown that water plays no role in the destruction of the amino acid.

  8. ANI-1, A data set of 20 million calculated off-equilibrium conformations for organic molecules

    Science.gov (United States)

    Smith, Justin S.; Isayev, Olexandr; Roitberg, Adrian E.

    2017-12-01

    One of the grand challenges in modern theoretical chemistry is designing and implementing approximations that expedite ab initio methods without loss of accuracy. Machine learning (ML) methods are emerging as a powerful approach to constructing various forms of transferable atomistic potentials. They have been successfully applied in a variety of applications in chemistry, biology, catalysis, and solid-state physics. However, these models are heavily dependent on the quality and quantity of data used in their fitting. Fitting highly flexible ML potentials, such as neural networks, comes at a cost: a vast amount of reference data is required to properly train these models. We address this need by providing access to a large computational DFT database, which consists of more than 20 M off equilibrium conformations for 57,462 small organic molecules. We believe it will become a new standard benchmark for comparison of current and future methods in the ML potential community.

  9. Spectral, stoichiometric ratio, physicochemical, polarity and photostability studies of newly synthesized chalcone dye in organized media

    Energy Technology Data Exchange (ETDEWEB)

    Marwani, Hadi M., E-mail: hmarwani@kau.edu.sa [Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Asiri, Abdullah M. [Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Khan, Salman A. [Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia)

    2013-04-15

    The main focus of this study was to investigate spectroscopic properties, stoichiometric ratios, physicochemical parameters, polarity and photostability behaviors of newly synthesized chalcone dye in organized media. The chalcone dye, 1-(2,5-Dimethyl-thiophen-3-yl)-3-(9-etnyl-9H-carbazol-3-yl)-propenone (DTEP), was prepared by the reaction of carbazole aldehyde with 3-acetyl-2,5-dimethythiophene. Data obtained from FT-IR, {sup 1}H-–NMR, {sup 13}C-NMR and elemental analysis were consistent with chemical structure of newly prepared DTEP. Increases in fluorescence intensities of DTEP with cetyltrimethyl ammonium bromide (CTAB) were observed. In comparison of fluorescence intensities for DTEP with CTAB, reductions in fluorescence intensities for DTEP with sodium dodecyl sulfate (SDS) were noticed under the same experimental and instrumental conditions. Additionally, Benesi–Hildebrand method was applied to determine stoichiometric ratios and association constants of DTEP with CTAB and SDS. Stern–Volmer plot was used in order to further confirm the stoichiometric ratio and association constant of DTEP with SDS. Physicochemical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment and fluorescence quantum yield of DTEP were also determined. Fluorescence polarity study displayed that DTEP was sensitive to the polarity of the microenvironment provided by different solvents. Finally, fluorescence steady-state measurements revealed that DTEP has high photostability against photobleaching. -- Highlights: ► Mechanistic understanding of molecular structure of newly synthesized chalcone dye. ► Exploring spectral behaviors and physicochemical parameters of chalcone dye. ► Determination of stoichiometric ratios and association constants of chalcone dye. ► Determination of fluorescence quantum yield in different solvents. ► High photostability against photobleaching of chalcone dye was observed.

  10. Spectral, stoichiometric ratio, physicochemical, polarity and photostability studies of newly synthesized chalcone dye in organized media

    International Nuclear Information System (INIS)

    Marwani, Hadi M.; Asiri, Abdullah M.; Khan, Salman A.

    2013-01-01

    The main focus of this study was to investigate spectroscopic properties, stoichiometric ratios, physicochemical parameters, polarity and photostability behaviors of newly synthesized chalcone dye in organized media. The chalcone dye, 1-(2,5-Dimethyl-thiophen-3-yl)-3-(9-etnyl-9H-carbazol-3-yl)-propenone (DTEP), was prepared by the reaction of carbazole aldehyde with 3-acetyl-2,5-dimethythiophene. Data obtained from FT-IR, 1 H-–NMR, 13 C-NMR and elemental analysis were consistent with chemical structure of newly prepared DTEP. Increases in fluorescence intensities of DTEP with cetyltrimethyl ammonium bromide (CTAB) were observed. In comparison of fluorescence intensities for DTEP with CTAB, reductions in fluorescence intensities for DTEP with sodium dodecyl sulfate (SDS) were noticed under the same experimental and instrumental conditions. Additionally, Benesi–Hildebrand method was applied to determine stoichiometric ratios and association constants of DTEP with CTAB and SDS. Stern–Volmer plot was used in order to further confirm the stoichiometric ratio and association constant of DTEP with SDS. Physicochemical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment and fluorescence quantum yield of DTEP were also determined. Fluorescence polarity study displayed that DTEP was sensitive to the polarity of the microenvironment provided by different solvents. Finally, fluorescence steady-state measurements revealed that DTEP has high photostability against photobleaching. -- Highlights: ► Mechanistic understanding of molecular structure of newly synthesized chalcone dye. ► Exploring spectral behaviors and physicochemical parameters of chalcone dye. ► Determination of stoichiometric ratios and association constants of chalcone dye. ► Determination of fluorescence quantum yield in different solvents. ► High photostability against photobleaching of chalcone dye was observed

  11. FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

    International Nuclear Information System (INIS)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-01-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude

  12. Vibronic coupling in ionized organic molecules. Structural distortions and chemical reactions

    International Nuclear Information System (INIS)

    Williams, F.

    2002-01-01

    Complete text of publication follows. Ionized organic molecules (radical cations, RC) are prone to undergo vibronic coupling whenever there is a relatively small energy gap ( 2v point group of the neutral parent molecule by twisting at the olefinic π bond to the lower C 2 symmetry in the RC (Chem. Eur. J. 2002, 8, 1074). These experiments clearly revealed a double minimum in the potential energy surface along the a 2 torsional mode. This is in accord with the coupling of the 2 B 1 and 2 B 2 Born-Oppenheimer states in C 2v symmetry, this mixing of the 2 B 1 π-ionized ground state and the 2 B 2 δ-ionized excited state being facilitated by the low (∼ 1.0 eV) gap between these states, as estimated from photoelectron spectroscopy. Turning to the second class of RC where unimolecular rearrangement reactions are promoted by vibronic interaction, several cases have emerged where the rearrangement would not be expected if it were based only on the ground-state properties of the RC. It was found (Chem. Phy. Lett. 1988, 143, 521) that the ethylene oxide RC undergoes C-C ring opening to the oxallyl species despite the fact that the ground state corresponds to ionization from the nonbonding oxygen π lone-pair orbital. The reaction develops excited-state character as a result of the vibronic mixing so that the activation barrier to ring opening is lowered. We will discuss the unusual rearrangements of the bicyclo[1.1.1.]pentane and [1.1.1]propellane RC from a similar perspective, emphasis being placed on the decisive role of symmetry in predicting the course of these rearrangements. We illustrate how this approach can reconcile conflicting considerations on some of the 'unexpected' reaction pathways followed by highly strained organic RC

  13. Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

    Science.gov (United States)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-04-01

    During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

  14. "Molecules-in-Medicine": Peer-Evaluated Presentations in a Fast-Paced Organic Chemistry Course for Medical Students

    Science.gov (United States)

    Kadnikova, Ekaterina N.

    2013-01-01

    To accentuate the importance of organic chemistry in development of contemporary pharmaceuticals, a three-week unit entitled "Molecules-in-Medicine" was included in the curriculum of a comprehensive one-semester four-credit organic chemistry course. After a lecture on medicinal chemistry concepts and pharmaceutical practices, students…

  15. Modeling Stretching Modes of Common Organic Molecules with the Quantum Mechanical Harmonic Oscillator: An Undergraduate Vibrational Spectroscopy Laboratory Exercise

    Science.gov (United States)

    Parnis, J. Mark; Thompson, Matthew G. K.

    2004-01-01

    An introductory undergraduate physical organic chemistry exercise that introduces the harmonic oscillator's use in vibrational spectroscopy is developed. The analysis and modeling exercise begins with the students calculating the stretching modes of common organic molecules with the help of the quantum mechanical harmonic oscillator (QMHO) model.

  16. Comparison of the sampling rates and partitioning behaviour of polar and non-polar contaminants in the polar organic chemical integrative sampler and a monophasic mixed polymer sampler for application as an equilibrium passive sampler.

    Science.gov (United States)

    Jeong, Yoonah; Schäffer, Andreas; Smith, Kilian

    2018-06-15

    In this work, Oasis HLB® beads were embedded in a silicone matrix to make a single phase passive sampler with a higher affinity for polar and ionisable compounds than silicone alone. The applicability of this mixed polymer sampler (MPS) was investigated for 34 aquatic contaminants (log K OW -0.03 to 6.26) in batch experiments. The influence of flow was investigated by comparing uptake under static and stirred conditions. The sampler characteristics of the MPS was assessed in terms of sampling rates (R S ) and sampler-water partition coefficients (K SW ), and these were compared to those of the polar organic chemical integrative sampler (POCIS) as a reference kinetic passive sampler. The MPS was characterized as an equilibrium sampler for both polar and non-polar compounds, with faster uptake rates and a shorter time to reach equilibrium than the POCIS. Water flow rate impacted sampling rates by up to a factor of 12 when comparing static and stirred conditions. In addition, the relative accumulation of compounds in the polyethersulfone (PES) membranes versus the inner Oasis HLB sorbent was compared for the POCIS, and ranged from <1% to 83% depending on the analyte properties. This is indicative of a potentially significant lag-phase for less polar compounds within POCIS. The findings of this study can be used to quantitatively describe the partitioning and kinetic behaviour of MPS and POCIS for a range of aquatic organic contaminants for application in field sampling. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. Living Cells and Dynamic Molecules Observed with the Polarized Light Microscope: the Legacy of Shinya Inoué.

    Science.gov (United States)

    Tani, Tomomi; Shribak, Michael; Oldenbourg, Rudolf

    2016-08-01

    In 1948, Shinya Inoué arrived in the United States for graduate studies at Princeton. A year later he came to Woods Hole, starting a long tradition of summer research at the Marine Biological Laboratory (MBL), which quickly became Inoué's scientific home. Primed by his Japanese mentor, Katsuma Dan, Inoué followed Dan's mantra to work with healthy, living cells, on a fundamental problem (mitosis), with a unique tool set that he refined for precise and quantitative observations (polarized light microscopy), and a fresh and brilliant mind that was unafraid of challenging current dogma. Building on this potent combination, Inoué contributed landmark observations and concepts in cell biology, including the notion that there are dynamic, fine structures inside living cells, in which molecular assemblies such as mitotic spindle fibers exist in delicate equilibrium with their molecular building blocks suspended in the cytoplasm. In the late 1970s and 1980s, Inoué and others at the MBL were instrumental in conceiving video microscopy, a groundbreaking technique which married light microscopy and electronic imaging, ushering in a revolution in how we know and what we know about living cells and the molecular mechanisms of life. Here, we recount some of Inoué's accomplishments and describe how his legacy has shaped current activities in polarized light imaging at the MBL. © 2016 Marine Biological Laboratory.

  18. Interaction of polar and nonpolar organic pollutants with soil organic matter: sorption experiments and molecular dynamics simulation.

    Science.gov (United States)

    Ahmed, Ashour A; Thiele-Bruhn, Sören; Aziz, Saadullah G; Hilal, Rifaat H; Elroby, Shaaban A; Al-Youbi, Abdulrahman O; Leinweber, Peter; Kühn, Oliver

    2015-03-01

    The fate of organic pollutants in the environment is influenced by several factors including the type and strength of their interactions with soil components especially SOM. However, a molecular level answer to the question "How organic pollutants interact with SOM?" is still lacking. In order to explore mechanisms of this interaction, we have developed a new SOM model and carried out molecular dynamics (MD) simulations in parallel with sorption experiments. The new SOM model comprises free SOM functional groups (carboxylic acid and naphthalene) as well as SOM cavities (with two different sizes), simulating the soil voids, containing the same SOM functional groups. To examine the effect of the hydrophobicity on the interaction, the organic pollutants hexachlorobenzene (HCB, non-polar) and sulfanilamide (SAA, polar) were considered. The experimental and theoretical investigations explored four major points regarding sorption of SAA and HCB on soil, yielding the following results. 1--The interaction depends on the SOM chemical composition more than the SOM content. 2--The interaction causes a site-specific adsorption on the soil surfaces. 3--Sorption hysteresis occurs, which can be explained by inclusion of these pollutants inside soil voids. 4--The hydrophobic HCB is adsorbed on soil stronger than the hydrophilic SAA. Moreover, the theoretical results showed that HCB forms stable complexes with all SOM models in the aqueous solution, while most of SAA-SOM complexes are accompanied by dissociation into SAA and the free SOM models. The SOM-cavity modeling had a significant effect on binding of organic pollutants to SOM. Both HCB and SAA bind to the SOM models in the order of models with a small cavity>a large cavity>no cavity. Although HCB binds to all SOM models stronger than SAA, the latter is more affected by the presence of the cavity. Finally, HCB and SAA bind to the hydrophobic functional group (naphthalene) stronger than to the hydrophilic one (carboxylic acid

  19. Methodologies for Controlled Conjugated Polymer Synthesis and Characterization of Small Molecule Organic Semiconductors

    Science.gov (United States)

    Bakus, Ronald C., II

    Conjugated polymers can broadly be described as materials which have a structure composed of repeating monomeric units that show extended electronic communication along the backbone. The extended pi-conjugated nature of these materials gives them a set of unique electronic and optical properties, and has lead to their application in a multitude of various technologies. Of specific interest is the application of these materials in various organic electronics applications, such as solution processed plastic solar cells, light emitting diodes, and field effect transistors. Herein is described the synthesis of a class of well-defined, highly active organometallic initiators for use in controlled polymer synthesis. The polymers prepared using the nickel based initiators in Grignard metathesis polymerization posses the following characteristics: rapid generation of high molecular weight polymers, low polydispersity, linear relation between monomer conversion and molecular weight growth, and the selective transfer of an initiating moiety from the organometallic initiator to one polymer chain end. This initiator was then used to prepare a new class of biosensor materials wherein the polymer had a well defined biosensing end group. Additionally, a series of small molecule donors have been developed that have shown promise in a wide variety of organic electronic applications. These materials can broadly be described as having a D'ADAD' type structure where D, D', and A correspond to electron rich and electron deficient aromatic heterocycles, respectively. By tuning the identity of these groups and the side-chains attached to them, one can subtly influence the optical, electronic, and physical properties of the materials. These materials were investigated via single crystal x-ray diffraction studies to gain insight into how changes to the molecule structure such as heteroatom regioisomerism and isoelectronic substitutions effected the molecular structure. These changes in

  20. Process for preparing organoclays for aqueous and polar-organic systems

    Science.gov (United States)

    Chaiko, David J.

    2001-01-01

    A process for preparing organoclays as thixotropic agents to control the rheology of water-based paints and other aqueous and polar-organic systems. The process relates to treating low-grade clay ores to achieve highly purified organoclays and/or to incorporate surface modifying agents onto the clay by adsorption and/or to produce highly dispersed organoclays without excessive grinding or high shear dispersion. The process involves the treatment of impure, or run-of-mine, clay using an aqueous biphasic extraction system to produce a highly dispersed clay, free of mineral impurities and with modified surface properties brought about by adsorption of the water-soluble polymers used in generating the aqueous biphasic extraction system. This invention purifies the clay to greater than 95%.

  1. Cucurbit[7]uril host-guest complexes with small polar organic guests in aqueous solution.

    Science.gov (United States)

    Wyman, Ian W; Macartney, Donal H

    2008-05-21

    The host-guest stability constants for the inclusion of a series of small neutral polar organic guests in cucurbit[7]uril (CB[7]) have been determined in aqueous solution by (1)H NMR titrations. The dependence of the stability constant on the nature of the guests indicates that hydrophobic and dipole-quadrupole interactions are responsible for the binding. The complexation-induced chemical shift changes in the guest proton resonances, coupled with energy-minimization calculations, suggest that the guests are located such that their dipole moment is aligned perpendicular with the quadrupole moment of the CB[7] host. The stability constants for acetone and acetophenone decrease in the presence of Na(+) or K(+) cations as a result of cation capping of the CB[7] portals.

  2. The Detection of Hot Cores and Complex Organic Molecules in the Large Magellanic Cloud

    Science.gov (United States)

    Sewiło, Marta; Indebetouw, Remy; Charnley, Steven B.; Zahorecz, Sarolta; Oliveira, Joana M.; van Loon, Jacco Th.; Ward, Jacob L.; Chen, C.-H. Rosie; Wiseman, Jennifer; Fukui, Yasuo; Kawamura, Akiko; Meixner, Margaret; Onishi, Toshikazu; Schilke, Peter

    2018-02-01

    We report the first extragalactic detection of the complex organic molecules (COMs) dimethyl ether (CH3OCH3) and methyl formate (CH3OCHO) with the Atacama Large Millimeter/submillimeter Array (ALMA). These COMs, together with their parent species methanol (CH3OH), were detected toward two 1.3 mm continuum sources in the N 113 star-forming region in the low-metallicity Large Magellanic Cloud (LMC). Rotational temperatures ({T}{rot}∼ 130 K) and total column densities ({N}{rot}∼ {10}16 cm‑2) have been calculated for each source based on multiple transitions of CH3OH. We present the ALMA molecular emission maps for COMs and measured abundances for all detected species. The physical and chemical properties of two sources with COMs detection, and the association with H2O and OH maser emission, indicate that they are hot cores. The fractional abundances of COMs scaled by a factor of 2.5 to account for the lower metallicity in the LMC are comparable to those found at the lower end of the range in Galactic hot cores. Our results have important implications for studies of organic chemistry at higher redshift.

  3. Functionalized organic semiconductor molecules to enhance charge carrier injection in electroluminescent cell

    Science.gov (United States)

    Yalcin, Eyyup; Kara, Duygu Akin; Karakaya, Caner; Yigit, Mesude Zeliha; Havare, Ali Kemal; Can, Mustafa; Tozlu, Cem; Demic, Serafettin; Kus, Mahmut; Aboulouard, Abdelkhalk

    2017-07-01

    Organic semiconductor (OSC) materials as a charge carrier interface play an important role to improve the device performance of organic electroluminescent cells. In this study, 4,4″-bis(diphenyl amino)-1,1':3‧,1″-terphenyl-5'-carboxylic acid (TPA) and 4,4″-di-9H-carbazol-9-yl-1,1':3‧,1″-terphenyl-5'-carboxylic acid (CAR) has been designed and synthesized to modify indium tin oxide (ITO) layer as interface. Bare ITO and PEDOT:PSS coated on ITO was used as reference anode electrodes for comparison. Furthermore, PEDOT:PSS coated over CAR/ITO and TPA/ITO to observe stability of OSC molecules and to completely cover the ITO surface. Electrical, optical and surface characterizations were performed for each device. Almost all modified devices showed around 36% decrease at the turn on voltage with respect to bare ITO. The current density of bare ITO, ITO/CAR and ITO/TPA were measured as 288, 1525 and 1869 A/m2, respectively. By increasing current density, luminance of modified devices showed much better performance with respect to unmodified devices.

  4. Scanning transmission X-ray microscopy as a speciation tool for natural organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Rothe, J.; Plaschke, M.; Denecke, M.A. [Inst. fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Karlsruhe (Germany)

    2004-07-01

    A molecular-scale understanding of the basic processes affecting stability and transport behavior of actinide cations, complexes or hydroxide ('eigencolloid') species is prerequisite to performance assessment of nuclear waste disposal in geological formations. Depending on their functional group chemistry and macromolecular structure, naturally occurring organic molecules (NOM) possess a high tendency towards actinide complexation reactions. However, the compositional and structural heterogeneity of NOM and mixed aggregates with inorganic phases makes speciation by spectromicroscopy techniques highly desirable. The applicability of Scanning Transmission X-ray Microscopy (STXM) as a speciation tool for the characterization of NOM is demonstrated for a multifunctional natural organic acid (chlorogenic acid), Eu(III)-loaded humic acid (HA) aggregates and Eu(III)-oxo/hydroxide/HA hetero-aggregates. It is shown that in situ probing of HA functional group chemistry down to a spatial resolution < 100 nm (i.e., less than femto-liter sampled volumes) is feasible, at the same time revealing morphological details on NOM aggregates and NOM/mineral associations. (orig.)

  5. Technical Note: Development of chemoinformatic tools to enumerate functional groups in molecules for organic aerosol characterization

    Science.gov (United States)

    Ruggeri, Giulia; Takahama, Satoshi

    2016-04-01

    Functional groups (FGs) can be used as a reduced representation of organic aerosol composition in both ambient and controlled chamber studies, as they retain a certain chemical specificity. Furthermore, FG composition has been informative for source apportionment, and various models based on a group contribution framework have been developed to calculate physicochemical properties of organic compounds. In this work, we provide a set of validated chemoinformatic patterns that correspond to (1) a complete set of functional groups that can entirely describe the molecules comprised in the α-pinene and 1,3,5-trimethylbenzene MCMv3.2 oxidation schemes, (2) FGs that are measurable by Fourier transform infrared spectroscopy (FTIR), (3) groups incorporated in the SIMPOL.1 vapor pressure estimation model, and (4) bonds necessary for the calculation of carbon oxidation state. We also provide example applications for this set of patterns. We compare available aerosol composition reported by chemical speciation measurements and FTIR for different emission sources, and calculate the FG contribution to the O : C ratio of simulated gas-phase composition generated from α-pinene photooxidation (using the MCMv3.2 oxidation scheme).

  6. Electronic coupling effects and charge transfer between organic molecules and metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Forker, Roman

    2010-07-01

    We employ a variant of optical absorption spectroscopy, namely in situ differential reflectance spectroscopy (DRS), for an analysis of the structure-properties relations of thin epitaxial organic films. Clear correlations between the spectra and the differently intense coupling to the respective substrates are found. While rather broad and almost structureless spectra are obtained for a quaterrylene (QT) monolayer on Au(111), the spectral shape resembles that of isolated molecules when QT is grown on graphite. We even achieve an efficient electronic decoupling from the subjacent Au(111) by inserting an atomically thin organic spacer layer consisting of hexa-peri-hexabenzocoronene (HBC) with a noticeably dissimilar electronic behavior. These observations are further consolidated by a systematic variation of the metal substrate (Au, Ag, and Al), ranging from inert to rather reactive. For this purpose, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) is chosen to ensure comparability of the molecular film structures on the different metals, and also because its electronic alignment on various metal surfaces has previously been studied with great intensity. We present evidence for ionized PTCDA at several interfaces and propose the charge transfer to be related to the electronic level alignment governed by interface dipole formation on the respective metals. (orig.)

  7. Ion—polar-molecule reactions: A CRESU study of He +, C +, N + + H 2O, NH 3 at 27, 68 and 163 K

    Science.gov (United States)

    Marquette, J. B.; Rowe, B. R.; Dupeyrat, G.; Poissant, G.; Rebrion, C.

    1985-12-01

    The first measurements of ion—polar-molecule reaction rate constants at very low temperatures are presented. They have been obtained using the CRESU (cine_.tique de reactions en ecoulement supersonique uniforme) technique for H +.C + and N + ions reacting with H 2O and NH 3 at 27 and 68 K in helium buffer. Additional data have been obtained for N + reactions at 163 K in nitrogen buffer. In the 27-300 K (27-163 K for N + + NH 3) temperature range, all the results yield a power law, k = k0T- n (0 < n < 1), for the rate coefficient of each reaction, which should be applied in interstellar cloud model in place of the room-temperature values. The results are compared with various theoretical calculations. Rather good agreement is found although no general behavior can be simply drawn from these experiments.

  8. Structural Ordering of Semiconducting Polymers and Small-Molecules for Organic Electronics

    Science.gov (United States)

    O'Hara, Kathryn Allison

    Semiconducting polymers and small-molecules can be readily incorporated into electronic devices such as organic photovoltaics (OPVs), thermoelectrics (OTEs), organic light emitting diodes (OLEDs), and organic thin film transistors (OTFTs). Organic materials offer the advantage of being processable from solution to form flexible and lightweight thin films. The molecular design, processing, and resulting thin film morphology of semiconducting polymers drastically affect the optical and electronic properties. Charge transport within films of semiconducting polymers relies on the nanoscale organization to ensure electronic coupling through overlap of molecular orbitals and to provide continuous transport pathways. While the angstrom-scale packing details can be studied using X-ray scattering methods, an understanding of the mesoscale, or the length scale over which smaller ordered regions connect, is much harder to achieve. Grain boundaries play an important role in semiconducting polymer thin films where the average grain size is much smaller than the total distance which charges must traverse in order to reach the electrodes in a device. The majority of semiconducting polymers adopt a lamellar packing structure in which the conjugated backbones align in parallel pi-stacks separated by the alkyl side-chains. Only two directions of transport are possible--along the conjugated backbone and in the pi-stacking direction. Currently, the discussion of transport between crystallites is centered around the idea of tie-chains, or "bridging" polymer chains connecting two ordered regions. However, as molecular structures become increasingly complex with the development of new donor-acceptor copolymers, additional forms of connectivity between ordered domains should be considered. High resolution transmission electron microscopy (HRTEM) is a powerful tool for directly imaging the crystalline grain boundaries in polymer and small-molecule thin films. Recently, structures

  9. Polarity-Tunable Host Materials and Their Applications in Thermally Activated Delayed Fluorescence Organic Light-Emitting Diodes.

    Science.gov (United States)

    Xie, Gaozhan; Chen, Dongjun; Li, Xianglong; Cai, Xinyi; Li, Yunchuan; Chen, Dongcheng; Liu, Kunkun; Zhang, Qian; Cao, Yong; Su, Shi-Jian

    2016-10-04

    A series of polarity-tunable host materials were developed based on oligocarbazoles and diphenylphosphine oxide, and their polarities can be tuned through increasing distance of acceptor and donor units. Density functional theory calculations were employed, and photoluminescence spectra in different polar solvents were measured to illustrate different polarities of these host materials. As CZPO has relatively stronger polarity, electroluminescence (EL) spectrum of solution-processed device based on 6 wt % PXZDSO2:CZPO is 7 nm red-shifted relative to that of other host materials based devices. Besides, a comparable impressive external quantum efficiency (EQE) value of 18.7% is achieved for an evaporation-processed yellow device consisting of FCZBn, which is superior to that of the device based on CBP (4,4'-dicarbazolyl-1,1'-biphenyl) (17.0%), and its efficiency roll-off is also obviously reduced, giving an EQE value as high as 16.3% at the luminance of 1000 cd/m 2 . In addition, from CZPO to FCZBn as the polarities of host materials decrease, EL spectra of solution-processed devices based on DMAC-DPS emitter blue-shift constantly from 496 to 470 nm. The current work gives a constructive approach to control EL spectra of organic light-emitting diodes with a fixed thermally activated delayed fluorescence emitter by tuning the polarities of host materials.

  10. Metal-Organic Frameworks for Resonant-Gravimetric Detection of Trace-Level Xylene Molecules.

    Science.gov (United States)

    Xu, Tao; Xu, Pengcheng; Zheng, Dan; Yu, Haitao; Li, Xinxin

    2016-12-20

    As one of typical VOCs, xylene is seriously harmful to human health. Nowadays, however, there is really lack of portable sensing method to directly detect environmental xylene that has chemical inertness. Especially when the concentration of xylene is lower than the human olfactory threshold of 470 ppb, people are indeed hard to be aware of and avoid this harmful vapor. Herein the metal-organic framework (MOF) of HKUST-1 is first explored for sensing to the nonpolar molecule of p-xylene. And the sensing mechanism is identified that is via host-guest interaction of MOF with xylene molecule. By loading MOFs on mass-gravimetric resonant-cantilevers, sensing experiments for four MOFs of MOF-5, HKUST-1, ZIF-8, and MOF-177 approve that HKUST-1 has the highest sensitivity to p-xylene. The resonant-gravimetric sensing experiments with our HKUST-1 based sensors have demonstrated that trace-level p-xylene of 400 ppb can be detected that is lower than the human olfactory threshold of 470 ppb. We analyze that the specificity of HKUST-1 to xylene comes from Cu 2+ -induced moderate Lewis acidity and the "like dissolves like" interaction of the benzene ring. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used to elucidate the adsorbing/sensing mechanism of HKUST-1 to p-xylene, where p-xylene adsorbing induced blue-shift phenomenon is observed that confirms the sensing mechanism. Our study also indicates that the sensor shows good selectivity to various kinds of common interfering gases. And the long-term repeatability and stability of the sensing material are also approved for the usage/storage period of two months. This research approves that the MOF materials exhibit potential usages for high performance chemical sensors applications.

  11. Multi-solution processes of small molecule for flexible white organic light-emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Yu-Sheng, E-mail: ystsai@nfu.edu.tw [Institute of Electro-optical and Materials Science, National Formosa University, Yunlin 63201, Taiwan, ROC (China); Chittawanij, Apisit; Hong, Lin-Ann; Guo, Siou-Wei [Institute of Electro-optical and Materials Science, National Formosa University, Yunlin 63201, Taiwan, ROC (China); Wang, Ching-Chiun [Department of Solid State Lighting Technology, Mechanical and Systems Research Laboratories, Industrial Technology Research Institute, Hsinchu 31040, Taiwan, ROC (China); Juang, Fuh-Shyang [Institute of Electro-optical and Materials Science, National Formosa University, Yunlin 63201, Taiwan, ROC (China); Lai, Shih-Hsiang [Department of Solid State Lighting Technology, Mechanical and Systems Research Laboratories, Industrial Technology Research Institute, Hsinchu 31040, Taiwan, ROC (China); Lin, Yang-Ching [Institute of Electro-optical and Materials Science, National Formosa University, Yunlin 63201, Taiwan, ROC (China)

    2016-04-01

    Most small molecule organic light emitting diode (SM-OLED) device structures are made in one layer using solution-based processing because the solution is usually a high dissolvent material that easily attacks the layer below it. We demonstrate a simple and reliable stamping technique for fabricating multi-solution process flexible white SM-OLEDs. The structure is anode/spin-hole injection layer/spin-emitting layer/stamping-electron transport layer/cathode. Poly(di-methyl silane) (PDMS) stamp is used for transferring electron transport layer. An intermediate ultraviolet-ozone surface treatment is introduced to temporarily modify the PDMS stamp surface. Then, the solution-based electron transport layer film can therefore be uniformly formed on top of the PDMS surface. After that the electron transport layer film on the PDMS stamp is transfer-printed onto the emitting layer with suitable heating and pressing. A solution-based processing is successfully established to efficiently fabricate flexible white SM-OLEDs. The SM-OLEDs were obtained at the current density of 20 mA/cm{sup 2}, luminance of 1062 cd/m{sup 2}, current efficiency of 5.57 cd/A, and Commission internationale de l'éclairage coordinate of (0.32, 0.35). - Highlights: • All solution-processed small molecule materials (emitting layer, electron transport layer). • Poly(di-methylsilane) (PDMS) stamp is subsequently used for stamping transfer. • The flexible white SM-OLEDs are based on solution-processes with a low-cost method.

  12. Synthesis of complex organic molecules in simulated methane rich astrophysical ices

    Science.gov (United States)

    Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon; Huels, Michael A.

    2017-12-01

    It has been proposed that organic molecules required for life on earth may be formed by the radiation processing of molecular ices in space environments, e.g., within our solar system. Such processes can be studied in the laboratory with surface science analytical techniques and by using low-energy electron (LEE) irradiation to simulate the effects of the secondary electrons that are generated in great abundance whenever ionizing radiation interacts with matter. Here we present new measurements of 70 eV LEE irradiation of multilayer films of CH4, 18O2, and CH4/18O2 mixtures (3:1 ratio) at 22 K. The electron stimulated desorption (ESD) yields of cations and anions have been recorded as a function of electron fluence. At low fluence, the prompt desorption of more massive multi-carbon or C—O containing cationic fragments agrees with our earlier measurements. However, new anion ESD signals of C2-, C2H-, and C2H2- from CH4/18O2 mixtures increase with fluence, indicating the gradual synthesis (and subsequent electron-induced fragmentation) of new, more complex species containing several C and possibly O atoms. Comparisons between the temperature programed desorption (TPD) mass spectra of irradiated and unirradiated films show the electron-induced formation of new chemical species, the identities of which are confirmed by reference to the NIST database of electron impact mass spectra and by TPD measurements of films composed of the proposed products. New species observed in the TPD of irradiated mixture films include C3H6, C2H5OH, and C2H6. Furthermore, X-ray photoelectron spectroscopy of irradiated films confirms the formation of C—O, C=O, and O=C—O— bonds of newly formed molecules. Our experiments support the view that secondary LEEs produced by ionizing radiation drive the chemistry in irradiated ices in space, irrespective of the radiation type.

  13. Multi-solution processes of small molecule for flexible white organic light-emitting diodes

    International Nuclear Information System (INIS)

    Tsai, Yu-Sheng; Chittawanij, Apisit; Hong, Lin-Ann; Guo, Siou-Wei; Wang, Ching-Chiun; Juang, Fuh-Shyang; Lai, Shih-Hsiang; Lin, Yang-Ching

    2016-01-01

    Most small molecule organic light emitting diode (SM-OLED) device structures are made in one layer using solution-based processing because the solution is usually a high dissolvent material that easily attacks the layer below it. We demonstrate a simple and reliable stamping technique for fabricating multi-solution process flexible white SM-OLEDs. The structure is anode/spin-hole injection layer/spin-emitting layer/stamping-electron transport layer/cathode. Poly(di-methyl silane) (PDMS) stamp is used for transferring electron transport layer. An intermediate ultraviolet-ozone surface treatment is introduced to temporarily modify the PDMS stamp surface. Then, the solution-based electron transport layer film can therefore be uniformly formed on top of the PDMS surface. After that the electron transport layer film on the PDMS stamp is transfer-printed onto the emitting layer with suitable heating and pressing. A solution-based processing is successfully established to efficiently fabricate flexible white SM-OLEDs. The SM-OLEDs were obtained at the current density of 20 mA/cm 2 , luminance of 1062 cd/m 2 , current efficiency of 5.57 cd/A, and Commission internationale de l'éclairage coordinate of (0.32, 0.35). - Highlights: • All solution-processed small molecule materials (emitting layer, electron transport layer). • Poly(di-methylsilane) (PDMS) stamp is subsequently used for stamping transfer. • The flexible white SM-OLEDs are based on solution-processes with a low-cost method.

  14. In situ patterning of organic molecules in aqueous solutions using an inverted electron-beam lithography system

    Science.gov (United States)

    Miyazako, Hiroki; Ishihara, Kazuhiko; Mabuchi, Kunihiko; Hoshino, Takayuki

    2016-06-01

    A method for in situ controlling the detachment and deposition of organic molecules such as sugars and biocompatible polymers in aqueous solutions by electron-beam (EB) scan is proposed and evaluated. It was demonstrated that EB irradiation could detach 2-methacryloyloxyethyl phosphorylcholine (MPC) polymers from a silicon nitride membrane. Moreover, organic molecules such as cationic polymers and sugars could be deposited on the membrane by EB irradiation. Spatial distributions of scattered electrons were numerically simulated, and acceleration voltage dependences of the detachment and deposition phenomena were experimentally measured. The simulations and experimental results suggest that the detachment of MPC polymers is mainly due to electrical effects of primary electrons, and that the deposition of organic molecules is mainly due to chemical reactions induced by primary electrons. In view of these findings, the proposed method can be applied to in situ and nanoscale patterning such as the fabrication of cell scaffolds.

  15. Modeling the Emission Spectra of Organic Molecules: A Competition between Franck-Condon and Nuclear Ensemble Methods.

    Science.gov (United States)

    de Sousa, Leonardo Evaristo; Ribeiro, Luiz Antonio; Fonseca, Antonio Luciano de Almeida; da Silva Filho, Demétrio Antonio

    2016-07-14

    The emission spectra of flexible and rigid organic molecules are theoretically investigated in the framework of the Franck-Condon (FC) and nuclear ensemble (NE) approaches, both of which rely on results from density functional theory but differ in the way vibrational contributions are taken into account. Our findings show that the emission spectra obtained using the NE approach are in better agreement with experiment than the ones produced by FC calculations considering both rigid and flexible molecules. Surprisingly, the description of a suitable balance between the vibronic progression and the emission spectra envelope shows dependency on the initial sampling for the NE calculations which must be judiciously selected. Our results intend to provide guidance for a better theoretical description of light emission properties of organic molecules with applications in organic electronic devices.

  16. FRET structure with non-radiative acceptor provided by dye-linker-glass surface complex and single-molecule photodynamics by TIRFM-polarized imaging

    International Nuclear Information System (INIS)

    Tani, Toshiro; Mashimo, Kei; Suzuki, Tetsu; Horiuchi, Hiromi; Oda, Masaru

    2008-01-01

    We present our recent study of microscopic single-molecule imaging on the artificial complex of tetramethylrhodamine linked with a propyl chain onto silica glass surface, i.e. an asymmetric fluorescence resonance energy transfer (FRET) structure with non-radiative acceptor. In the synthesis of the complex, we used a mixture of two kinds of isomers to introduce rather small photodynamic difference among them. This isomeric structure change will provide more or less a distinctive photophysical change in e.g. non-radiative relaxation rate. Our recent observation at room temperatures, so far, shows that such contributions can be discriminated in the histograms of the fluorescent spot intensities; broad but distinctive multi-components appear. To identify the isomeric difference as a cause of structures, some configurational assumptions are necessary. One such basic prerequisite is that the transition dipoles of the chromophores should be oriented almost parallel to the glass surface. In order to make clear the modeling, we also provide preliminary experiments on the polarization dependence of the imaging under rotating polarization in epi-illumination

  17. Enhancing the intestinal absorption of molecules containing the polar guanidino functionality: a double-targeted prodrug approach.

    Science.gov (United States)

    Sun, Jing; Dahan, Arik; Amidon, Gordon L

    2010-01-28

    A prodrug strategy was applied to guanidino-containing analogues to increase oral absorption via hPEPT1 and hVACVase. l-Valine, l-isoleucine, and l-phenylalanine esters of [3-(hydroxymethyl)phenyl]guanidine (3-HPG) were synthesized and evaluated for transport and activation. In HeLa/hPEPT1 cells, Val-3-HPG and Ile-3-HPG exhibited high affinity to hPEPT1 (IC(50): 0.65 and 0.63 mM, respectively), and all three l-amino acid esters showed higher uptake (2.6- to 9-fold) than the parent compound 3-HPG. Val-3-HPG and Ile-3-HPG demonstrated remarkable Caco-2 permeability enhancement, and Val-3-HPG exhibited comparable permeability to valacyclovir. In rat perfusion studies, Val-3-HPG and Ile-3-HPG permeabilities were significantly higher than 3-HPG and exceeded/matched the high-permeability standard metoprolol, respectively. All the l-amino acid 3-HPG esters were effectively activated in HeLa and Caco-2 cell homogenates and were found to be good substrates of hVACVase (k(cat)/K(m) in mM(-1) x s(-1): Val-3-HPG, 3370; Ile-3-HPG, 1580; Phe-3-HPG, 1660). In conclusion, a prodrug strategy is effective at increasing the intestinal permeability of polar guanidino analogues via targeting hPEPT1 for transport and hVACVase for activation.

  18. Identification of Small-Molecule Inhibitors of the HuR/RNA Interaction Using a Fluorescence Polarization Screening Assay Followed by NMR Validation.

    Directory of Open Access Journals (Sweden)

    Zhonghua Wang

    Full Text Available The human antigen R (HuR stabilizes many mRNAs of proto-oncogene, transcription factors, cytokines and growth factors by recognizing AU-rich elements (AREs presented in their 3' or 5' untranslated region (UTR. Multiple lines of experimental evidence suggest that this process plays a key role in cancer development. Thus, destabilizing HuR/RNA interaction by small molecules presents an opportunity for cancer treatment/prevention. Here we present an integrated approach to identify inhibitors of HuR/RNA interaction using a combination of fluorescence-based and NMR-based high throughput screening (HTS. The HTS assay with fluorescence polarization readout and Z'-score of 0.8 was used to perform a screen of the NCI diversity set V library in a 384 well plate format. An NMR-based assay with saturation transfer difference (STD detection was used for hits validation. Protein NMR spectroscopy was used to demonstrate that some hit compounds disrupt formation of HuR oligomer, whereas others block RNA binding. Thus, our integrated high throughput approach provides a new avenue for identification of small molecules targeting HuR/RNA interaction.

  19. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography.

    Science.gov (United States)

    Lin, Shu-Ling; Wu, Yu-Ru; Lin, Tzuen-Yeuan; Fuh, Ming-Ren

    2015-04-29

    In this study, methacrylic acid (MAA) was incorporated with alkyl methacrylates to increase the hydrophilicity of the synthesized ethylene dimethacrylate-based (EDMA-based) monoliths for separating polar small molecules by capillary LC analysis. Different alkyl methacrylate-MAA ratios were investigated to prepare a series of 30% alkyl methacrylate-MAA-EDMA monoliths in fused-silica capillaries (250-μm i.d.). The porosity, permeability, and column efficiency of the synthesized MAA-incorporated monolithic columns were characterized. A mixture of phenol derivatives is employed to evaluate the applicability of using the prepared monolithic columns for separating small molecules. Fast separation of six phenol derivatives was achieved in 5 min with gradient elution using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. In addition, the effect of acetonitrile content in mobile phase on retention factor and plate height as well as the plate height-flow velocity curves were also investigated to further examine the performance of the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Moreover, the applicability of prepared polymer-based monolithic column for potential food safety applications was also demonstrated by analyzing five aflatoxins and three phenicol antibiotics using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Theoretical study on the ground state of the polar alkali-metal-barium molecules: Potential energy curve and permanent dipole moment

    International Nuclear Information System (INIS)

    Gou, Dezhi; Kuang, Xiaoyu; Gao, Yufeng; Huo, Dongming

    2015-01-01

    In this paper, we systematically investigate the electronic structure for the 2 Σ + ground state of the polar alkali-metal-alkaline-earth-metal molecules BaAlk (Alk = Li, Na, K, Rb, and Cs). Potential energy curves and permanent dipole moments (PDMs) are determined using power quantum chemistry complete active space self-consistent field and multi-reference configuration interaction methods. Basic spectroscopic constants are derived from ro-vibrational bound state calculation. From the calculations, it is shown that BaK, BaRb, and BaCs molecules have moderate values of PDM at the equilibrium bond distance (BaK:1.62 D, BaRb:3.32 D, and BaCs:4.02 D). Besides, the equilibrium bond length (4.93 Å and 5.19 Å) and dissociation energy (0.1825 eV and 0.1817 eV) for the BaRb and BaCs are also obtained

  1. The use of charge extraction by linearly increasing voltage in polar organic light-emitting diodes

    Science.gov (United States)

    Züfle, Simon; Altazin, Stéphane; Hofmann, Alexander; Jäger, Lars; Neukom, Martin T.; Schmidt, Tobias D.; Brütting, Wolfgang; Ruhstaller, Beat

    2017-05-01

    We demonstrate the application of the CELIV (charge carrier extraction by linearly increasing voltage) technique to bilayer organic light-emitting devices (OLEDs) in order to selectively determine the hole mobility in N,N0-bis(1-naphthyl)-N,N0-diphenyl-1,10-biphenyl-4,40-diamine (α-NPD). In the CELIV technique, mobile charges in the active layer are extracted by applying a negative voltage ramp, leading to a peak superimposed to the measured displacement current whose temporal position is related to the charge carrier mobility. In fully operating devices, however, bipolar carrier transport and recombination complicate the analysis of CELIV transients as well as the assignment of the extracted mobility value to one charge carrier species. This has motivated a new approach of fabricating dedicated metal-insulator-semiconductor (MIS) devices, where the extraction current contains signatures of only one charge carrier type. In this work, we show that the MIS-CELIV concept can be employed in bilayer polar OLEDs as well, which are easy to fabricate using most common electron transport layers (ETLs), like Tris-(8-hydroxyquinoline)aluminum (Alq3). Due to the macroscopic polarization of the ETL, holes are already injected into the hole transport layer below the built-in voltage and accumulate at the internal interface with the ETL. This way, by a standard CELIV experiment only holes will be extracted, allowing us to determine their mobility. The approach can be established as a powerful way of selectively measuring charge mobilities in new materials in a standard device configuration.

  2. Permeation of protons, potassium ions, and small polar molecules through phospholipid bilayers as a function of membrane thickness

    Science.gov (United States)

    Paula, S.; Volkov, A. G.; Van Hoek, A. N.; Haines, T. H.; Deamer, D. W.

    1996-01-01

    Two mechanisms have been proposed to account for solute permeation of lipid bilayers. Partitioning into the hydrophobic phase of the bilayer, followed by diffusion, is accepted by many for the permeation of water and other small neutral solutes, but transient pores have also been proposed to account for both water and ionic solute permeation. These two mechanisms make distinctively different predictions about the permeability coefficient as a function of bilayer thickness. Whereas the solubility-diffusion mechanism predicts only a modest variation related to bilayer thickness, the pore model predicts an exponential relationship. To test these models, we measured the permeability of phospholipid bilayers to protons, potassium ions, water, urea, and glycerol. Bilayers were prepared as liposomes, and thickness was varied systematically by using unsaturated lipids with chain lengths ranging from 14 to 24 carbon atoms. The permeability coefficient of water and neutral polar solutes displayed a modest dependence on bilayer thickness, with an approximately linear fivefold decrease as the carbon number varied from 14 to 24 atoms. In contrast, the permeability to protons and potassium ions decreased sharply by two orders of magnitude between 14 and 18 carbon atoms, and leveled off, when the chain length was further extended to 24 carbon atoms. The results for water and the neutral permeating solutes are best explained by the solubility-diffusion mechanism. The results for protons and potassium ions in shorter-chain lipids are consistent with the transient pore model, but better fit the theoretical line predicted by the solubility-diffusion model at longer chain lengths.

  3. Photoluminescence polarization anisotropy for studying long-range structural ordering within semiconductor multi-atomic alloys and organic crystals

    Energy Technology Data Exchange (ETDEWEB)

    Prutskij, T.; Percino, J. [Instituto de Ciencias, BUAP, Privada 17 Norte, No 3417, col. San Miguel Huyeotlipan, 72050, Puebla, Pue. (Mexico); Orlova, T. [Department of Chemical and Biochemical Engineering, University of Notre Dame, Notre Dame, IN (United States); Vavilova, L. [Ioffe Physical-Technical Institute, 26 Polytekhnicheskaya, St Petersburg 194021, Russian Federation (Russian Federation)

    2013-12-04

    Long-range structural ordering within multi-component semiconductor alloys and organic crystals leads to significant optical anisotropy and, in particular, to anisotropy of the photoluminescence (PL) emission. The PL emission of ternary and quaternary semiconductor alloys is polarized if there is some amount of the atomic ordering within the crystal structure. We analyze the polarization of the PL emission from the quaternary GaInAsP semiconductor alloy grown by Liquid Phase Epitaxy (LPE) and conclude that it could be caused by low degree atomic ordering within the crystal structure together with the thermal biaxial strain due to difference between the thermal expansion coefficients of the layer and the substrate. We also study the state of polarization of the PL from organic crystals in order to identify different features of the crystal PL spectrum.

  4. Design and Synthesis of Organic Small Molecules for Industrial and Biomedical Technology Nanomaterial Augmentation

    Science.gov (United States)

    Chapman, James Vincent, III

    Organic chemistry used to augment nanoparticles and nanotubes, as well as more traditional materials, is a subject of great interest across multiple fields of applied chemistry. Herein we present an example of both nanoparticle and nanotube augmentation with organic small molecules to achieve an enhanced or otherwise infeasible application. The first chapter discusses the modification of two different types of Microbial Fuel Cell (MFC) anode brush bristle fibers with positive surface charge increasing moieties to increase quantitative bacterial adhesion to these bristle fibers, and therefore overall MFC electrogenicity. Type-1 brush bristles, comprised of polyacrylonitrile, were modified via the electrostatic attachment of 1-pyrenemethylamine hydrochloride. Type-2 brush bristles, comprised of nylon, were modified via the covalent attachment of ethylenediamine. Both modified brush types were immersed in an E. Coli broth for 1 hour, stained with SYTORTM 9 Green Fluorescent Nucleic Acid Stain from ThermoFisher Scientific (SYTO-9), and examined under a Biotek Citation 3 fluorescent microscope to visually assess differences in bacterial adherence. In both trials, a clear increase in amount of bacterial adhesion to the modified bristles was observed over that of the control. The second chapter demonstrates a potential biomedical technology application wherein a polymerizable carbocyanine-type dye was synthesized and bound to a chitosan backbone to produce a water-soluble photothermal nanoparticle. Laser stimulation of both free and NP-conjugated aqueous solutions of the carbocyanine dye with Near-Infrared (NIR) Spectrum Radiation showed an increase in temperature directly correlated with the concentration of the dye which was more pronounced in the free particle solutions.

  5. Efficient small-molecule organic solar cells incorporating a doped buffer layer

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Dei-Wei [Department of aviation and Communication Electronics, Air Force Institute of Technology, Kaohsiung 820, Taiwan (China); Chen, Kan-Lin [Department of Electronic Engineering, Fortune Institute of Technology, Kaohsiung 831, Taiwan (China); Huang, Chien-Jung, E-mail: chien@nuk.edu.tw [Department of Applied Physics, National University of Kaohsiung, Nanzih, Kaohsiung 811, Taiwan (China); Tsao, Yao-Jen [Department of Applied Physics, National University of Kaohsiung, Nanzih, Kaohsiung 811, Taiwan (China); Chen, Wen-Ray; Meen, Teen-Hang [Department of Electronic Engineering, National Formosa University, Hu-Wei, Yunlin 632, Taiwan (China)

    2013-06-01

    Small-molecule organic solar cells (OSCs) with an optimized structure of indium tin oxide/poly (3,4-ethylenedioxythioxythiophene):poly(styrenesulfonate)/copper phthalocyanine (CuPc) (10 nm)/CuPc: fullerene (C{sub 60}) mixed (20 nm)/C{sub 60} (20 nm)/4,7-diphenyl-1,10-phenanthroline (BPhen) (5 nm)/Ag were fabricated. In this study, the cesium carbonate-doped BPhen (Cs{sub 2}CO{sub 3}:BPhen) was adopted as the buffer layer to enhance the efficiency of the OSCs. The photovoltaic parameters of the OSCs, such as the short-circuit current density and fill factor, depend on the doping concentration of Cs{sub 2}CO{sub 3} in the BPhen layer. The cell with a Cs{sub 2}CO{sub 3}:BPhen (1:4) cathode buffer layer exhibits a power conversion efficiency (PCE) of 3.51%, compared to 3.37% for the device with the pristine BPhen layer. The enhancement of PCE was attributed to the energy-level alignment between the C{sub 60} layer and the Cs{sub 2}CO{sub 3}:BPhen layer. In addition, the characterization measured using atomic force microscopy shows that the Cs{sub 2}CO{sub 3}:BPhen layers have smoother surfaces. - Highlight: • Cs2CO3-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) cathode buffer layer. • Cs2CO3:BPhen layer with different ratios affects organic solar cells performance. • Cell with 1:4 (Cs2CO3:BPhen) ratio shows 3.51% power conversion efficiency.

  6. Electrochemical Reduction of Carbon Dioxide on Pyrite as a Pathway for Abiogenic Formation of Organic Molecules

    Science.gov (United States)

    Vladimirov, M. G.; Ryzhkov, Y. F.; Alekseev, V. A.; Bogdanovskaya, V. A.; Otroshchenko, V. A.; Kritsky, M. S.

    2004-08-01

    A wide spectrum of electrode potentials of minerals that compose sulfide ores enables the latter, when in contact with hydrothermal solutions, to form galvanic pairs with cathode potentials sufficient for electrochemical reduction of CO2. The experiments performed demonstrated the increase of cathode current on the rotating pyrite disc electrode in a range of potentials more negative than -800 mV in presence of CO2. In high-pressure experiments performed in a specially designed electrochemical cell equipped with a pyrite cathode and placed into autoclave, accumulation of formate was demonstrated after 24 hr passing of CO2 (50 atm, room temperature) through electrolyte solution. The formation of this product started on increasing the cathode potential to -800 mV (with respect to saturated silver chloride electrode). The yield grew exponentially upon cathode potential increase up to -1200 mV. The maximum current efficiency (0.12%) was registered at cathode potentials of about -1000 mV. No formate production was registered under normal atmospheric pressure and in the absence of imposed cathode potential. Neither in experiments, nor in control was formaldehyde found. It is proposed that the electrochemical reduction of CO2 takes part in the formation of organic molecules in hydrothermal solutions accompanying sulfide ore deposits and in `black smokers' on the ocean floor.

  7. Improved Reliability of Small Molecule Organic Solar Cells by Double Anode Buffer Layers

    Directory of Open Access Journals (Sweden)

    Pao-Hsun Huang

    2014-01-01

    Full Text Available An optimized hybrid planar heterojunction (PHJ of small molecule organic solar cells (SM-OSCs based on copper phthalocyanine (CuPc as donor and fullerene (C60 as acceptor was fabricated, which obviously enhanced the performance of device by sequentially using both MoO3 and pentacene as double anode buffer layers (ABL, also known as hole extraction layer (HEL. A series of the vacuum-deposited ABL, acting as an electron and exciton blocking layer, were examined for their characteristics in SM-OSCs. The performance and reliability were compared between conventional ITO/ABL/CuPc/C60/BCP/Ag cells and the new ITO/double ABL/CuPc/C60/BCP/Ag cells. The effect on the electrical properties of these materials was also investigated to obtain the optimal thickness of ABL. The comparison shows that the modified cell has an enhanced reliability compared to traditional cells. The improvement of lifetime was attributed to the idea of double layers to prevent humidity and oxygen from diffusing into the active layer. We demonstrated that the interfacial extraction layers are necessary to avoid degradation of device. That is to say, in normal temperature and pressure, a new avenue for the device within double buffer layers has exhibited the highest values of open circuit voltage (Voc, fill factor (FF, and lifetime in this work compared to monolayer of ABL.

  8. Chemically modified polymeric resins for separation of cations, organic acids, and small polar moleculea by high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Morris, John B. [Iowa State Univ., Ames, IA (United States)

    1993-07-01

    This thesis is divided into 4 parts: a review, ion chromatography of metal cations on carboxylic resins, separation of hydrophilic organic acids and small polar compounds on macroporous resin columns, and use of eluent modifiers for liquid chromatographic separation of carboxylic acids using conductivity detection.

  9. NMR diffusion and relaxation measurements of organic molecules adsorbed in porous media

    International Nuclear Information System (INIS)

    Gjerdaaker, Lars

    2002-01-01

    The work in this thesis can be divided into two parts. The first part is focused on dynamic investigations of plastic crystals, both in bulk phases but also confined in porous materials (paper 1-3). This part was done together with professor Liudvikas Kimtys, Vilnius, Lithuania. The second part, with emphasis on diffusion, employed PFG NMR to measure the true intra-crystalline diffusivity, including development of a new pulse sequence with shorter effective diffusion time. This work was performed in collaboration with Dr. Geir H. Soerland, Trondheim, Norway and has resulted in three papers (paper 4-6). Paper 1-3: In these papers the dynamics of three organic compounds confined within mesoporous silica have been studied, and the results are discussed with reference to the bulk material. The three investigated compounds form disordered (plastic) phases of high symmetry on solidification (solid I). Thus, bulk cyclohexane exhibits a disordered phase between the solid-solid phase transition at 186 K and the melting point at 280 K. X-ray diffraction measurements have shown that solid I is face-centred cubic (Z=4, a=0.861 nm at 195 K), while the ordered solid II is monoclinic. Tert-butyl cyanide exhibits a plastic phase between the solid-solid transition point at 233 K and the melting point at 292 K. Neutron scattering techniques have established that solid I is tetragonal (Z=2, a=b=0.683 nm, c=0.674 nm, beta=90 deg at 234 K), while solid II is monoclinic. Finally, the disordered phase of pivalic acid melts at 310 K and undergoes a solid-solid phase transition at 280 K. The disordered phase is face-centred cubic, (Z=4, a=0.887 nm), while the low temperature phase (solid II) is triclinic. Paper 4-6; If one is aiming to measure true intra-crystallite diffusivities in porous media the distance travelled by the molecules during the pulse must be shorter than the size of the crystallite. The length of the diffusion time is therefore important. Working with heterogeneous media

  10. Life in extreme environments: single molecule force spectroscopy as a tool to explore proteins from extremophilic organisms.

    Science.gov (United States)

    Tych, Katarzyna M; Hoffmann, Toni; Batchelor, Matthew; Hughes, Megan L; Kendrick, Katherine E; Walsh, Danielle L; Wilson, Michael; Brockwell, David J; Dougan, Lorna

    2015-04-01

    Extremophiles are organisms which survive and thrive in extreme environments. The proteins from extremophilic single-celled organisms have received considerable attention as they are structurally stable and functionally active under extreme physical and chemical conditions. In this short article, we provide an introduction to extremophiles, the structural adaptations of proteins from extremophilic organisms and the exploitation of these proteins in industrial applications. We provide a review of recent developments which have utilized single molecule force spectroscopy to mechanically manipulate proteins from extremophilic organisms and the information which has been gained about their stability, flexibility and underlying energy landscapes.

  11. Major Histocompatibility Complex Class I Chain-Related A (MICA) Molecules: Relevance in Solid Organ Transplantation

    Science.gov (United States)

    Baranwal, Ajay Kumar; Mehra, Narinder K.

    2017-01-01

    An ever growing number of reports on graft rejection and/or failure even with good HLA matches have highlighted an important role of non-HLA antigens in influencing allograft immunity. The list of non-HLA antigens that have been implicated in graft rejection in different types of organ transplantation has already grown long. Of these, the Major Histocompatibility Complex class I chain-related molecule A (MICA) is one of the most polymorphic and extensively studied non-HLA antigenic targets especially in the kidney transplantation. Humoral response to MICA antigens has repeatedly been associated with lower graft survival and an increased risk of acute and chronic rejection following kidney and liver transplantation with few studies showing conflicting results. Although there are clear indications of MICA antibodies being associated with adverse graft outcome, a definitive consensus on this relationship has not been arrived yet. Furthermore, only a few studies have dealt with the impact of MICA donor-specific antibodies as compared to those that are not donor specific on graft outcome. In addition to the membrane bound form, a soluble isoform of MICA (sMICA), which has the potential to engage the natural killer cell-activating receptor NKG2D resulting in endocytosis and degradation of receptor–ligand interaction complex leading to suppression of NKG2D-mediated host innate immunity, has been a subject of intense discussion. Most studies on sMICA have been directed toward understanding their influence on tumor growth, with limited literature focusing its role in transplant biology. Furthermore, a unique dimorphism (methionine to valine) at position 129 in the α2 domain categorizes MICA alleles into strong (MICA-129 met) and weak (MICA-129 val) binders of NKG2D receptor depending on whether they have methionine or valine at this position. Although the implications of MICA 129 dimorphism have been highlighted in hematopoietic stem cell transplantation, its role in

  12. Structure-Property Relationships of Small Organic Molecules as a Prelude to the Teaching of Polymer Science

    Science.gov (United States)

    Wnek, Gary E.

    2017-01-01

    Small organic molecules offer a rich opportunity to discuss the interplay of chemical structure with properties such as the melting point and phenomena such as glass formation and can form the basis of fundamental considerations of structure-property relationships in macromolecules. Of particular importance are thermal transitions, specifically…

  13. Introducing Bond-Line Organic Structures in High School Biology: An Activity that Incorporates Pleasant-Smelling Molecules

    Science.gov (United States)

    Rios, Andro C.; French, Gerald

    2011-01-01

    Chemical education occurs in settings other than just the chemistry classroom. High school biology courses are frequently where students are introduced to organic molecules and their importance to cellular chemistry. However, structural representations are often intimidating because students have not been introduced to the language. As part of a…

  14. Evolution of complex organic molecules in hot molecular cores. Synthetic spectra at (sub-)mm wavebands

    Science.gov (United States)

    Choudhury, R.; Schilke, P.; Stéphan, G.; Bergin, E.; Möller, T.; Schmiedeke, A.; Zernickel, A.

    2015-03-01

    Context. Hot molecular cores (HMCs) are intermediate stages of high-mass star formation and are also known for their rich chemical reservoirs and emission line spectra at (sub-)mm wavebands. Complex organic molecules (COMs) such as methanol (CH3OH), ethanol (C2H5OH), dimethyl ether (CH3OCH3), and methyl formate (HCOOCH3) produce most of these observed lines. The observed spectral feature of HMCs such as total number of emission lines and associated line intensities are also found to vary with evolutionary stages. Aims: We aim to investigate the spectral evolution of these COMs to explore the initial evolutionary stages of high-mass star formation including HMCs. Methods: We developed various 3D models for HMCs guided by the evolutionary scenarios proposed by recent empirical and modeling studies. We then investigated the spatio-temporal variation of temperature and molecular abundances in HMCs by consistently coupling gas-grain chemical evolution with radiative transfer calculations. We explored the effects of varying physical conditions on molecular abundances including density distribution and luminosity evolution of the central protostar(s) among other parameters. Finally, we simulated the synthetic spectra for these models at different evolutionary timescales to compare with observations. Results: Temperature has a profound effect on the formation of COMs through the depletion and diffusion on grain surface to desorption and further gas-phase processing. The time-dependent temperature structure of the hot core models provides a realistic framework for investigating the spatial variation of ice mantle evaporation as a function of evolutionary timescales. We find that a slightly higher value (15 K) than the canonical dark cloud temperature (10 K) provides a more productive environment for COM formation on grain surface. With increasing protostellar luminosity, the water ice evaporation font (~100 K) expands and the spatial distribution of gas phase abundances of

  15. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

    Science.gov (United States)

    Poch, Olivier; Dequaire, Tristan; Stalport, Fabien; Jaber, Maguy; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-04-01

    The search for organic carbon-containing molecules at the surface of Mars, as clues of past habitability or remnants of life, is a major scientific goal for Mars exploration. Several lines of evidence, including the detection of phyllosilicates, suggest that early Mars offered favorable conditions for long-term sustaining of water. As a consequence, we can assume that in those days, endogenous chemical processes, or even primitive life, may have produced organic matter on Mars. Moreover, exogenous delivery from small bodies or dust particles is likely to have brought fresh organic molecules to the surface of Mars up today. Organic matter is therefore expected to be present at the surface/subsurface of the planet. But the current environmental conditions at the surface - UV radiation, oxidants and energetic particles - generate physico-chemical processes that may affect organic molecules. On the other hand, on Earth, phyllosilicates are known to accumulate and preserve organic matter. But are phyllosilicates efficient at preserving organic molecules under the current environmental conditions at the surface of Mars? We have monitored the qualitative and quantitative evolutions of glycine, urea and adenine interacting with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated Martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) in a laboratory simulation setup. We have tested organic-rich samples which may be representative of the evaporation of a warm little pond of liquid water having concentrated organics on Mars. For each molecule, we have observed how the nontronite influences the quantum efficiency of its photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine: their efficiencies of photodecomposition are reduced by a factor

  16. Larger spontaneous polarization ferroelectric inorganic-organic hybrids: [PbI3](infinity) chains directed organic cations aggregation to Kagomé-shaped tubular architecture.

    Science.gov (United States)

    Zhao, Hai-Rong; Li, Dong-Ping; Ren, Xiao-Ming; Song, You; Jin, Wan-Qin

    2010-01-13

    Four isostructural inorganic-organic hybrid ferroelectric compounds, assembled from achiral 3-R-benzylidene-1-aminopyridiniums (R = NO(2), Br, Cl, or F for 1-4, respectively) and [PbI(3)](-) anions with the chiral Kagomé-shaped tubular aggregating architecture, show larger spontaneous polarizations.

  17. Terminal moiety-driven electrical performance of asymmetric small-molecule-based organic solar cells

    DEFF Research Database (Denmark)

    Huang, Jianhua; Zhang, Shanlin; jiang, Bo

    2016-01-01

    With respect to the successes from symmetric small molecules, asymmetric ones have recently emerged as an alternative choice. In this paper, we present the synthesis and photovoltaic properties of four asymmetric small molecule donors. The benzo[1,2-b:4,5-b']dithiophene (BDT) end in the asymmetri...

  18. Adsorption configuration effects on the surface diffusion of large organic molecules

    DEFF Research Database (Denmark)

    Sato, F.; Legoas, S.B.; Hummelink, F.

    2010-01-01

    results show that it has its physical basis on the interplay of the molecular hydrogens and the Cu(110) atomic spacing, which is a direct consequence of the matching between molecule and surface dimensions. This information could be used to find new molecules capable of displaying lock-and-key behavior...

  19. Fossilized intact polar lipids of photosynthetic organisms in ancient subsurface sediments

    Science.gov (United States)

    Bauersachs, T.; Schouten, S.; Hopmans, E. C.; Sinninghe Damsté, J. S.

    2009-12-01

    In recent years, the idea of a rich microbial biosphere in the marine sea floor has been widely accepted. This so-called “deep biosphere” is estimated to contain ca. 50 % of Earth’s total prokaryotic biomass with the overall order of magnitude of microbial cells in the sea floor being the same as the biomass of all surface plant life (Whitman et al. 1998). Evidence for the existence of a deep biosphere comes, among others, from the analysis of intact polar lipids (IPLs). This approach presumes that IPLs almost instantaneously lose their polar head group after cell death and thus do not preserve on geological timescales. Consequently, IPLs in the subsurface should derive from in situ production and hence indicate the presence of living prokaryotic cells. For example, in various oceanic subsurface sediments archaeal IPLs have been found, suggesting that Archaea constitute a major fraction of the deep biosphere biomass (Lipp et al. 2008). In this study, we found IPLs of heterocystous cyanobacteria in a number of ancient and deeply buried sediments. Heterocystous cyanobacteria are strictly photoautotrophic organisms that are a common constituent of the phytoplankton community in many freshwater and brackish environments but are also encountered in the marine realm as endosymbionts of diatom species. Under nitrogen-depleted conditions, these organisms carry out nitrogen fixation in specialized cells, known as heterocysts. These cells contain a suite of heterocyst glycolipids (HGs) that have not been identified in any other organism and are thus unique biological markers for nitrogen-fixing heterocystous cyanobacteria. Using high performance liquid chromatography coupled to electrospray ionisation tandem mass spectrometry (HPLC/ESI-MS/MS), we detected HGs in Pleistocene and Pliocene Mediterranean sapropels buried up to 60 m below the seafloor. In addition, these HGs were also found in lacustrine deposits of the Oligocene Lake Enspel (35 Ma), the Eocene Lake Messel

  20. Monitoring of 45 pesticides in Lebanese surface water using Polar Organic Chemical Integrative Sampler (POCIS)

    Science.gov (United States)

    Aisha, Al Ashi; Hneine, Wael; Mokh, Samia; Devier, Marie-Hélène; Budzinski, Hélèn; Jaber, Farouk

    2017-09-01

    The aim of this study is to assess the dissolved concentration of 45 pesticides in the surface waters of the Lebanese Republic using Polar Organic Chemical Integrative Sampler "POCIS". All of the sampling sites are located in the major agricultural land areas in Lebanon. POCIS (n = 3) were deployed at Ibrahim River, Qaraoun Lake and Hasbani River for a duration of 14 days. The total concentration of pesticides ranged from not detected (nd) to 137.66 ng.L-1. Chlorpyrifos, DDE-pp, diazinon and Fenpropathrin were the most abundant compounds. Qaraoun Lake and Hasbani River were found to be more polluted than Ibrahim River, since they receive large amounts of waste water derived from nearby agricultural lands and they had the lowest dilution factor. The aqueous average concentration of the target compounds were estimated using sampling rates obtained from the literature. Comparison between Time Weighed Average concentrations "TWA" using POCIS and spot sampling is presented. Results showed that POCIS TWA concentrations are in agreement with spot sampling concentrations for Ibrahim and Hasbani Rivers. The toxicity of the major detected pesticides on three representative aquatic species ( Daphnia magna, Scenedesmus quadricauda and Oncorhynchus mykiss) is also reported.

  1. EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents.

    Science.gov (United States)

    Loos, Robert; Carvalho, Raquel; António, Diana C; Comero, Sara; Locoro, Giovanni; Tavazzi, Simona; Paracchini, Bruno; Ghiani, Michela; Lettieri, Teresa; Blaha, Ludek; Jarosova, Barbora; Voorspoels, Stefan; Servaes, Kelly; Haglund, Peter; Fick, Jerker; Lindberg, Richard H; Schwesig, David; Gawlik, Bernd M

    2013-11-01

    In the year 2010, effluents from 90 European wastewater treatment plants (WWTPs) were analyzed for 156 polar organic chemical contaminants. The analyses were complemented by effect-based monitoring approaches aiming at estrogenicity and dioxin-like toxicity analyzed by in vitro reporter gene bioassays, and yeast and diatom culture acute toxicity optical bioassays. Analyses of organic substances were performed by solid-phase extraction (SPE) or liquid-liquid extraction (LLE) followed by liquid chromatography tandem mass spectrometry (LC-MS-MS) or gas chromatography high-resolution mass spectrometry (GC-HRMS). Target microcontaminants were pharmaceuticals and personal care products (PPCPs), veterinary (antibiotic) drugs, perfluoroalkyl substances (PFASs), organophosphate ester flame retardants, pesticides (and some metabolites), industrial chemicals such as benzotriazoles (corrosion inhibitors), iodinated x-ray contrast agents, and gadolinium magnetic resonance imaging agents; in addition biological endpoints were measured. The obtained results show the presence of 125 substances (80% of the target compounds) in European wastewater effluents, in concentrations ranging from low nanograms to milligrams per liter. These results allow for an estimation to be made of a European median level for the chemicals investigated in WWTP effluents. The most relevant compounds in the effluent waters with the highest median concentration levels were the artificial sweeteners acesulfame and sucralose, benzotriazoles (corrosion inhibitors), several organophosphate ester flame retardants and plasticizers (e.g. tris(2-chloroisopropyl)phosphate; TCPP), pharmaceutical compounds such as carbamazepine, tramadol, telmisartan, venlafaxine, irbesartan, fluconazole, oxazepam, fexofenadine, diclofenac, citalopram, codeine, bisoprolol, eprosartan, the antibiotics trimethoprim, ciprofloxacine, sulfamethoxazole, and clindamycine, the insect repellent N,N'-diethyltoluamide (DEET), the pesticides

  2. Two-photon Photoemission of Organic Semiconductor Molecules on Ag(111)

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Aram [Univ. of California, Berkeley, CA (United States)

    2008-05-01

    Angle- and time-resolved two-photon photoemission (2PPE) was used to study systems of organic semiconductors on Ag(111). The 2PPE studies focused on electronic behavior specific to interfaces and ultrathin films. Electron time dynamics and band dispersions were characterized for ultrathin films of a prototypical n-type planar aromatic hydrocarbon, PTCDA, and representatives from a family of p-type oligothiophenes.In PTCDA, electronic behavior was correlated with film morphology and growth modes. Within a fewmonolayers of the interface, image potential states and a LUMO+1 state were detected. The degree to which the LUMO+1 state exhibited a band mass less than a free electron mass depended on the crystallinity of the layer. Similarly, image potential states were measured to have free electron-like effective masses on ordered surfaces, and the effective masses increased with disorder within the thin film. Electron lifetimes were correlated with film growth modes, such that the lifetimes of electrons excited into systems created by layer-by-layer, amorphous film growth increased by orders of magnitude by only a few monolayers from the surface. Conversely, the decay dynamics of electrons in Stranski-Krastanov systems were limited by interaction with the exposed wetting layer, which limited the barrier to decay back into the metal.Oligothiophenes including monothiophene, quaterthiophene, and sexithiophene were deposited on Ag(111), and their electronic energy levels and effective masses were studied as a function of oligothiophene length. The energy gap between HOMO and LUMO decreased with increasing chain length, but effective mass was found to depend on domains from high- or low-temperature growth conditions rather than chain length. In addition, the geometry of the molecule on the surface, e.g., tilted or planar, substantially affected the electronic structure.

  3. Formation and Atmosphere of Complex Organic Molecules of the HH 212 Protostellar Disk

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chin-Fei; Ho, Paul T. P.; Hirano, Naomi; Shang, Hsien [Academia Sinica Institute of Astronomy and Astrophysics, P.O. Box 23-141, Taipei 106, Taiwan (China); Li, Zhi-Yun [Astronomy Department, University of Virginia, Charlottesville, VA 22904 (United States); Zhang, Qizhou, E-mail: cflee@asiaa.sinica.edu.tw [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

    2017-07-01

    HH 212 is a nearby (400 pc) Class 0 protostellar system recently found to host a “hamburger”-shaped dusty disk with a radius of ∼60 au, deeply embedded in an infalling-rotating flattened envelope. We have spatially resolved this envelope-disk system with the Atacama Large Millimeter/submillimeter Array at up to ∼16 au (0.″04) resolution. The envelope is detected in HCO{sup +} J = 4–3 down to the dusty disk. Complex organic molecules (COMs) and doubly deuterated formaldehyde (D{sub 2}CO) are detected above and below the dusty disk within ∼40 au of the central protostar. The COMs are methanol (CH{sub 3}OH), deuterated methanol (CH{sub 2}DOH), methyl mercaptan (CH{sub 3}SH), and formamide (NH{sub 2}CHO, a prebiotic precursor). We have modeled the gas kinematics in HCO{sup +} and COMs and found a centrifugal barrier (CB) at a radius of ∼44 au, within which a Keplerian rotating disk is formed. This indicates that HCO{sup +} traces the infalling-rotating envelope down to the CB and COMs trace the atmosphere of a Keplerian rotating disk within the CB. The COMs are spatially resolved for the first time, both radially and vertically, in the atmosphere of a disk in the earliest, Class 0 phase of star formation. Our spatially resolved observations of COMs favor their formation in the disk rather than a rapidly infalling (warm) inner envelope. The abundances and spatial distributions of the COMs provide strong constraints on models of their formation and transport in low-mass star formation.

  4. Polar Organic Compounds in Surface Waters Collected Near Lead-Zinc Mine and Milling Operations in Missouri

    Science.gov (United States)

    Rostad, C. E.; Schmitt, C. J.; Schumacher, J. G.; Leiker, T. J.

    2007-12-01

    Surface-water samples were collected near a lead mine and mill tailings about 70 miles southwest of St. Louis, Missouri, during the summer of 2006. The purpose of this sampling was to determine if polar organic compounds were present that could be a cause of documented negative impacts to biota downstream. Water samples contained relatively high concentrations of dissolved organic carbon for surface waters (greater than 20 mg/L), but were colorless, which precluded naturally occurring aquatic humic or fulvic acids. Previous analysis indicated that samples were devoid of pesticides and acid/base/neutral extractable semi-volatile organic compounds, such as polycyclic aromatic hydrocarbons. After isolation by three different types of solid phase extraction, samples were analyzed by electrospray ionization/mass spectrometry. Polar organic compounds commonly used in the milling process, such as alkyl xanthates, were not found; however, xanthate degradation products were detected. Most of the polar organic compounds identified contained sulfonate groups, which are characteristic of some of the reagents used in the milling process. Sulfonate compounds may have low sorption onto soil or sediments and be mobile in the aqueous environment.

  5. Biotransformation model of neutral and weakly polar organic compounds in fish incorporating internal partitioning.

    Science.gov (United States)

    Kuo, Dave T F; Di Toro, Dominic M

    2013-08-01

    A model for whole-body in vivo biotransformation of neutral and weakly polar organic chemicals in fish is presented. It considers internal chemical partitioning and uses Abraham solvation parameters as reactivity descriptors. It assumes that only chemicals freely dissolved in the body fluid may bind with enzymes and subsequently undergo biotransformation reactions. Consequently, the whole-body biotransformation rate of a chemical is retarded by the extent of its distribution in different biological compartments. Using a randomly generated training set (n = 64), the biotransformation model is found to be: log (HLφfish ) = 2.2 (±0.3)B - 2.1 (±0.2)V - 0.6 (±0.3) (root mean square error of prediction [RMSE] = 0.71), where HL is the whole-body biotransformation half-life in days, φfish is the freely dissolved fraction in body fluid, and B and V are the chemical's H-bond acceptance capacity and molecular volume. Abraham-type linear free energy equations were also developed for lipid-water (Klipidw ) and protein-water (Kprotw ) partition coefficients needed for the computation of φfish from independent determinations. These were found to be 1) log Klipidw  = 0.77E - 1.10S - 0.47A - 3.52B + 3.37V + 0.84 (in Lwat /kglipid ; n = 248, RMSE = 0.57) and 2) log Kprotw  = 0.74E - 0.37S - 0.13A - 1.37B + 1.06V - 0.88 (in Lwat /kgprot ; n = 69, RMSE = 0.38), where E, S, and A quantify dispersive/polarization, dipolar, and H-bond-donating interactions, respectively. The biotransformation model performs well in the validation of HL (n = 424, RMSE = 0.71). The predicted rate constants do not exceed the transport limit due to circulatory flow. Furthermore, the model adequately captures variation in biotransformation rate between chemicals with varying log octanol-water partitioning coefficient, B, and V and exhibits high degree of independence from the choice of training chemicals. The

  6. Pore Polarity and Charge Determine Differential Block of Kir1.1 and Kir7.1 Potassium Channels by Small-Molecule Inhibitor VU590.

    Science.gov (United States)

    Kharade, Sujay V; Sheehan, Jonathan H; Figueroa, Eric E; Meiler, Jens; Denton, Jerod S

    2017-09-01

    VU590 was the first publicly disclosed, submicromolar-affinity (IC 50 = 0.2 μ M), small-molecule inhibitor of the inward rectifier potassium (Kir) channel and diuretic target, Kir1.1. VU590 also inhibits Kir7.1 (IC 50 ∼ 8 μ M), and has been used to reveal new roles for Kir7.1 in regulation of myometrial contractility and melanocortin signaling. Here, we employed molecular modeling, mutagenesis, and patch clamp electrophysiology to elucidate the molecular mechanisms underlying VU590 inhibition of Kir1.1 and Kir7.1. Block of both channels is voltage- and K + -dependent, suggesting the VU590 binding site is located within the pore. Mutagenesis analysis in Kir1.1 revealed that asparagine 171 (N171) is the only pore-lining residue required for high-affinity block, and that substituting negatively charged residues (N171D, N171E) at this position dramatically weakens block. In contrast, substituting a negatively charged residue at the equivalent position in Kir7.1 enhances block by VU590, suggesting the VU590 binding mode is different. Interestingly, mutations of threonine 153 (T153) in Kir7.1 that reduce constrained polarity at this site (T153C, T153V, T153S) make wild-type and binding-site mutants (E149Q, A150S) more sensitive to block by VU590. The Kir7.1-T153C mutation enhances block by the structurally unrelated inhibitor VU714 but not by a higher-affinity analog ML418, suggesting that the polar side chain of T153 creates a barrier to low-affinity ligands that interact with E149 and A150. Reverse mutations in Kir1.1 suggest that this mechanism is conserved in other Kir channels. This study reveals a previously unappreciated role of membrane pore polarity in determination of Kir channel inhibitor pharmacology. Copyright © 2017 by The American Society for Pharmacology and Experimental Therapeutics.

  7. Exploiting single photon vacuum ultraviolet photoionization to unravel the synthesis of complex organic molecules in interstellar ices

    Science.gov (United States)

    Abplanalp, Matthew J.; Förstel, Marko; Kaiser, Ralf I.

    2016-01-01

    Complex organic molecules (COM) such as aldehydes, ketones, carboxylic acids, esters, and amides are ubiquitous in the interstellar medium, but traditional gas phase astrochemical models cannot explain their formation routes. By systematically exploiting on line and in situ vacuum ultraviolet photoionization coupled with reflectron time of flight mass spectrometry (PI-ReTOF-MS) and combining these data with infrared spectroscopy (FTIR), we reveal that complex organic molecules can be synthesized within interstellar ices that are condensed on interstellar grains via non-equilibrium reactions involving suprathermal hydrogen atoms at temperatures as low as 5 K. By probing for the first time specific structural isomers without their degradation (fragment-free), the incorporation of tunable vacuum ultraviolet photoionization allows for a much greater understanding of reaction mechanisms that exist in interstellar ices compared to traditional methods, thus eliminating the significant gap between observational and laboratory data that existed for the last decades. With the commission of the Atacama Large Millimeter/Submillimeter Array (ALMA), the number of detections of more complex organic molecules in space will continue to grow ⿿ including biorelevant molecules connected to the Origins of Life theme ⿿ and an understanding of these data will rely on future advances in sophisticated physical chemistry laboratory experiments.

  8. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shu-Ling; Wu, Yu-Ru; Lin, Tzuen-Yeuan; Fuh, Ming-Ren, E-mail: msfuh@scu.edu.tw

    2015-04-29

    Highlights: • Methacrylic acid (MAA) was used to increase hydrophilicity of polymeric monoliths. • Fast separation of phenol derivatives was achieved in 5 min using MAA-incorporated column. • Separations of aflatoxins and phenicol antibiotics were achieved using MAA-incorporated column. - Abstract: In this study, methacrylic acid (MAA) was incorporated with alkyl methacrylates to increase the hydrophilicity of the synthesized ethylene dimethacrylate-based (EDMA-based) monoliths for separating polar small molecules by capillary LC analysis. Different alkyl methacrylate–MAA ratios were investigated to prepare a series of 30% alkyl methacrylate–MAA–EDMA monoliths in fused-silica capillaries (250-μm i.d.). The porosity, permeability, and column efficiency of the synthesized MAA-incorporated monolithic columns were characterized. A mixture of phenol derivatives is employed to evaluate the applicability of using the prepared monolithic columns for separating small molecules. Fast separation of six phenol derivatives was achieved in 5 min with gradient elution using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. In addition, the effect of acetonitrile content in mobile phase on retention factor and plate height as well as the plate height-flow velocity curves were also investigated to further examine the performance of the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Moreover, the applicability of prepared polymer-based monolithic column for potential food safety applications was also demonstrated by analyzing five aflatoxins and three phenicol antibiotics using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column.

  9. A membrane introduction mass spectrometer utilizing ion-molecule reactions for the on-line speciation and quantitation of volatile organic molecules.

    Science.gov (United States)

    Davey, Nicholas G; Bell, Ryan J; Krogh, Erik T; Gill, Chris G

    2015-12-15

    The ability of membrane introduction mass spectrometry to quantitatively resolve low molecular weight volatile organic compounds (VOCs) such as benzene, toluene, ethylbenzene and xylene (BTEX) using electron ionization (EI) can be compromised by isobaric interferences. This work focuses on reducing isobaric interferences with ion-molecule reactions in a portable quadrupole ion trap mass spectrometer for the analysis of VOCs. EI was used to produce reagent ions from precursors (chloroform, methyl iodide, trichloroethylene or chlorobenzene) that were continually infused into the helium acceptor phase upstream of the membrane introduction mass spectrometry (MIMS) sampling interface. The reagent ions were selectively stored in the ion trap, and then allowed to react with target VOC analytes in air samples via ion-molecule reactions within the trap storage volume. A variety of reaction times were examined (50-5000 ms), and the resulting product ions were analyzed in positive ion mode. The detection limits achieved were comparable with those obtained using EI (low ppbv), and in some cases better than for EI coupled with tandem mass spectrometry (MS/MS). For the VOCs studied, isobaric interferences were greatly reduced or eliminated using chloroform as a reagent gas. The predominant ionization mechanism was via adduct formation, although charge transfer and hydride abstractions were also observed. An internal standard was shown to be effective at correcting for signal changes due to consumption of reagent ions when complex mixtures were sampled. Ion-molecule reactions were exploited to eliminate isobaric interferences that are often encountered in direct, real-time analysis strategies for atmospheric VOC mixtures. The use of a continuously infused internal standard will improve quantitative results in field applications where analyte concentration and sample complexity may be wide ranging. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Searching for amino-acid homochirality on Mars with the Mars Organic Molecule Analyzer (MOMA) onboard ExoMars

    Science.gov (United States)

    Buch, A.; Freissinet, C.; Sternberg, R.; Brault, A.; Szopa, C.; Claude-Geffroy, C.; Coll, P. J.; Grand, N.; Raulin, F.; Pinick, V.; Goesmann, F.

    2012-12-01

    The joint ESA-Roscosmos Exo-Mars-2018 rover mission plans to seek the signs of a past or a present life on Mars. The Mars Organic Molecule Analyzer (MOMA) experiment onboard theExoMars rover will be a key analytical tool in providing molecular information from Mars solid samples, with a specific focus on the characterization of their organic content. In this purpose, one of MOMA's main instruments is a gas chromatograph-mass spectrometer (GC-MS), which provides a unique ability to characterize a broad range of compounds and allow chemical analyses on volatile and refractory species. The challenge with the analysis of this refractory matter embedded in soil is their primary extraction before their analysis by GC-MS. Since the extraction of organic matter is not possible by liquid solvent extraction, we have developed a method based on the thermodesorption and subsequent derivatization of the organic molecules. The goal of the thermodesorption is to extract the organic matter by heating the sample quickly enough not to degrade its organic content. One of the main focuses is to determine the chirality of this organic matter, notably amino acids. Indeed, on Earth, homochirality of molecules is an indicator for the presence of life. Amino acids appear to bear only the left-handed form (L) in living system. However, other refractory compounds can raise interest: nucleobases, carboxylic acids and PAHs are among molecules supported by life as we know it, and all of them can display chirality. The intrinsic chirality of molecules being thermosensitive, the thermodesorption parameters have been adjusted to occur within a range of temperatures from 150 °C to 300 °C over a period of 30 s to 10 min, depending on the chemical compound. Under these conditions, we have shown that amino acids are not degraded and that their chirality is preserved. Once extracted, refractory molecules with labile hydrogens (e.g. amino acids, nucleobases, carboxylic acids, etc.) are derivatized

  11. Interstellar PAH analogs in the laboratory: A step toward the identification and the quantification of organic molecules in space

    Science.gov (United States)

    Biennier, L.; Salama, F.; Gupta, M.; O'Keefe, A.

    In spite of recent progress in our understanding of the organic component of interstellar dust, little has been revealed about the identification and the quantification of large organic molecules in space (e.g., column densities of specific molecular species, physical and chemical processes of formation and destruction, etc...). Experimental studies of "true" cosmic organic analogs are essential to address theses issues. In our laboratory, we have developed a dedicated chamber to generate species under space-like conditions (i.e., free, cold, neutral and ionized species). The chamber is combined with a powerful state-of-the-art instrument to characterize the spectral fingerprints of these molecular species. Polycylic Aromatic Hydrocarbon (PAH) molecules are the precursors/building blocks of complex organic molecules and have been the first targets studied using this innovative approach. Our measurements provide data that can now be directly compared to astronomical spectra of the interstellar (IS) extinction curve and of the diffuse interstellar bands (DIBs), both tracers of cosmic organics. The harsh physical conditions of the diffuse IS medium - characterized by a low temperature, an absence of collisions and strong VUV radiation fields - are simulated in the laboratory by associating a free jet expansion with an ionizing discharge that altogether generate a cold plasma expansion in the chamber. The spectra of these organics are measured using two complementary high sensitivity techniques: Cavity Ring Down Spectroscopy (CRDS) and Multiplex Integrated Cavity Output Spectroscopy (MICOS). These two techniques have been applied to the measurement of the electronic spectrum of a set of representative PAHs such as the cold Naphthalene (C10H_8}) cation, neutral Methylnaphthalene (C11H10}), neutral and ionized Acenaphtene (C12H10), neutral Phenanthrene (C14H10), and neutral and ionized Pyrene (C16H10). These experiments provide unique information on the spectra of free

  12. Synthesis of many different types of organic small molecules using one automated process.

    Science.gov (United States)

    Li, Junqi; Ballmer, Steven G; Gillis, Eric P; Fujii, Seiko; Schmidt, Michael J; Palazzolo, Andrea M E; Lehmann, Jonathan W; Morehouse, Greg F; Burke, Martin D

    2015-03-13

    Small-molecule synthesis usually relies on procedures that are highly customized for each target. A broadly applicable automated process could greatly increase the accessibility of this class of compounds to enable investigations of their practical potential. Here we report the synthesis of 14 distinct classes of small molecules using the same fully automated process. This was achieved by strategically expanding the scope of a building block-based synthesis platform to include even C(sp3)-rich polycyclic natural product frameworks and discovering a catch-and-release chromatographic purification protocol applicable to all of the corresponding intermediates. With thousands of compatible building blocks already commercially available, many small molecules are now accessible with this platform. More broadly, these findings illuminate an actionable roadmap to a more general and automated approach for small-molecule synthesis. Copyright © 2015, American Association for the Advancement of Science.

  13. Nonvolatile Memory Elements Based on the Intercalation of Organic Molecules Inside Carbon Nanotubes

    Science.gov (United States)

    Meunier, Vincent; Kalinin, Sergei V.; Sumpter, Bobby G.

    2007-02-01

    We propose a novel class of nonvolatile memory elements based on the modification of the transport properties of a conducting carbon nanotube by the presence of an encapsulated molecule. The guest molecule has two stable orientational positions relative to the nanotube that correspond to conducting and nonconducting states. The mechanism, governed by a local gating effect of the molecule on the electronic properties of the nanotube host, is studied using density functional theory. The mechanisms of reversible reading and writing of information are illustrated with a F4TCNQ molecule encapsulated inside a metallic carbon nanotube. Our results suggest that this new type of nonvolatile memory element is robust, fatigue-free, and can operate at room temperature.

  14. Characteristic Contrast in Δfmin Maps of Organic Molecules Using Atomic Force Microscopy

    NARCIS (Netherlands)

    van der Heijden, Nadine J; Hapala, Prokop; Rombouts, Jeroen A; van der Lit, Joost; Smith, Daniël; Mutombo, Pingo; Švec, Martin; Jelinek, Pavel; Swart, Ingmar

    2016-01-01

    Scanning tunneling microscopy and atomic force microscopy can provide detailed information about the geometric and electronic structure of molecules with submolecular spatial resolution. However, an essential capability to realize the full potential of these techniques for chemical applications is

  15. Combustion of Organic Molecules by the Thermal Decomposition of Perchlorate Salts: Implications for Organics at the Mars Phoenix Scout Landing Site

    Science.gov (United States)

    Ming, D.W.; Morris, R.V.; Niles, B.; Lauer, H.V.; Archer, P.D.; Sutter, B.; Boynton, W.V.; Golden, D.C.

    2009-01-01

    The Mars 2007 Phoenix Scout Mission successfully landed on May 25, 2008 and operated on the northern plains of Mars for 150 sols. The primary mission objective was to study the history of water and evaluate the potential for past and present habitability in Martian arctic ice-rich soil [1]. Phoenix landed near 68 N latitude on polygonal terrain created by ice layers that are a few centimeters under loose soil materials. The Phoenix Mission is assessing the potential for habitability by searching for organic molecules in the ice or icy soils at the landing site. Organic molecules are necessary building blocks for life, although their presence in the ice or soil does not indicate life itself. Phoenix searched for organic molecules by heating soil/ice samples in the Thermal and Evolved-Gas Analyzer (TEGA, [2]). TEGA consists of 8 differential scanning calorimeter (DSC) ovens integrated with a magnetic-sector mass spectrometer with a mass range of 2-140 daltons [2]. Endothermic and exothermic reactions are recorded by the TEGA DSC as samples are heated from ambient to 1000 C. Evolved gases, including any organic molecules and their fragments, are simultaneously measured by the mass spectrometer during heating. Phoenix TEGA data are still under analysis; however, no organic fragments have been identified to date in the evolved gas analysis (EGA). The MECA Wet Chemistry Lab (WCL) discovered a perchlorate salt in the Phoenix soils and a mass 32 peak evolved between 325 and 625 C for one surface sample dubbed Baby Bear [3]. The mass 32 peak is attributed to evolved O2 generated during the thermal decomposition of the perchlorate salt. Perchlorates are very strong oxidizers when heated, so it is possible that organic fragments evolved in the temperature range of 300-600 C were combusted by the O2 released during the thermal decomposition of the perchlorate salt. The byproduct of the combustion of organic molecules is CO2. There is a prominent release of CO2 between 200

  16. Dipole polarizability of alkali-metal (Na, K, Rb)–alkaline-earth-metal (Ca, Sr) polar molecules: Prospects for alignment

    Energy Technology Data Exchange (ETDEWEB)

    Gopakumar, Geetha, E-mail: geetha@tmu.ac.jp; Abe, Minori; Hada, Masahiko [Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan); JST, CREST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Kajita, Masatoshi [National Institute of Information and Communications Technology, Koganei, Tokyo 184-8795 (Japan)

    2014-06-14

    Electronic open-shell ground-state properties of selected alkali-metal–alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the {sup 2}Σ{sup +} ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes ({sup 23}Na, {sup 39}K, {sup 85}Rb)–({sup 40}Ca, {sup 88}Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  17. CAL3JHH: a Java program to calculate the vicinal coupling constants (3J H,H) of organic molecules.

    Science.gov (United States)

    Aguirre-Valderrama, Alonso; Dobado, José A

    2008-12-01

    Here, we present a free web-accessible application, developed in the JAVA programming language for the calculation of vicinal coupling constant (3J(H,H)) of organic molecules with the H-Csp3-Csp3-H fragment. This JAVA applet is oriented to assist chemists in structural and conformational analyses, allowing the user to calculate the averaged 3J(H,H) values among conformers, according to its Boltzmann populations. Thus, the CAL3JHH program uses the Haasnoot-Leeuw-Altona equation, and, by reading the molecule geometry from a protein data bank (PDB) file format or from multiple pdb files, automatically detects all the coupled hydrogens, evaluating the data needed for this equation. Moreover, a "Graphical viewer" menu allows the display of the results on the 3D molecule structure, as well as the plotting of the Newman projection for the couplings.

  18. "Trampoline" ejection of organic molecules from graphene and graphite via keV cluster ions impacts.

    Science.gov (United States)

    Verkhoturov, Stanislav V; Gołuński, Mikołaj; Verkhoturov, Dmitriy S; Geng, Sheng; Postawa, Zbigniew; Schweikert, Emile A

    2018-04-14

    We present the data on ejection of molecules and emission of molecular ions caused by single impacts of 50 keV C 60 2+ on a molecular layer of deuterated phenylalanine (D8Phe) deposited on free standing, 2-layer graphene. The projectile impacts on the graphene side stimulate the abundant ejection of intact molecules and the emission of molecular ions in the transmission direction. To gain insight into the mechanism of ejection, Molecular Dynamic simulations were performed. It was found that the projectile penetrates the thin layer of graphene, partially depositing the projectile's kinetic energy, and molecules are ejected from the hot area around the hole that is made by the projectile. The yield, Y, of negative ions of deprotonated phenylalanine, (D8Phe-H) - , emitted in the transmission direction is 0.1 ions per projectile impact. To characterize the ejection and ionization of molecules, we have performed the experiments on emission of (D8Phe-H) - from the surface of bulk D8Phe (Y = 0.13) and from the single molecular layer of D8Phe deposited on bulk pyrolytic graphite (Y = 0.15). We show that, despite the similar yields of molecular ions, the scenario of the energy deposition and ejection of molecules is different for the case of graphene due to the confined volume of projectile-analyte interaction. The projectile impact on the graphene-D8Phe sample stimulates the collective radial movement of analyte atoms, which compresses the D8Phe layer radially from the hole. At the same time, this compression bends and stretches the graphene membrane around the hole thus accumulating potential energy. The accumulated potential energy is transformed into the kinetic energy of correlated movement upward for membrane atoms, thus the membrane acts as a trampoline for the molecules. The ejected molecules are effectively ionized; the ionization probability is ∼30× higher compared to that obtained for the bulk D8Phe target. The proposed mechanism of ionization involves

  19. APECS: A Model Organization for Bridging Past to Present and Developing a New Generation of Polar Scientists (Invited)

    Science.gov (United States)

    Timm, K.; Baeseman, J. L.; Membership, Association Of Polar Early Career Scientists

    2010-12-01

    One of the greatest legacies of the International Polar Year (IPY) is the creation of APECS, the Association of Polar Early Career Scientists. As a grassroots effort, APECS was proposed, formed, and developed by and for early career polar researchers. While the young investigators who founded APECS had talent, ambition, and the desire to make things happen, partnerships with key organizations and experienced leaders in polar science were essential to provide the funding, leadership, and mentorship that has taken the organization well beyond the IPY and to over 2000 members. In four years, APECS has strived to foster the skills of and develop a group of early career interdisciplinary polar scientists through networking and mentoring among themselves and with senior scientists. Through diverse activities including, panel discussions, career development workshops, online seminars, a comprehensive job listing, formal mentoring, meeting travel support, and the APECS Virtual Poster Session, APECS goal is to support the early career researcher being trained to do the science, to become a well-rounded scientist prepared for 21st century careers in science. As part of that training, APECS members are encouraged to participate in activities and training related to science communication, education, and outreach; working with the media; participating in the science / public policy interface; and working with arctic communities and indigenous peoples. During the IPY, APECS members were guest speakers and presenters on International Polar Day activities; they contributed to resources for education and outreach such as the book: Polar Science and Global Climate: An International Resource for Education and Outreach; and they made connections with educators, community groups, the media through in-person presentations, blogs from the field, videos, and much more. Workshops, panels, and online discussions focusing on these activities helped develop the capacity to conduct such

  20. Automated polarization control for the precise alignment of laser-induced self-organized nanostructures

    Science.gov (United States)

    Hermens, Ulrike; Pothen, Mario; Winands, Kai; Arntz, Kristian; Klocke, Fritz

    2018-02-01

    Laser-induced periodic surface structures (LIPSS) found in particular applications in the fields of surface functionalization have been investigated since many years. The direction of these ripple structures with a periodicity in the nanoscale can be manipulated by changing the laser polarization. For industrial use, it is useful to manipulate the direction of these structures automatically and to obtain smooth changes of their orientation without any visible inhomogeneity. However, currently no system solution exists that is able to control the polarization direction completely automated in one software solution so far. In this paper, a system solution is presented that includes a liquid crystal polarizer to control the polarization direction. It is synchronized with a scanner, a dynamic beam expander and a five axis-system. It provides fast switching times and small step sizes. First results of fabricated structures are also presented. In a systematic study, the conjunction of LIPSS with different orientation in two parallel line scans has been investigated.

  1. Organic molecules deposited on graphene: A computational investigation of self-assembly and electronic structure

    International Nuclear Information System (INIS)

    Oliveira, I. S. S. de; Miwa, R. H.

    2015-01-01

    We use ab initio simulations to investigate the adsorption and the self-assembly processes of tetracyanoquinodimethane (TCNQ), tetrafluoro-tetracyanoquinodimethane (F4-TCNQ), and tetrasodium 1,3,6,8-pyrenetetrasulfonic acid (TPA) on the graphene surface. We find that there are no chemical bonds at the molecule–graphene interface, even at the presence of grain boundaries on the graphene surface. The molecules bond to graphene through van der Waals interactions. In addition to the molecule–graphene interaction, we performed a detailed study of the role played by the (lateral) molecule–molecule interaction in the formation of the, experimentally verified, self-assembled layers of TCNQ and TPA on graphene. Regarding the electronic properties, we calculate the electronic charge transfer from the graphene sheet to the TCNQ and F4-TCNQ molecules, leading to a p-doping of graphene. Meanwhile, such charge transfer is reduced by an order of magnitude for TPA molecules on graphene. In this case, it is not expected a significant doping process upon the formation of self-assembled layer of TPA molecules on the graphene sheet

  2. Planar Cell Polarity Breaks the Symmetry of PAR Protein Distribution prior to Mitosis in Drosophila Sensory Organ Precursor Cells.

    Science.gov (United States)

    Besson, Charlotte; Bernard, Fred; Corson, Francis; Rouault, Hervé; Reynaud, Elodie; Keder, Alyona; Mazouni, Khalil; Schweisguth, François

    2015-04-20

    During development, cell-fate diversity can result from the unequal segregation of fate determinants at mitosis. Polarization of the mother cell is essential for asymmetric cell division (ACD). It often involves the formation of a cortical domain containing the PAR complex proteins Par3, Par6, and atypical protein kinase C (aPKC). In the fly notum, sensory organ precursor cells (SOPs) divide asymmetrically within the plane of the epithelium and along the body axis to generate two distinct cells. Fate asymmetry depends on the asymmetric localization of the PAR complex. In the absence of planar cell polarity (PCP), SOPs divide with a random planar orientation but still asymmetrically, showing that PCP is dispensable for PAR asymmetry at mitosis. To study when and how the PAR complex localizes asymmetrically, we have used a quantitative imaging approach to measure the planar polarization of the proteins Bazooka (Baz, fly Par3), Par6, and aPKC in living pupae. By using imaging of functional GFP-tagged proteins with image processing and computational modeling, we find that Baz, Par6, and aPKC become planar polarized prior to mitosis in a manner independent of the AuroraA kinase and that PCP is required for the planar polarization of Baz, Par6, and aPKC during interphase. This indicates that a "mitosis rescue" mechanism establishes asymmetry at mitosis in PCP mutants. This study therefore identifies PCP as the initial symmetry-breaking signal for the planar polarization of PAR proteins in asymmetrically dividing SOPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. A Dual Source Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer of ExoMars 2018

    Science.gov (United States)

    Brickerhoff, William B.; vanAmerom, F. H. W.; Danell, R. M.; Arevalo, R.; Atanassova, M.; Hovmand, L.; Mahaffy, P. R.; Cotter, R. J.

    2011-01-01

    We present details on the objectives, requirements, design and operational approach of the core mass spectrometer of the Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars mission. The MOMA mass spectrometer enables the investigation to fulfill its objective of analyzing the chemical composition of organic compounds in solid samples obtained from the near surface of Mars. Two methods of ionization are realized, associated with different modes of MOMA operation, in a single compact ion trap mass spectrometer. The stringent mass and power constraints of the mission have led to features such as low voltage and low frequency RF operation [1] and pulse counting detection.

  4. Partition Coefficients of Organic Molecules in Squalane and Water/Ethanol Mixtures by Molecular Dynamics Simulations

    DEFF Research Database (Denmark)

    Lundsgaard, Rasmus; Kontogeorgis, Georgios; Economou, Ioannis G.

    2011-01-01

    the GROMACS software, by slowly decoupling of firstly the electrostatic and then the Lennard–Jones interactions between molecules in the simulation box. These calculations depend very much on the choice of force field. Two force fields have been tested in this work, the TraPPE-UA (united-atom) and the OPLS...

  5. Characteristic contrast in Deltafmin maps of organic molecules using atomic force microscopy

    Czech Academy of Sciences Publication Activity Database

    van der Heijden, N.J.; Hapala, Prokop; Rombouts, J.A.; van der Lit, J.; Smith, D.; Mutombo, Pingo; Švec, Martin; Jelínek, Pavel; Swart, I.

    2016-01-01

    Roč. 10, č. 9 (2016), 8517-8525 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GC14-16963J Institutional support: RVO:68378271 Keywords : nc AFM * chemical contrast * DFT * molecules Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 13.942, year: 2016

  6. Fluorescent molecule incorporated metal-organic framework for fluoride sensing in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Xudong, E-mail: zhaoxd_tykj@163.com; Wang, Yuanyang; Hao, Xiuli; Liu, Wen, E-mail: 13700509372@163.com

    2017-04-30

    Highlights: • Fluorescein sodium was successfully encapsulated in UiO-66 via in-situ synthesis. • FS@UiO-66 is one of the few Zr-MOF-based probes for fluoride so far. • FS@UiO-66 is a highly effective, fast-response and naked-eye sensor for fluoride. - Abstract: In this work, the fluorescent molecule (fluorescein sodium, FS) was successfully incorporated in the zirconium-based MOF (UiO-66) via in-situ synthesis method, which can be confirmed by FTIR spectra and fluorescence microscopic images. Based on this in-situ synthesis strategy, FS molecule can be immobilized tightly in the framework. Furthermore, the resulting FS@UiO-66 demonstrates to be a highly selective, real-time and naked-eye chemical sensor for fluoride in aqueous solution, which is mainly due to the release of FS molecule from FS@UiO-66 into the aqueous solution. Meanwhile, to the best of our knowledge, such Zr-MOF-based fluoride sensor is very rare so far. These results provide a promising approach to rationally design novel MOF-based fluorescent sensor for the target molecules.

  7. Formation of Complex Organics by Gas Phase and Intracluster Ion-Molecule Reactions Involving Acetylene and Hydrogen Cyanide

    Science.gov (United States)

    El-Shall, S.; Hamed, A.; Soliman, A. R.; Momoh, P. O.

    2011-05-01

    Many complex organics including polycyclic aromatic hydrocarbons are present in flames and combustion processes as well as in interstellar clouds and solar nebulae. Here, we present evidence for the formation of complex covalent organics by gas phase and intracluster reactions of the benzene, phenylium, pyridine, pyrimidine, phenylacetylene and benzonitrile cations with acetylene and hydrogen cyanide molecules. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. Measurements of collision cross sections in helium provide structural information on the adducts and allow probing structural changes at different temperatures (isomerization). We observed multiple additions of five acetylene molecules on the pyridine cation at room temperature. This is a remarkable result considering that only two acetylene molecules were added to the phenyl cation and no addition was observed on the benzene cation at room temperature. The experimental results are in full agreement with the ab initio calculations which predict that the first and second acetylenes add to the pyridine ion in barrierless, highly exothermic reactions. Similar reactions have been observed for the pyrimidine radical cation although the extent of the addition reactions is limited to only two acetylene molecules at room temperature. The results provide the first evidence for the incorporation of nitrogen in the formation cyclic hydrocarbons via the gas phase reactions of pyridine and pyrimidine ions with acetylene molecules. In addition, the formation of covalent adducts in the ionized acetylene/HCN system will be reported for the first time. Sequential reactions leading to the formation of pyridine and pyrimidine radical cations and higher adducts are observed over a wide range of temperature and pressure. The formation of these covalent adducts may represent a general class of addition reactions that can form complex

  8. Evaluation of polar organic micropollutants as indicators for wastewater-related coastal water quality impairment

    International Nuclear Information System (INIS)

    Nödler, Karsten; Tsakiri, Maria; Aloupi, Maria; Gatidou, Georgia; Stasinakis, Athanasios S.; Licha, Tobias

    2016-01-01

    Results from coastal water pollution monitoring (Lesvos Island, Greece) are presented. In total, 53 samples were analyzed for 58 polar organic micropollutants such as selected herbicides, biocides, corrosion inhibitors, stimulants, artificial sweeteners, and pharmaceuticals. Main focus is the application of a proposed wastewater indicator quartet (acesulfame, caffeine, valsartan, and valsartan acid) to detect point sources and contamination hot-spots with untreated and treated wastewater. The derived conclusions are compared with the state of knowledge regarding local land use and infrastructure. The artificial sweetener acesulfame and the stimulant caffeine were used as indicators for treated and untreated wastewater, respectively. In case of a contamination with untreated wastewater the concentration ratio of the antihypertensive valsartan and its transformation product valsartan acid was used to further refine the estimation of the residence time of the contamination. The median/maximum concentrations of acesulfame and caffeine were 5.3/178 ng L −1 and 6.1/522 ng L −1 , respectively. Their detection frequency was 100%. Highest concentrations were detected within the urban area of the capital of the island (Mytilene). The indicator quartet in the gulfs of Gera and Kalloni (two semi-enclosed embayments on the island) demonstrated different concentration patterns. A comparatively higher proportion of untreated wastewater was detected in the gulf of Gera, which is in agreement with data on the wastewater infrastructure. The indicator quality of the micropollutants to detect wastewater was compared with electrical conductivity (EC) data. Due to their anthropogenic nature and low detection limits, the micropollutants are superior to EC regarding both sensitivity and selectivity. The concentrations of atrazine, diuron, and isoproturon did not exceed the annual average of their environmental quality standards (EQS) defined by the European Commission. At two

  9. Highlight on the indigenous organic molecules detected on Mars by SAM and potential sources of artifacts and backgrounds generated by the sample preparation

    Science.gov (United States)

    Buch, A.; Belmahdi, I.; Szopa, C.; Freissinet, C.; Glavin, D. P.; Coll, P. J.; Cabane, M.; Millan, M.; Eigenbrode, J. L.; Navarro-Gonzalez, R.; Stern, J. C.; Pinnick, V. T.; Coscia, D.; Teinturier, S.; Stambouli, M.; Dequaire, T.; Mahaffy, P. R.

    2015-12-01

    Among the experiments which explore the martian soil aboard the Curiosity Rover, SAM experiment is mainly dedicated to the search for indigenous organic compounds. To reach its goals SAM can operate in different analysis modes: Pyrolysis-GC-MS and Pyrolysis-MS (EGA). In addition SAM includes wet chemistry experiments [1] to supports extraction of polar organic compounds from solid samples that improves their detection either by increasing the release of chemical species from solid sample matrices, or by changing their chemical structure to make compounds more amenable to gas chromatography mass spectrometry (GCMS). The two wet chemistry experimental capabilities of SAM provide alternatives to the nominal inert-thermal desorption/pyrolysis analytical protocol and are more aptly suited for polar components: MTBSTFA derivatization [2-3] and TMAH thermochemolysis [4-5]. Here we focus on the MTBSTFA derivatization experiment. In order to build a support used to help the interpretation of SAM results, we have investigated the artifacts and backgrounds sources generated by the all analysis process: Solid sample were heated up to approximately 840°C at a rate of 35°C/min under He flow. For GC analyses, the majority of the gas released was trapped on a hydrocarbon trap (Tenax®) over a specific temperature range. Adsorbed volatiles on the GC injection trap (IT) were then released into the GC column (CLP-MXT 30m x 0.25mm x 0.25μm) by rapidly heating the IT to 300°C. Then, in order better understand the part of compounds detected coming from internal reaction we have performed several lab experiments to mimic the SAM device: Among the sources of artifact, we test: (1) the thermal stability and the organic material released during the degradation of Tenax® and carbosieve, (2) the impact of MTBSTFA and a mixture of DMF and MTBSTFA on the adsorbent, (3) the reaction between the different adsorbents (Tenax® and Carbosieve) and calcium perchlorate and then (4) the sources

  10. Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

    Science.gov (United States)

    Millan, M.; Szopa, C.; Buch, A.; Belmahdi, I.; Glavin, D. P.; Freissinet, C.; Eigenbrode, J. L.; Archer, P. D., Jr,; Sutter, B.; Mahaffy, P.

    2017-01-01

    One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

  11. A DFT and QTAIM study of the adsorption of organic molecules over the copper-doped coronene and circumcoronene

    Science.gov (United States)

    Malček, Michal; Cordeiro, M. Natalia D. S.

    2018-01-01

    Graphene based materials are nowadays extensively studied because of their potential applications as gas sensors, biosensors or adsorbents. Doping the graphene surface with heteroatoms or transition metals can improve its electronic properties and chemical reactivity. Polyaromatic hydrocarbons coronene and circumcoronene can be used as models of tiny graphene quantum dots. The adsorption of a set of organic molecules (water, hydrogen peroxide, hydrogen sulfide, methanol, ethanol and oxygen molecule) over the copper-doped coronene and circumcoronene was theoretically studied using density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM). In the case of coronene, only one site was considered for the Cu-doping, whereas in the case of circumcoronene being a polyaromatic hydrocarbon composed of 54 carbon atoms, three different sites for Cu-doping were considered. For the systems under study, the adsorption of O2 was found energetically the most favorable, with energetic outcome ranging from -3.1 to -3.7 eV related to the position of dopant Cu atom. Changes in the topology of charge densities at Cu and in its vicinity after the adsorption of studied molecules were investigated in the framework of QTAIM. In addition, QTAIM analysis of bond critical points (BCP) was employed to study the character of the newly formed chemical bonds. The results of this study point out the suitability of Cu-doped graphene materials as sensors and/or adsorbents in practical applications.

  12. From Molecules to Living Organisms : an Interplay between Biology and Physics : Lecture Notes of the Les Houches School of Physics

    CERN Document Server

    Nury, Hughes; Parcy, François; Ruigrok, Rob W H; Ziegler, Christine; Cugliandolo, Leticia F; Session CII

    2016-01-01

    The aim of this book is to provide new ideas for studying living matter by a simultaneous understanding of behavior from molecules to the cell, to the whole organism in the light of physical concepts. Indeed, forces guide most biological phenomena. In some cases these forces can be well-described and thus used to model a particular biological phenomenon. This is exemplified here by the study of membranes, where their shapes and curvatures can be modeled using a limited number of parameters that are measured experimentally. The growth of plants is another example where the combination of physics, biology and mathematics leads to a predictive model. The laws of thermodynamics are essential, as they dictate the behavior of proteins, or more generally biological molecules, in an aqueous environment. Integrated studies from the molecule to a larger scale need a combination of cutting-edge approaches, such as the use of new X-ray sources, in-cell NMR, cryo-electron microscopy or single-molecule microscopy. Some are...

  13. Exploring Charge Transport in Guest Molecule Infiltrated Cu3(BTC)2 Metal Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, Francois Leonard [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Stavila, Vitalie [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Allendorf, Mark D. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2014-09-01

    The goal of this Exploratory Express project was to expand the understanding of the physical properties of our recently discovered class of materials consisting of metal-organic frameworks with electroactive ‘guest’ molecules that together form an electrically conducting charge-transfer complex (molecule@MOF). Thin films of Cu3(BTC)2 were grown on fused silica using solution step-by-step growth and were infiltrated with the molecule tetracyanoquinodimethane (TCNQ). The infiltrated MOF films were extensively characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy, electrical conductivity, and thermoelectric properties. Thermopower measurements on TCNQ@Cu3(BTC)2 revealed a positive Seebeck coefficient of ~400 μV/k, indicating that holes are the primary carriers in this material. The high value of the Seebeck coefficient and the expected low thermal conductivity suggest that molecule@MOF materials may be attractive for thermoelectric power conversion applications requiring low cost, solution-processable, and non-toxic active materials.

  14. Photobleaching Dynamics in Small Molecule vs. Polymer Organic Photovoltaic Blends with 1,7-Bis-Trifluoromethylfullerene

    Energy Technology Data Exchange (ETDEWEB)

    Braunecker, Wade A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Garner, Logan E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Arias, Dylan H [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christensen, Steven T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Ferguson, Andrew J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Kopidakis, Nikos [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Larson, Bryon W [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Owczarczyk, Zbyslaw [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pfeilsticker, Jason [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Viswanathan, Vinila Nellissery [Indian Institute of Science; Brook, Colin P. [Colorado State University; Ramamurthy, Praveen C. [Indian Institute of Science; Strauss, Steven H. [Colorado State University; Boltalina, Olga V. [Colorado State University

    2018-02-27

    Two organic photovoltaic (OPV) donor materials (one polymer and one small molecule) are synthesized from the same constituent building blocks, namely thiophene units, cyclopentathiophene dione (CTD), and cyclopentadithiophene (CPDT). Photobleaching dynamics of these donor materials are then studied under white light illumination in air with blends of PC70BM and the bis-trifluoromethylfullerene 1,7-C60(CF3)2. For both the polymer and small molecule blends, C60(CF3)2 stabilizes the initial rate of photobleaching by a factor of 15 relative to PC70BM. However, once the small molecule:C60(CF3)2 blend bleaches to ~80% of its initial optical density, the rate of photobleaching dramatically accelerates, which is not observed in the analogous polymer blend. We probe that phenomenon using time-resolved photoluminescence (TRPL) to measure PL quenching efficiencies at defined intervals during the photobleaching experiments. The data indicates the small molecule donor and C60(CF3)2 acceptor significantly de-mix with time, after which the blend begins to bleach at approximately the same rate as the neat donor sample. The work suggests that perfluoroalkylfullerenes have great potential to stabilize certain OPV active layers toward photodegradation, provided their morphology is stable.

  15. Organic Zeolite Analogues Based on Multi-Component Liquid Crystals: Recognition and Transformation of Molecules within Constrained Environments

    Directory of Open Access Journals (Sweden)

    Yasuhiro Ishida

    2011-01-01

    Full Text Available In liquid crystals (LCs, molecules are confined in peculiar environments, where ordered alignment and certain mobility are realized at the same time. Considering these characteristics, the idea of “controlling molecular events within LC media” seems reasonable. As a suitable system for investigating this challenge, we have recently developed a new class of ionic LCs; the salts of amphiphilic carboxylic acids with 2-amino alcohols, or those of carboxylic acids with amphiphilic 2-amino alcohols, have a strong tendency to exhibit thermotropic LC phases. Because of the noncovalent nature of the interaction between molecules, one of the two components can easily be exchanged with, or transformed into, another molecule, without distorting the original LC architecture. In addition, both components are common organic molecules, and a variety of compounds are easily available. Taking advantage of these characteristics, we have succeeded in applying two‑component LCs as chiral media for molecular recognition and reactions. This review presents an overview of our recent studies, together with notable reports related to this field.

  16. Organic Zeolite Analogues Based on Multi-Component Liquid Crystals: Recognition and Transformation of Molecules within Constrained Environments.

    Science.gov (United States)

    Ishida, Yasuhiro

    2011-01-11

    In liquid crystals (LCs), molecules are confined in peculiar environments, where ordered alignment and certain mobility are realized at the same time. Considering these characteristics, the idea of "controlling molecular events within LC media" seems reasonable. As a suitable system for investigating this challenge, we have recently developed a new class of ionic LCs; the salts of amphiphilic carboxylic acids with 2-amino alcohols, or those of carboxylic acids with amphiphilic 2-amino alcohols, have a strong tendency to exhibit thermotropic LC phases. Because of the noncovalent nature of the interaction between molecules, one of the two components can easily be exchanged with, or transformed into, another molecule, without distorting the original LC architecture. In addition, both components are common organic molecules, and a variety of compounds are easily available. Taking advantage of these characteristics, we have succeeded in applying two‑component LCs as chiral media for molecular recognition and reactions. This review presents an overview of our recent studies, together with notable reports related to this field.

  17. Multivariate Metal-Organic Frameworks for Dialing-in the Binding and Programming the Release of Drug Molecules.

    Science.gov (United States)

    Dong, Zhiyue; Sun, Yangzesheng; Chu, Jun; Zhang, Xianzheng; Deng, Hexiang

    2017-10-11

    We report the control of guest release profiles by dialing-in desirable interactions between guest molecules and pores in metal-organic frameworks (MOFs). The interactions can be derived by the rate constants that were quantitatively correlated with the type of functional group and its proportion in the porous structure; thus the release of guest molecules can be predicted and programmed. Specifically, three probe molecules (ibuprofen, rhodamine B, and doxorubicin) were studied in a series of robust and mesoporous MOFs with multiple functional groups [MIL-101(Fe)-(NH 2 ) x , MIL-101(Fe)-(C 4 H 4 ) x , and MIL-101(Fe)-(C 4 H 4 ) x (NH 2 ) 1-x ]. The release rate can be adjusted by 32-fold [rhodamine from MIL-101(Fe)-(NH 2 ) x ], and the time of release peak can be shifted by up to 12 days over a 40-day release period [doxorubicin from MIL-101(Fe)-(C 4 H 4 ) x (NH 2 ) 1-x ], which was not obtained in the physical mixture of the single component MOF counterparts nor in other porous materials. The corelease of two pro-drug molecules (ibuprofen and doxorubicin) was also achieved.

  18. Probing the site-dependent Kondo response of nanostructured graphene with organic molecules.

    Science.gov (United States)

    Garnica, Manuela; Stradi, Daniele; Calleja, Fabián; Barja, Sara; Díaz, Cristina; Alcamí, Manuel; Arnau, Andrés; Vázquez de Parga, Amadeo L; Martín, Fernando; Miranda, Rodolfo

    2014-08-13

    TCNQ molecules are used as a sensitive probe for the Kondo response of the electron gas of a nanostructured graphene grown on Ru(0001) presenting a moiré pattern. All adsorbed molecules acquired an extra electron by charge transfer from the substrate, but only those adsorbed in the FCC-Top areas of the moiré show magnetic moment and Kondo resonance in the STS spectra. DFT calculations trace back this behavior to the existence of a surface resonance in the low areas of the graphene moiré, whose density distribution strongly depends on the stacking sequence of the moiré area and effectively quenches the magnetic moment for HCP-Top sites.

  19. Enzyme Inhibitory and Molecular Docking Studies on Some Organic Molecules of Natural Occurrence

    International Nuclear Information System (INIS)

    Abbasi, M. A.; Hussain, G.; Rehman, A. U.; Shahwar, D.; Mohyuddin, A.; Ashraf, M.; Rahman, J.; Lodhi, M. A.; Khan, F. A.

    2016-01-01

    In the present study, in vitro enzyme inhibitory studies on cinchonidine (1), cinchonine (2), quinine (3), noscapine (narcotine, 4) and santonine (5) were carried out. The various enzymes included in the study were lipoxygenase, xanthine oxidase, acetyl cholinesterase, butyryl cholinesterase and protease. The results revealed that 2, 3, and 4 were moderate active against lipoxygenase and xanthine oxidase enzymes. The molecule 3 possessed weak activity against butyryl cholinesterase enzyme while remaining molecules were inactive against this enzyme. However, all these compounds were inactive against acetyl cholinestrase and protease enzymes. The synthesized compounds were computationally docked into the active site of lipoxygenase enzyme. The compounds 3 and 4 showed decent interactions, hence strengthening the observed results. (author)

  20. Graphical prediction of quantum interference-induced transmission nodes in functionalized organic molecules

    DEFF Research Database (Denmark)

    Markussen, Troels; Stadler, Robert; Thygesen, Kristian Sommer

    2011-01-01

    with tight-binding and density functional theory calculations to investigate QI in linear molecular chains and aromatic molecules with different side groups. For the molecular chains we find a linear relation between the position of the transmission nodes and the side group π orbital energy. In contrast......Quantum interference (QI) in molecular transport junctions can lead to dramatic reductions of the electron transmission at certain energies. In a recent work [Markussen et al., Nano Lett., 2010, 10, 4260] we showed how the presence of such transmission nodes near the Fermi energy can be predicted......, the transmission functions of functionalized aromatic molecules generally display a rather complex nodal structure due to the interplay between molecular topology and the energy of the side group orbital....

  1. Use of a commercially available nucleating agent to control the morphological development of solution-processed small molecule bulk heterojunction organic solar cells

    KAUST Repository

    Sharenko, Alexander

    2014-08-12

    © the Partner Organisations 2014. The nucleating agent DMDBS is used to modulate the crystallization of solution-processed small molecule donor molecules in bulk heterojunction organic photovoltaic (BHJ OPV) devices. This control over donor molecule crystallization leads to a reduction in optimized thermal annealing times as well as smaller donor molecule crystallites, and therefore more efficient devices, when using an excessive amount of solvent additive. We therefore demonstrate the use of nucleating agents as a powerful and versatile processing strategy for solution-processed, small molecule BHJ OPVs. This journal is

  2. Chemical modelling of complex organic molecules with peptide-like bonds in star-forming regions

    Science.gov (United States)

    Quénard, David; Jiménez-Serra, Izaskun; Viti, Serena; Holdship, Jonathan; Coutens, Audrey

    2018-02-01

    Peptide bonds (N-C = O) play a key role in metabolic processes since they link amino acids into peptide chains or proteins. Recently, several molecules containing peptide-like bonds have been detected across multiple environments in the interstellar medium, growing the need to fully understand their chemistry and their role in forming larger pre-biotic molecules. We present a comprehensive study of the chemistry of three molecules containing peptide-like bonds: HNCO, NH2CHO, and CH3NCO. We also included other CHNO isomers (HCNO, HOCN) and C2H3NO isomers (CH3OCN, CH3CNO) to the study. We have used the UCLCHEM gas-grain chemical code and included in our chemical network all possible formation/destruction pathways of these peptide-like molecules recently investigated either by theoretical calculations or in laboratory experiments. Our predictions are compared to observations obtained towards the proto-star IRAS 16293-2422 and the L1544 pre-stellar core. Our results show that some key reactions involving the CHNO and C2H3NO isomers need to be modified to match the observations. Consistently with recent laboratory findings, hydrogenation is unlikely to produce NH2CHO on grain surfaces, while a combination of radical-radical surface reactions and gas-phase reactions is a better alternative. In addition, better results are obtained for NH2CHO when a slightly higher activation energy of 25 K is considered for the gas-phase reaction NH2 + H2CO → NH2CHO + H. Finally, our modelling shows that the observed correlation between NH2CHO and HNCO in star-forming regions may come from the fact that HNCO and NH2CHO react to temperature in the same manner rather than from a direct chemical link between the two species.

  3. QSPR studies for predicting polarity parameter of organic compounds in methanol using support vector machine and enhanced replacement method.

    Science.gov (United States)

    Golmohammadi, H; Dashtbozorgi, Z

    2016-12-01

    In the present work, enhanced replacement method (ERM) and support vector machine (SVM) were used for quantitative structure-property relationship (QSPR) studies of polarity parameter (p) of various organic compounds in methanol in reversed phase liquid chromatography based on molecular descriptors calculated from the optimized structures. Diverse kinds of molecular descriptors were calculated to encode the molecular structures of compounds, such as geometric, thermodynamic, electrostatic and quantum mechanical descriptors. The variable selection method of ERM was employed to select an optimum subset of descriptors. The five descriptors selected using ERM were used as inputs of SVM to predict the polarity parameter of organic compounds in methanol. The coefficient of determination, r 2 , between experimental and predicted polarity parameters for the prediction set by ERM and SVM were 0.952 and 0.982, respectively. Acceptable results specified that the ERM approach is a very effective method for variable selection and the predictive aptitude of the SVM model is superior to those obtained by ERM. The obtained results demonstrate that SVM can be used as a substitute influential modeling tool for QSPR studies.

  4. Inclusion of DNA into organic gelator fibers made of amphipathic molecules and its controlled release.

    Science.gov (United States)

    Karinaga, Ryouji; Jeong, Yeonhwan; Shinkai, Seiji; Kaneko, Kenji; Sakurai, Kazuo

    2005-10-11

    When methyl 4,6-O-(p-nitrobenzylidene)-alpha-D-glucopyranoside (p-NO(2)Glu) was dissolved in water, p-NO(2)Glu molecules self-assembled to form a fiber (elemental fiber), and as a result, the solution became a partially transparent gel. When an equal (or more) amount of DNA was added to the gel, a white and crystalline gel was obtained. Energy-dispersive X-ray spectroscopy coupled with TEM and confocal microscopy suggested that DNA was included in the gel fibers made of p-NO(2)Glu molecules. The results imply that p-NO(2)Glu molecules are self-assembled to form an elemental fiber and these elemental fibers and DNA are twisted together to form higher hierarchic fibers. When the complexed gel made of plasmid DNA (pDNA) and p-NO(2)Glu was added to E. coli T7 S30 extract solution, the pDNA had less expression ability compared with naked one. When we added methyl-beta-cyclodextrin (MbetaCyD), the expression rate was recovered with increasing added amount of MbetaCyD. The present paper shows inclusion and controlled release of DNA from a novel supporting material of DNA and that technology could play an important role in the development of localized approaches to gene therapy.

  5. Electron beam controlled covalent attachment of small organic molecules to graphene.

    Science.gov (United States)

    Markevich, Alexander; Kurasch, Simon; Lehtinen, Ossi; Reimer, Oliver; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Khlobystov, Andrei N; Kaiser, Ute; Besley, Elena

    2016-02-07

    The electron beam induced functionalization of graphene through the formation of covalent bonds between free radicals of polyaromatic molecules and C=C bonds of pristine graphene surface has been explored using first principles calculations and high-resolution transmission electron microscopy. We show that the energetically strongest attachment of the radicals occurs along the armchair direction in graphene to carbon atoms residing in different graphene sub-lattices. The radicals tend to assume vertical position on graphene substrate irrespective of direction of the bonding and the initial configuration. The "standing up" molecules, covalently anchored to graphene, exhibit two types of oscillatory motion--bending and twisting--caused by the presence of acoustic phonons in graphene and dispersion attraction to the substrate. The theoretically derived mechanisms are confirmed by near atomic resolution imaging of individual perchlorocoronene (C24Cl12) molecules on graphene. Our results facilitate the understanding of controlled functionalization of graphene employing electron irradiation as well as mechanisms of attachment of impurities via the processing of graphene nanoelectronic devices by electron beam lithography.

  6. Electron transport in disordered films of metal nanoparticles linked by organic molecules

    International Nuclear Information System (INIS)

    Mueller, K.H.; Wei, G.; Herrmann, J.; Raguse, B.; Baxter, G.

    2004-01-01

    Full text: We have investigated theoretically and experimentally the mechanism of electron transport in films made of ∼10 nm sized gold nanoparticles linked by alkanedithiol molecules. Conduction in these films is due to linker-molecule assisted single-electron tunnelling between neighbouring nanoparticles where electrons have to overcome the Coulomb blockade energy. Strong disorder in our films in the form of separation gap fluctuations between adjacent nanoparticles and variations in Coulomb blockade energies cause electron current percolation. We have found that the dependence of the conduction on the length of the alkanedithiol molecules is affected by the degree of disorder. In addition, we have observed that percolation leads to a non-Arrhenius-like temperature dependence of the conduction and to a film-thickness dependent conductivity. I-V characteristics at low temperatures reveal Coulomb blockade effects. The strong dependence of the electrical conduction on the separation gaps between adjacent nanoparticles can be utilized in strain gauge and gas sensor applications

  7. An A-D-A'-D-A type small molecule acceptor with a broad absorption spectrum for organic solar cells.

    Science.gov (United States)

    Miao, Junhui; Meng, Bin; Liu, Jun; Wang, Lixiang

    2018-01-02

    Organic molecules with wide absorption spectra exhibit great sunlight harvesting capability and are critically important for solar cell applications. In this manuscript, we develop an A-D-A'-D-A type small molecule acceptor (IID-IC) using isoindigo (IID) as the electron-deficient core unit (A'), thiophene as the electron-rich bridging units (D) and 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC) as the electron-deficient endcapping groups (A). IID-IC shows a wide absorption spectrum with the full width at half maximum (FWHM) of 190 nm, which is almost twice that of a typical A-D-A type molecule acceptor. The wide absorption spectrum of IID-IC is possibly due to the partially suppressed intramolecular charge transfer effect with the additional electron-deficient core unit. An organic solar cell (OSC) device based on IID-IC exhibits the power conversion efficiency of 2.82% with broad photoresponse from 320 nm to 780 nm.

  8. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated martian surface ultraviolet radiation conditions.

    Science.gov (United States)

    Poch, Olivier; Jaber, Maguy; Stalport, Fabien; Nowak, Sophie; Georgelin, Thomas; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-03-01

    Most of the phyllosilicates detected at the surface of Mars today are probably remnants of ancient environments that sustained long-term bodies of liquid water at the surface or subsurface and were possibly favorable for the emergence of life. Consequently, phyllosilicates have become the main mineral target in the search for organics on Mars. But are phyllosilicates efficient at preserving organic molecules under current environmental conditions at the surface of Mars? We monitored the qualitative and quantitative evolutions of glycine, urea, and adenine in interaction with the Fe(3+)-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K), and pressure (6 ± 1 mbar) in a laboratory simulation setup. We tested organic-rich samples that were representative of the evaporation of a small, warm pond of liquid water containing a high concentration of organics. For each molecule, we observed how the nontronite influences its quantum efficiency of photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine; their efficiencies of photodecomposition were reduced by a factor of 5 when mixed at a concentration of 2.6 × 10(-2) mol of molecules per gram of nontronite. Moreover, when the amount of nontronite in the sample of glycine was increased by a factor of 2, the gain of photoprotection was multiplied by a factor of 5. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect but is also due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate.

  9. Directional cell migration establishes the axes of planar polarity in the posterior lateral-line organ of the zebrafish.

    Science.gov (United States)

    López-Schier, Hernán; Starr, Catherine J; Kappler, James A; Kollmar, Richard; Hudspeth, A J

    2004-09-01

    The proper orientation of mechanosensory hair cells along the lateral-line organ of a fish or amphibian is essential for the animal's ability to sense directional water movements. Within the sensory epithelium, hair cells are polarized in a stereotyped manner, but the mechanisms that control their alignment relative to the body axes are unknown. We have found, however, that neuromasts can be oriented either parallel or perpendicular to the anteroposterior body axis. By characterizing the strauss mutant zebrafish line and by tracking labeled cells, we have demonstrated that neuromasts of these two orientations originate from, respectively, the first and second primordia. Furthermore, altering the migratory pathway of a primordium reorients a neuromast's axis of planar polarity. We propose that the global orientation of hair cells relative to the body axes is established through an interaction between directional movement by primordial cells and the timing of neuromast maturation.

  10. Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities

    Directory of Open Access Journals (Sweden)

    Margaux eMesle

    2015-06-01

    Full Text Available Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich rocks, shales and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e. the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility of the carbon and energy source. Indeed, bitumen has a colloidal structure that may limit the accessibility to asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix.

  11. Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities.

    Science.gov (United States)

    Meslé, Margaux; Dromart, Gilles; Haeseler, Frank; Oger, Philippe M

    2015-01-01

    Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich sedimentary rocks, shale, and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes) and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e., the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility to the carbon and energy source. Indeed, bitumen has a colloidal structure that may prevent the microbial consortia from reaching the asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix.

  12. Continuously Adjustable, Molecular-Sieving “Gate” on 5A Zeolite for Distinguishing Small Organic Molecules by Size

    Science.gov (United States)

    Song, Zhuonan; Huang, Yi; Xu, Weiwei L.; Wang, Lei; Bao, Yu; Li, Shiguang; Yu, Miao

    2015-01-01

    Zeolites/molecular sieves with uniform, molecular-sized pores are important for many adsorption-based separation processes. Pore size gaps, however, exist in the current zeolite family. This leads to a great challenge of separating molecules with size differences at ~0.01 nm level. Here, we report a novel concept, pore misalignment, to form a continuously adjustable, molecular-sieving “gate” at the 5A zeolite pore entrance without sacrificing the internal capacity. Misalignment of the micropores of the alumina coating with the 5A zeolite pores was related with and facilely adjusted by the coating thickness. For the first time, organic molecules with sub-0.01 nm size differences were effectively distinguished via appropriate misalignment. This novel concept may have great potential to fill the pore size gaps of the zeolite family and realize size-selective adsorption separation. PMID:26358480

  13. Continuously Adjustable, Molecular-Sieving "Gate" on 5A Zeolite for Distinguishing Small Organic Molecules by Size.

    Science.gov (United States)

    Song, Zhuonan; Huang, Yi; Xu, Weiwei L; Wang, Lei; Bao, Yu; Li, Shiguang; Yu, Miao

    2015-09-11

    Zeolites/molecular sieves with uniform, molecular-sized pores are important for many adsorption-based separation processes. Pore size gaps, however, exist in the current zeolite family. This leads to a great challenge of separating molecules with size differences at ~0.01 nm level. Here, we report a novel concept, pore misalignment, to form a continuously adjustable, molecular-sieving "gate" at the 5A zeolite pore entrance without sacrificing the internal capacity. Misalignment of the micropores of the alumina coating with the 5A zeolite pores was related with and facilely adjusted by the coating thickness. For the first time, organic molecules with sub-0.01 nm size differences were effectively distinguished via appropriate misalignment. This novel concept may have great potential to fill the pore size gaps of the zeolite family and realize size-selective adsorption separation.

  14. In-situ Evaluation of Soil Organic Molecules: Functional Group Chemistry Aggregate Structures, Metal and Surface Complexation Using Soft X-Ray

    International Nuclear Information System (INIS)

    Myneni, Satish C.

    2008-01-01

    Organic molecules are common in all Earth surface environments, and their composition and chemistry play an important role in a variety of biogeochemical reactions, such as mineral weathering, nutrient cycling and the solubility and transport of contaminants. However, most of what we know about the chemistry of these molecules comes from spectroscopy and microscopy studies of organic molecules extracted from different natural systems using either inorganic or organic solvents. Although all these methods gave us clues about the composition of these molecules, their composition and structure change with the extraction and the type of ex-situ analysis, their true behavior is less well understood. The goal of this project is to develop synchrotron instrumentation for studying natural organics, and to apply these recently developed synchrotron X-ray spectroscopy and microscopy techniques for understanding the: (1) functional group composition of naturally occurring organic molecules; (2) macromolecular structures of organic molecules; and (3) the nature of interactions of organic molecules with mineral surfaces in different environmental conditions.

  15. Crystalline self-assembly of organic molecules with metal ions at the air-aqueous solution interface. A grazing incidence X-ray scattering study

    DEFF Research Database (Denmark)

    Weissbuch, I.; Buller, R.; Kjær, K.

    2002-01-01

    The advent of intense X-rays from synchrotron sources made possible to probe, at the molecular level, the structural aspects of self-assemblies generated at interfaces. Here we present the two-dimensional (2-D) packing arrangements of two-, three- and multi-component organo-metallic self-assembli......The advent of intense X-rays from synchrotron sources made possible to probe, at the molecular level, the structural aspects of self-assemblies generated at interfaces. Here we present the two-dimensional (2-D) packing arrangements of two-, three- and multi-component organo-metallic self......-assemblies formed via interfacial reaction at the air-aqueous solution interface, as determined by grazing incidence X-ray diffraction (GIRD) and X-ray specular reflectivity techniques. GIXD yields structural information on the crystalline part of the Langmuir film, including the ions and counterions lateral order...... of metal ions bound to the polar head groups of amphipilic molecules; use of bolaamphiphiles to generate oriented thin films with metal ions arranged in periodic layers; delineation of differences in the lateral organization of metal ions at interfaces as induced by racemates and enantiomerically pure...

  16. Mass spectral characterisation of a polar, esterified fraction of an organic extract of an oil sands process water.

    Science.gov (United States)

    Rowland, S J; Pereira, A S; Martin, J W; Scarlett, A G; West, C E; Lengger, S K; Wilde, M J; Pureveen, J; Tegelaar, E W; Frank, R A; Hewitt, L M

    2014-11-15

    Characterising complex mixtures of organic compounds in polar fractions of heavy petroleum is challenging, but is important for pollution studies and for exploration and production geochemistry. Oil sands process-affected water (OSPW) stored in large tailings ponds by Canadian oil sands industries contains such mixtures. A polar OSPW fraction was obtained by silver ion solid-phase extraction with methanol elution. This was examined by numerous methods, including electrospray ionisation (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) and ultra-high-pressure liquid chromatography (uHPLC)/Orbitrap MS, in multiple ionisation and MS/MS modes. Compounds were also synthesised for comparison. The major ESI ionisable compounds detected (+ion mode) were C15-28 SO3 species with 3-7 double bond equivalents (DBE) and C27-28 SO5 species with 5 DBE. ESI-MS/MS collision-induced losses were due to water, methanol, water plus methanol and water plus methyl formate, typical of methyl esters of hydroxy acids. Once the fraction was re-saponified, species originally detected by positive ion MS, could be detected only by negative ion MS, consistent with their assignment as sulphur-containing hydroxy carboxylic acids. The free acid of a keto dibenzothiophene alkanoic acid was added to an unesterified acid extract of OSPW in known concentrations as a putative internal standard, but attempted quantification in this way proved unreliable. The results suggest the more polar acidic organic SO3 constituents of OSPW include C15-28  S-containing, alicyclic and aromatic hydroxy carboxylic acids. SO5 species are possibly sulphone analogues of these. The origin of such compounds is probably via further biotransformation (hydroxylation) of the related S-containing carboxylic acids identified previously in a less polar OSPW fraction. The environmental risks, corrosivity and oil flow assurance effects should be easier to assess, given that partial structures are now known

  17. Perylene-Diimide Based Donor-Acceptor-Donor Type Small-Molecule Acceptors for Solution-Processable Organic Solar Cells

    Science.gov (United States)

    Ganesamoorthy, Ramasamy; Vijayaraghavan, Rajagopalan; Sakthivel, Pachagounder

    2017-12-01

    Development of nonfullerene acceptors plays an important role in the commercial availability of plastic solar cells. We report herein synthesis of bay-substituted donor-acceptor-donor (D-A-D)-type perylene diimide (PDI)-based small molecules (SM-1 to SM-4) by Suzuki coupling method and their use as acceptors in bulk heterojunction organic solar cells (BHJ-OSCs) with poly(3-hexylthiophene) (P3HT) polymer donor. We varied the number of electron-rich thiophene units and the solubilizing side chains and also evaluated the optical and electrochemical properties of the small molecules. The synthesized small molecules were confirmed by Fourier-transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and high-resolution mass spectroscopy (HR-MS). The small molecules showed extensive and strong absorption in the ultraviolet-visible (UV-Vis) region up to 750 nm, with bandgap (E_{{g}}^{{opt}} ) reduced below P3HT polymer donor showed maximum power conversion efficiency (PCE) of 0.19% with V oc of 0.30 V, J sc of 1.72 mA cm-2, and fill factor (FF) of 37%. The PCE decreased with the number of thiophene units. The PCE of SM-2 was lower than that of SM-1. This difference in PCE can be explained by the higher aggregation tendency of the bithiophene compared with the thiophene unit. Introduction of the solubilizing group in the bay position increased the aggregation property, leading to much lower PCE than for the small molecules without solubilizing group.

  18. New models for intermolecular repulsion and their application to Van Der Waals complexes and crystals of organic molecules

    International Nuclear Information System (INIS)

    Tsui, H.H.Y.

    2001-01-01

    Model intermolecular potentials are required for simulations of molecules in the gas, liquid, or solid phase. The widely used isotropic atom-atom model potentials are empirically fitted and based on the assumptions of transferability, combining rules and that atoms in molecules are spherical. This thesis develops a non-empirical method of modelling repulsion by applying the overlap model, which we show as a general non-empirical method of deriving repulsion potentials for a specific molecule. In this thesis, the repulsion parameters for an exponential atom-atom model potential are obtained from the ab initio charge density of a small organic molecule by making the assumption that the repulsion is proportional to the overlap of a pair of molecules. The proportionality constant is fixed by a limited number of intermolecular perturbation theory (IMPT) calculations. To complete the model potential, the electrostatic interaction is represented by a distributed multipole analysis, and the Slater-Kirkwood formula is used for the dispersion. These non-empirical potentials can reproduce experimental crystal structure when applied to crystal structure prediction of an oxyboryl derivative. A detailed study on further improving the overlap model was carried out for phenol-water, by including other minor intermolecular contributions of charge-transfer and penetration. High quality ab initio calculations on the complex were performed for use in comparison. To compare with experimental data, diffusion Monte Carlo simulations were performed with the potential, so that the effects of anharmonic zero-point motion on structure and energy of the system are included. When the system is too large for an IMPT calculation, the proportionality constant can be determined empirically by fitting the cell volume as shown in our study of crystal structures of chlorothalonil. This is used with an anisotropic repulsion model that has been derived for Cl and N atoms in chlorothalonil. This model

  19. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    CERN Document Server

    Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

  20. Adsorption of Organic Molecules to van der Waals Materials: Comparison of Fluorographene and Fluorographite with Graphene and Graphite.

    Science.gov (United States)

    Karlický, František; Otyepková, Eva; Lo, Rabindranath; Pitoňák, Michal; Jurečka, Petr; Pykal, Martin; Hobza, Pavel; Otyepka, Michal

    2017-03-14

    Understanding strength and nature of noncovalent binding to surfaces imposes significant challenge both for computations and experiments. We explored the adsorption of five small nonpolar organic molecules (acetone, acetonitrile, dichloromethane, ethanol, ethyl acetate) to fluorographene and fluorographite using inverse gas chromatography and theoretical calculations, providing new insights into the strength and nature of adsorption of small organic molecules on these surfaces. The measured adsorption enthalpies on fluorographite range from -7 to -13 kcal/mol and are by 1-2 kcal/mol lower than those measured on graphene/graphite, which indicates higher affinity of organic adsorbates to fluorographene than to graphene. The dispersion-corrected functionals performed well, and the nonlocal vdW DFT functionals (particularly optB86b-vdW) achieved the best agreement with the experimental data. Computations show that the adsorption enthalpies are controlled by the interaction energy, which is dominated by London dispersion forces (∼70%). The calculations also show that bonding to structural features, like edges and steps, as well as defects does not significantly increase the adsorption enthalpies, which explains a low sensitivity of measured adsorption enthalpies to coverage. The adopted Langmuir model for fitting experimental data enabled determination of adsorption entropies. The adsorption on the fluorographene/fluorographite surface resulted in an entropy loss equal to approximately 40% of the gas phase entropy.

  1. Multi-Chlorine-Substituted Self-Assembled Molecules As Anode Interlayers: Tuning Surface Properties and Humidity Stability for Organic Photovoltaics.

    Science.gov (United States)

    Cheng, Xiaofang; Huang, Liqiang; Zhang, Lifu; Ai, Qingyun; Chen, Lie; Chen, Yiwang

    2017-03-15

    Self-assembled small molecules (SASMs) are effective materials to improve the interfacial properties between a metal/metal oxide and the overlying organic layer. In this work, surface modification of indium tin oxide (ITO) electrode by a series of Cl-containing SASMs has been exploited to control the surface properties of ITO and device performance for organic photovoltaics. Depending on the position and degrees of chlorination for SASMs, we could precisely manipulate the work function of the ITO electrode, and chemisorption of SASMs on ITO as well. Consequently, a power conversion efficiency (PCE) of 9.1% was achieved with tetrachlorobenzoic acid (2,3,4,5-CBA) SASM by a simple solution-processed method based on PTB7-Th-PC 71 BM heterojunction. More intriguingly, we discover that device performance is closely associated with the humidity of ambient conditions. When the humidity increases from 35-55% to 80-95%, device performance with 2,3,4,5-CBA has negligible reduction, in contrast with other SASMs that show a sharp reduction in PCEs. The increased device performance is primarily attributed to a matched work function, stable chemisorption, and beneficial wettability with overlying active layer. These findings suggest an available approach for manufacturing inexpensive, stable, efficient, and environmentally friendly organic photovoltaics by appropriate self-assembled small molecules.

  2. DFT and TD-DFT calculation of new thienopyrazine-based small molecules for organic solar cells.

    Science.gov (United States)

    Bourass, Mohamed; Benjelloun, Adil Touimi; Benzakour, Mohammed; Mcharfi, Mohammed; Hamidi, Mohammed; Bouzzine, Si Mohamed; Bouachrine, Mohammed

    2016-01-01

    Novel six organic donor-π-acceptor molecules (D-π-A) used for Bulk Heterojunction organic solar cells (BHJ), based on thienopyrazine were studied by density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches, to shed light on how the π-conjugation order influence the performance of the solar cells. The electron acceptor group was 2-cyanoacrylic for all compounds, whereas the electron donor unit was varied and the influence was investigated. The TD-DFT method, combined with a hybrid exchange-correlation functional using the Coulomb-attenuating method (CAM-B3LYP) in conjunction with a polarizable continuum model of salvation (PCM) together with a 6-31G(d,p) basis set, was used to predict the excitation energies, the absorption and the emission spectra of all molecules. The trend of the calculated HOMO-LUMO gaps nicely compares with the spectral data. In addition, the estimated values of the open-circuit photovoltage (V oc ) for these compounds were presented in two cases/PC 60 BM and/PC 71 BM. The study of structural, electronics and optical properties for these compounds could help to design more efficient functional photovoltaic organic materials.

  3. Solid state proton spin-lattice relaxation in four structurally related organic molecules

    International Nuclear Information System (INIS)

    Beckmann, Peter A.; Burbank, Kendra S.; Lau, Matty M.W.; Ree, Jessica N.; Weber, Tracy L.

    2003-01-01

    We report and interpret the temperature dependence of the proton spin-lattice relaxation rate at 8.50 and 22.5 MHz in four polycrystalline solids composed of structurally related molecules: 2-ethylanthracene, 2-t-butylanthracene, 2-ethylanthraquinone, and 2-t-butylanthraquinone. We have been unable to grow single crystals and therefore do not know the crystal structures. Hence, we use the NMR relaxometry data to make predictions about the solid state structures. As expected, we are able to conclude that the ethyl groups do not reorient in the solid state but that the t-butyl groups do. The anthraquinones have a ''simpler'' structure than the anthracenes. The best dynamical models suggest that there is a unique crystallographic site for the t-butyl groups in 2-t-butylanthraquinone and two sites, each with half the molecules, for the ethyl groups in 2-ethylanthraquinone. There are also two sites in 2-ethylanthracene, but with unequal weights, suggesting four sites in the unit cell with lower symmetry than the two anthraquinones. Finally, the observed relaxation rate data in 2-t-butylanthracene is very complex and its interpretation demonstrates the uniqueness problem that arises in interpreting relaxometry data without the knowledge of the crystal structure

  4. IR spectral studies of the formation of prebiological organic molecules in ion-bombarded ices

    Science.gov (United States)

    Hudson, R.; Moore, M.

    To better understand the formation of C- and CN-containing molecules in cold cosmic environments we have performed a variety of processing experiments on icy mixtures. We will discuss details of condensed-phase synthetic pathways for several acids, alcohols, and aldehydes. For N2 -rich ices containing CH4 , we will show that several CN-bonded acids are easily formed. We will compare carbonic and formic acid production in H O-, CO- and CO2 -dominated ices.2 Condensed-phase pathways for the synthesis of several alcohols including methanol and ethylene glycol, along with several aldehydes including formaldehyde and acetaldehyde, will be discussed. While warming irradiated ices, IR spectra help track the formation of new species from, for example, radical or acid-base reactions, and the loss of species due to vaporization. These experiments demonstrate that condensed-phase reactions lead to cometary and interstellar molecules of varying volatilities. Several newly synthesized species are particularly relevant to recent radio detections, and are of high interest to astronomers and astrobiologists. This research is funded through NRA 344-33-01 and 344-02-57.

  5. Semiexperimental equilibrium structures for building blocks of organic and biological molecules: the B2PLYP route.

    Science.gov (United States)

    Penocchio, Emanuele; Piccardo, Matteo; Barone, Vincenzo

    2015-10-13

    The B2PLYP double hybrid functional, coupled with the correlation-consistent triple-ζ cc-pVTZ (VTZ) basis set, has been validated in the framework of the semiexperimental (SE) approach for deriving accurate equilibrium structures of molecules containing up to 15 atoms. A systematic comparison between new B2PLYP/VTZ results and several equilibrium SE structures previously determined at other levels, in particular B3LYP/SNSD and CCSD(T) with various basis sets, has put in evidence the accuracy and the remarkable stability of such model chemistry for both equilibrium structures and vibrational corrections. New SE equilibrium structures for phenylacetylene, pyruvic acid, peroxyformic acid, and phenyl radical are discussed and compared with literature data. Particular attention has been devoted to the discussion of systems for which lack of sufficient experimental data prevents a complete SE determination. In order to obtain an accurate equilibrium SE structure for these situations, the so-called templating molecule approach is discussed and generalized with respect to our previous work. Important applications are those involving biological building blocks, like uracil and thiouracil. In addition, for more general situations the linear regression approach has been proposed and validated.

  6. Exploring mechanochemistry to turn organic bio-relevant molecules into metal-organic frameworks: a short review

    Directory of Open Access Journals (Sweden)

    Vânia André

    2017-11-01

    Full Text Available Mechanochemistry is a powerful and environmentally friendly synthetic technique successfully employed in different fields of synthetic chemistry. Application spans from organic to inorganic chemistry including the synthesis of coordination compounds. Metal-organic frameworks (MOFs are a class of compounds with numerous applications, from which we highlight herein their application in the pharmaceutical field (BioMOFs, whose importance has been growing and is now assuming a relevant and promising domain. The need to find cleaner, greener and more energy and material-efficient synthetic procedures led to the use of mechanochemistry into the synthesis of BioMOFs.

  7. Organic molecule-based photothermal agents: an expanding photothermal therapy universe.

    Science.gov (United States)

    Jung, Hyo Sung; Verwilst, Peter; Sharma, Amit; Shin, Jinwoo; Sessler, Jonathan L; Kim, Jong Seung

    2018-04-03

    Over the last decade, organic photothermal therapy (PTT) agents have attracted increasing attention as a potential complement for, or alternative to, classical drugs and sensitizers involving inorganic nanomaterials. In this tutorial review, we provide a structured description of the main classes of organic photothermal agents and their characteristics. Representative agents that have been studied in the context of photothermal therapy since 2000 are summarized and recent advances in using PTT agents to address various cancers indications are highlighted.

  8. Charge trapping at organic/self-assembly molecule interfaces studied by electrical switching behaviour in a crosspoint structure

    International Nuclear Information System (INIS)

    Li Yun; Pan Lijia; Pu Lin; Shi Yi; Liu Chuan; Tsukagoshi, Kazuhito

    2012-01-01

    Charge trapping at organic/self-assembly molecule (SAM) interfaces is studied by the electrical switching behaviour in a crosspoint structure, where interfacial charge trapping tunes the potential barrier of the SAM layer. The sample with rubrene exhibits the write-once read-many-times memory effect, which is due to the interfacial charges trapped at deep states. On the other hand, the sample with 2-amino-4,5-dicyanoimidazole presents recyclable conduction transition, which results from the trapped charges distributed at shallow states. Moreover, the percentage of the charges trapped at shallow states can be estimated from electrical transition levels. (paper)

  9. Charge trapping at organic/self-assembly molecule interfaces studied by electrical switching behaviour in a crosspoint structure

    Science.gov (United States)

    Li, Yun; Liu, Chuan; Pan, Lijia; Pu, Lin; Tsukagoshi, Kazuhito; Shi, Yi

    2012-01-01

    Charge trapping at organic/self-assembly molecule (SAM) interfaces is studied by the electrical switching behaviour in a crosspoint structure, where interfacial charge trapping tunes the potential barrier of the SAM layer. The sample with rubrene exhibits the write-once read-many-times memory effect, which is due to the interfacial charges trapped at deep states. On the other hand, the sample with 2-amino-4,5-dicyanoimidazole presents recyclable conduction transition, which results from the trapped charges distributed at shallow states. Moreover, the percentage of the charges trapped at shallow states can be estimated from electrical transition levels.

  10. Study on detection of terrestrial and marine fractions in marine organic molecules by spectrophoto- and spectrofluorometric methods

    Science.gov (United States)

    Drozdowska, Violetta; Wróbel, Iwona; Piskozub, Jacek

    2017-04-01

    The sea surface is a highly productive and active interface between the sea and the atmosphere. Sea surface films are created by organic matter from sea and land sources and they dissipate due to loss of material at the sea surface, including microbial degradation, chemical and photo chemical processes, and loss due to absorption and adsorption onto particulates. However the surface microlayer is almost ubiquitous and cover most of the surface of the ocean, even under conditions of high turbulence. Surface active molecules (surfactants) present in the surface microlayer (SML) may modify the number of physical processes taking place there: among others they affect the depth of penetration of solar radiation and gas exchange. Therefore, research on the influence of surfactants on the sea surface properties become an important task, especially in coastal waters and in vicinity of the river mouths. Surfactants comprises a mixture of organic molecules rich in lipids, polymeric and humus whose proportions determine the various properties of the SML. A unique structure of the energy levels of the organic molecules results in a unique spectral distribution of the light intensity absorbed and emitted by the molecules. Hence, the absorption and fluorescence spectra of organic compounds may allow the identification of the sources of organic matter. Additionally, several absorption (E2:E3, S, SR) and fluorescence (fluorescence intensities at peaks: A, C, M, T, the ratio (M+T)/(A+C), HIX) indices help in describing the changes in molecular size and weight as well as composition of organic matter during the humification processes and caused by photobleaching and biodegradation. Investigations included the region of Gulf of Gdańsk, along a transect from the Vistula River outlet to open sea. The fluorescence and absorption measurements of the samples collected from a surface films and a subsurface layer (SS, a depth of 1 m) during three research cruises in Gulf of Gdańsk, the

  11. Design of C18 Organic Phases with Multiple Embedded Polar Groups for Ultraversatile Applications with Ultrahigh Selectivity.

    Science.gov (United States)

    Mallik, Abul K; Qiu, Hongdeng; Oishi, Tomohiro; Kuwahara, Yutaka; Takafuji, Makoto; Ihara, Hirotaka

    2015-07-07

    For the first time, we synthesized multiple embedded polar groups (EPGs) containing linear C18 organic phases. The new materials were characterized by elemental analysis, IR spectroscopy, (1)H NMR, diffuse reflectance infrared Fourier transform (DRIFT), solid-state (13)C cross-polarization magic angle spinning (CP/MAS) NMR, suspended-state (1)H NMR, and differential scanning calorimetry (DSC). (29)Si CP/MAS NMR was carried out to investigate the degree of cross-linking of the silane and silane functionality of the modified silica. Solid-state (13)C CP/MAS NMR and suspended-state (1)H NMR spectroscopy indicated a higher alkyl chain order for the phase containing four EPGs than for the phase with three EPGs. To correlate the NMR results with temperature-dependent chromatographic studies, standard reference materials (SRM 869b and SRM 1647e), a column selectivity test mixture for liquid chromatography was employed. A single EPG containing the C18 phase was also prepared in a similar manner to be used as a reference column especially for the separation of basic and polar compounds in reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), respectively. Detailed chromatographic characterization of the new phases was performed in terms of their surface coverage, hydrophobic selectivity, shape selectivity, hydrogen bonding capacity, and ion-exchange capacity at pH 2.7 and 7.6 for RPLC as well as their hydrophilicity, the selectivity for hydrophilic-hydrophobic substituents, the selectivity for the region and configurational differences in hydrophilic substituents, the evaluation of electrostatic interactions, and the evaluation of the acidic-basic nature for HILIC-mode separation. Furthermore, peak shapes for the basic analytes propranolol and amitriptyline were studied as a function of the number of EPGs on the C18 phases in the RPLC. The chromatographic performance of multiple EPGs containing C18 HILIC phases is illustrated

  12. Comment on "Conformational analysis of small organic molecules using NOE and RDC data: A discussion of strychnine and α-methylene-γ-butyrolactone"

    Science.gov (United States)

    Khodov, I. A.; Kiselev, M. G.; Efimov, S. V.; Klochkov, V. V.

    2016-05-01

    In a recent paper published in this journal, Kolmer et al. [1] reported an experimental approach for conformational analysis of small organic molecules using NOE and RDC techniques. The authors obtained information on conformation of strychnine and α-methylene-γ-butyrolactone molecules. In addition, possible sources of error in the measurement and analysis process and ideas of how to exclude them were discussed.

  13. Structure investigation of organic molecules on Au(111) surfaces; Strukturuntersuchung organischer Molekuele auf Au(111)-Oberflaechen

    Energy Technology Data Exchange (ETDEWEB)

    Kazempoor, Michel

    2009-02-02

    The present work covers two topics namely the coadsorption of formic acid and water on Au(111) and the structure of biphenylalkanthiole SAMs on Au(111) surfaces. The coadsorption of formic acid and water on Au(111) surfaces has been investigated by means of vibrational and photoelectron spectroscopy (HREELS, XPS). Formic acid adsorbs at 90 K molecularly with vibrational modes characteristic for flat lying zig-zag chains in the mono- and multilayer regime, like in solid formic acid. The structure of the flat lying formic acid chains was determined by low energy electron diffraction (LEED) as a (2r3 x r19) unit cell. Annealing results in a complete desorption at 190 K. Sequential adsorption of formic acid and water at 90 K shows no significant chemical interaction. Upon annealing the coadsorbed layer to 140 K a hydrogenbonded cyclic complex of formic acid with one water molecule could be identified using isotopically labelled adsorbates. Upon further annealing this complex decomposes leaving molecularly adsorbed formic acid on the surface at 160 K, accompanied by a proton exchange between formic acid and water. The influence of the alkane spacer chain length on the structure of biphenylalkanethiols on Au(111) surfaces was investigated as well. A systematic study was done on BPn-SAMs deposited from the gas phase. For every chain length a structure was found by LEED. Furthermore the influence of temperature on the structure was investigated in the range from room temperature up to about 400 K. To obviate influences from different preparation methods BP3 and BP4 was deposited from gas phase and from solution. No LEED spots were observed on BP4 SAMs deposited from solution. For BP3 an influence of the preparation could be excluded. For all BPn-SAMs a good agreement between LEED and STM data's was found. Nevertheless different unit cells were determined by LEED and STM consistent structures could be suggested considering the unit cell size given by LEED and the

  14. Percolation model for electron conduction in films of metal nanoparticles linked by organic molecules

    International Nuclear Information System (INIS)

    Muller, K.H.; Herrmann, J.; Raguse, B.; Baxter, G.; Reda, T.

    2002-01-01

    Full text: We have investigated theoretically and experimentally the temperature dependence of the conductance of films of Au nanoparticles linked by alkane dithiol molecules in the temperature range between 5 K and 300 K. Conduction in these films is due to tunneling of single electrons between neighbouring metal nanoparticles. During tunnelling an electron has to overcome the Coulomb charging energy. We find that the observed temperature dependence of the conductance is non-Arrhenius like and can be described in terms of a percolation theory which takes account of disorder in the system. Disorder in our nanoparticle films is caused by variations in the nanoparticle size, fluctuations in the separation gaps between adjacent nanoparticles and by offset charges. To explain in detail our experimental data, a wide distribution of separation gaps and charging energies is needed. We find that a wide Coulomb charging energy distribution can arise from random offset charges even if the nanoparticle size distribution is narrow

  15. Interaction of mineral surfaces with simple organic molecules by diffuse reflectance IR spectroscopy (DRIFT)

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, Joan E.; Kelley, Michael J.

    2008-06-01

    Diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS) was used to characterize multi-layers of lysine, glutamic acid and salicylic acid on -alumina and kaolinite surfaces. The results agreed well with those previously obtained by ATR-IR in aqueous media where available, indicating that DRIFT may be regarded as effectively an in-situ spectroscopy for these materials. In the case of salicylic acid adsorption onto γ-alumina, DRIFTS was used to identify monolayer coverage and to detect molecules down to coverage of 3% of a monolayer. The spectroscopic results as to coverage were confirmed by analysis of the solutions used for treatment. The spectra obtained allowed identification of changes in the bonding environment with increasing surface coverage. DRIFTS, offers several advantages in terms of materials, experimental technique and data treatment, motivating further investigations.

  16. Desorption of organic molecules with fast incident atomic and polyatomic ions

    International Nuclear Information System (INIS)

    Hunt, J.E.; Salehpour, M.; Fishel, D.L.

    1989-01-01

    In 1974, Macfarlane and coworkers introduced a new mass spectrometric technique based on desorption-ionization of sample molecules from solid targets by the impact of fast heavy ions (fission fragments) from 252 Cf. The process of ion-induced desorption of molecular ions from surfaces is not yet fully understood, although a large amount of experimental data related to the mechanism has been published. This paper concerns the use of fast incident polyatomic ions to induce desorption of secondary molecular ions of valine and chlorophyll from surfaces. Polyatomic ions are unique in that they are a collection of temporally and spatially correlated atoms. The main finding in this study is that incident polyatomic ions produce drastic enhancements in the secondary ion yields over atomic ions. Also, two types of nonlinear effects in desorption have been observed and will be discussed

  17. Ozonolysis and Subsequent Photolysis of unsaturated organic molecules: Model Systems for Photochemical Aging of Organic Aerosol Particles

    Science.gov (United States)

    Park, J.; Gomez, A. L.; Walser, M. L.; Lin, A.; Nizkorodov, S. A.

    2005-12-01

    Chemical and photochemical aging of organic species adsorbed on aerosol particle surfaces is believed to have a significant effect on cloud condensation properties of atmospheric aerosols. Ozone initiated oxidation reactions of thin films of undecylenic acid and alkene-terminated self assembled monolayers (SAMs) on SiO2 surface were investigated using a combination of spectroscopic and mass spectrometric techniques. Photolysis of the oxidized film in the tropospheric actinic region (λ>290 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the enhanced photochemical activity. The presence of peroxides in the oxidized sample was confirmed by mass-spectrometric analysis and by an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is also observed. The reaction mechanism and its implications for photochemical aging of atmospheric aerosol particles will be discussed.

  18. Multi-layer solid-phase extraction and evaporation-enrichment methods for polar organic chemicals from aqueous matrices.

    Science.gov (United States)

    Köke, Niklas; Zahn, Daniel; Knepper, Thomas P; Frömel, Tobias

    2018-03-01

    Analysis of polar