Sample records for abundant organic molecules

  1. Abundance of complex organic molecules in comets

    NASA Astrophysics Data System (ADS)

    Biver, N.; Bockelée-Morvan, D.; Debout, V.; Crovisier, J.; Moreno, R.; Boissier, J.; Lis, D.; Colom, P.; Paubert, G.; Dello Russo, N.; Vervack, R.; Weaver, H.

    2014-07-01

    The IRAM-30m submillimetre radio telescope has now an improved sensitivity and versality thanks to its wide-band EMIR receivers and high-resolution FFT spectrometer. Since 2012, we have undertaken ~70 GHz wide spectral surveys in the 1-mm band in several comets: C/2009 P1 (Garradd), C/2011 L4 (PanSTARRS), C/2012 F6 (Lemmon), C/2012 S1 (ISON), and C/2013 R1 (Lovejoy). Since their discovery in comet C/1995 O1 (Hale-Bopp) in 1997 (Bockelée-Morvan et al. 2000, Crovisier et al. 2004a, 2004b), we have detected complex CHO(N)-molecules such as formic acid (HCOOH), formamide (NH_2CHO), acetaldehyde (CH_3CHO), and ethylene glycol ((CH_2OH)_2) in several other comets. HCOOH has now been detected in 6 other comets since 2004, and formamide, ethylene glycol, and acetaldehyde were re-detected for the first time in comets Lemmon or Lovejoy in 2013 (Biver et al. 2014). We will present the abundances relative to water we derive for these species, and the sensitive upper limits we obtain for other complex CHO-bearing molecules. We will discuss the implication of these findings on the origin of cometary material in comparison with observations of such molecules in the interstellar medium.

  2. Organic Molecules in Meteorites

    NASA Astrophysics Data System (ADS)

    Martins, Zita

    2015-08-01

    Carbonaceous meteorites are primitive samples from the asteroid belt, containing 3-5wt% organic carbon. The exogenous delivery of organic matter by carbonaceous meteorites may have contributed to the organic inventory of the early Earth. The majority (>70%) of the meteoritic organic material consist of insoluble organic matter (IOM) [1]. The remaining meteoritic organic material (<30%) consists of a rich organic inventory of soluble organic compounds, including key compounds important in terrestrial biochemistry [2-4]. Different carbonaceous meteorites contain soluble organic molecules with different abundances and distributions, which may reflect the extension of aqueous alteration or thermal metamorphism on the meteorite parent bodies. Extensive aqueous alteration on the meteorite parent body may result on 1) the decomposition of α-amino acids [5, 6]; 2) synthesis of β- and γ-amino acids [2, 6-9]; 3) higher relative abundances of alkylated polycyclic aromatic hydrocarbons (PAHs) [6, 10]; and 4) higher L-enantiomer excess (Lee) value of isovaline [6, 11, 12].The soluble organic content of carbonaceous meteorites may also have a contribution from Fischer-Tropsch/Haber-Bosch type gas-grain reactions after the meteorite parent body cooled to lower temperatures [13, 14].The analysis of the abundances and distribution of the organic molecules present in meteorites helps to determine the physical and chemical conditions of the early solar system, and the prebiotic organic compounds available on the early Earth.[1] Cody and Alexander (2005) GCA 69, 1085. [2] Cronin and Chang (1993) in: The Chemistry of Life’s Origin. pp. 209-258. [3] Martins and Sephton (2009) in: Amino acids, peptides and proteins in organic chemistry. pp. 1-42. [4] Martins (2011) Elements 7, 35. [5] Botta et al. (2007) MAPS 42, 81. [6] Martins et al. (2015) MAPS, in press. [7] Cooper and Cronin (1995) GCA 59, 1003. [8] Glavin et al. (2006) MAPS. 41, 889. [9] Glavin et al. (2011) MAPS 45, 1948. [10

  3. Our Galactic Neighbor Hosts Complex Organic Molecules

    NASA Astrophysics Data System (ADS)

    Hensley, Kerry

    2018-03-01

    small amounts of methanol, the parentmolecule of the two newly-discovered compounds. By revealing the spectral signatures of dimethyl ether and methyl formate, Sewio and collaboratorsfurther prove thatorganic chemistry is hard at work in hot cores in the LMC.This discovery is momentous because dwarf galaxies like theLMC tend to have a lower abundance of the heavy elements that make up complex organic molecules most importantly, oxygen, carbon, and nitrogen. Beyond lacking the raw materials necessary to create complex molecules, the gas of low-metallicity galaxies does a poorer job preventing the penetration of high-energy photons. The impinging photons warm dust grains, resulting in a lower probability of forming and maintaining complex organic molecules. Despite this, organic molecules appear to beable todevelop and persist which has exciting implications for organic chemistry in low-metallicity environments.ALMA observation of emission by methyl formate in a hot core in the LMC.[Adapted from Sewio et al. 2018]A Lens into the PastIn the early universe, before the budding galaxies have had time to upcycle their abundant hydrogen into heavier elements, organic chemistry is thought to proceed slowly or not at all. The discovery of complex organic molecules in a nearby low-metallicity galaxy upends this theory and propels us toward a better understanding of the organic chemistry in the early universe.CitationMarta Sewio et al 2018ApJL853L19. doi:10.3847/2041-8213/aaa079

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Organic Molecules in Oxygen-Rich Circumstellar Envelopes: Methanol and Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Charnley, S. B.; Tielens, A. G. G. M.; Kress, M. E.

    1995-01-01

    The existence of anomalously high abundances of gaseous CH4 has been invoked to explain the unexpectedly high abundances of the carbon-bearing molecules HCN and H2CO in the outflows from O-rich red giants. We have modelled the chemistry that proceeds in the outer envelope when CH4 is injected from the inner envelope. We find that photolysis by the interstellar radiation field drives an ion-neutral chemistry which produces several organic molecules. The calculated abundances of CH3OH, C2H and C2 can be comparable to those calculated for H2CO and HCN. Species such as C2H4, C2H2 and CH3CN can also be abundant. A search for CH3OH and C2H in several O-rich outflows known to exhibit strong HCN emission is needed. As it derives entirely from the CH4 photochain, is insensitive to the envelope temperature distribution, and has accessible transitions at millimetre wavelengths, the detection of the C2H radical would provide further indirect support for the presence of the hypothesized methane.

  6. Interstellar grain chemistry and organic molecules

    NASA Technical Reports Server (NTRS)

    Allamandola, L. J.; Sandford, S. A.

    1990-01-01

    The detection of prominant infrared absorption bands at 3250, 2170, 2138, 1670 and 1470 cm(-1) (3.08, 4.61, 4.677, 5.99 and 6.80 micron m) associated with molecular clouds show that mixed molecular (icy) grain mantles are an important component of the interstellar dust in the dense interstellar medium. These ices, which contain many organic molecules, may also be the production site of the more complex organic grain mantles detected in the diffuse interstellar medium. Theoretical calculations employing gas phase as well as grain surface reactions predict that the ices should be dominated only by the simple molecules H2O, H2CO, N2, CO, O2, NH3, CH4, possibly CH3OH, and their deuterated counterparts. However, spectroscopic observations in the 2500 to 1250 cm(-1)(4 to 8 micron m) range show substantial variation from source reactions alone. By comparing these astronomical spectra with the spectra of laboratory-produced analogs of interstellar ices, one can determine the composition and abundance of the materials frozen on the grains in dense clouds. Experiments are described in which the chemical evolution of an interstellar ice analog is determined during irradiation and subsequent warm-up. Particular attention is paid to the types of moderately complex organic materials produced during these experiments which are likely to be present in interstellar grains and cometary ices.

  7. Complex organic molecules in the Galactic Centre: the N-bearing family

    NASA Astrophysics Data System (ADS)

    Zeng, S.; Jiménez-Serra, I.; Rivilla, V. M.; Martín, S.; Martín-Pintado, J.; Requena-Torres, M. A.; Armijos-Abendaño, J.; Riquelme, D.; Aladro, R.

    2018-05-01

    We present an unbiased spectral line survey toward the Galactic Centre (GC) quiescent giant molecular cloud (QGMC), G+0.693 using the GBT and IRAM 30 telescopes. Our study highlights an extremely rich organic inventory of abundant amounts of nitrogen (N)-bearing species in a source without signatures of star formation. We report the detection of 17 N-bearing species in this source, of which 8 are complex organic molecules (COMs). A comparison of the derived abundances relative to H2 is made across various galactic and extragalactic environments. We conclude that the unique chemistry in this source is likely to be dominated by low-velocity shocks with X-rays/cosmic rays also playing an important role in the chemistry. Like previous findings obtained for O-bearing molecules, our results for N-bearing species suggest a more efficient hydrogenation of these species on dust grains in G+0.693 than in hot cores in the Galactic disk, as a consequence of the low dust temperatures coupled with energetic processing by X-ray/cosmic ray radiation in the GC.

  8. The molecular inventory around protostars: water, organic molecules, and the missing oxygen problem

    NASA Astrophysics Data System (ADS)

    Neufeld, David A.

    2018-06-01

    Massive star formation is accompanied by significant chemical evolution in the surrounding interstellar gas. Here, grains are heated up and icy mantles evaporate, releasing a rich inventory of water and organic molecules into the gas-phase within “hot core” regions surrounding massive protostars. Because molecules on the grain surface present broad infrared features without rotational structure, only the most abundant molecules can be identified unambiguously in the solid phase; once released into the gas-phase, however, where they are free to rotate, the constituents of grain mantles can be identified easily by means of rotational spectroscopy at millimeter and submillimeter wavelengths or through rovibrational spectroscopy in the mid-infrared. While observations of pure-rotational emission lines provide a broad view of hot core chemistry, absorption line spectroscopy of rovibrational transitions can probe the very hottest material closest to the protostar. With access to the mid-infrared spectral region from above 99% of Earth’s water vapor, SOFIA provides a unique platform for high-resolution rovibrational spectroscopy of water and organic molecules, many of which have vibrational transitions in the 5 – 8 micron spectral region that is unobservable from the ground. High spectral resolution is essential for disentangling the rotational structure and providing reliable measurements of the molecular column densities and temperatures. Future SOFIA observations will help elucidate the inventory of water and organic molecules around young protostars, and can address a puzzle related to the “oxygen budget” in the interstellar medium: surprisingly, the main interstellar reservoirs of the third-most abundant element in the Universe have yet to be identified.

  9. Organic Molecules On the Surfaces of Iapetus and Phoebe

    NASA Technical Reports Server (NTRS)

    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.

  10. Recent observations of organic molecules in nearby cold, dark interstellar clouds

    NASA Technical Reports Server (NTRS)

    Suzuki, H.; Ohishi, M.; Morimoto, M.; Kaifu, N.; Friberg, P.

    1985-01-01

    Recent investigations of the organic chemistry of relatively nearby cold, dark interstellar clouds are reported. Specifically, the presence of interstellar tricarbon monoxide (C3O) in Taurus Molecular Cloud 1 (TMC-1) is confirmed. The first detection in such regions of acetaldehyde (CH3CHO), the most complex oxygen-containing organic molecule yet found in dark clouds is reported, as well as the first astronomical detection of several molecular rotational transitions, including the J = 18-17 and 14-13 transitions of cyanodiacetylene (HC5N), the 1(01)-0(00) transition of acetaldehyde, and the J = 5-4 transition of C3O. A significant upper limit is set on the abundance of cyanocarbene (HCCN) as a result of the first reported interstellar search for this molecule.

  11. Complex organic molecules during low-mass star formation: Pilot survey results

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Öberg, Karin I.; Graninger, Dawn; Lauck, Trish, E-mail: koberg@cfa.harvard.edu

    Complex organic molecules (COMs) are known to be abundant toward some low-mass young stellar objects (YSOs), but how these detections relate to typical COM abundance are not yet understood. We aim to constrain the frequency distribution of COMs during low-mass star formation, beginning with this pilot survey of COM lines toward six embedded YSOs using the IRAM 30 m Telescope. The sample was selected from the Spitzer c2d ice sample and covers a range of ice abundances. We detect multiple COMs, including CH{sub 3}CN, toward two of the YSOs, and tentatively toward a third. Abundances with respect to CH{sub 3}OHmore » vary between 0.7% and 10%. This sample is combined with previous COM observations and upper limits to obtain a frequency distributions of CH{sub 3}CN, HCOOCH{sub 3}, CH{sub 3}OCH{sub 3}, and CH{sub 3}CHO. We find that for all molecules more than 50% of the sample have detections or upper limits of 1%-10% with respect to CH{sub 3}OH. Moderate abundances of COMs thus appear common during the early stages of low-mass star formation. A larger sample is required, however, to quantify the COM distributions, as well as to constrain the origins of observed variations across the sample.« less

  12. Triton - Stratospheric molecules and organic sediments

    NASA Technical Reports Server (NTRS)

    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.

  13. Meteors do not break exogenous organic molecules into high yields of diatomics

    NASA Technical Reports Server (NTRS)

    Jenniskens, Peter; Schaller, Emily L.; Laux, Christophe O.; Wilson, Michael A.; Schmidt, Greg; Rairden, Rick L.

    2004-01-01

    Meteoroids that dominate the Earth's extraterrestrial mass influx (50-300 microm size range) may have contributed a unique blend of exogenous organic molecules at the time of the origin of life. Such meteoroids are so large that most of their mass is ablated in the Earth's atmosphere. In the process, organic molecules are decomposed and chemically altered to molecules differently from those delivered to the Earth's surface by smaller (<50 microm) micrometeorites and larger (>10 cm) meteorites. The question addressed here is whether the organic matter in these meteoroids is fully decomposed into atoms or diatomic compounds during ablation. If not, then the ablation products made available for prebiotic organic chemistry, and perhaps early biology, might have retained some memory of their astrophysical nature. To test this hypothesis we searched for CN emission in meteor spectra in an airborne experiment during the 2001 Leonid meteor storm. We found that the meteor's light-emitting air plasma, which included products of meteor ablation, contained less than 1 CN molecule for every 30 meteoric iron atoms. This contrasts sharply with the nitrogen/iron ratio of 1:1.2 in the solid matter of comet 1P/Halley. Unless the nitrogen content or the abundance of complex organic matter in the Leonid parent body, comet 55P/Tempel-Tuttle, differs from that in comet 1P/Halley, it appears that very little of that organic nitrogen decomposes into CN molecules during meteor ablation in the rarefied flow conditions that characterize the atmospheric entry of meteoroids approximately 50 microm-10 cm in size. We propose that the organics of such meteoroids survive instead as larger compounds.

  14. Organizing and addressing magnetic molecules.

    PubMed

    Gatteschi, Dante; Cornia, Andrea; Mannini, Matteo; Sessoli, Roberta

    2009-04-20

    Magnetic molecules ranging from simple organic radicals to single-molecule magnets (SMMs) are intensively investigated for their potential applications in molecule-based information storage and processing. The goal of this Article is to review recent achievements in the organization of magnetic molecules on surfaces and in their individual probing and manipulation. We stress that the inherent fragility and redox sensitivity of most SMM complexes, combined with the noninnocent role played by the substrate, ask for a careful evaluation of the structural and electronic properties of deposited molecules going beyond routine methods for surface analysis. Detailed magnetic information can be directly obtained using X-ray magnetic circular dichroism or newly emerging scanning probe techniques with magnetic detection capabilities.

  15. Organic molecules on Mars

    NASA Astrophysics Data System (ADS)

    ten Kate, Inge Loes

    2018-06-01

    On 6 August 2012, the Sample Analysis at Mars (SAM) instrument suite (1) arrived on Mars onboard the Curiosity rover. SAM's main aim was to search for organic molecules on the martian surface. On page 1096 of this issue, Eigenbrode et al. (2) report SAM data that provide conclusive evidence for the presence of organic compounds—thiophenic, aromatic, and aliphatic compounds—in drill samples from Mars' Gale crater. In a related paper on page 1093, Webster et al. (3) report a strong seasonal variation in atmospheric methane, the simplest organic molecule, in the martian atmosphere. Both these finding are breakthroughs in astrobiology.

  16. Unified Microscopic-Macroscopic Monte Carlo Simulations of Complex Organic Molecule Chemistry in Cold Cores

    NASA Astrophysics Data System (ADS)

    Chang, Qiang; Herbst, Eric

    2016-03-01

    The recent discovery of methyl formate and dimethyl ether in the gas phase of cold cores with temperatures as cold as 10 K challenges our previous astrochemical models concerning the formation of complex organic molecules (COMs). The strong correlation between the abundances and distributions of methyl formate and dimethyl ether further shows that current astrochemical models may be missing important chemical processes in cold astronomical sources. We investigate a scenario in which COMs and the methoxy radical can be formed on dust grains via a so-called chain reaction mechanism, in a similar manner to CO2. A unified gas-grain microscopic-macroscopic Monte Carlo approach with both normal and interstitial sites for icy grain mantles is used to perform the chemical simulations. Reactive desorption with varying degrees of efficiency is included to enhance the nonthermal desorption of species formed on cold dust grains. In addition, varying degrees of efficiency for the surface formation of methoxy are also included. The observed abundances of a variety of organic molecules in cold cores can be reproduced in our models. The strong correlation between the abundances of methyl formate and dimethyl ether in cold cores can also be explained. Nondiffusive chemical reactions on dust grain surfaces may play a key role in the formation of some COMs.

  17. Search for complex organic molecules in space

    NASA Astrophysics Data System (ADS)

    Ohishi, Masatoshi

    2016-07-01

    It was 1969 when the first organic molecule in space, H2CO, was discovered. Since then many organic molecules were discovered by using the NRAO 11 m (upgraded later to 12 m), Nobeyama 45 m, IRAM 30 m, and other highly sensitive radio telescopes as a result of close collaboration between radio astronomers and microwave spectroscopists. It is noteworthy that many famous organic molecules such as CH3OH, C2H5OH, (CH3)2O and CH3NH2 were detected by 1975. Organic molecules were found in so-called hot cores where molecules were thought to form on cold dust surfaces and then to evaporate by the UV photons emitted from the central star. These days organic molecules are known to exist not only in hot cores but in hot corinos (a warm, compact molecular clump found in the inner envelope of a class 0 protostar) and even protoplanetary disks. As was described above, major organic molecules were known since 1970s. It was very natural that astronomers considered a relationship between organic molecules in space and the origin of life. Several astronomers challenged to detect glycine and other prebiotic molecules without success. ALMA is expected to detect such important materials to further consider the gexogenous deliveryh hypothesis. In this paper I summarize the history in searching for complex organic molecules together with difficulties in observing very weak signals from larger species. The awfully long list of references at the end of this article may be the most useful part for readers who want to feel the exciting discovery stories.

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

    DOEpatents

    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.

  19. The gas phase origin of complex organic molecules precursors in prestellar cores

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; Faure, A.

    2015-05-01

    Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

  20. Abundances and Reactions of Sulfur Contianing Molecules in Interstellar Ices- Spectroscopic and Radiation-Chemical Investigations

    NASA Astrophysics Data System (ADS)

    Hudson, Reggie

    Infrared (IR) telescopes, such as ISO, Spitzer, KAO, Keck, VLT, and IRTF, have revealed a rich variety of molecules trapped in interstellar ices. However, quantifying the abundances of these molecules has been difficult because reference IR data, such as band strengths and optical constants, often are poorly known. This scarcity of data has severe implications for the study of sulfur-containing molecules, such as OCS and SO2, since accurate molecular abundances are needed to address the missing-sulfur problem in interstellar space. The expected abundances of sulfur-containing species in dense molecular clouds are much higher than reported from telescopic observations, although the latter are based on laboratory data of questionable relevance, such as with liquids at room temperature compared to the 10 K ices of some interstellar regions. Exacerbating the problem is that few sulfur-containing molecules of any type have been examined in the laboratory under the necessary, relevant icy conditions. We propose to address and correct the problems associated with abundance determinations of interstellar sulfur-containing ices. We will combine several recent successful efforts from our laboratory and measure near- and mid-IR spectral intensities for ices containing SO2, OCS, H2S, CS2, CH3SH, and C2H5SH both in the presence and absence of H2O-ice. This work will be done at multiple temperatures and ice phases to generate reference IR spectra and band strengths, accompanied by refractive indices, and optical constants. Moreover, we will study the radiation chemistry of these molecules to determine their radiolytic half-lives (stabilities) and uncover product molecules that can become candidates for future searches and perhaps help better understand the missingsulfur problem. This proposal is a convergence of three lines of work in our laboratory: recent successes in deriving IR optical constants of interstellar molecular ices (Hudson et al. 2014a, 2014b), measurements of

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

    NASA Technical Reports Server (NTRS)

    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.

  2. Constraining the Abundances of Complex Organics in the Inner Regions of Solar-Type Protostars

    NASA Astrophysics Data System (ADS)

    López-Sepulcre, A.; Taquet, V.; Ceccarelli, C.; Neri, R.; Kahane, C.; Charnley, S. B.

    2015-12-01

    We present arcsecond-resolution observations, obtained with the IRAM Plateau de Bure interferometer, of multiple complex organic molecules in two hot corino protostars: IRAS 2A and IRAS 4A, in the NGC 1333 star-forming region. The distribution of the line emission is very compact, indicating the presence of COMs is mostly concentrated in the inner hot corino regions. A comparison of the COMs abundances with astrochemical models favours a gas-phase formation route for CH3OCH3, and a grain formation of C2H5OH, C2H5CN, and HCOCH2OH. The high abundances of methyl formate (HCOOCH3) remain underpredicted by an order of magnitude.

  3. The Census of Complex Organic Molecules in the Solar-type Protostar IRAS16293-2422

    NASA Astrophysics Data System (ADS)

    Jaber, Ali A.; Ceccarelli, C.; Kahane, C.; Caux, E.

    2014-08-01

    Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (gsim30-40 K) and released in the gas phase at dust temperatures of gsim100 K. However, recent detections of COMs in lsim20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we present a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (lsim30 K) envelope of IRAS16293-2422, with abundances of 0.03-2 × 10-10. Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.

  4. Terahertz Time Domain Spectroscopy of Complex Organic Molecules in Astrophysically Relevant Ices

    NASA Astrophysics Data System (ADS)

    McGuire, Brett A.; Ioppolo, Sergio; Allodi, Marco A.; Kelley, Matthew J.; Blake, Geoffrey A.

    2013-06-01

    We have constructed a new system to study the spectra of astrophysically-relevant ice analogs using THz time-domain spectroscopy from 300 GHz - 7 THz. Here, we present our initial efforts to explore the spectra of pure ices of simple, abundant interstellar species as well as complex organic molecules (COMs) and COM-doped ice mixtures. We will present preliminary spectra of pure H_2O, CO_2, methanol (CH_3OH), and methyl formate (CH_3COOH) ices, as well as spectra of these molecules embedded in a variety of other relevant interstellar analogs. Our results are discussed in the context of astronomical observations and the possibility of probing ice compositions in the absence of a background radiation source.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

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

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  7. The census of complex organic molecules in the solar-type protostar IRAS16293-2422

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jaber, Ali A.; Ceccarelli, C.; Kahane, C.

    2014-08-10

    Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (≳30-40 K) and released in the gas phase at dust temperatures of ≳100 K. However, recent detections of COMs in ≲20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we presentmore » a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (≲30 K) envelope of IRAS16293-2422, with abundances of 0.03-2 × 10{sup –10}. Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.« less

  8. Complex organic molecules and star formation

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; Faure, A.

    2014-12-01

    Star forming regions are characterised by the presence of a wealth of chemical species. For the past two to three decades, ever more complex organic species have been detected in the hot cores of protostars. The evolution of these molecules in the course of the star forming process is still uncertain, but it is likely that they are partially incorporated into protoplanetary disks and then into planetesimals and the small bodies of planetary systems. The complex organic molecules seen in star forming regions are particularly interesting since they probably make up building blocks for prebiotic chemistry. Recently we showed that these species were also present in the cold gas in prestellar cores, which represent the very first stages of star formation. These detections question the models which were until now accepted to account for the presence of complex organic molecules in star forming regions. In this article, we shortly review our current understanding of complex organic molecule formation in the early stages of star formation, in hot and cold cores alike and present new results on the formation of their likely precursor radicals.

  9. Ocean metabolism and dissolved organic matter: How do small dissolved molecules persist in the ocean?

    NASA Astrophysics Data System (ADS)

    Benner, Ronald

    2010-05-01

    The ocean reservoir of dissolved organic matter (DOM) is among the largest global reservoirs (~700 Pg C) of reactive organic carbon. Marine primary production (~50 Pg C/yr) by photosynthetic microalgae and cyanobacteria is the major source of organic matter to the ocean and the principal substrate supporting marine food webs. The direct release of DOM from phytoplankton and other organisms as well as a variety of other processes, such as predation and viral lysis, contribute to the ocean DOM reservoir. Continental runoff and atmospheric deposition are relatively minor sources of DOM to the ocean, but some components of this material appear to be resistant to decomposition and to have a long residence time in the ocean. Concentrations of DOM are highest in surface waters and decrease with depth, a pattern that reflects the sources and diagenesis of DOM in the upper ocean. Most (70-80%) marine DOM exists as small molecules of low molecular weight (<1 kDalton). Surprisingly, high-molecular-weight (>1 kDalton) DOM is relatively enriched in major biochemicals, such as combined neutral sugars and amino acids, and is more bioavailable than low-molecular-weight DOM. The observed relationships among the size, composition, and reactivity of DOM have led to the size-reactivity continuum model, which postulates that diagenetic processes lead to the production of smaller molecules that are structurally altered and resistant to microbial degradation. The radiocarbon content of these small dissolved molecules also indicates these are the most highly aged components of DOM. Chemical signatures of bacteria are abundant in DOM and increase during diagenesis, indicating bacteria are an important source of slowly cycling biochemicals. Recent analyses of DOM isolates by ultrahigh-resolution mass spectrometry have revealed an incredibly diverse mixture of molecules. Carboxyl-rich alicyclic molecules are abundant in DOM, and they appear to be derived from diagenetically

  10. Circularly Polarized Luminescence from Simple Organic Molecules.

    PubMed

    Sánchez-Carnerero, Esther M; Agarrabeitia, Antonia R; Moreno, Florencio; Maroto, Beatriz L; Muller, Gilles; Ortiz, María J; de la Moya, Santiago

    2015-09-21

    This article aims to show the identity of "circularly polarized luminescent active simple organic molecules" as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Formation and Recondensation of Complex Organic Molecules During Protostellar Luminosity Outbursts

    NASA Technical Reports Server (NTRS)

    Taquet, Vianney; Wirstrom, 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. Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

    NASA Astrophysics Data System (ADS)

    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.

  13. FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

    2016-04-10

    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 modelmore » 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.« less

  14. Exploring biology with small organic molecules

    PubMed Central

    Stockwell, Brent R.

    2011-01-01

    Small organic molecules have proven to be invaluable tools for investigating biological systems, but there is still much to learn from their use. To discover and to use more effectively new chemical tools to understand biology, strategies are needed that allow us to systematically explore ‘biological-activity space’. Such strategies involve analysing both protein binding of, and phenotypic responses to, small organic molecules. The mapping of biological-activity space using small molecules is akin to mapping the stars — uncharted territory is explored using a system of coordinates that describes where each new feature lies. PMID:15602550

  15. Production of complex organic molecules: H-atom addition versus UV irradiation

    NASA Astrophysics Data System (ADS)

    Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

    2017-05-01

    Complex organic molecules (COMs) have been identified in different environments in star-forming regions. Laboratory studies show that COMs form in the solid state, on icy grains, typically following a 'non-energetic' (atom-addition) or 'energetic' (UV-photon absorption) trigger. So far, such studies have been largely performed for single processes. Here, we present the first work that quantitatively investigates both the relative importance and the cumulative effect of '(non-)energetic' processing. We focus on astronomically relevant CO:CH3OH = 4:1 ice analogues exposed to doses relevant for the collapse stage of dense clouds. Hydrogenation experiments result in the formation of methyl formate (MF; HC(O)OCH3), glycolaldehyde (GA; HC(O)CH2OH) and ethylene glycol (EG; H2C(OH)CH2OH) at 14 K. The absolute abundances and the abundance fractions are found to be dependent on the H-atom/CO:CH3OH-molecule ratios and on the overall deposition rate. In the case that ices are exposed to UV photons only, several different COMs are found. Typically, the abundance fractions are 0.2 for MF, 0.3 for GA and 0.5 for EG as opposed to the values found in pure hydrogenation experiments without UV in which MF is largely absent: 0.0, 0.2-0.6 and 0.8-0.4, respectively. In experiments where both are applied, overall COM abundances drop to about half of those found in the pure UV irradiation experiments, but the composition fractions are very similar. This implies COM ratios can be used as a diagnostic tool to derive the processing history of an ice. Solid-state branching ratios derived here for GA and EG compare well with observations, while the MF case cannot be explained by solid-state conditions investigated here.

  16. Formation of ethylene glycol and other complex organic molecules in star-forming regions

    NASA Astrophysics Data System (ADS)

    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

  17. Circularly Polarized Luminescence from Simple Organic Molecules

    PubMed Central

    Sánchez-Carnerero, Esther M.; Agarrabeitia, Antonia R.; Moreno, Florencio; Maroto, Beatriz L.; Muller, Gilles; Ortiz, María J.

    2015-01-01

    This article aims to show the identity of “CPL-active simple organic molecules” as a new concept in Organic Chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and nonaggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented. PMID:26136234

  18. Quantitative Study of Ether Group Molecules in Insoluble Organic Matter from Carbonaceous Chondrites by CuO-NaOH Selective Degradation

    NASA Astrophysics Data System (ADS)

    Yabuta, H.; Cody, G. D.; Alexander, C. M. O'd.

    2006-03-01

    CuO-NaOH degradation of the insoluble organic matter (IOM) from the Murchison meteorite was conducted. A variety of carboxylic acids were indentified. Oxalic acid was most abundant. It was estimated that approximately ~30% of the IOM included ether groups containing molecules.

  19. Acyl homoserine lactone changes the abundance of proteins and the levels of organic acids associated with stationary phase in Salmonella Enteritidis.

    PubMed

    de Almeida, Felipe Alves; Pimentel-Filho, Natan de Jesus; Carrijo, Lanna Clícia; Bento, Cláudia Braga Pereira; Baracat-Pereira, Maria Cristina; Pinto, Uelinton Manoel; de Oliveira, Leandro Licursi; Vanetti, Maria Cristina Dantas

    2017-01-01

    Quorum sensing (QS) is cell-cell communication mechanism mediated by signaling molecules known as autoinducers (AIs) that lead to differential gene expression. Salmonella is unable to synthesize the AI-1 acyl homoserine lactone (AHL), but is able to recognize AHLs produced by other microorganisms through SdiA protein. Our study aimed to evaluate the influence of AI-1 on the abundance of proteins and the levels of organic acids of Salmonella Enteritidis. The presence of N-dodecyl-homoserine lactone (C12-HSL) did not interfere on the growth or the total amount of extracted proteins of Salmonella. However, the abundance of the proteins PheT, HtpG, PtsI, Adi, TalB, PmgI (or GpmI), Eno, and PykF enhanced while the abundance of the proteins RplB, RplE, RpsB, Tsf, OmpA, OmpC, OmpD, and GapA decreased when Salmonella Enteritidis was anaerobically cultivated in the presence of C12-HSL. Additionally, the bacterium produced less succinic, lactic, and acetic acids in the presence of C12-HSL. However, the concentration of extracellular formic acid reached 20.46 mM after 24 h and was not detected when the growth was in the absence of AI-1. Considering the cultivation period for protein extraction, their abundance, process and function, as well as the levels of organic acids, we observed in cells cultivated in presence of C12-HSL a correlation with what is described in the literature as entry into the stationary phase of growth, mainly related to nitrogen and amino acid starvation and acid stress. Further studies are needed in order to determine the specific role of the differentially abundant proteins and extracellular organic acids secreted by Salmonella in the presence of quorum sensing signaling molecules. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. The missing organic molecules on Mars

    NASA Technical Reports Server (NTRS)

    Benner, S. A.; Devine, K. G.; Matveeva, L. N.; Powell, D. H.

    2000-01-01

    GC-MS on the Viking 1976 Mars missions did not detect organic molecules on the Martian surface, even those expected from meteorite bombardment. This result suggested that the Martian regolith might hold a potent oxidant that converts all organic molecules to carbon dioxide rapidly relative to the rate at which they arrive. This conclusion is influencing the design of Mars missions. We reexamine this conclusion in light of what is known about the oxidation of organic compounds generally and the nature of organics likely to come to Mars via meteorite. We conclude that nonvolatile salts of benzenecarboxylic acids, and perhaps oxalic and acetic acid, should be metastable intermediates of meteoritic organics under oxidizing conditions. Salts of these organic acids would have been largely invisible to GC-MS. Experiments show that one of these, benzenehexacarboxylic acid (mellitic acid), is generated by oxidation of organic matter known to come to Mars, is rather stable to further oxidation, and would not have been easily detected by the Viking experiments. Approximately 2 kg of meteorite-derived mellitic acid may have been generated per m(2) of Martian surface over 3 billion years. How much remains depends on decomposition rates under Martian conditions. As available data do not require that the surface of Mars be very strongly oxidizing, some organic molecules might be found near the surface of Mars, perhaps in amounts sufficient to be a resource. Missions should seek these and recognize that these complicate the search for organics from entirely hypothetical Martian life.

  1. The missing organic molecules on Mars

    PubMed Central

    Benner, Steven A.; Devine, Kevin G.; Matveeva, Lidia N.; Powell, David H.

    2000-01-01

    GC-MS on the Viking 1976 Mars missions did not detect organic molecules on the Martian surface, even those expected from meteorite bombardment. This result suggested that the Martian regolith might hold a potent oxidant that converts all organic molecules to carbon dioxide rapidly relative to the rate at which they arrive. This conclusion is influencing the design of Mars missions. We reexamine this conclusion in light of what is known about the oxidation of organic compounds generally and the nature of organics likely to come to Mars via meteorite. We conclude that nonvolatile salts of benzenecarboxylic acids, and perhaps oxalic and acetic acid, should be metastable intermediates of meteoritic organics under oxidizing conditions. Salts of these organic acids would have been largely invisible to GC-MS. Experiments show that one of these, benzenehexacarboxylic acid (mellitic acid), is generated by oxidation of organic matter known to come to Mars, is rather stable to further oxidation, and would not have been easily detected by the Viking experiments. Approximately 2 kg of meteorite-derived mellitic acid may have been generated per m2 of Martian surface over 3 billion years. How much remains depends on decomposition rates under Martian conditions. As available data do not require that the surface of Mars be very strongly oxidizing, some organic molecules might be found near the surface of Mars, perhaps in amounts sufficient to be a resource. Missions should seek these and recognize that these complicate the search for organics from entirely hypothetical Martian life. PMID:10706606

  2. The missing organic molecules on Mars.

    PubMed

    Benner, S A; Devine, K G; Matveeva, L N; Powell, D H

    2000-03-14

    GC-MS on the Viking 1976 Mars missions did not detect organic molecules on the Martian surface, even those expected from meteorite bombardment. This result suggested that the Martian regolith might hold a potent oxidant that converts all organic molecules to carbon dioxide rapidly relative to the rate at which they arrive. This conclusion is influencing the design of Mars missions. We reexamine this conclusion in light of what is known about the oxidation of organic compounds generally and the nature of organics likely to come to Mars via meteorite. We conclude that nonvolatile salts of benzenecarboxylic acids, and perhaps oxalic and acetic acid, should be metastable intermediates of meteoritic organics under oxidizing conditions. Salts of these organic acids would have been largely invisible to GC-MS. Experiments show that one of these, benzenehexacarboxylic acid (mellitic acid), is generated by oxidation of organic matter known to come to Mars, is rather stable to further oxidation, and would not have been easily detected by the Viking experiments. Approximately 2 kg of meteorite-derived mellitic acid may have been generated per m(2) of Martian surface over 3 billion years. How much remains depends on decomposition rates under Martian conditions. As available data do not require that the surface of Mars be very strongly oxidizing, some organic molecules might be found near the surface of Mars, perhaps in amounts sufficient to be a resource. Missions should seek these and recognize that these complicate the search for organics from entirely hypothetical Martian life.

  3. Diffusion Rates of Organic Molecules in Secondary Organic Aerosol Particle

    NASA Astrophysics Data System (ADS)

    Bertram, A. K.; Chenyakin, Y.; Song, M.; Grayson, J. W.; Ullmann, D.; Evoy, E.; Renbaum-Wolff, L.; Liu, P.; Zhang, Y.; Kamal, S.; Martin, S. T.

    2016-12-01

    Information on the diffusion rates of organic molecules in secondary organic aerosol (SOA) particles are needed when predicting their size distribution, growth rates, photochemistry and heterogeneous chemistry. We have used two approaches to determine diffusion rates of organic molecules in SOA particles and proxies of SOA. In the first approach, we measured viscosities and then predicted diffusion rates using the Stokes-Einstein relation. In the second approach, we measured diffusion rates directly using a technique referred to as fluorescence recovery after photobleaching. Results from these measurements, including diffusion coefficients as a function of water activity, will be presented and the implications discussed.

  4. Conductivity Modifications of Graphene by Electron Donative Organic Molecules

    NASA Astrophysics Data System (ADS)

    Masujima, Hiroaki; Mori, Takehiko; Hayamizu, Yuhei

    2017-07-01

    Graphene has been studied for the application of transparent electrodes in flexible electrical devices with semiconductor organics. Control of the charge carrier density in graphene is crucial to reduce the contact resistance between graphene and the active layer of organic semiconductor. Chemical doping of graphene is an approach to change the carrier density, where the adsorbed organic molecules donate or accept electrons form graphene. While various acceptor organic molecules have been demonstrated so far, investigation about donor molecules is still poor. In this work, we have investigated doping effect in graphene field-effect transistors functionalized by organic donor molecules such as dibenzotetrathiafulvalene (DBTTF), hexamethyltetrathiafulvalene (HMTTF), 1,5-diaminonaphthalene (DAN), and N, N, N', N'-tetramethyl- p-phenylenediamine (TMPD). Based on conductivity measurements of graphene transistors, the former three molecules do not have any significant effect to graphene transistors. However, TMPD shows effective n-type doping. The doping effect has a correlation with the level of highest occupied molecular orbital (HOMO) of each molecule, where TMPD has the highest HOMO level.

  5. Complex organic molecules in strongly UV-irradiated gas⋆

    PubMed Central

    Cuadrado, S.; Goicoechea, J. R.; Cernicharo, J.; Fuente, A.; Pety, J.; Tercero, B.

    2017-01-01

    We investigate the presence of complex organic molecules (COMs) in strongly UV-irradiated interstellar molecular gas. We have carried out a complete millimetre (mm) line survey using the IRAM 30 m telescope towards the edge of the Orion Bar photodissociation region (PDR), close to the H2 dissociation front, a position irradiated by a very intense far-UV (FUV) radiation field. These observations have been complemented with 8.5″ resolution maps of the H2CO JKa,Kc = 51,5 → 41,4 and C18O J = 3 → 2 emission at 0.9 mm. Despite being a harsh environment, we detect more than 250 lines from COMs and related precursors: H2CO, CH3OH, HCO, H2CCO, CH3CHO, H2CS, HCOOH, CH3CN, CH2NH, HNCO, H213CO, and HC3N (in decreasing order of abundance). For each species, the large number of detected lines allowed us to accurately constrain their rotational temperatures (Trot) and column densities (N). Owing to subthermal excitation and intricate spectroscopy of some COMs (symmetric- and asymmetric-top molecules such as CH3CN and H2CO, respectively), a correct determination of N and Trot requires building rotational population diagrams of their rotational ladders separately. The inferred column densities are in the 1011 – 1013cm−2 range. We also provide accurate upper limit abundances for chemically related molecules that might have been expected, but are not conclusively detected at the edge of the PDR (HDCO, CH3O, CH3NC, CH3CCH, CH3OCH3, HCOOCH3, CH3CH2OH, CH3CH2CN, and CH2CHCN). A non-thermodynamic equilibrium excitation analysis for molecules with known collisional rate coefficients suggests that some COMs arise from different PDR layers but we cannot resolve them spatially. In particular, H2CO and CH3CN survive in the extended gas directly exposed to the strong FUV flux (Tk = 150 – 250 K and Td ≳ 60 K), whereas CH3OH only arises from denser and cooler gas clumps in the more shielded PDR interior (Tk = 40 – 50 K). The non-detection of HDCO towards the PDR edge is

  6. Complex organic molecules in strongly UV-irradiated gas.

    PubMed

    Cuadrado, S; Goicoechea, J R; Cernicharo, J; Fuente, A; Pety, J; Tercero, B

    2017-07-01

    We investigate the presence of complex organic molecules (COMs) in strongly UV-irradiated interstellar molecular gas. We have carried out a complete millimetre (mm) line survey using the IRAM 30 m telescope towards the edge of the Orion Bar photodissociation region (PDR), close to the H 2 dissociation front, a position irradiated by a very intense far-UV (FUV) radiation field. These observations have been complemented with 8.5″ resolution maps of the H 2 CO J K a , K c = 5 1,5 → 4 1,4 and C 18 O J = 3 → 2 emission at 0.9 mm. Despite being a harsh environment, we detect more than 250 lines from COMs and related precursors: H 2 CO, CH 3 OH, HCO, H 2 CCO, CH 3 CHO, H 2 CS, HCOOH, CH 3 CN, CH 2 NH, HNCO, [Formula: see text] and HC 3 N (in decreasing order of abundance). For each species, the large number of detected lines allowed us to accurately constrain their rotational temperatures ( T rot ) and column densities ( N ). Owing to subthermal excitation and intricate spectroscopy of some COMs (symmetric- and asymmetric-top molecules such as CH 3 CN and H 2 CO, respectively), a correct determination of N and T rot requires building rotational population diagrams of their rotational ladders separately. The inferred column densities are in the 10 11 - 10 13 cm -2 range. We also provide accurate upper limit abundances for chemically related molecules that might have been expected, but are not conclusively detected at the edge of the PDR (HDCO, CH 3 O, CH 3 NC, CH 3 CCH, CH 3 OCH 3 , HCOOCH 3 , CH 3 CH 2 OH, CH 3 CH 2 CN, and CH 2 CHCN). A non-thermodynamic equilibrium excitation analysis for molecules with known collisional rate coefficients suggests that some COMs arise from different PDR layers but we cannot resolve them spatially. In particular, H 2 CO and CH 3 CN survive in the extended gas directly exposed to the strong FUV flux ( T k = 150 - 250 K and T d ≳ 60 K), whereas CH 3 OH only arises from denser and cooler gas clumps in the more shielded PDR interior

  7. CHEMICAL TRANSPORT FACILITATED BY COLLOIDAL-SIZED ORGANIC MOLECULES

    EPA Science Inventory

    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. ...

  8. Toxicology of organic-inorganic hybrid molecules: bio-organometallics and its toxicology.

    PubMed

    Fujie, Tomoya; Hara, Takato; Kaji, Toshiyuki

    2016-01-01

    Bio-organometallics is a research strategy of biology that uses organic-inorganic hybrid molecules. The molecules are expected to exhibit useful bioactivities based on the unique structure formed by interaction between the organic structure and intramolecular metal(s). However, studies on both biology and toxicology of organic-inorganic hybrid molecules have been incompletely performed. There can be two types of toxicological studies of bio-organometallics; one is evaluation of organic-inorganic hybrid molecules and the other is analysis of biological systems from the viewpoint of toxicology using organic-inorganic hybrid molecules. Our recent studies indicate that cytotoxicity of hybrid molecules containing a metal that is nontoxic in inorganic forms can be more toxic than that of hybrid molecules containing a metal that is toxic in inorganic forms when the structure of the ligand is the same. Additionally, it was revealed that organic-inorganic hybrid molecules are useful for analysis of biological systems important for understanding the toxicity of chemical compounds including heavy metals.

  9. Small Molecule Organic Optoelectronic Devices

    NASA Astrophysics Data System (ADS)

    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

  10. Constraining the Abundances of Complex Organics in the Inner Regions of Solar-type Protostars

    NASA Astrophysics Data System (ADS)

    Taquet, Vianney; López-Sepulcre, Ana; Ceccarelli, Cecilia; Neri, Roberto; Kahane, Claudine; Charnley, Steven B.

    2015-05-01

    The high abundances of Complex Organic Molecules (COMs) with respect to methanol, the most abundant COM, detected toward low-mass protostars, tend to be underpredicted by astrochemical models. This discrepancy might come from the large beam of the single-dish telescopes, encompassing several components of the studied protostar, commonly used to detect COMs. To address this issue, we have carried out multi-line observations of methanol and several COMs toward the two low-mass protostars NGC 1333-IRAS 2A and -IRAS 4A with the Plateau de Bure interferometer at an angular resolution of 2″, resulting in the first multi-line detection of the O-bearing species glycolaldehyde and ethanol and of the N-bearing species ethyl cyanide toward low-mass protostars other than IRAS 16293. The high number of detected transitions from COMs (more than 40 methanol transitions for instance) allowed us to accurately derive the source size of their emission and the COM column densities. The COM abundances with respect to methanol derived toward IRAS 2A and IRAS 4A are slightly, but not substantitally, lower than those derived from previous single-dish observations. The COM abundance ratios do not vary significantly with the protostellar luminosity, over five orders of magnitude, implying that low-mass hot corinos are quite chemically rich as high-mass hot cores. Astrochemical models still underpredict the abundances of key COMs, such as methyl formate or di-methyl ether, suggesting that our understanding of their formation remains incomplete.

  11. Evolution of organic molecules under Mars-like UV radiation with EXPOSE-R2, a photochemistry experiment outside the International Space Station

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    The detection and identification of organic molecules on 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.The EXPOSE R2 facility has been placed in low Earth orbit (LEO) under solar radiation, outside the International Space Station (ISS) in 2014. One of the EXPOSE R2 experiment, called PSS (Photochemistry on the Space Station), is dedicated to astrobiology- and astrochemistry-related studies. Part of PSS samples have been dedicated to the study of the evolution of organic molecules under Mars-like surface radiation conditions. Indeed, UV radiation above 200 nm reaches the surface of Mars and could degrade organic matter. Organic samples have been exposed directly to the Sun under KBr filters (>200 nm) from November 2014 to February 2016, mimicking the UV radiation conditions of the surface of Mars. Four types of samples were exposed as thin layers of solid molecules: adenine, adenine with nontronite (a kind of clay mineral detected on Mars), chrysene and glycine with nontronite.To characterize the evolution of our samples under irradiation, infrared (IR) transmission analyses were performed, before the launch of EXPOSE R2 to the ISS in 2014, and after the exposure in space and the return on Earth, this year. These analyses allowed determining whether each molecule is preserved or photodegraded, and if so, its photolysis rate. The effect of nontronite on organic molecules preservation has been investigated as well. We also compared these results from LEO with laboratory data, obtained by irradiating organic samples under a UV lamp.

  12. Complex organic molecules in strongly UV-irradiated gas

    NASA Astrophysics Data System (ADS)

    Cuadrado, S.; Goicoechea, J. R.; Cernicharo, J.; Fuente, A.; Pety, J.; Tercero, B.

    2017-07-01

    We investigate the presence of complex organic molecules (COMs) in strongly UV-irradiated interstellar molecular gas. We have carried out a complete millimetre (mm) line survey using the IRAM 30 m telescope towards the edge of the Orion Bar photodissociation region (PDR), close to the H2 dissociation front, a position irradiated by a very intense far-UV (FUV) radiation field. These observations have been complemented with 8.5'' resolution maps of the H2CO JKa,Kc = 51,5 → 41,4 and C18O J = 3 → 2 emission at 0.9 mm. Despite being a harsh environment, we detect more than 250 lines from COMs and related precursors: H2CO, CH3OH, HCO, H2CCO, CH3CHO, H2CS, HCOOH, CH3CN, CH2NH, HNCO, H213CO, and HC3N (in decreasing order of abundance). For each species, the large number of detected lines allowed us to accurately constrain their rotational temperatures (Trot) and column densities (N). Owing to subthermal excitation and intricate spectroscopy of some COMs (symmetric- and asymmetric-top molecules such as CH3CN and H2CO, respectively), a correct determination of N and Trot requires building rotational population diagrams of their rotational ladders separately. The inferred column densities are in the 1011-1013 cm-2 range. We also provide accurate upper limit abundances for chemically related molecules that might have been expected, but are not conclusively detected at the edge of the PDR (HDCO, CH3O, CH3NC, CH3CCH, CH3OCH3, HCOOCH3, CH3CH2OH, CH3CH2CN, and CH2CHCN). A non-thermodynamic equilibrium excitation analysis for molecules with known collisional rate coefficients suggests that some COMs arise from different PDR layers but we cannot resolve them spatially. In particular, H2CO and CH3CN survive in the extended gas directly exposed to the strong FUV flux (Tk = 150-250 K and Td≳ 60 K), whereas CH3OH only arises from denser and cooler gas clumps in the more shielded PDR interior (Tk = 40-50 K). The non-detection of HDCO towards the PDR edge is consistent with the

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

    DOEpatents

    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.

  14. CONSTRAINING THE ABUNDANCES OF COMPLEX ORGANICS IN THE INNER REGIONS OF SOLAR-TYPE PROTOSTARS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Taquet, Vianney; Charnley, Steven B.; López-Sepulcre, Ana

    The high abundances of Complex Organic Molecules (COMs) with respect to methanol, the most abundant COM, detected toward low-mass protostars, tend to be underpredicted by astrochemical models. This discrepancy might come from the large beam of the single-dish telescopes, encompassing several components of the studied protostar, commonly used to detect COMs. To address this issue, we have carried out multi-line observations of methanol and several COMs toward the two low-mass protostars NGC 1333-IRAS 2A and -IRAS 4A with the Plateau de Bure interferometer at an angular resolution of 2″, resulting in the first multi-line detection of the O-bearing species glycolaldehydemore » and ethanol and of the N-bearing species ethyl cyanide toward low-mass protostars other than IRAS 16293. The high number of detected transitions from COMs (more than 40 methanol transitions for instance) allowed us to accurately derive the source size of their emission and the COM column densities. The COM abundances with respect to methanol derived toward IRAS 2A and IRAS 4A are slightly, but not substantitally, lower than those derived from previous single-dish observations. The COM abundance ratios do not vary significantly with the protostellar luminosity, over five orders of magnitude, implying that low-mass hot corinos are quite chemically rich as high-mass hot cores. Astrochemical models still underpredict the abundances of key COMs, such as methyl formate or di-methyl ether, suggesting that our understanding of their formation remains incomplete.« less

  15. The Detection of Hot Cores and Complex Organic Molecules in the Large Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    Sewilo, Marta; Indebetouw, Remy; Charnley, Steven; 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

    2018-01-01

    We report the detection of the complex organic molecules (COMs) dimethyl ether (CH3OCH3) and methyl formate (CH3OCHO), and their parent species methanol (CH3OH), toward the N113 star-formation region in the Large Magellanic Cloud (LMC) with the Atacama Large Millimeter/submillimeter Array (ALMA). This constitutes the first detection of CH3OCH3 and CH3OCHO outside the Milky Way. We calculated the rotational temperatures (Trot ~ 130 K) and total column densities (Nrot ~ 1016 cm-2) for two sources in N113 with the COMs detection based on multiple transitions of CH3OH, and measured abundances for all detected species. The physical and chemical properties of these sources, and the association with H2O and OH maser emission indicate that they are hot molecular 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.

  16. The Detection of Hot Cores and Complex Organic Molecules in the Large Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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

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

    DOEpatents

    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.

  19. Organic molecules in translucent interstellar clouds.

    PubMed

    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. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.

    Quantum chemical calculations were employed to model the interactions of the [(NH 4 +) 4(HSO 4 -) 4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH 4 +) 4(SOmore » 4 -) 4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

  1. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    DOE PAGES

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; ...

    2015-10-21

    Quantum chemical calculations were employed to model the interactions of the [(NH 4 +) 4(HSO 4 -) 4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH 4 +) 4(SOmore » 4 -) 4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

  2. Exploring molecular complexity with ALMA (EMoCA): Deuterated complex organic molecules in Sagittarius B2(N2)

    NASA Astrophysics Data System (ADS)

    Belloche, A.; Müller, H. S. P.; Garrod, R. T.; Menten, K. M.

    2016-03-01

    Context. Deuteration is a powerful tracer of the history of the cold prestellar phase in star-forming regions. Apart from methanol, little is known about deuterium fractionation of complex organic molecules in the interstellar medium, especially in regions forming high-mass stars. Aims: Our goal is to detect deuterated complex organic molecules toward the high mass star-forming region Sagittarius B2 (Sgr B2) and derive the level of deuteration for these molecules. Methods: We use a complete 3-mm spectral line survey performed with the Atacama Large Millimeter/submillimeter Array (ALMA) to search for deuterated complex organic molecules toward the hot molecular core Sgr B2(N2). We constructed population diagrams and integrated intensity maps to fit rotational temperatures and emission sizes for each molecule. Column densities are derived by modeling the full spectrum under the assumption of local thermodynamic equilibrium. We compare the results to predictions of two astrochemical models that treat the deuteration process. Results: We report the detection of CH2DCN toward Sgr B2(N2) with a deuteration level of 0.4%, and tentative detections of CH2DOH, CH2DCH2CN, the chiral molecule CH3CHDCN, and DC3N with levels in the range 0.05%-0.12%. A stringent deuteration upper limit is obtained for CH3OD (<0.07%). Upper limits in the range 0.5-1.8% are derived for the three deuterated isotopologues of vinyl cyanide, the four deuterated species of ethanol, and CH2DOCHO. Ethyl cyanide is less deuterated than methyl cyanide by at least a factor five. The [CH2DOH]/[CH3OD] abundance ratio is higher than 1.8. It may still be consistent with the value obtained in Orion KL. Except for methyl cyanide, the measured deuteration levels lie at least a factor four below the predictions of current astrochemical models. The deuteration levels in Sgr B2(N2) are also lower than in Orion KL by a factor of a few up to a factor ten. Conclusions: The discrepancy between the deuteration levels of

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

    PubMed

    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.

  4. The activated sludge ecosystem contains a core community of abundant organisms

    PubMed Central

    Saunders, Aaron M; Albertsen, Mads; Vollertsen, Jes; Nielsen, Per H

    2016-01-01

    Understanding the microbial ecology of a system requires that the observed population dynamics can be linked to their metabolic functions. However, functional characterization is laborious and the choice of organisms should be prioritized to those that are frequently abundant (core) or transiently abundant, which are therefore putatively make the greatest contribution to carbon turnover in the system. We analyzed the microbial communities in 13 Danish wastewater treatment plants with nutrient removal in consecutive years and a single plant periodically over 6 years, using Illumina sequencing of 16S ribosomal RNA amplicons of the V4 region. The plants contained a core community of 63 abundant genus-level operational taxonomic units (OTUs) that made up 68% of the total reads. A core community consisting of abundant OTUs was also observed within the incoming wastewater to three plants. The net growth rate for individual OTUs was quantified using mass balance, and it was found that 10% of the total reads in the activated sludge were from slow or non-growing OTUs, and that their measured abundance was primarily because of immigration with the wastewater. Transiently abundant organisms were also identified. Among them the genus Nitrotoga (class Betaproteobacteria) was the most abundant putative nitrite oxidizer in a number of activated sludge plants, which challenges previous assumptions that Nitrospira (phylum Nitrospirae) are the primary nitrite-oxidizers in activated sludge systems with nutrient removal. PMID:26262816

  5. Metal oxide charge transport material doped with organic molecules

    DOEpatents

    Forrest, Stephen R.; Lassiter, Brian E.

    2016-08-30

    Doping metal oxide charge transport material with an organic molecule lowers electrical resistance while maintaining transparency and thus is optimal for use as charge transport materials in various organic optoelectronic devices such as organic photovoltaic devices and organic light emitting devices.

  6. 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?

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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

  8. Driving Organic Molecule Crystalliztion with Surface Reconstructions

    NASA Astrophysics Data System (ADS)

    Bickel, Jessica; Trovato, Gianfranco

    This work examines how surface reconstructions can drive crystallization of organic molecules via self-assembly. Organic electronic molecules have low conductivities compared to inorganic materials, but crystallizing these polymers increases their conductivity. This project uses surface reconstructions with periodically repeating topographies to drive the crystallization process. The samples are grown by placing a drop of a dilute PEDOT solution on the clean Si(001)-(2x1) or Si(111)-(7x7) surface reconstruction and heating the surface up to both evaporate the solvent and promote diffusion of the polymer to the thermodynamically defined lowest energy position. The resulting samples are characterized by scanning tunneling microscopy (STM) with respect to their crystallinity and electronic properties. Of particular interest is whether there is a preferential location for the PEDOT molecule to adsorb and whether there are any conformational changes upon adsorption that modify the HOMO-LUMO gap. This work is being done in a new pan-style RHK-STM enclosed in a glovebox at Cleveland State University. The glovebox has O2 and H2O levels of less than 1ppm. This allows for sample preparation and imaging in a controlled environment that is free from contamination.

  9. Organization of Single Molecule Magnets on Surfaces

    NASA Astrophysics Data System (ADS)

    Sessoli, Roberta

    2006-03-01

    The field of magnetic molecular clusters showing slow relaxation of the magnetization has attracted a great interest for the spectacular quantum effects in the dynamics of the magnetization that range from resonant quantum tunneling to topological interferences. Recently these systems, known as Single Molecule Magnets (SMMs), have also been proposed as model systems for the investigation of flame propagation in flammable substances. A renewed interest in SMMs also comes from the possibility to exploit their rich and complex magnetic behavior in nano-spintronics. However, at the crystalline state these molecular materials are substantially insulating. They can however exhibit significant transport properties if the conduction occurs through one molecule connected to two metal electrodes, or through a tunneling mechanism when the SMM is grafted on a conducting surface, as occurs in scanning tunnel microscopy experiments. Molecular compounds can be organized on surfaces thanks to the self assembly technique that exploits the strong affinity of some groups for the surface, e.g. thiols for gold surfaces. However the deposition of large molecules mainly comprising relatively weak coordinative bonds is far from trivial. Several different approaches have started to be investigated. We will briefly review here the strategies developed in a collaboration between the Universities of Florence and Modena. Well isolated molecules on Au(111) surfaces have been obtained with sub-monolayer coverage and different spacers. Organization on a large scale of micrometric structures has been obtained thanks to micro-contact printing. The magnetic properties of the grafted molecules have been investigated through magneto-optical techniques and the results show a significant change in the magnetization dynamics whose origin is still object of investigations.

  10. Organic synthesis toward small-molecule probes and drugs

    PubMed Central

    Schreiber, Stuart L.

    2011-01-01

    Organic synthesis” is a compound-creating activity often focused on biologically active small molecules. This special issue of PNAS explores innovations and trends in the field that are enabling the synthesis of new types of small-molecule probes and drugs. This perspective article frames the research described in the special issue but also explores how these modern capabilities can both foster a new and more extensive view of basic research in the academy and promote the linkage of life-science research to the discovery of novel types of small-molecule therapeutics [Schreiber SL (2009) Chem Bio Chem 10:26–29]. This new view of basic research aims to bridge the chasm between basic scientific discoveries in life sciences and new drugs that treat the root cause of human disease—recently referred to as the “valley of death” for drug discovery. This perspective article describes new roles that modern organic chemistry will need to play in overcoming this challenge. PMID:21464328

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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.

  12. Anisotropic behavior of organic molecules on prepatterned surfaces

    NASA Astrophysics Data System (ADS)

    Hopp, Stefan Frieder; Heuer, Andreas

    2012-04-01

    The nucleation of organic molecules on surfaces, prepatterned with stripes, is investigated with emphasis on anisotropy effects. Representing the molecules as ellipsoids, the related particle-particle interaction is modeled by means of a generalized Gay-Berne potential for similar biaxial particles. The orientation behavior of these ellipsoidal molecules induced by the stripe pattern is studied for the first monolayer by performing kinetic Monte Carlo simulations. It is shown how the properties of the particle alignment depend on energy scales, temperature, and flux. Based on the fact the particles strictly arrange in rows, it is furthermore instructive to analyze the orientation behavior within the different rows. Finally, the transfer of orientation from a preset row of molecules with fixed orientation to other nucleating particles is examined.

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

    NASA Technical Reports Server (NTRS)

    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.

  14. Laboratory simulation to support the search for organic molecules at the surface of Mars

    NASA Astrophysics Data System (ADS)

    Poch, Olivier; Szopa, Cyril; Coll, Patrice; Jaber, Maguy; Georgelin, Thomas; Lambert, Jean-Francois; Stalport, Fabien

    The search for organic carbon at the surface of Mars, as clues of past habitability or remnants of life, is a major science goal of Mars’ exploration. Understanding the chemical evolution of organic molecules under current Martian environmental conditions is essential to support the analyses performed in situ. What molecule can be preserved? What is the timescale of organic evolution at the surface? Here we present results of laboratory investigations dedicated to monitor qualitative and quantitative evolutions of several organic molecules under simulated Martian surface ultraviolet incident light, mean ground temperature and pressure, using the Mars Organic Molecules Irradiation and Evolution setup (1) . For each organic molecule studied, the nature of the evolution products (solid or gaseous) and the kinetic parameters (extrapolated half-life at Mars, quantum yields) were experimentally determined. The results show that when exposed to UV radiation, specific organic molecules lead to the formation of solid residues, probably of macromolecular nature, which could reach long term stability. On the other hand, the study of the evolution of molecules in presence of nontronite, a clay mineral detected at the surface of Mars, highlights a strong protective effect of the clay reducing dissociation rates for some molecules, whereas a possible catalytic effect is tentatively observed for one studied molecule. These results are essential to support the analyses performed in situ during the past, current and future exploration missions. Moreover, the experimentally determined kinetic parameters provide new inputs for numerical modeling of current reservoirs of organic molecules on Mars. (1) O. Poch et al., Planetary and Space Science 85, 188-197, http://dx.doi.org/10.1016/j.pss.2013.06.013

  15. Spatial Variations of Chemical Abundances in Titan's Atmosphere as Revealed by ALMA

    NASA Astrophysics Data System (ADS)

    Thelen, Alexander E.; Nixon, Conor; Chanover, Nancy J.; Molter, Edward; Serigano, Joseph; Cordiner, Martin; Charnley, Steven B.; Teanby, Nicholas A.; Irwin, Patrick

    2016-10-01

    Complex organic molecules in Titan's atmosphere - formed through the dissociation of N2 and CH4 - exhibit latitudinal variations in abundance as observed by Cassini. Chemical species including hydrocarbons - such as CH3CCH - and nitriles - HCN, HC3N, CH3CN, and C2H5CN - may show spatial abundance variations as a result of atmospheric circulation, photochemical production and subsequent destruction throughout Titan's seasonal cycle. Recent calibration images of Titan taken by the Atacama Large Millimeter/Submillimeter Array (ALMA) with beam sizes of ~0.3'' allow for measurements of rotational transition lines of these species in spatially resolved regions of Titan's disk. We present abundance profiles obtained from public ALMA data taken in 2014, as Titan transitioned into northern summer. Abundance profiles in Titan's lower/middle atmosphere were retrieved by modeling high resolution ALMA spectra using the Non-linear Optimal Estimator for MultivariatE Spectral analySIS (NEMESIS) radiative transfer code. These retrievals were performed using spatial temperature profiles obtained by modeling strong CO lines from datasets taken in similar times with comparable resolution. We compare the abundance variations of chemical species to measurements made using Cassini data. Comparisons of chemical species with strong abundance enhancements over the poles will inform our knowledge of chemical lifetimes in Titan's atmosphere, and allow us to observe the important changes in production and circulation of numerous organic molecules which are attributed to Titan's seasons.

  16. Temporal trends in arthropod abundances after the transition to organic farming in paddy fields.

    PubMed

    Tsutsui, Masaru H; Kobayashi, Kazuhiko; Miyashita, Tadashi

    2018-01-01

    Organic farming aims to reduce the effect on the ecosystem and enhance biodiversity in agricultural areas, but the long-term effectiveness of its application is unclear. Assessments have rarely included various taxonomic groups with different ecological and economic roles. In paddy fields with different numbers of years elapsed since the transition from conventional to organic farming, we investigated changes in the abundance of insect pests, generalist predators, and species of conservation concern. The abundance of various arthropods exhibited diverse trends with respect to years elapsed since the transition to organic farming. Larval lepidopterans, Tetragnatha spiders, and some planthoppers and stink bugs showed non-linear increases over time, eventually reaching saturation, such as the abundance increasing for several years and then becoming stable after 10 years. This pattern can be explained by the effects of residual pesticides, the lag time of soil mineralization, and dispersal limitation. A damselfly (Ischnura asiatica) did not show a particular trend over time, probably due to its rapid immigration from source habitats. Unexpectedly, both planthoppers and some leafhoppers exhibited gradual decreases over time. As their abundances were negatively related to the abundance of Tetragnatha spiders, increased predation by natural enemies might gradually decrease these insect populations. These results suggest that the consideration of time-dependent responses of organisms is essential for the evaluation of the costs and benefits of organic farming, and such evaluations could provide a basis for guidelines regarding the length of time for organic farming to restore biodiversity or the economic subsidy needed to compensate for pest damage.

  17. Temporal trends in arthropod abundances after the transition to organic farming in paddy fields

    PubMed Central

    Tsutsui, Masaru H.; Kobayashi, Kazuhiko

    2018-01-01

    Organic farming aims to reduce the effect on the ecosystem and enhance biodiversity in agricultural areas, but the long-term effectiveness of its application is unclear. Assessments have rarely included various taxonomic groups with different ecological and economic roles. In paddy fields with different numbers of years elapsed since the transition from conventional to organic farming, we investigated changes in the abundance of insect pests, generalist predators, and species of conservation concern. The abundance of various arthropods exhibited diverse trends with respect to years elapsed since the transition to organic farming. Larval lepidopterans, Tetragnatha spiders, and some planthoppers and stink bugs showed non-linear increases over time, eventually reaching saturation, such as the abundance increasing for several years and then becoming stable after 10 years. This pattern can be explained by the effects of residual pesticides, the lag time of soil mineralization, and dispersal limitation. A damselfly (Ischnura asiatica) did not show a particular trend over time, probably due to its rapid immigration from source habitats. Unexpectedly, both planthoppers and some leafhoppers exhibited gradual decreases over time. As their abundances were negatively related to the abundance of Tetragnatha spiders, increased predation by natural enemies might gradually decrease these insect populations. These results suggest that the consideration of time-dependent responses of organisms is essential for the evaluation of the costs and benefits of organic farming, and such evaluations could provide a basis for guidelines regarding the length of time for organic farming to restore biodiversity or the economic subsidy needed to compensate for pest damage. PMID:29324809

  18. Detection and mapping of organic molecules in Titan's atmosphere using ALMA

    NASA Astrophysics Data System (ADS)

    Cordiner, Martin

    2016-06-01

    Titan's atmospheric photochemistry results in the production of a wide range of organic molecules, including hydrocarbons, nitriles, aromatics and other complex species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of organic matter in primitive (terrestrial) planetary atmospheres. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. Results will be presented from our ongoing studies of Titan using ALMA data obtained during the period 2012-2014 [1,2], including detection and mapping of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH. In addition, combining data from multiple ALMA Band 6 observations, we obtained high-resolution spectra with unprecedented sensitivity, enabling the first detection of C2H3CN (vinyl cyanide) on Titan, and derived a mean C2H3CN C2H5CN abundance ratio above 300 km of 0.3. Vinyl cyanide has recently been investigated as a possible constituent of (pre-biotic) vesicle membranes in Titan's liquid CH4 oceans [3]. Radiative transfer models and possible chemical formation pathways for the detected molecules will be discussed. ALMA observations provide instantaneous snapshot mapping of Titan's entire Earth-facing hemisphere for gases inaccessible to previous studies, and therefore provide new insights into photochemical production and transport, particularly at higher altitudes. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with the molecular distributions found in previous studies at infrared wavelengths by Voyager and Cassini, but high-altitude longitudinal asymmetries in our nitrile data indicate that the mesosphere may be more spatially variable than previously thought.

  19. Metal‐Catalysed Azidation of Organic Molecules

    PubMed Central

    Goswami, Monalisa

    2016-01-01

    The azide moiety is a desirable functionality in organic molecules, useful in a variety of transformations such as olefin aziridination, C–H bond amination, isocyanate synthesis, the Staudinger reaction and the formation of azo compounds. To harness the versatility of the azide functionality fully it is important that these compounds be easy to prepare, in a clean and cost‐effective manner. Conventional (non‐catalysed) methods to synthesise azides generally require quite harsh reaction conditions that are often not tolerant of functional groups. In the last decade, several metal‐catalysed azidations have been developed in attempts to circumvent this problem. These methods are generally faster, cleaner and more functional‐group‐tolerant than conventional methods to prepare azides, and can sometimes even be conveniently combined with one‐pot follow‐up transformations of the installed azide moiety. This review highlights metal‐catalysed approaches to azide synthesis, with a focus on the substrate scopes and mechanisms, as well as on advantages and disadvantages of the methods. Overall, metal‐catalysed azidation reactions provide shorter routes to a variety of potentially useful organic molecules containing the azide moiety. PMID:28344503

  20. Water and complex organic molecules in the warm inner regions of solar-type protostars

    NASA Astrophysics Data System (ADS)

    Coutens, A.; Jørgensen, J. K.; Persson, M. V.; Lykke, J. M.; Taquet, V.; van Dishoeck, E. F.; Vastel, C.; Wampfler, S. F.

    2015-12-01

    Water and complex organic molecules play an important role in the emergence of Life. They have been detected in different types of astrophysical environments (protostars, prestellar cores, outflows, protoplanetary disks, comets, etc). In particular, they show high abundances towards the warm inner regions of protostars, where the icy grain mantles thermally desorb. Can a part of the molecular content observed in these regions be preserved during the star formation process and incorporated into asteroids and comets, that can deliver it to planetary embryos through impacts? By comparison with cometary studies, interferometric observations of solar-type protostars can help to address this important question. We present recent results obtained with the Plateau de Bure interferometer about water deuteration, glycolaldehyde and ethylene glycol towards the low-mass protostar NGC 1333 IRAS2A.

  1. Analytical Protocols for Analysis of Organic Molecules in Mars Analog Materials

    NASA Technical Reports Server (NTRS)

    Mahaffy, Paul R.; Brinkerhoff, W.; Buch, A.; Demick, J.; Glavin, D. P.

    2004-01-01

    A range of analytical techniques and protocols that might be applied b in situ investigations of martian fines, ices, and rock samples are evaluated by analysis of organic molecules m Mars analogues. These simulants 6om terrestrial (i.e. tephra from Hawaii) or extraterrestrial (meteoritic) samples are examined by pyrolysis gas chromatograph mass spectrometry (GCMS), organic extraction followed by chemical derivatization GCMS, and laser desorption mass spectrometry (LDMS). The combination of techniques imparts analysis breadth since each technique provides a unique analysis capability for Certain classes of organic molecules.

  2. The Mars Organic Analyzer: Instrumentation and Methods for Detecting Trace Organic Molecules in our Solar System

    NASA Astrophysics Data System (ADS)

    Stockton, A. M.; Kim, J.; Willis, P. A.; Lillis, R.; Amundson, R.; Beegle, L.; Butterworth, A.; Curtis, D.; Ehrenfreund, P.; Grunthaner, F.; Hazen, R.; Kaiser, R.; Ludlam, M.; Mora, M. F.; Scherer, J.; Turin, P.; Welten, K.; Williford, K.; Mathies, R. A.

    2014-07-01

    Mars Organic Analyzer was designed to give the Mars 2020 Mission capability to look for organic molecules, including amines, aldehydes, ketones, organic acids, thiols and polycyclic aromatic hydrocarbons, in martian samples with sub-ppb sensitivity.

  3. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

    NASA Astrophysics Data System (ADS)

    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

  4. Single Molecule Study of DNA Organization and Recombination

    NASA Astrophysics Data System (ADS)

    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

  5. Comprehensive mass spectrometric analysis of novel organic semiconductor molecules

    NASA Astrophysics Data System (ADS)

    Prada, Svitlana

    This work presents a comprehensive mass spectrometry (MS) study of novel organic semiconductor molecules including ion mobility/reactivity measurements and trace elemental analysis. The organic molecules investigated here are important semiconductor materials for molecular electronic devices such as Organic Field-Effect Transistors (OFETs) and Light Emitted Diodes (LED). A high-performance orthogonal time-of flight mass spectrometer (TOF-MS) in combination with a matrix assisted laser desorption/ionization (MALDI) source operating at elevated pressure was used to perform MALDI/TOF analyses of pentacene and some of its derivatives with and without an added matrix. The observation of ion-molecule reactions between "cold" analyte ions and neutral analyte molecules in the gas phase has provided some insight into the mechanism of pentacene cluster formation and its functionalized derivatives. Furthermore, some of the matrices employed to assist the desorption/ionization process of these compounds were observed to influence the outcome via ion-molecule reactions of analyte ions and matrix molecules in the gas phase. The stability and reactivity of the compounds and their clusters in the MALDI plume during gas-phase expansion were evaluated; possible structures of the resulting clusters are discussed. The MALDI/TOF technique was also helpful in distinguishing between two isomeric forms of bis-[(triisopropylsilyl)-ethynyl]-pentacene. Furthermore, we reported ion mobility measurements of functionalized pentacene ions with a modified triple quadrupole mass spectrometer fitted with an ion molecule reactor (IMR). The IMR is equipped with a variable axial electrostatic drift field (ADF) and is able to trap ions for a prolong period of time. These capabilities were successfully employed in the measurement of ion mobilities in different modes of the IMR operation. Theoretical modeling of the drift dynamics and the special localization of the large ion packet was successfully

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

    PubMed

    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.

  7. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    PubMed Central

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-01-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

  8. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

  9. Oligomer Molecules for Efficient Organic Photovoltaics.

    PubMed

    Lin, Yuze; Zhan, Xiaowei

    2016-02-16

    Solar cells, a renewable, clean energy technology that efficiently converts sunlight into electricity, are a promising long-term solution for energy and environmental problems caused by a mass of production and the use of fossil fuels. Solution-processed organic solar cells (OSCs) have attracted much attention in the past few years because of several advantages, including easy fabrication, low cost, lightweight, and flexibility. Now, OSCs exhibit power conversion efficiencies (PCEs) of over 10%. In the early stage of OSCs, vapor-deposited organic dye materials were first used in bilayer heterojunction devices in the 1980s, and then, solution-processed polymers were introduced in bulk heterojunction (BHJ) devices. Relative to polymers, vapor-deposited small molecules offer potential advantages, such as a defined molecular structure, definite molecular weight, easy purification, mass-scale production, and good batch-to-batch reproducibility. However, the limited solubility and high crystallinity of vapor-deposited small molecules are unfavorable for use in solution-processed BHJ OSCs. Conversely, polymers have good solution-processing and film-forming properties and are easily processed into flexible devices, whereas their polydispersity of molecular weights and difficulty in purification results in batch to batch variation, which may hamper performance reproducibility and commercialization. Oligomer molecules (OMs) are monodisperse big molecules with intermediate molecular weights (generally in the thousands), and their sizes are between those of small molecules (generally with molecular weights <1000) and polymers (generally with molecular weights >10000). OMs not only overcome shortcomings of both vapor-deposited small molecules and solution-processed polymers, but also combine their advantages, such as defined molecular structure, definite molecular weight, easy purification, mass-scale production, good batch-to-batch reproducibility, good solution processability

  10. Single-molecule microscopy reveals membrane microdomain organization of cells in a living vertebrate.

    PubMed

    Schaaf, Marcel J M; Koopmans, Wiepke J A; Meckel, Tobias; van Noort, John; Snaar-Jagalska, B Ewa; Schmidt, Thomas S; Spaink, Herman P

    2009-08-19

    It has been possible for several years to study the dynamics of fluorescently labeled proteins by single-molecule microscopy, but until now this technology has been applied only to individual cells in culture. In this study, it was extended to stem cells and living vertebrate organisms. As a molecule of interest we used yellow fluorescent protein fused to the human H-Ras membrane anchor, which has been shown to serve as a model for proteins anchored in the plasma membrane. We used a wide-field fluorescence microscopy setup to visualize individual molecules in a zebrafish cell line (ZF4) and in primary embryonic stem cells. A total-internal-reflection microscopy setup was used for imaging in living organisms, in particular in epidermal cells in the skin of 2-day-old zebrafish embryos. Our results demonstrate the occurrence of membrane microdomains in which the diffusion of membrane proteins in a living organism is confined. This membrane organization differed significantly from that observed in cultured cells, illustrating the relevance of performing single-molecule microscopy in living organisms.

  11. Sputtering and detection of large organic molecules from Europa

    NASA Astrophysics Data System (ADS)

    Johnson, R. E.; Sundqvist, B. U. R.

    2018-07-01

    Mass spectroscopy of bio-molecules by heavy ion induced sputtering, which became a practical laboratory procedure, was also suggested as a potential tool for spacecraft studies of targets of interest in astrobiology. With the planning of new missions to Europa, there is renewed interest in the possibility of detecting organic molecules that might have originated in its subsurface ocean and can be sputtered from its surface often intact by impacting energetic heavy ions trapped in Jupiter's magnetosphere. Here we review the laboratory data and modeling bearing on this issue. We then give estimates of the ejection into the gas-phase of trace organic species embedded in an ice matrix on Europa's surface and their possible detection during a flyby mission.

  12. An algorithm to identify functional groups in organic molecules.

    PubMed

    Ertl, Peter

    2017-06-07

    The concept of functional groups forms a basis of organic chemistry, medicinal chemistry, toxicity assessment, spectroscopy and also chemical nomenclature. All current software systems to identify functional groups are based on a predefined list of substructures. We are not aware of any program that can identify all functional groups in a molecule automatically. The algorithm presented in this article is an attempt to solve this scientific challenge. An algorithm to identify functional groups in a molecule based on iterative marching through its atoms is described. The procedure is illustrated by extracting functional groups from the bioactive portion of the ChEMBL database, resulting in identification of 3080 unique functional groups. A new algorithm to identify all functional groups in organic molecules is presented. The algorithm is relatively simple and full details with examples are provided, therefore implementation in any cheminformatics toolkit should be relatively easy. The new method allows the analysis of functional groups in large chemical databases in a way that was not possible using previous approaches. Graphical abstract .

  13. Chemisorption of polysulfides through redox reactions with organic molecules for lithium-sulfur batteries.

    PubMed

    Li, Ge; Wang, Xiaolei; Seo, Min Ho; Li, Matthew; Ma, Lu; Yuan, Yifei; Wu, Tianpin; Yu, Aiping; Wang, Shun; Lu, Jun; Chen, Zhongwei

    2018-02-16

    Lithium-sulfur battery possesses high energy density but suffers from severe capacity fading due to the dissolution of lithium polysulfides. Novel design and mechanisms to encapsulate lithium polysulfides are greatly desired by high-performance lithium-sulfur batteries towards practical applications. Herein, we report a strategy of utilizing anthraquinone, a natural abundant organic molecule, to suppress dissolution and diffusion of polysulfides species through redox reactions during cycling. The keto groups of anthraquinone play a critical role in forming strong Lewis acid-based chemical bonding. This mechanism leads to a long cycling stability of sulfur-based electrodes. With a high sulfur content of ~73%, a low capacity decay of 0.019% per cycle for 300 cycles and retention of 81.7% over 500 cycles at 0.5 C rate can be achieved. This finding and understanding paves an alternative avenue for the future design of sulfur-based cathodes toward the practical application of lithium-sulfur batteries.

  14. Protostellar Interferometric Line Survey (PILS): Constraining the formation of complex organic molecules with ALMA

    NASA Astrophysics Data System (ADS)

    Jorgensen, Jes K.; Coutens, Audrey; Bourke, Tyler L.; Favre, Cecile; Garrod, Robin; Lykke, Julie; Mueller, Holger; Oberg, Karin I.; Schmalzl, Markus; van der Wiel, Matthijs; van Dishoeck, Ewine; Wampfler, Susanne F.

    2015-08-01

    Understanding how, when and where complex organic and potentially prebiotic molecules are formed is a fundamental goal of astrochemistry and an integral part of origins of life studies. Already now ALMA is showing its capabilities for studies of the chemistry of solar-type stars with its high sensitivity for faint lines, high spectral resolution which limits line confusion, and high angular resolution making it possible to study the structure of young protostars on solar-system scales. We here present the first results from a large unbiased survey “Protostellar Interferometric Line Survey (PILS)” targeting one of the astrochemical template sources, the low-mass protostellar binary IRAS 16293-2422. The survey is more than an order of magnitude more sensitive than previous surveys of the source and provide imaging down to 25 AU scales (radius) around each of the two components of the binary. An example of one of the early highlights from the survey is unambiguous detections of the (related) prebiotic species glycolaldehyde, ethylene glycol (two lowest energy conformers), methyl formate and acetic acid. The glycolaldehyde-ethylene glycol abundance ratio is high in comparison to comets and other protostars - but agrees with previous measurements, e.g., in the Galactic Centre clouds possibly reflecting different environments and/or evolutionary histories. Complete mapping of this and other chemical networks in comparison with detailed chemical models and laboratory experiments will reveal the origin of complex organic molecules in a young protostellar system and investigate the link between these protostellar stages and the early Solar System.

  15. Organic amendments enhance microbial diversity and abundance of functional genes in Australian Soils

    NASA Astrophysics Data System (ADS)

    Aldorri, Sind; McMillan, Mary; Pereg, Lily

    2016-04-01

    Food and cash crops play important roles in Australia's economy with black, grey and red clay soil, widely use for growing cotton, wheat, corn and other crops in rotation. While the majority of cotton growers use nitrogen and phosphate fertilizers only in the form of agrochemicals, a few experiment with the addition of manure or composted plant material before planting. We hypothesized that the use of such organic amendments would enhance the soil microbial function through increased microbial diversity and abundance, thus contribute to improved soil sustainability. To test the hypothesis we collected soil samples from two cotton-growing farms in close geographical proximity and with mostly similar production practices other than one grower has been using composted plants as organic amendment and the second farmer uses only agrochemicals. We applied the Biolog Ecoplate system to study the metabolic signature of microbial communities and used qPCR to estimate the abundance of functional genes in the soil. The soil treated with organic amendments clearly showed higher metabolic activity of a more diverse range of carbon sources as well as higher abundance of genes involved in the nitrogen and phosphorous cycles. Since microbes undertake a large number of soil functions, the use of organic amendments can contribute to the sustainability of agricultural soils.

  16. Effects of Functional Groups in Redox-Active Organic Molecules: A High-Throughput Screening Approach

    DOE PAGES

    Pelzer, Kenley M.; Cheng, Lei; Curtiss, Larry A.

    2016-12-08

    Nonaqueous redox flow batteries have attracted recent attention with their potential for high electrochemical storage capacity, with organic electrolytes serving as solvents with a wide electrochemical stability window. Organic molecules can also serve as electroactive species, where molecules with low reduction potentials or high oxidation potentials can provide substantial chemical energy. To identify promising electrolytes in a vast chemical space, high-throughput screening (HTS) of candidate molecules plays an important role, where HTS is used to calculate properties of thousands of molecules and identify a few organic molecules worthy of further attention in battery research. Here, in this work, we presentmore » reduction and oxidation potentials obtained from HTS of 4178 molecules. The molecules are composed of base groups of five- or six-membered rings with one or two functional groups attached, with the set of possible functional groups including both electron-withdrawing and electron-donating groups. In addition to observing the trends in potentials that result from differences in organic base groups and functional groups, we analyze the effects of molecular characteristics such as multiple bonds, Hammett parameters, and functional group position. In conclusion, this work provides useful guidance in determining how the identities of the base groups and functional groups are correlated with desirable reduction and oxidation potentials.« less

  17. Effects of Functional Groups in Redox-Active Organic Molecules: A High-Throughput Screening Approach

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pelzer, Kenley M.; Cheng, Lei; Curtiss, Larry A.

    Nonaqueous redox flow batteries have attracted recent attention with their potential for high electrochemical storage capacity, with organic electrolytes serving as solvents with a wide electrochemical stability window. Organic molecules can also serve as electroactive species, where molecules with low reduction potentials or high oxidation potentials can provide substantial chemical energy. To identify promising electrolytes in a vast chemical space, high-throughput screening (HTS) of candidate molecules plays an important role, where HTS is used to calculate properties of thousands of molecules and identify a few organic molecules worthy of further attention in battery research. Here, in this work, we presentmore » reduction and oxidation potentials obtained from HTS of 4178 molecules. The molecules are composed of base groups of five- or six-membered rings with one or two functional groups attached, with the set of possible functional groups including both electron-withdrawing and electron-donating groups. In addition to observing the trends in potentials that result from differences in organic base groups and functional groups, we analyze the effects of molecular characteristics such as multiple bonds, Hammett parameters, and functional group position. In conclusion, this work provides useful guidance in determining how the identities of the base groups and functional groups are correlated with desirable reduction and oxidation potentials.« less

  18. A solid state physics approach to the interaction between organic molecules and interstellar dust grains: (C60) on SiC

    NASA Astrophysics Data System (ADS)

    Merino, P.; Martin-Gago, J. A.; Cernicharo, J.

    2011-05-01

    We have modeled the interaction of large organic molecules and dust grains in the interstellar medium by means of conventional surface science techniques such as scanning probe microscopes (SPM) and X-ray photoelectron spectroscopy (XPS) among others. With these surface analysis techniques, no frequently used in astrochemistry, we can recreate model systems where the interstellar environment, in a wide range of conditions of pressure and temperature, can be studied. The accurate control of the species that can be studied enables us to simulate in our laboratory the reactions of important molecules on the surface of dust grains. These new kind of experiments provide new information about the chemical mechanisms of the interaction between dust grains and organic molecules which can be compared with the models and the observations. We use a state of the art ultra high vacuum chamber (UHV) with base pressure of 1× 10-10 mbar (2× 106 ppcm^3) where we can prepare macroscopic single-crystal samples simulating a particular dust grain surface. The clean surfaces are exposed to different molecules. The complete system molecule-substrate can be characterized down to the Armstrong scale with the scanning tunneling microscope (STM) and even single molecule orbitals can be resolved. The combination of this technique with diffraction and spectroscopic tools allows us to fully understand the adsorption configuration and chemistry of a particular molecular species on a modeled dust grain surface. Here we present, as a proof-of-concept, the study of a broadly studied molecule, fullerene, (C60) on a silicon carbide (SiC) surface. The stellar winds of carbon-rich red-giants are rich in SiC grains in the inner hot (1500K) shell. These grains can then be covered with C_2 H_2, C H_4 and other hydrocarbons that could lead to complex organic molecules, even PAHs, when they move apart from the star. In the present study we simulate the reaction of C60 molecules with the Si rich (3x3) 6H

  19. Interstellar Dust Models Consistent with Extinction, Emission, and Abundance Constraints

    NASA Technical Reports Server (NTRS)

    Zubko, Viktor; Dwek, Eli; Arendt, Richard G.

    2004-01-01

    We present new interstellar dust models which have been derived by simultaneously fitting the far ultraviolet to near infrared extinction, the diffuse infrared emission, and, unlike previous models, the elemental abundances in dust for the diffuse interstellar medium. We found that dust models consisting of a mixture of spherical graphite and silicate grains, polycyclic aromatic hydrocarbon (PAH) molecules, in addition to porous composite particles containing silicate, organic refractory, and water ice, provide an improved .t to the UV-to-infrared extinction and infrared emission measurements, while consuming the amounts of elements well within the uncertainties of adopted interstellar abundances, including B star abundances. These models are a signi.cant improvement over the recent Li & Draine (2001, ApJ, 554, 778) model which requires an excessive amount of silicon to be locked up in dust: 48 ppm (atoms per million of H atoms), considerably more than the solar abundance of 34 ppm or the B star abundance of 19 ppm.

  20. Single-Cell and Single-Molecule Analysis of Gene Expression Regulation.

    PubMed

    Vera, Maria; Biswas, Jeetayu; Senecal, Adrien; Singer, Robert H; Park, Hye Yoon

    2016-11-23

    Recent advancements in single-cell and single-molecule imaging technologies have resolved biological processes in time and space that are fundamental to understanding the regulation of gene expression. Observations of single-molecule events in their cellular context have revealed highly dynamic aspects of transcriptional and post-transcriptional control in eukaryotic cells. This approach can relate transcription with mRNA abundance and lifetimes. Another key aspect of single-cell analysis is the cell-to-cell variability among populations of cells. Definition of heterogeneity has revealed stochastic processes, determined characteristics of under-represented cell types or transitional states, and integrated cellular behaviors in the context of multicellular organisms. In this review, we discuss novel aspects of gene expression of eukaryotic cells and multicellular organisms revealed by the latest advances in single-cell and single-molecule imaging technology.

  1. Evidence of thermal transport anisotropy in stable glasses of vapor deposited organic molecules

    NASA Astrophysics Data System (ADS)

    Ràfols-Ribé, Joan; Dettori, Riccardo; Ferrando-Villalba, Pablo; Gonzalez-Silveira, Marta; Abad, Llibertat; Lopeandía, Aitor F.; Colombo, Luciano; Rodríguez-Viejo, Javier

    2018-03-01

    Vapor deposited organic glasses are currently in use in many optoelectronic devices. Their operation temperature is limited by the glass transition temperature of the organic layers and thermal management strategies become increasingly important to improve the lifetime of the device. Here we report the unusual finding that molecular orientation heavily influences heat flow propagation in glassy films of small molecule organic semiconductors. The thermal conductivity of vapor deposited thin-film semiconductor glasses is anisotropic and controlled by the deposition temperature. We compare our data with extensive molecular dynamics simulations to disentangle the role of density and molecular orientation on heat propagation. Simulations do support the view that thermal transport along the backbone of the organic molecule is strongly preferred with respect to the perpendicular direction. This is due to the anisotropy of the molecular interaction strength that limits the transport of atomic vibrations. This approach could be used in future developments to implement small molecule glassy films in thermoelectric or other organic electronic devices.

  2. Characterizing Abundances of Volatiles in Comets Through Multiwavelength Observations

    NASA Technical Reports Server (NTRS)

    Milam, Stefanie N.; Charnley, Steven B.; Kuan, Yi-Jehng; Chuang, Yo-Ling; DiSanti, Michael A.; Bonev, Boncho P.; Remijan, Anthony J.; Coulson, Iain; Haynes, Lillian; Stenborg, Maria

    2012-01-01

    Recently, there have been complimentary observations from multiple facilities to try to unravel the chemical complexity of comets. Incorporating results from various techniques, including: single-dish millimeter wavelength observations, interferometers, and/or IR spectroscopy, one can gain further insight into the abundances, production rates, distributions, and formation mechanisms of molecules in these objects [I]. Such studies have provided great detail towards molecules with a-typical chemistries, such as H2CO [2]. We report spectral observations of C/2007 N3 (Lulin), C/2009 R1 (McNaught), 103P/Hartley 2, and C/2009 P1 (Garradd) with the Arizona Radio Observatory's SMT and 12-m telescopes, as well as the NRAO Greenbank telescope and IRTF-CSHELL. Multiple parent volatiles (HCN, CH3OH, CO, CH4, C2H6, and H2O) as well as a number of daughter products (CS and OH) have been detected in these objects. We will present a comparison of molecular abundances in these comets to those observed in others, supporting a long-term effort of building a comet taxonomy based on composition. Previous work has revealed a range of abundances of parent species (from "organics-poor" to "organics-rich") with respect to water among comets [3,4,5], however the statistics are still poorly constrained and interpretations of the observed compositional diversity are uncertain. We gratefully acknowledge support from the NSF Astronomy and Astrophysics Program, the NASA Planetary Astronomy Program, NASA Planetary Atmospheres Program, and the NASA Astrobiology Program.

  3. Small organic molecule based flow battery

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Huskinson, Brian; Marshak, Michael; Aziz, Michael J.

    The invention provides an electrochemical cell based on a new chemistry for a flow battery for large scale, e.g., gridscale, electrical energy storage. Electrical energy is stored chemically at an electrochemical electrode by the protonation of small organic molecules called quinones to hydroquinones. The proton is provided by a complementary electrochemical reaction at the other electrode. These reactions are reversed to deliver electrical energy. A flow battery based on this concept can operate as a closed system. The flow battery architecture has scaling advantages over solid electrode batteries for large scale energy storage.

  4. Modeling Adsorption and Reactions of Organic Molecules at Metal Surfaces

    PubMed Central

    2014-01-01

    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+vdWsurf method that accurately accounts for the collective electronic

  5. The formation of prebiotic molecules in star-forming regions

    NASA Astrophysics Data System (ADS)

    Rivilla, V. M.

    New sensitive observations using the current generation of (sub)millimeter telescopes have revealed in several star-forming regions molecular species of different chemical families (e.g. sugars, esters, isocyanates, phosphorus-bearing species) that may play an important role in prebiotic chemistry, and eventually in the origin of life. The observed molecular abundances of complex organic molecules (glycolaldehyde, ethylene glycol and ethyl formate) are better explained by surface-phase chemistry on dust grains, although gas-phase reactions can also play an important role, as in the case of methyl isocyanate. The PO molecule - a basic chemical bond to build-up the backbone of the DNA - has been detected for the first time in star-forming regions. These new observations indicate that phosphorus, a key element for the development of life, is much more abundant in star-forming regions than previously thought.

  6. Organic matter degradation drives benthic cyanobacterial mat abundance on Caribbean coral reefs.

    PubMed

    Brocke, Hannah J; Polerecky, Lubos; de Beer, Dirk; Weber, Miriam; Claudet, Joachim; Nugues, Maggy M

    2015-01-01

    Benthic cyanobacterial mats (BCMs) are impacting coral reefs worldwide. However, the factors and mechanisms driving their proliferation are unclear. We conducted a multi-year survey around the Caribbean island of Curaçao, which revealed highest BCM abundance on sheltered reefs close to urbanised areas. Reefs with high BCM abundance were also characterised by high benthic cover of macroalgae and low cover of corals. Nutrient concentrations in the water-column were consistently low, but markedly increased just above substrata (both sandy and hard) covered with BCMs. This was true for sites with both high and low BCM coverage, suggesting that BCM growth is stimulated by a localised, substrate-linked release of nutrients from the microbial degradation of organic matter. This hypothesis was supported by a higher organic content in sediments on reefs with high BCM coverage, and by an in situ experiment which showed that BCMs grew within days on sediments enriched with organic matter (Spirulina). We propose that nutrient runoff from urbanised areas stimulates phototrophic blooms and enhances organic matter concentrations on the reef. This organic matter is transported by currents and settles on the seabed at sites with low hydrodynamics. Subsequently, nutrients released from the organic matter degradation fuel the growth of BCMs. Improved management of nutrients generated on land should lower organic loading of sediments and other benthos (e.g. turf and macroalgae) to reduce BCM proliferation on coral reefs.

  7. Solution Based Functionalization of Nanostructured Oxides with Organic Molecules

    NASA Astrophysics Data System (ADS)

    Pearce, Brady Lawrence

    The surface modification of wide bandgap semiconductors with organic molecules provides novel functionalities to the composite material. These functionalities can include tuning of the optical properties, providing solution stability of the inorganic material, as well as many others. The use of an in-situ functionalization method for surface attachment of phosphonic group containing molecules to the surface of gallium nitride (GaN) has shown promise. This technique is particularly advantageous due to the etching and functionalization steps occurring at the same time, in the same beaker, as well as not being reliant on organic solvents or high temperatures. In this functionalization process, surface hydroxide groups are preferentially grown on the surface of GaN, which serve as attachment sites for phosphonic groups on organic moieties. Molecules with these hydroxyl groups available natively on their surface, such as AlOOH and GaOOH, provide a unique advantage. The requirement for an etching step is removed, and the functionalization process could be performed in a simple one-step modification. The work in this dissertation seeks to address the possibility of using these materials as the inorganic component in organic/inorganic composite material in devices. Of particular importance in solar cell and bioelectronic devices is the ability to withstand varying pH environments, and to avoid the leaching of toxic ionic species. Lysine has shown to reduce the leaching of ionic species, when particles of inorganic molecules are cross-linking agents for the amino acid. In this work, the aqueous stability of both AlOOH and GaOOH in a lysine environment will be explored. The optical and size characteristics observed in nanostructured forms of the mixed composition AlxGa1-xOOH material system is of interest, due optical tunability providing a distinct advantage in optoelectronic devices containing these organic/inorganic hybrids. Immobilizing phosphonic group containing

  8. Interstellar abundances - Gas and dust

    NASA Technical Reports Server (NTRS)

    Field, G. B.

    1974-01-01

    Data on abundances of interstellar atoms, ions and molecules in front of zeta Oph are assembled and analyzed. The gas-phase abundances of at least 11 heavy elements are significantly lower, relative to hydrogen, than in the solar system. The abundance deficiencies of certain elements correlate with the temperatures derived theoretically for particle condensation in stellar atmospheres or nebulae, suggesting that these elements have condensed into dust grains near stars. There is evidence that other elements have accreted onto such grains after their arrival in interstellar space. The extinction spectrum of zeta Oph can be explained qualitatively and, to a degree, quantitatively by dust grains composed of silicates, graphite, silicon carbide, and iron, with mantles composed of complex molecules of H, C, N, and O. This composition is consistent with the observed gas-phase deficiencies.

  9. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated martian surface ultraviolet radiation conditions.

    PubMed

    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.

  10. Abundant ammonia in primitive asteroids and the case for a possible exobiology

    PubMed Central

    Pizzarello, Sandra; Williams, Lynda B.; Lehman, Jennifer; Holland, Gregory P.; Yarger, Jeffery L.

    2011-01-01

    Carbonaceous chondrites are asteroidal meteorites that contain abundant organic materials. Given that meteorites and comets have reached the Earth since it formed, it has been proposed that the exogenous influx from these bodies provided the organic inventories necessary for the emergence of life. The carbonaceous meteorites of the Renazzo-type family (CR) have recently revealed a composition that is particularly enriched in small soluble organic molecules, such as the amino acids glycine and alanine, which could support this possibility. We have now analyzed the insoluble and the largest organic component of the CR2 Grave Nunataks (GRA) 95229 meteorite and found it to be of more primitive composition than in other meteorites and to release abundant free ammonia upon hydrothermal treatment. The findings appear to trace CR2 meteorites’ origin to cosmochemical regimes where ammonia was pervasive, and we speculate that their delivery to the early Earth could have fostered prebiotic molecular evolution. PMID:21368183

  11. Sampling and Analysis of Organic Molecules in the Plumes of Enceladus

    NASA Astrophysics Data System (ADS)

    Monroe, A. A.; Williams, P.; Anbar, A. D.; Tsou, P.

    2012-12-01

    The recent detection of organic molecules in the plumes of Enceladus, which also contain water and nitrogen (Waite et al., 2006; Matson et al., 2007), suggests that the geologically active South polar region contains habitable, subsurface water (McKay et al., 2008). Characterizing these molecules will be a high priority for any future mission to Enceladus. Sample return is highly desirable, but can it capture useful samples at Enceladus? Using Stardust mission parameters for comparison, we consider the survival of complex organic molecules during collection to assess the feasibility of one aspect of a sample return mission. A successful sample return mission must include the capability to capture and recover intact or partly intact molecules of particular astrobiological interest: lipids, amino and nucleic acids, polypeptides, and polynucleotides. The Stardust mission to comet Wild 2 successfully captured amino acids, amines, and PAHs using a combination of aerogel and Al foil (Sandford et al., 2006, 2010). For larger and more fragile molecules, particularly polypeptides and polynucleotides, low collisional damage is achieved by impact on low molecular weight surfaces. A particularly intriguing possibility is a capture surface pre-coated with organic matrices identified as ideal for analysis of various biomolecules using MALDI-MS (matrix-assisted laser desorption/ionization mass spectrometry) (Hillenkamp and Karas, 2007). MALDI is a standard technique with attomole sensitivity, exceptional mass resolution, and (bio)molecular specificity (Vestal, 2011). Capture surfaces appropriate for MALDI-MS analysis could be analyzed directly without post-return manipulation, minimizing post-capture damage to these molecules and the risk of contamination during handling. A hypothetical sample collection encounter speed of ~ 5 km/s corresponds to ~0.13 eV kinetic energy per amu. Studies of molecule survival and fragmentation exist for free hexapeptides impacting hydrocarbon

  12. Elucidating Turnover Pathways of Bioactive Small Molecules by Isotopomer Analysis: The Persistent Organic Pollutant DDT

    PubMed Central

    Ehlers, Ina; Betson, Tatiana R.; Vetter, Walter; Schleucher, Jürgen

    2014-01-01

    The persistent organic pollutant DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) 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-chlorophenyl)ethyl]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. PMID:25350380

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Effects of Perchlorate on Organic Molecules under Simulated Mars Conditions

    NASA Astrophysics Data System (ADS)

    Carrier, B. L.; Kounaves, S. P.

    2014-12-01

    Perchlorate (ClO4-) was discovered in the northern polar region of Mars by the Mars Phoenix Lander in 2008 and has also been recently detected by the Curiosity Rover in Gale Crater [1,2]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [3]. The discovery of perchlorate on Mars has raised important questions about the effects of perchlorate on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [4], few studies have been conducted on the potential effects of perchlorate on organic molecules under martian surface conditions. Although perchlorate is typically inert under Mars-typical temperatures [5], perchlorate does absorb high energy UV radiation, and has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-) when exposed to martian conditions including UV or ionizing radiation [6,7]. Here we investigate the effects of perchlorate on the organic molecules tryptophan, benzoic acid and mellitic acid in order to determine how perchlorate may alter these compounds under Mars conditions. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of SiO2 and each organic, as well as varying concentrations of perchlorate salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination. References: [1] Kounaves et al., J. Geophys. Res. Planets, Vol. 115, p. E00E10, 2010 [2] Glavin et al., J. Geophys. Res. Planets, Vol

  15. ALMA Observations of the IRDC Clump G34.43+00.24 MM3: Complex Organic and Deuterated Molecules

    NASA Astrophysics Data System (ADS)

    Sakai, Takeshi; Yanagida, Takahiro; Furuya, Kenji; Aikawa, Yuri; Sanhueza, Patricio; Sakai, Nami; Hirota, Tomoya; Jackson, James M.; Yamamoto, Satoshi

    2018-04-01

    We have observed complex organic molecules (COMs) and deuterated species toward a hot core/corino (HC) associated with the infrared dark cloud clump G34.43+00.24 MM3 with the Atacama Large Millimeter/submillimeter Array. We have detected six normal-COMs (CH3OH, CH3CHO, CH3CH2CN, CH3OCH3, HCOOCH3, and NH2CHO), one deuterated-COM (CH2DCN), and two deuterated fundamental molecules (D2CO and DNC) toward G34.43+00.24 MM3 HC. None of these lines, except for CH3OH, are detected toward the shocked regions in our data, which suggests that COMs do not originate in shocks. The abundance of the COMs relative to CH3OH in G34.43+00.24 MM3 HC is found to be similar to those in high-mass hot cores, rather than those in hot corinos in low-mass star-forming regions. This result suggests that the physical conditions of the warm-up phase of G34.43+00.24 MM3 HC are similar to those of high-mass sources. On the other hand, the D2CO abundance relative to CH3OH in G34.43+00.24 MM3 HC is higher than that of other hot cores, and seems to be comparable to that of hot corinos. The relatively high D2CO/CH3OH ratio of G34.43+00.24 MM3 HC implies a long cold starless phase of G34.43+00.24 MM3 HC.

  16. Design and engineering of organic molecules for customizable Terahertz tags

    NASA Astrophysics Data System (ADS)

    Ray, Shaumik; Dash, Jyotirmayee; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin; Ambade, Ashootosh; Joshi, Kavita; Pesala, Bala

    2014-03-01

    Terahertz (THz) frequency band lies between the microwave and infrared region of the electromagnetic spectrum. Molecules having strong resonances in this frequency range are ideal for realizing "Terahertz tags" which can be easily incorporated into various materials. THz spectroscopy of molecules, especially at frequencies below 10 THz, provides valuable information on the low frequency vibrational modes, viz. intermolecular vibrational modes, hydrogen bond stretching, torsional vibrations in several chemical and biological compounds. So far there have been very few attempts to engineer molecules which can demonstrate customizable resonances in the THz frequency region. In this paper, Diamidopyridine (DAP) based molecules are used as a model system to demonstrate engineering of THz resonances (< 10 THz) by fine-tuning the molecular mass and bond strengths. Density Functional Theory (DFT) simulations have been carried out to explain the origin of THz resonances and factors contributing to the shift in resonances due to the addition of various functional groups. The design approach presented here can be easily extended to engineer various organic molecules suitable for THz tags application.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  19. Structural Design Principle of Small-Molecule Organic Semiconductors for Metal-Free, Visible-Light-Promoted Photocatalysis.

    PubMed

    Wang, Lei; Huang, Wei; Li, Run; Gehrig, Dominik; Blom, Paul W M; Landfester, Katharina; Zhang, Kai A I

    2016-08-08

    Herein, we report on the structural design principle of small-molecule organic semiconductors as metal-free, pure organic and visible light-active photocatalysts. Two series of electron-donor and acceptor-type organic semiconductor molecules were synthesized to meet crucial requirements, such as 1) absorption range in the visible region, 2) sufficient photoredox potential, and 3) long lifetime of photogenerated excitons. The photocatalytic activity was demonstrated in the intermolecular C-H functionalization of electron-rich heteroaromates with malonate derivatives. A mechanistic study of the light-induced electron transport between the organic photocatalyst, substrate, and the sacrificial agent are described. With their tunable absorption range and defined energy-band structure, the small-molecule organic semiconductors could offer a new class of metal-free and visible light-active photocatalysts for chemical reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    ERIC Educational Resources Information Center

    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…

  1. Orchid bees as bio-indicators for organic coffee farms in Costa Rica: does farm size affect their abundance?

    PubMed

    Hedström, Ingemar; Denzel, Andrew; Owens, Gareth

    2006-09-01

    The potential of Euglossini bees, especially Euglossa, as biological indicators of organic vs nonorganic coffee farms was studied in Atenas and San Isidro, Alajuela, Costa Rica using 1.8-cineole as lure. Observations were made for three days at each of four farms and complemented with data from a year of observations. Orchid bees were in greater abundance in the organic farms (t-Student test). However, lower abundances suggest that an organic farm may be negatively affected by the proximity of non-organic farms, depending on its size and distance. Orchid bees may be indicators of organic coffee farms.

  2. Model reduction for stochastic chemical systems with abundant species.

    PubMed

    Smith, Stephen; Cianci, Claudia; Grima, Ramon

    2015-12-07

    Biochemical processes typically involve many chemical species, some in abundance and some in low molecule numbers. We first identify the rate constant limits under which the concentrations of a given set of species will tend to infinity (the abundant species) while the concentrations of all other species remains constant (the non-abundant species). Subsequently, we prove that, in this limit, the fluctuations in the molecule numbers of non-abundant species are accurately described by a hybrid stochastic description consisting of a chemical master equation coupled to deterministic rate equations. This is a reduced description when compared to the conventional chemical master equation which describes the fluctuations in both abundant and non-abundant species. We show that the reduced master equation can be solved exactly for a number of biochemical networks involving gene expression and enzyme catalysis, whose conventional chemical master equation description is analytically impenetrable. We use the linear noise approximation to obtain approximate expressions for the difference between the variance of fluctuations in the non-abundant species as predicted by the hybrid approach and by the conventional chemical master equation. Furthermore, we show that surprisingly, irrespective of any separation in the mean molecule numbers of various species, the conventional and hybrid master equations exactly agree for a class of chemical systems.

  3. Combustion of Organic Molecules by the Thermal Decomposition of Perchlorate Salts: Implications for Organics at the Mars Phoenix Scout Landing Site

    NASA Technical Reports Server (NTRS)

    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

  4. Electron and hole transport in the organic small molecule α-NPD

    NASA Astrophysics Data System (ADS)

    Rohloff, R.; Kotadiya, N. B.; Crǎciun, N. I.; Blom, P. W. M.; Wetzelaer, G. A. H.

    2017-02-01

    Electron and hole transport properties of the organic small molecule N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine are investigated by space-charge-limited current measurements. The hole transport shows trap-free behavior with a mobility of 2.3 × 10-8 m2/Vs at vanishing carrier density and electric field. The electron transport, on the other hand, shows heavily trap-limited behavior, which leads to highly unbalanced transport. A trap concentration of 1.3 × 1024 m-3 was found by modeling the electron currents, similar to the universal trap concentration found in conjugated polymers. This indicates that electron trapping is a generic property of organic semiconductors, ranging from vacuum-deposited small-molecules to solution-processed conjugated polymers.

  5. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    NASA Technical Reports Server (NTRS)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  6. Giant increase in the metal-enhanced fluorescence of organic molecules in nanoporous alumina templates and large molecule-specific red/blue-shift of the fluorescence peak.

    PubMed

    Sarkar, S; Kanchibotla, B; Nelson, J D; Edwards, J D; Anderson, J; Tepper, G C; Bandyopadhyay, S

    2014-10-08

    The fluorescence of organic fluorophore molecules is enhanced when they are placed in contact with certain metals (Al, Ag, Cu, Au, etc.) whose surface plasmon waves couple into the radiative modes of the molecules and increase the radiative efficiency. Here, we report a hitherto unknown size dependence of this metal-enhanced fluorescence (MEF) effect in the nanoscale. When the molecules are deposited in nanoporous anodic alumina films with exposed aluminum at the bottom of the pores, they form organic nanowires standing on aluminum nanoparticles whose plasmon waves have much larger amplitudes. This increases the MEF strongly, resulting in several orders of magnitude increase in the fluorescence intensity of the organic fluorophores. The increase in intensity shows an inverse superlinear dependence on nanowire diameter because the nanowires also act as plasmonic "waveguides" that concentrate the plasmons and increase the coupling of the plasmons with the radiative modes of the molecules. Furthermore, if the nanoporous template housing the nanowires has built-in electric fields due to space charges, a strong molecule-specific red- or blue-shift is induced in the fluorescence peak owing to a renormalization of the dipole moment of the molecule. This can be exploited to detect minute amounts of target molecules in a mixture using their optical signature (fluorescence) despite the presence of confounding background signals. It can result in a unique new technology for biosensing and chemical sensing.

  7. Complex organic molecules in the interstellar medium: IRAM 30 m line survey of Sagittarius B2(N) and (M)

    NASA Astrophysics Data System (ADS)

    Belloche, A.; Müller, H. S. P.; Menten, K. M.; Schilke, P.; Comito, C.

    2013-11-01

    Context. The discovery of amino acids in meteorites fallen to Earth and the detection of glycine, the simplest of them, in samples returned from a comet to Earth strongly suggest that the chemistry of the interstellar medium is capable of producing such complex organic molecules and that they may be widespread in our Galaxy. Aims: Our goal is to investigate the degree of chemical complexity that can be reached in the interstellar medium, in particular in dense star-forming regions. Methods: We performed an unbiased, spectral line survey toward Sgr B2(N) and (M), two regions where high-mass stars are formed, with the IRAM 30 m telescope in the 3 mm atmospheric transmission window. Partial surveys at 2 and 1.3 mm were performed in parallel. The spectra were analyzed with a simple radiative transfer model that assumes local thermodynamic equilibrium but takes optical depth effects into account. Results: About 3675 and 945 spectral lines with a peak signal-to-noise ratio higher than 4 are detected at 3 mm toward Sgr B2(N) and (M), i.e. about 102 and 26 lines per GHz, respectively. This represents an increase by about a factor of two over previous surveys of Sgr B2. About 70% and 47% of the lines detected toward Sgr B2(N) and (M) are identified and assigned to 56 and 46 distinct molecules as well as to 66 and 54 less abundant isotopologues of these molecules, respectively. In addition, we report the detection of transitions from 59 and 24 catalog entries corresponding to vibrationally or torsionally excited states of some of these molecules, respectively, up to a vibration energy of 1400 cm-1 (2000 K). Excitation temperatures and column densities were derived for each species but should be used with caution. The rotation temperatures of the detected complex molecules typically range from ~50 to 200 K. Among the detected molecules, aminoacetonitrile, n-propyl cyanide, and ethyl formate were reported for the first time in space based on this survey, as were five rare

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

    NASA Astrophysics Data System (ADS)

    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

  9. The Mars Organic Molecule Analyzer (MOMA) Instrument: Characterization of Organic Material in Martian Sediments

    PubMed Central

    Goesmann, Fred; Brinckerhoff, William B.; Raulin, François; Danell, Ryan M.; Getty, Stephanie A.; Siljeström, Sandra; Mißbach, Helge; Steininger, Harald; Arevalo, Ricardo D.; Buch, Arnaud; Freissinet, Caroline; Grubisic, Andrej; Meierhenrich, Uwe J.; Pinnick, Veronica T.; Stalport, Fabien; Szopa, Cyril; Vago, Jorge L.; Lindner, Robert; Schulte, Mitchell D.; Brucato, John Robert; Glavin, Daniel P.; Grand, Noel; Li, Xiang; van Amerom, Friso H. W.

    2017-01-01

    Abstract The Mars Organic Molecule Analyzer (MOMA) instrument onboard the ESA/Roscosmos ExoMars rover (to launch in July, 2020) will analyze volatile and refractory organic compounds in martian surface and subsurface sediments. In this study, we describe the design, current status of development, and analytical capabilities of the instrument. Data acquired on preliminary MOMA flight-like hardware and experimental setups are also presented, illustrating their contribution to the overall science return of the mission. Key Words: Mars—Mass spectrometry—Life detection—Planetary instrumentation. Astrobiology 17, 655–685.

  10. Model reduction for stochastic chemical systems with abundant species

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Smith, Stephen; Cianci, Claudia; Grima, Ramon

    2015-12-07

    Biochemical processes typically involve many chemical species, some in abundance and some in low molecule numbers. We first identify the rate constant limits under which the concentrations of a given set of species will tend to infinity (the abundant species) while the concentrations of all other species remains constant (the non-abundant species). Subsequently, we prove that, in this limit, the fluctuations in the molecule numbers of non-abundant species are accurately described by a hybrid stochastic description consisting of a chemical master equation coupled to deterministic rate equations. This is a reduced description when compared to the conventional chemical master equationmore » which describes the fluctuations in both abundant and non-abundant species. We show that the reduced master equation can be solved exactly for a number of biochemical networks involving gene expression and enzyme catalysis, whose conventional chemical master equation description is analytically impenetrable. We use the linear noise approximation to obtain approximate expressions for the difference between the variance of fluctuations in the non-abundant species as predicted by the hybrid approach and by the conventional chemical master equation. Furthermore, we show that surprisingly, irrespective of any separation in the mean molecule numbers of various species, the conventional and hybrid master equations exactly agree for a class of chemical systems.« less

  11. SEASONAL ABUNDANCE OF ORGANIC MOLECULAR MARKERS IN URBAN PARTICULATE MATTER FROM PHILADELPHIA, PA

    EPA Science Inventory

    Organic molecular markers were measured in airborne particulate matter (PM10) from the City of Philadelphia North Broad Street air quality monitoring site to identify the seasonal abundances of key tracer compounds together with their dominant sources. Daily PM10...

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  14. A-π-D-π-A Electron-Donating Small Molecules for Solution-Processed Organic Solar Cells: A Review.

    PubMed

    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.

  15. Endogenous Synthesis of Prebiotic Organic Molecules

    NASA Technical Reports Server (NTRS)

    Miller, Stanley L.

    1996-01-01

    The necessary condition for the synthesis of organic compounds on the primitive earth is the presence of reducing conditions. This means an atmosphere of CH4, CO, or CO2 + H2. The atmospheric nitrogen can be N2 with a trace of NH3, but NH4(+) is needed in the ocean at least for amino acid synthesis. Many attempts have been made to use CO2 + H2O atmospheres for prebiotic synthesis, but these give at best extremely low yields of organic compounds, except in the presence of H2. Even strong reducing agents such as FeS + H2S or the mineral assemblages of the submarine vents fail to give significant yields of organic compounds with CO2. There appears to be a high kinetic barrier to the non-biological reduction of CO2 at low temperatures using geological reducing agents. The most abundant source of energy for prebiotic synthesis is ultraviolet light followed by electric discharges, with electric discharges being more efficient, although it is not clear which was the important energy source. Photochemical process would also make significant contributions. In an atmosphere Of CO2, N2, and H2O with no H2, the production rates of HCN and H2CO would be very low, 0.001 or less than that of a relatively reducing atmosphere. The concentration of organic compounds under these non-reducing conditions would be so low that there is doubt whether the concentration mechanism would be adequate for further steps toward the origin of life. A number of workers have calculated the influx of comets and meteorites on the primitive earth as a source of organic compounds. We conclude that while some organic material was added to the earth from comets and meteorites the amount available from these sources at a given time was at best only a few percent of that from earth bases syntheses under reducing conditions.

  16. Reversible multi-electron redox chemistry of π-conjugated N-containing heteroaromatic molecule-based organic cathodes

    NASA Astrophysics Data System (ADS)

    Peng, Chengxin; Ning, Guo-Hong; Su, Jie; Zhong, Guiming; Tang, Wei; Tian, Bingbing; Su, Chenliang; Yu, Dingyi; Zu, Lianhai; Yang, Jinhu; Ng, Man-Fai; Hu, Yong-Sheng; Yang, Yong; Armand, Michel; Loh, Kian Ping

    2017-07-01

    Even though organic molecules with well-designed functional groups can be programmed to have high electron density per unit mass, their poor electrical conductivity and low cycle stability limit their applications in batteries. Here we report a facile synthesis of π-conjugated quinoxaline-based heteroaromatic molecules (3Q) by condensation of cyclic carbonyl molecules with o-phenylenediamine. 3Q features a number of electron-deficient pyrazine sites, where multiple redox reactions take place. When hybridized with graphene and coupled with an ether-based electrolyte, an organic cathode based on 3Q molecules displays a discharge capacity of 395 mAh g-1 at 400 mA g-1 (1C) in the voltage range of 1.2-3.9 V and a nearly 70% capacity retention after 10,000 cycles at 8 A g-1. It also exhibits a capacity of 222 mAh g-1 at 20C, which corresponds to 60% of the initial specific capacity. Our results offer evidence that heteroaromatic molecules with multiple redox sites are promising in developing high-energy-density, long-cycle-life organic rechargeable batteries.

  17. Mechanochemical synthesis of small organic molecules

    PubMed Central

    Achar, Tapas Kumar; Bose, Anima

    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. PMID:29062410

  18. Lab-on-a-Chip Instrumentation and Method for Detecting Trace Organic and Bioorganic Molecules in Planetary Exploration: The Enceladus Organic Analyzer (EOA)

    NASA Astrophysics Data System (ADS)

    Butterworth, A.; Stockton, A. M.; Turin, P.; Ludlam, M.; Diaz-Aguado, M.; Kim, J.; Mathies, R. A.

    2015-12-01

    Lab-on-a-chip instrumentation is providing an ever more powerful in situ approach for detecting organic molecules relevant for chemical/biochemical evolution in our solar system obviating the cost, risk and long mission duration associated with sample return. Microfabricated analysis systems are particularly feasible when directly sampling from comet comae, or ejecta from icy moons, such as targeting organic molecules in plumes from Enceladus. Furthermore, the superb ppm to ppb sensitivity of chip analyzers, like the Enceladus Organic Analyzer (EOA), coupled with the ability to examine organics with a wide variety of functional groups enhance the probability of detecting organic molecules and determining whether they have a biological origin. The EOA is based on 20 years of research and development of microfabricated capillary electrophoresis (CE) analyzers at Berkeley that provide ppb sensitivity for a wide variety of organic molecules including amino acids, carboxylic acids, amines, aldehydes, ketones and polycyclic aromatic hydrocarbons [1]. Organic molecules are labeled with a fluorescent reagent according to their functional group in a programmable microfluidic processor [2,3] and then separated in a CE system followed by laser-induced fluorescence detection to determine molecular size and concentration. The EOA will be flown through Enceladus plumes and uses a specially designed impact plate/door to capture ice-particles. After closing the door, the material in the capture chamber is dissolved, labeled and analyzed by the microfabricated CE system. Only a few thousand 2 μm diameter particles containing ppm organic concentrations will provide an EOA detectable signal. If amino acids are detected, their chirality is determined because chirality is the best indicator of a biologically produced molecule. We have developed a flight design of this instrument for planetary exploration that is compact (16x16x12 cm), has low mass (3 kg), and requires very low power

  19. The abundance and organization of polypeptides associated with antigens of the Rh blood group system.

    PubMed

    Gardner, B; Anstee, D J; Mawby, W J; Tanner, M J; von dem Borne, A E

    1991-06-01

    Twelve murine monoclonal antibodies, which react with human red cells of common Rh phenotype but give weak or negative reactions with Rh null erythrocytes, were used in quantitative binding assays and competitive binding assays to investigate the abundance and organization of polypeptides involved in the expression of antigens of the Rh blood group system. Antibodies of the R6A-type (R6A, BRIC-69, BRIC-207) and the 2D10-type (MB-2D10, LA18.18, LA23.40) recognize related structures and 100,000-200,000 molecules of each antibody bind maximally to erythrocytes of common Rh phenotype. Antibodies of the BRIC-125 type (BRICs 32, 122, 125, 126, 168, 211) recognize structures that are unrelated to those recognized by R6A-type and 2D10-type antibodies and between 10,000 and 50,000 antibody molecules bind maximally to erythrocytes of the common Rh phenotype. The binding of antibodies of the R6A-type and the 2D10-type, but not of antibodies of the BRIC-125-type could be partially inhibited by human anti-D antibodies (polyclonal and monoclonal) and a murine anti-e-like antibody. These results are consistent with evidence (Moore & Green 1987; Avent et al., 1988b) that the Rh blood group antigens are associated with a complex that comprises two groups of related polypeptides of M(r) 30,000 and M(r) 35,000-100,000, respectively, and suggest that there are 1-2 x 10(5) copies of this complex per erythrocyte. The polypeptide recognized by antibodies of the BRIC-125 type is likely to be associated with this complex.

  20. Hydrogen transfer reactions of interstellar Complex Organic Molecules

    NASA Astrophysics Data System (ADS)

    Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

    2018-06-01

    Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

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

    NASA Technical Reports Server (NTRS)

    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.

  2. Indistinguishable near-infrared single photons from an individual organic molecule

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Trebbia, Jean-Baptiste; Tamarat, Philippe; Lounis, Brahim

    2010-12-15

    By using the zero-phonon line emission of an individual organic molecule, we realized a source of indistinguishable single photons in the near infrared. A Hong-Ou-Mandel interference experiment is performed and a two-photon coalescence probability higher than 50% at 2 K is obtained. The contribution of the temperature-dependent dephasing processes to the two-photon interference contrast is studied. We show that the molecule delivers nearly ideal indistinguishable single photons at the lowest temperatures when the dephasing is nearly lifetime limited. This source is used to generate postselected polarization-entangled photon pairs as a test bench for applications in quantum information.

  3. Degradation of small-molecule organic solar cells

    NASA Astrophysics Data System (ADS)

    Song, Q. L.; Wang, M. L.; Obbard, E. G.; Sun, X. Y.; Ding, X. M.; Hou, X. Y.; Li, C. M.

    2006-12-01

    Small-molecule organic solar cells with a structure of indium tin oxide (ITO)tris-8-hydroxy-quinolinato aluminum (Alq3) (2nm)fullerene (C60) (40nm)\\copper phthalocyanine (CuPc) (32nm)Au (40nm) were fabricated. The shelf lifetime of unencapsulated devices was over 1500h, and the power conversion efficiency reached 0.76% under AM1.5G (air mass 1.5 global) 75mW/cm2. The long lifetime was attributed to the inverted structure compared to the conventional ITO CuPcC60bufferAl structure since the former could effectively protect C60 from the diffusion of oxygen and modify interfacial electrical properties. The introduction of a 2nm Alq3 layer into the cells enhanced the power conversion efficiency by more than 20 times. The presence of the thin Alq3 film on the ITO substrate lowered the substrate work function and hence increased the electric field in the organic layers, which was beneficial to the collection of free carriers. The reasons for the degradation of such kind of organic solar cells are analyzed in detail.

  4. Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules

    NASA Astrophysics Data System (ADS)

    Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar; Venugopalan, Vijay

    2017-06-01

    Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 °C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 × 10-5 cm2/V s.

  5. Many-body perturbation theory for understanding optical excitations in organic molecules and solids

    NASA Astrophysics Data System (ADS)

    Sharifzadeh, Sahar

    2018-04-01

    Semiconductors composed of organic molecules are promising as components for flexible and inexpensive optoelectronic devices, with many recent studies aimed at understanding their electronic and optical properties. In particular, computational modeling of these complex materials has provided new understanding of the underlying properties which give rise to their excited-state phenomena. This article provides an overview of recent many-body perturbation theory (MBPT) studies of optical excitations within organic molecules and solids. We discuss the accuracy of MBPT within the GW/BSE approach in predicting excitation energies and absorption spectra, and assess the impact of two commonly used approximations, the DFT starting point and the Tamm–Dancoff approximation. Moreover, we summarize studies that elucidate the role of solid-state structure on the nature of excitons in organic crystals. These studies show that a rich physical understanding of organic materials can be obtained from GW/BSE.

  6. Evolution of complex organic molecules in hot molecular cores. Synthetic spectra at (sub-)mm wavebands

    NASA Astrophysics Data System (ADS)

    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

  7. Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

    NASA Technical Reports Server (NTRS)

    Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

    1994-01-01

    The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

  8. Laboratory insights into the chemical and kinetic evolution of several organic molecules under simulated Mars surface UV radiation conditions

    NASA Astrophysics Data System (ADS)

    Poch, O.; Kaci, S.; Stalport, F.; Szopa, C.; Coll, P.

    2014-11-01

    The search for organic carbon at the surface of Mars, as clues of past habitability or remnants of life, is a major science goal of Mars' exploration. Understanding the chemical evolution of organic molecules under current martian environmental conditions is essential to support the analyses performed in situ. What molecule can be preserved? What is the timescale of organic evolution at the surface? This paper presents the results of laboratory investigations dedicated to monitor the evolution of organic molecules when submitted to simulated Mars surface ultraviolet radiation (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) conditions. Experiments are done with the MOMIE simulation setup (for Mars Organic Molecules Irradiation and Evolution) allowing both a qualitative and quantitative characterization of the evolution the tested molecules undergo (Poch, O. et al. [2013]. Planet. Space Sci. 85, 188-197). The chemical structures of the solid products and the kinetic parameters of the photoreaction (photolysis rate, half-life and quantum efficiency of photodecomposition) are determined for glycine, urea, adenine and chrysene. Mellitic trianhydride is also studied in order to complete a previous study done with mellitic acid (Stalport, F., Coll, P., Szopa, C., Raulin, F. [2009]. Astrobiology 9, 543-549), by studying the evolution of mellitic trianhydride. The results show that solid layers of the studied molecules have half-lives of 10-103 h at the surface of Mars, when exposed directly to martian UV radiation. However, organic layers having aromatic moieties and reactive chemical groups, as adenine and mellitic acid, lead to the formation of photoresistant solid residues, probably of macromolecular nature, which could exhibit a longer photostability. Such solid organic layers are found in micrometeorites or could have been formed endogenously on Mars. Finally, the quantum efficiencies of photodecomposition at wavelengths from 200 to 250 nm

  9. 9.73% Efficiency Nonfullerene All Organic Small Molecule Solar Cells with Absorption-Complementary Donor and Acceptor.

    PubMed

    Bin, Haijun; Yang, Yankang; Zhang, Zhi-Guo; Ye, Long; Ghasemi, Masoud; Chen, Shanshan; Zhang, Yindong; Zhang, Chunfeng; Sun, Chenkai; Xue, Lingwei; Yang, Changduk; Ade, Harald; Li, Yongfang

    2017-03-29

    In the last two years, polymer solar cells (PSCs) developed quickly with n-type organic semiconductor (n-OSs) as acceptor. In contrast, the research progress of nonfullerene organic solar cells (OSCs) with organic small molecule as donor and the n-OS as acceptor lags behind. Here, we synthesized a D-A structured medium bandgap organic small molecule H11 with bithienyl-benzodithiophene (BDTT) as central donor unit and fluorobenzotriazole as acceptor unit, and achieved a power conversion efficiency (PCE) of 9.73% for the all organic small molecules OSCs with H11 as donor and a low bandgap n-OS IDIC as acceptor. A control molecule H12 without thiophene conjugated side chains on the BDT unit was also synthesized for investigating the effect of the thiophene conjugated side chains on the photovoltaic performance of the p-type organic semiconductors (p-OSs). Compared with H12, the 2D-conjugated H11 with thiophene conjugated side chains shows intense absorption, low-lying HOMO energy level, higher hole mobility and ordered bimodal crystallite packing in the blend films. Moreover, a larger interaction parameter (χ) was observed in the H11 blends calculated from Hansen solubility parameters and differential scanning calorimetry measurements. These special features combined with the complementary absorption of H11 donor and IDIC acceptor resulted in the best PCE of 9.73% for nonfullerene all small molecule OSCs up to date. Our results indicate that fluorobenzotriazole based 2D conjugated p-OSs are promising medium bandgap donors in the nonfullerene OSCs.

  10. Relative Sizes of Organic Molecules

    NASA Technical Reports Server (NTRS)

    2000-01-01

    This computer graphic depicts the relative complexity of crystallizing large proteins in order to study their structures through x-ray crystallography. Insulin is a vital protein whose structure has several subtle points that scientists are still trying to determine. Large molecules such as insuline are complex with structures that are comparatively difficult to understand. For comparison, a sugar molecule (which many people have grown as hard crystals in science glass) and a water molecule are shown. These images were produced with the Macmolecule program. Photo credit: NASA/Marshall Space Flight Center (MSFC)

  11. Synthesis of complex organic molecules in simulated methane rich astrophysical ices

    NASA Astrophysics Data System (ADS)

    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.

  12. Chemical and electrochemical oxidation of small organic molecules

    NASA Astrophysics Data System (ADS)

    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

  13. Interstellar molecules and dense clouds.

    NASA Technical Reports Server (NTRS)

    Rank, D. M.; Townes, C. H.; Welch, W. J.

    1971-01-01

    Current knowledge of the interstellar medium is discussed on the basis of recent published studies. The subjects considered include optical identification of interstellar molecules, radio molecular lines, interstellar clouds, isotopic abundances, formation and disappearance of interstellar molecules, and interstellar probing techniques. Diagrams are plotted for the distribution of galactic sources exhibiting molecular lines, for hydrogen molecule, hydrogen atom and electron abundances due to ionization, for the densities, velocities and temperature of NH3 in the direction of Sagitarius B2, for the lower rotational energy levels of H2CO, and for temporal spectral variations in masing H2O clouds of the radio source W49. Future applications of the maser and of molecular microscopy in this field are visualized.

  14. Formation and Destruction Processes of Interstellar Dust: From Organic Molecules to carbonaceous Grains

    NASA Technical Reports Server (NTRS)

    Salama, F.; Biennier, L.

    2004-01-01

    The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. interstellar dust presents a continuous size distribution from large molecules, radicals and ions to nanometer-sized particles to micron-sized grains. The lower end of the dust size distribution is thought to be responsible for the ubiquitous spectral features that are seen in emission in the IR (UIBs) and in absorption in the visible (DIBs). The higher end of the dust-size distribution is thought to be responsible for the continuum emission plateau that is seen in the IR and for the strong absorption seen in the interstellar UV extinction curve. All these spectral signatures are characteristic of cosmic organic materials that are ubiquitous and present in various forms from gas-phase molecules to solid-state grains. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of dust. Recent space observations in the UV (HST) and in the IR (ISO) help place size constraints on the molecular component of carbonaceous IS dust and indicate that small (ie., subnanometer) PAHs cannot contribute significantly to the IS features in the UV and in the IR. Studies of large molecular and nano-sized IS dust analogs formed from PAH precursors have been performed in our laboratory under conditions that simulate diffuse ISM environments (the particles are cold -100 K vibrational energy, isolated in the gas phase and exposed to a high-energy discharge environment in a cold plasma). The species (molecules, molecular fragments, ions, nanoparticles, etc) formed in the pulsed discharge nozzle (PDN) plasma source are detected with a high-sensitivity cavity ring-down spectrometer (CRDS). We will present new experimental results that indicate that nanoparticles are generated in the

  15. Difficulties in Laboratory Studies and Astronomical Observations of Organic Molecules: Hydroxyacetone and Lactic Acid

    NASA Technical Reports Server (NTRS)

    Apponi, A. J.; Brewster, M. A.; Hoy, J.; Ziurys, L. M.

    2006-01-01

    For the past 35 years, radio astronomy has revealed a rich organic chemistry in the interstellar gas, which is exceptionally complex towards active star-forming regions. New solar systems condense out of this gas and may influence the evolution of life on newly formed planets. Much of the biologically important functionality is present among the some 130 gas-phase molecules found to date, including alcohols, aldehydes, ketones, acids, amines, amides and even the simplest sugar - glycolaldehyde. Still, many unidentified interstellar radio signals remain, and their identification relies on further laboratory study. The molecules hydroxyacetone and lactic acid are relatively small organic molecules, but possess rather complex rotational spectra owing to their high asymmetry. Hydroxyacetone is particularly problematic because it possess a very low barrier to internal rotation, and exhibits strong coupling of the free-rotor states with the overall rotation of the molecule. As in the case of acetamide, a full decomposition method was employed to order the resultant eigenstates onto normal asymmetric top eigenvectors.

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

    PubMed

    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.

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

    DOE PAGES

    Bi, Sheng; He, Zhengran; Chen, Jihua; ...

    2015-07-24

    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 cm 2/V s, whichmore » is the highest mobility from SMDPPEH ever reported.« less

  18. Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

    PubMed

    Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

    2015-04-13

    Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Many-Body Perturbation Theory for Understanding Optical Excitations in Organic Molecules and Solids

    NASA Astrophysics Data System (ADS)

    Sharifzadeh, Sahar

    Organic semiconductors are promising as light-weight, flexible, and strongly absorbing materials for next-generation optoelectronics. The advancement of such technologies relies on understanding the fundamental excited-state properties of organic molecules and solids, motivating the development of accurate computational approaches for this purpose. Here, I will present first-principles many-body perturbation theory (MBPT) calculations aimed at understanding the spectroscopic properties of select organic molecules and crystalline semiconductors, and improving these properties for enhanced photovoltaic performance. We show that for both gas-phase molecules and condensed-phase crystals, MBPT within the GW/BSE approximation provides quantitative accuracy of transport gaps extracted from photoemission spectroscopy and conductance measurements, as well as with measured polarization-dependent optical absorption spectra. We discuss the implications of standard approximations within GW/BSE on accuracy of these results. Additionally, we demonstrate significant exciton binding energies and charge-transfer character in the crystalline systems, which can be controlled through solid-state morphology or change of conjugation length, suggesting a new strategy for the design of optoelectronic materials. We acknowledge NSF for financial support; NERSC and Boston University for computational resources.

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

    DOEpatents

    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.

  1. Graphite grain-size spectrum and molecules from core-collapse supernovae

    NASA Astrophysics Data System (ADS)

    Clayton, Donald D.; Meyer, Bradley S.

    2018-01-01

    Our goal is to compute the abundances of carbon atomic complexes that emerge from the C + O cores of core-collapse supernovae. We utilize our chemical reaction network in which every atomic step of growth employs a quantum-mechanically guided reaction rate. This tool follows step-by-step the growth of linear carbon chain molecules from C atoms in the oxygen-rich C + O cores. We postulate that once linear chain molecules reach a sufficiently large size, they isomerize to ringed molecules, which serve as seeds for graphite grain growth. We demonstrate our technique for merging the molecular reaction network with a parallel program that can follow 1017 steps of C addition onto the rare seed species. Due to radioactivity within the C + O core, abundant ambient oxygen is unable to convert C to CO, except to a limited degree that actually facilitates carbon molecular ejecta. But oxygen severely minimizes the linear-carbon-chain abundances. Despite the tiny abundances of these linear-carbon-chain molecules, they can give rise to a small abundance of ringed-carbon molecules that serve as the nucleations on which graphite grain growth builds. We expand the C + O-core gas adiabatically from 6000 K for 109 s when reactions have essentially stopped. These adiabatic tracks emulate the actual expansions of the supernova cores. Using a standard model of 1056 atoms of C + O core ejecta having O/C = 3, we calculate standard ejection yields of graphite grains of all sizes produced, of the CO molecular abundance, of the abundances of linear-carbon molecules, and of Buckminsterfullerene. None of these except CO was expected from the C + O cores just a few years past.

  2. Small molecule organic semiconductors on the move: promises for future solar energy technology.

    PubMed

    Mishra, Amaresh; Bäuerle, Peter

    2012-02-27

    This article is written from an organic chemist's point of view and provides an up-to-date review about organic solar cells based on small molecules or oligomers as absorbers and in detail deals with devices that incorporate planar-heterojunctions (PHJ) and bulk heterojunctions (BHJ) between a donor (p-type semiconductor) and an acceptor (n-type semiconductor) material. The article pays particular attention to the design and development of molecular materials and their performance in corresponding devices. In recent years, a substantial amount of both, academic and industrial research, has been directed towards organic solar cells, in an effort to develop new materials and to improve their tunability, processability, power conversion efficiency, and stability. On the eve of commercialization of organic solar cells, this review provides an overview over efficiencies attained with small molecules/oligomers in OSCs and reflects materials and device concepts developed over the last decade. Approaches to enhancing the efficiency of organic solar cells are analyzed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Electrophoretic assembly of organic molecules and composites for electrochemical supercapacitors.

    PubMed

    Su, Y; Zhitomirsky, I

    2013-02-15

    Electrophoretic deposition (EPD) method has been developed for the fabrication of 1-pyrenebutyric acid (PBH) films from aqueous solutions. The films can be deposited at constant voltage or potentiodynamic conditions. The method allowed the formation of 0.1-2 μm thick films, containing needle-shape PBH particles. The deposition mechanism involved the electrophoresis, pH decrease at the anode surface, charge neutralization and formation of insoluble PBH films. The film morphology and shape of the PBH particles are controlled by the π-π stacking mechanism of the polyaromatic PBH molecules. The important finding was the possibility of controlled EPD of multiwalled carbon nanotubes (MWCNTs) using PBH as a charging, dispersing and film forming agent. It was found that at low voltages or low PBH concentrations the deposits contained mainly MWCNT. The increase in the deposition voltage or/and PBH concentration resulted in co-deposition of MWCNT and needle-shape PBH particles. The new approach to the deposition of MWCNT was used for the fabrication of composite MnO(2)-MWCNT films for electrodes of electrochemical supercapacitors, which showed a specific capacitance of 250 F g(-1). The EPD method developed in this investigation paves the way for the deposition of other small organic molecules and composites and their applications in new materials and devices, utilizing functional properties of the organic molecules, CNT, and other advanced materials. Copyright © 2012 Elsevier Inc. All rights reserved.

  4. Photogenerated Intrinsic Free Carriers in Small-molecule Organic Semiconductors Visualized by Ultrafast Spectroscopy

    PubMed Central

    He, Xiaochuan; Zhu, Gangbei; Yang, Jianbing; Chang, Hao; Meng, Qingyu; Zhao, Hongwu; Zhou, Xin; Yue, Shuai; Wang, Zhuan; Shi, Jinan; Gu, Lin; Yan, Donghang; Weng, Yuxiang

    2015-01-01

    Confirmation of direct photogeneration of intrinsic delocalized free carriers in small-molecule organic semiconductors has been a long-sought but unsolved issue, which is of fundamental significance to its application in photo-electric devices. Although the excitonic description of photoexcitation in these materials has been widely accepted, this concept is challenged by recently reported phenomena. Here we report observation of direct delocalized free carrier generation upon interband photoexcitation in highly crystalline zinc phthalocyanine films prepared by the weak epitaxy growth method using ultrafast spectroscopy. Transient absorption spectra spanning the visible to mid-infrared region revealed the existence of short-lived free electrons and holes with a diffusion length estimated to cross at least 11 molecules along the π−π stacking direction that subsequently localize to form charge transfer excitons. The interband transition was evidenced by ultraviolet-visible absorption, photoluminescence and electroluminescence spectroscopy. Our results suggest that delocalized free carriers photogeneration can also be achieved in organic semiconductors when the molecules are packed properly. PMID:26611323

  5. Organic Nitrogen-Driven Stimulation of Arbuscular Mycorrhizal Fungal Hyphae Correlates with Abundance of Ammonia Oxidizers

    PubMed Central

    Bukovská, Petra; Gryndler, Milan; Gryndlerová, Hana; Püschel, David; Jansa, Jan

    2016-01-01

    Large fraction of mineral nutrients in natural soil environments is recycled from complex and heterogeneously distributed organic sources. These sources are explored by both roots and associated mycorrhizal fungi. However, the mechanisms behind the responses of arbuscular mycorrhizal (AM) hyphal networks to soil organic patches of different qualities remain little understood. Therefore, we conducted a multiple-choice experiment examining hyphal responses to different soil patches within the root-free zone by two AM fungal species (Rhizophagus irregularis and Claroideoglomus claroideum) associated with Medicago truncatula, a legume forming nitrogen-fixing root nodules. Hyphal colonization of the patches was assessed microscopically and by quantitative real-time PCR (qPCR) using AM taxon-specific markers, and the prokaryotic and fungal communities in the patches (pooled per organic amendment treatment) were profiled by 454-amplicon sequencing. Specific qPCR markers were then designed and used to quantify the abundance of prokaryotic taxa showing the strongest correlation with the pattern of AM hyphal proliferation in the organic patches as per the 454-sequencing. The hyphal density of both AM fungi increased due to nitrogen (N)-containing organic amendments (i.e., chitin, DNA, albumin, and clover biomass), while no responses as compared to the non-amended soil patch were recorded for cellulose, phytate, or inorganic phosphate amendments. Abundances of several prokaryotes, including Nitrosospira sp. (an ammonium oxidizer) and an unknown prokaryote with affiliation to Acanthamoeba endosymbiont, which were frequently recorded in the 454-sequencing profiles, correlated positively with the hyphal responses of R. irregularis to the soil amendments. Strong correlation between abundance of these two prokaryotes and the hyphal responses to organic soil amendments by both AM fungi was then confirmed by qPCR analyses using all individual replicate patch samples. Further

  6. Organic Nitrogen-Driven Stimulation of Arbuscular Mycorrhizal Fungal Hyphae Correlates with Abundance of Ammonia Oxidizers.

    PubMed

    Bukovská, Petra; Gryndler, Milan; Gryndlerová, Hana; Püschel, David; Jansa, Jan

    2016-01-01

    Large fraction of mineral nutrients in natural soil environments is recycled from complex and heterogeneously distributed organic sources. These sources are explored by both roots and associated mycorrhizal fungi. However, the mechanisms behind the responses of arbuscular mycorrhizal (AM) hyphal networks to soil organic patches of different qualities remain little understood. Therefore, we conducted a multiple-choice experiment examining hyphal responses to different soil patches within the root-free zone by two AM fungal species (Rhizophagus irregularis and Claroideoglomus claroideum) associated with Medicago truncatula, a legume forming nitrogen-fixing root nodules. Hyphal colonization of the patches was assessed microscopically and by quantitative real-time PCR (qPCR) using AM taxon-specific markers, and the prokaryotic and fungal communities in the patches (pooled per organic amendment treatment) were profiled by 454-amplicon sequencing. Specific qPCR markers were then designed and used to quantify the abundance of prokaryotic taxa showing the strongest correlation with the pattern of AM hyphal proliferation in the organic patches as per the 454-sequencing. The hyphal density of both AM fungi increased due to nitrogen (N)-containing organic amendments (i.e., chitin, DNA, albumin, and clover biomass), while no responses as compared to the non-amended soil patch were recorded for cellulose, phytate, or inorganic phosphate amendments. Abundances of several prokaryotes, including Nitrosospira sp. (an ammonium oxidizer) and an unknown prokaryote with affiliation to Acanthamoeba endosymbiont, which were frequently recorded in the 454-sequencing profiles, correlated positively with the hyphal responses of R. irregularis to the soil amendments. Strong correlation between abundance of these two prokaryotes and the hyphal responses to organic soil amendments by both AM fungi was then confirmed by qPCR analyses using all individual replicate patch samples. Further

  7. Reactive Desorption and Radiative Association as Possible Drivers of Complex Molecule Formation in the Cold Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Vasyunin, A. I.; Herbst, Eric

    2013-05-01

    The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed "warm-up" scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

  8. Computational laser intensity stabilisation for organic molecule concentration estimation in low-resource settings

    NASA Astrophysics Data System (ADS)

    Haider, Shahid A.; Kazemzadeh, Farnoud; Wong, Alexander

    2017-03-01

    An ideal laser is a useful tool for the analysis of biological systems. In particular, the polarization property of lasers can allow for the concentration of important organic molecules in the human body, such as proteins, amino acids, lipids, and carbohydrates, to be estimated. However, lasers do not always work as intended and there can be effects such as mode hopping and thermal drift that can cause time-varying intensity fluctuations. The causes of these effects can be from the surrounding environment, where either an unstable current source is used or the temperature of the surrounding environment is not temporally stable. This intensity fluctuation can cause bias and error in typical organic molecule concentration estimation techniques. In a low-resource setting where cost must be limited and where environmental factors, like unregulated power supplies and temperature, cannot be controlled, the hardware required to correct for these intensity fluctuations can be prohibitive. We propose a method for computational laser intensity stabilisation that uses Bayesian state estimation to correct for the time-varying intensity fluctuations from electrical and thermal instabilities without the use of additional hardware. This method will allow for consistent intensities across all polarization measurements for accurate estimates of organic molecule concentrations.

  9. Abundance and Temperature Variations in Titan's Atmosphere as Revealed by ALMA

    NASA Astrophysics Data System (ADS)

    Thelen, A. E.; Nixon, C. A.; Chanover, N.; Molter, E.; Cordiner, M. A.; Serigano, J., IV; Irwin, P. G.; Charnley, S. B.; Teanby, N. A.

    2016-12-01

    Photochemistry in Titan's atmosphere produces a wealth of organic molecular species through the dissociation of it's main constituents: N2 and CH4. Chemical species including hydrocarbons (CXHY) and nitriles (CXHY[CN]Z) exhibit latitudinal variations in abundance as observed by Cassini, attributed to atmospheric circulation and Titan's seasonal cycle. Flux calibration images of Titan taken by the Atacama Large Millimeter/Submillimeter Array (ALMA) with beam sizes smaller than Titan's angular diameter ( 0.7'') allow for measurements of rotational transition lines in spatially resolved regions of Titan's disk. We present nitrile abundance profiles and temperature measurements derived from CO lines obtained by ALMA in 2014, as Titan transitioned into northern summer. Vertical profiles in Titan's lower/middle atmosphere were retrieved by modeling high resolution ALMA spectra using the Non-linear Optimal Estimator for MultivariatE Spectral analySIS (NEMESIS) radiative transfer code. We present a comparison of the abundance variations of chemical species to measurements made using Cassini data. Temperature profiles derived from CO lines are compared to Cassini Composite Infrared Spectrometer temperature fields. The techniques presented here will allow us to determine temporal changes in Titan's atmospheric chemical composition after the end of the Cassini mission by utilizing high resolution ALMA data. Comparisons of chemical species with strong abundance enhancements over the poles will inform our knowledge of chemical lifetimes in Titan's atmosphere, and allow us to observe the important changes in production and circulation of numerous organic molecules which are attributed to Titan's seasons.

  10. Determination of Natural 14C Abundances in Dissolved Organic Carbon in Organic-Rich Marine Sediment Porewaters by Thermal Sulfate Reduction

    NASA Astrophysics Data System (ADS)

    Johnson, L.; Komada, T.

    2010-12-01

    The abundances of natural 14C in dissolved organic carbon (DOC) in the marine environment hold clues regarding the processes that influence the biogeochemical cycling of this large carbon reservoir. At present, UV irradiation is the widely accepted method for oxidizing seawater DOC for determination of their 14C abundances. This technique yields precise and accurate values with low blanks, but it requires a dedicated vacuum line, and hence can be difficult to implement. As an alternative technique that can be conducted on a standard preparatory vacuum line, we modified and tested a thermal sulfate reduction method that was previously developed to determine δ13C values of marine DOC (Fry B. et al., 1996. Analysis of marine DOC using a dry combustion method. Mar. Chem., 54: 191-201.) to determine the 14C abundances of DOC in marine sediment porewaters. In this method, the sample is dried in a 100 ml round-bottom Pyrex flask in the presence of excess oxidant (K2SO4) and acid (H3PO4), and combusted at 550 deg.C. The combustion products are cryogenically processed to collect and quantify CO2 using standard procedures. Materials we have oxidized to date range from 6-24 ml in volume, and 95-1500 μgC in size. The oxidation efficiency of this method was tested by processing known amounts of reagent-grade dextrose and sucrose (as examples of labile organic matter), tannic acid and humic acid (as examples of complex natural organic matter), and porewater DOC extracted from organic-rich nearshore sediments. The carbon yields for all of these materials averaged 99±4% (n=18). The 14C abundances of standard materials IAEA C-6 and IAEA C-5 processed by this method using >1mgC aliquots were within error of certified values. The size and the isotopic value of the blank were determined by a standard dilution technique using IAEA C-6 and IAEA C-5 that ranged in size from 150 to 1500 μgC (n=4 and 2, respectively). This yielded a blank size of 6.7±0.7 μgC, and a blank isotopic

  11. Ultraviolet Pretreatment of Titanium Dioxide and Tin-Doped Indium Oxide Surfaces as a Promoter of the Adsorption of Organic Molecules in Dry Deposition Processes: Light Patterning of Organic Nanowires.

    PubMed

    Oulad-Zian, Youssef; Sanchez-Valencia, Juan R; Parra-Barranco, Julian; Hamad, Said; Espinos, Juan P; Barranco, Angel; Ferrer, Javier; Coll, Mariona; Borras, Ana

    2015-08-04

    In this article we present the preactivation of TiO2 and ITO by UV irradiation under ambient conditions as a tool to enhance the incorporation of organic molecules on these oxides by evaporation at low pressures. The deposition of π-stacked molecules on TiO2 and ITO at controlled substrate temperature and in the presence of Ar is thoroughly followed by SEM, UV-vis, XRD, RBS, and photoluminescence spectroscopy, and the effect is exploited for the patterning formation of small-molecule organic nanowires (ONWs). X-ray photoelectron spectroscopy (XPS) in situ experiments and molecular dynamics simulations add critical information to fully elucidate the mechanism behind the increase in the number of adsorption centers for the organic molecules. Finally, the formation of hybrid organic/inorganic semiconductors is also explored as a result of the controlled vacuum sublimation of organic molecules on the open thin film microstructure of mesoporous TiO2.

  12. Curiosity: organic molecules on Mars? (Italian Title: Curiosity: molecole organiche su Marte?)

    NASA Astrophysics Data System (ADS)

    Guaita, C.

    2015-05-01

    First analytical results from SAM instrument onboard of Curiosity are coherent with the presence, on Mars, of organic molecules possibly linked to bacterial metabolism. These data require also a modern revision of the debated results obtained by Viking landers.

  13. The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs)

    NASA Astrophysics Data System (ADS)

    Hogan, Greg Anthony

    The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs. Layered materials can mimic the behavior of naturally occurring clays, where guest molecules are absorbed and the layer will expand to accommodate the entering guest molecule. We have created a clay mimic composed of a metal pyridine-dicarboxylates and ammonium counterions (a layered HMOF), which is suitable for studying the ability of such materials to absorb guest molecules. We can control the distance of the interlayer region, as well as the chemical nature (hydrophobic or hydrophilic) by varying the organic amine. The metal complex contains axial water ligands that are replaceable, and such ligand exchange has precedence in coordination polymer (MOF) systems, and has been termed "coordinative intercalation". Using the synthesized layered material we examined the process of intercalation, having chosen a variety of guest molecules ranging from alkyl to aryl molecules, each of which have substituents varying in size, shape and electronics. The first set of guest molecules are non

  14. Multicomponent Gas Storage in Organic Cage Molecules

    DOE PAGES

    Zhang, Fei; He, Yadong; Huang, Jingsong; ...

    2017-05-18

    Porous liquids are a promising new class of materials featuring nanoscale cavity units dispersed in liquids that are suitable for applications such as gas storage and separation. In this work, we use molecular dynamics simulations to examine the multicomponent gas storage in a porous liquid consisting of crown-ether-substituted cage molecules dissolved in a 15-crown-5 solvent. We compute the storage of three prototypical small molecules including CO 2, CH 4, and N 2 and their binary mixtures in individual cage molecules. For porous liquids in equilibrium with a binary 1:1 gas mixture bath with partial gas pressure of 27.5 bar, amore » cage molecule shows a selectivity of 4.3 and 13.1 for the CO 2/CH 4 and CO 2/N 2 pairs, respectively. We provide a molecular perspective of how gas molecules are stored in the cage molecule and how the storage of one type of gas molecule is affected by other types of gas molecules. Finally, our results clarify the molecular mechanisms behind the selectivity of such cage molecules toward different gases.« less

  15. Label-free detection of protein molecules secreted from an organ-on-a-chip model for drug toxicity assays

    NASA Astrophysics Data System (ADS)

    Morales, Andres W.; Zhang, Yu S.; Aleman, Julio; Alerasool, Parissa; Dokmeci, Mehmet R.; Khademhosseini, Ali; Ye, Jing Yong

    2016-03-01

    Clinical attrition is about 30% from failure of drug candidates due to toxic side effects, increasing the drug development costs significantly and slowing down the drug discovery process. This partly originates from the fact that the animal models do not accurately represent human physiology. Hence there is a clear unmet need for developing drug toxicity assays using human-based models that are complementary to traditional animal models before starting expensive clinical trials. Organ-on-a-chip techniques developed in recent years have generated a variety of human organ models mimicking different human physiological conditions. However, it is extremely challenging to monitor the transient and long-term response of the organ models to drug treatments during drug toxicity tests. First, when an organ-on-a-chip model interacts with drugs, a certain amount of protein molecules may be released into the medium due to certain drug effects, but the amount of the protein molecules is limited, since the organ tissue grown inside microfluidic bioreactors have minimum volume. Second, traditional fluorescence techniques cannot be utilized for real-time monitoring of the concentration of the protein molecules, because the protein molecules are continuously secreted from the tissue and it is practically impossible to achieve fluorescence labeling in the dynamically changing environment. Therefore, direct measurements of the secreted protein molecules with a label-free approach is strongly desired for organs-on-a-chip applications. In this paper, we report the development of a photonic crystal-based biosensor for label-free assays of secreted protein molecules from a liver-on-a-chip model. Ultrahigh detection sensitivity and specificity have been demonstrated.

  16. Rational Design of Diketopyrrolopyrrole-Based Small Molecules as Donating Materials for Organic Solar Cells

    PubMed Central

    Jin, Ruifa; Wang, Kai

    2015-01-01

    A series of diketopyrrolopyrrole-based small molecules have been designed to explore their optical, electronic, and charge transport properties as organic solar cell (OSCs) materials. The calculation results showed that the designed molecules can lower the band gap and extend the absorption spectrum towards longer wavelengths. The designed molecules own the large longest wavelength of absorption spectra, the oscillator strength, and absorption region values. The optical, electronic, and charge transport properties of the designed molecules are affected by the introduction of different π-bridges and end groups. We have also predicted the mobility of the designed molecule with the lowest total energies. Our results reveal that the designed molecules are expected to be promising candidates for OSC materials. Additionally, the designed molecules are expected to be promising candidates for electron and/or hole transport materials. On the basis of our results, we suggest that molecules under investigation are suitable donors for [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and its derivatives as acceptors of OSCs. PMID:26343640

  17. Synchrotron-based soft X-ray spectroscopic studies of the electronic structure of organic semiconducting molecules

    NASA Astrophysics Data System (ADS)

    Demasi, Alexander

    Organic molecules have been the subject of many scientific studies due to their potential for use in a new generation of optoelectronic and semiconducting devices, such as organic photovoltaics and organic light emitting diodes. These studies are motivated by the fact that organic semiconductor devices have several advantages over traditional inorganic semiconductor devices. Unlike inorganic semiconductors, where the electronic properties are a result of the deliberate introduction of dopants to the material, the properties of organic semiconductors are often intrinsic to the molecules themselves. As a result, organic semiconductor devices are frequently less susceptible to contamination by impurities than their inorganic counterparts, which results in the relatively lower cost of producing such devices. Accurate experimental determination of the bulk and surface electronic structure of organic semiconductors is a prerequisite in developing a comprehensive understanding of such materials. The organic materials studied in this thesis were N,N-Ethylene-bis(1,1,1trifluoropentane-2,4-dioneiminato)-copper(ii) (abbreviated Cu-TFAC), aluminum tris-8hydroxyquinoline (A1g3), lithium quinolate (Liq), tetracyanoquinodimethane (TCNQ), and tetrafluorotetracyanoquinodimethane (F4TCNQ). The electronic structures of these materials were measured with several synchrotron-based x-ray spectroscopies. X-ray photoemission spectroscopy was used to measure the occupied total density of states and the core-level states of the aforementioned materials. X-ray absorption spectroscopy (XAS) was used to probe the element-specific unoccupied partial density of states (PDOS); its angle-resolved variant was used to measure the orientation of the molecules in a film and, in some circumstances, to gauge the extent of an organic film's crystallinity. Most notably, x-ray emission spectroscopy (XES) measures the element- specific occupied PDOS and, when aided by XAS, resonant XES can additionally be

  18. Nucleation of Organic Molecules via a Hot Precursor State: Pentacene on Amorphous Mica

    PubMed Central

    2013-01-01

    Organic thin films have attracted considerable interest due to their applicability in organic electronics. The classical scenario for thin film nucleation is the diffusion-limited aggregation (DLA). Recently, it has been shown that organic thin film growth is better described by attachment-limited aggregation (ALA). However, in both cases, an unusual relationship between the island density and the substrate temperature was observed. Here, we present an aggregation model that goes beyond the classical DLA or ALA models to explain this behavior. We propose that the (hot) molecules impinging on the surface cannot immediately equilibrate to the substrate temperature but remain in a hot precursor state. In this state, the molecules can migrate considerable distances before attaching to a stable or unstable island. This results in a significantly smaller island density than expected by assuming fast equilibration and random diffusion. We have applied our model to pentacene film growth on amorphous Muscovite mica. PMID:24340130

  19. Adsorption of organic molecules on mineral surfaces studied by first-principle calculations: A review.

    PubMed

    Zhao, Hongxia; Yang, Yong; Shu, Xin; Wang, Yanwei; Ran, Qianping

    2018-04-09

    First-principle calculations, especially by the density functional theory (DFT) methods, are becoming a power technique to study molecular structure and properties of organic/inorganic interfaces. This review introduces some recent examples on the study of adsorption models of organic molecules or oligomers on mineral surfaces and interfacial properties obtained from first-principles calculations. The aim of this contribution is to inspire scientists to benefit from first-principle calculations and to apply the similar strategies when studying and tailoring interfacial properties at the atomistic scale, especially for those interested in the design and development of new molecules and new products. Copyright © 2017. Published by Elsevier B.V.

  20. From molecule to solid: The prediction of organic crystal structures

    NASA Astrophysics Data System (ADS)

    Dzyabchenko, A. V.

    2008-10-01

    A method for predicting the structure of a molecular crystal based on the systematic search for a global potential energy minimum is considered. The method takes into account unequal occurrences of the structural classes of organic crystals and symmetry of the multidimensional configuration space. The programs of global minimization PMC, comparison of crystal structures CRYCOM, and approximation to the distributions of the electrostatic potentials of molecules FitMEP are presented as tools for numerically solving the problem. Examples of predicted structures substantiated experimentally and the experience of author’s participation in international tests of crystal structure prediction organized by the Cambridge Crystallographic Data Center (Cambridge, UK) are considered.

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

    NASA Astrophysics Data System (ADS)

    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

  2. A Nonfullerene Small Molecule Acceptor with 3D Interlocking Geometry Enabling Efficient Organic Solar Cells.

    PubMed

    Lee, Jaewon; Singh, Ranbir; Sin, Dong Hun; Kim, Heung Gyu; Song, Kyu Chan; Cho, Kilwon

    2016-01-06

    A new 3D nonfullerene small-molecule acceptor is reported. The 3D interlocking geometry of the small-molecule acceptor enables uniform molecular conformation and strong intermolecular connectivity, facilitating favorable nanoscale phase separation and electron charge transfer. By employing both a novel polymer donor and a nonfullerene small-molecule acceptor in the solution-processed organic solar cells, a high-power conversion efficiency of close to 6% is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Search for clues of life or habitability at Mars: laboratory simulation of the evolution of organic molecules at the surface of Mars

    NASA Astrophysics Data System (ADS)

    Poch, Olivier; Szopa, Cyril; Coll, Patrice; Jaber, Maguy; Georgelin, Thomas; Lambert, Jean-Francois; Stalport, Fabien

    Several lines of evidence suggest that early Mars offered favorable conditions for long-term sustaining 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 until now. Organic matter is therefore expected to be present at the surface/subsurface of the planet. The search for these organic relics is one of the main objectives of Mars exploration missions. But current environmental conditions at the surface - UV radiation, oxidants and energetic particles - can generate physico-chemical processes that may induce organic molecules evolution. Here we present results of laboratory investigations dedicated to monitor qualitative and quantitative evolutions of several organic molecules under simulated Martian surface ultraviolet incident light, mean ground temperature and pressure, using the Mars Organic Molecules Irradiation and Evolution setup (1) . For each organic molecule studied, the nature of the evolution products (solid or gaseous) and the kinetic parameters (extrapolated half-life at Mars, quantum yields) were experimentally determined. The results show that when exposed to UV radiation, specific organic molecules lead to the formation of solid residues, probably of macromolecular nature, which could reach long term stability. On the other hand, the study of the evolution of molecules in presence of nontronite, a clay mineral detected at the surface of Mars, highlights a strong protective effect of the clay reducing dissociation rates for some molecules, whereas a possible catalytic effect is tentatively observed for one studied molecule. These results are essential to support the analyses performed in situ during the past, current and future exploration missions. Moreover, the experimentally determined kinetic parameters

  4. Organic Optoelectronic Devices Employing Small Molecules

    NASA Astrophysics Data System (ADS)

    Fleetham, Tyler Blain

    Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, DeltaE DA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pan, Shanlin

    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 thatmore » 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

  6. Pursuing High-Mobility n-Type Organic Semiconductors by Combination of "Molecule-Framework" and "Side-Chain" Engineering.

    PubMed

    Zhang, Cheng; Zang, Yaping; Zhang, Fengjiao; Diao, Ying; McNeill, Christopher R; Di, Chong-An; Zhu, Xiaozhang; Zhu, Daoben

    2016-10-01

    "Molecule-framework" and "side-chain" engineering is powerful for the design of high-performance organic semiconductors. Based on 2DQTTs, the relationship between molecular structure, film microstructure, and charge-transport property in organic thin-film transistors (OTFTs) is studied. 2DQTT-o-B exhibits outstanding electron mobilities of 5.2 cm 2 V -1 s -1 , which is a record for air-stable solution-processable n-channel small-molecule OTFTs to date. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Imaging the cell surface and its organization down to the level of single molecules.

    PubMed

    Klenerman, David; Shevchuk, Andrew; Novak, Pavel; Korchev, Yuri E; Davis, Simon J

    2013-02-05

    Determining the organization of key molecules on the surface of live cells in two dimensions and how this changes during biological processes, such as signalling, is a major challenge in cell biology and requires methods with nanoscale spatial resolution and high temporal resolution. Here, we review biophysical tools, based on scanning ion conductance microscopy and single-molecule fluorescence and the combination of both of these methods, which have recently been developed to address these issues. We then give examples of how these methods have been be applied to provide new insights into cell membrane organization and function, and discuss some of the issues that will need to be addressed to further exploit these methods in the future.

  8. Complex organic molecules toward low-mass and high-mass star forming regions

    NASA Astrophysics Data System (ADS)

    Favre, C.; Ceccarelli, C.; Lefloch, B.; Bergin, E.; Carvajal, M.; Brouillet, N.; Despois, D.; Jørgensen, J.; Kleiner, I.

    2016-12-01

    One of the most important questions in molecular astrophysics is how, when, and where complex organic molecules, COMs (≥ 6 atoms) are formed. In the Interstellar-Earth connection context, could this have a bearing on the origin of life on Earth? Formation mechanisms of COMs, which include potentially prebiotic molecules, are still debated and may include grain-mantle and/or gas-phase chemistry. Understanding the mechanisms that lead to the interstellar molecular complexification, along with the involved physicochemical processes, is mandatory to answer the above questions. In that context, active researches are ongoing in theory, laboratory experiment, chemical modeling and observations. Thanks to recent progress in radioastronomy instrumentation for both single-dish and millimeter array (e.g. Herschel, NOEMA, ALMA), new results have been obtained. I will review some notable results on the detection of COMs, including prebiotic molecules, towards star forming regions.

  9. Isotope-selective high-order interferometry with large organic molecules in free fall

    NASA Astrophysics Data System (ADS)

    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.

  10. Enhancing the low frequency THz resonances (< 1 THz) of organic molecules via electronegative atom substitution

    NASA Astrophysics Data System (ADS)

    Dash, Jyotirmayee; Ray, Shaumik; Pesala, Bala

    2015-03-01

    Terahertz (THz) technology is an active area of research with various applications in non-intrusive imaging and spectroscopy. Very few organic molecules have significant resonances below 1 THz. Understanding the origin of low frequency THz modes in these molecules and their absence in other molecules could be extremely important in design and engineering molecules with low frequency THz resonances. These engineered molecules can be used as THz tags for anti-counterfeiting applications. Studies show that low frequency THz resonances are commonly observed in molecules having higher molecular mass and weak intermolecular hydrogen bonds. In this paper, we have explored the possibility of enhancing the strength of THz resonances below 1 THz through electronegative atom substitution. Adding an electronegative atom helps in achieving higher hydrogen bond strength to enhance the resonances below 1 THz. Here acetanilide has been used as a model system. THz-Time Domain Spectroscopy (THz-TDS) results show that acetanilide has a small peak observed below 1 THz. Acetanilide can be converted to 2-fluoroacetanilide by adding an electronegative atom, fluorine, which doesn't have any prominent peak below 1 THz. However, by optimally choosing the position of the electronegative atom as in 4-fluoroacetanilide, a significant THz resonance at 0.86 THz is observed. The origin of low frequency resonances can be understood by carrying out Density Functional Theory (DFT) simulations of full crystal structure. These studies show that adding an electronegative atom to the organic molecules at an optimized position can result in significantly enhanced resonances below 1 THz.

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

    NASA Astrophysics Data System (ADS)

    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

  12. Organic farming enhances soil microbial abundance and activity—A meta-analysis and meta-regression

    PubMed Central

    Symnaczik, Sarah; Mäder, Paul; De Deyn, Gerlinde; Gattinger, Andreas

    2017-01-01

    Population growth and climate change challenge our food and farming systems and provide arguments for an increased intensification of agriculture. A promising option is eco-functional intensification through organic farming, an approach based on using and enhancing internal natural resources and processes to secure and improve agricultural productivity, while minimizing negative environmental impacts. In this concept an active soil microbiota plays an important role for various soil based ecosystem services such as nutrient cycling, erosion control and pest and disease regulation. Several studies have reported a positive effect of organic farming on soil health and quality including microbial community traits. However, so far no systematic quantification of whether organic farming systems comprise larger and more active soil microbial communities compared to conventional farming systems was performed on a global scale. Therefore, we conducted a meta-analysis on current literature to quantify possible differences in key indicators for soil microbial abundance and activity in organic and conventional cropping systems. All together we integrated data from 56 mainly peer-reviewed papers into our analysis, including 149 pairwise comparisons originating from different climatic zones and experimental duration ranging from 3 to more than 100 years. Overall, we found that organic systems had 32% to 84% greater microbial biomass carbon, microbial biomass nitrogen, total phospholipid fatty-acids, and dehydrogenase, urease and protease activities than conventional systems. Exclusively the metabolic quotient as an indicator for stresses on microbial communities remained unaffected by the farming systems. Categorical subgroup analysis revealed that crop rotation, the inclusion of legumes in the crop rotation and organic inputs are important farming practices affecting soil microbial community size and activity. Furthermore, we show that differences in microbial size and activity

  13. Elastic Organic Crystals of a Fluorescent π-Conjugated Molecule.

    PubMed

    Hayashi, Shotaro; Koizumi, Toshio

    2016-02-18

    An elastic organic crystal of a π-conjugated molecule has been fabricated. A large fluorescent single crystal of 1,4-bis[2-(4-methylthienyl)]-2,3,5,6-tetrafluorobenzene (over 1 cm long) exhibited a fibril lamella morphology based on slip-stacked molecular wires, and it was found to be a remarkably elastic crystalline material. The straight crystal was capable of bending more than 180° under applied stress and then quickly reverted to its original shape upon relaxation. In addition, the fluorescence quantum yield of the crystal was about twice that of the compound in THF solution. Mechanical bending-relaxation resulted in reversible change of the morphology and fluorescence. This research offers a more general approach to flexible crystals as a promising new family of organic semiconducting materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Adsorption heights and bonding strength of organic molecules on a Pb-Ag surface alloy

    NASA Astrophysics Data System (ADS)

    Stadtmüller, Benjamin; Haag, Norman; Seidel, Johannes; van Straaten, Gerben; Franke, Markus; Kumpf, Christian; Cinchetti, Mirko; Aeschlimann, Martin

    2016-12-01

    The understanding of the fundamental geometric and electronic properties of metal-organic hybrid interfaces is a key issue on the way to improving the performance of organic electronic and spintronic devices. Here, we studied the adsorption heights of copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) on a Pb1Ag2 surface alloy on Ag(111) using the normal-incidence x-ray standing waves technique. We find a significantly larger adsorption height of both molecules on the Pb-Ag surface alloy compared to the bare Ag(111) surface which is caused by the larger size of Pb. This increased adsorption height suppresses the partial chemical interaction of both molecules with Ag surface atoms. Instead, CuPc and PTCDA molecules bond only to the Pb atoms with different interaction strength ranging from a van der Waals-like interaction for CuPc to a weak chemical interaction with additional local bonds for PTCDA. The different adsorption heights for CuPc and PTCDA on Pb1Ag2 are the result of local site-specific molecule-surface bonds mediated by functional molecular groups and the different charge donating and accepting character of CuPc and PTCDA.

  15. Fullerene-free small molecule organic solar cells with a high open circuit voltage of 1.15 V.

    PubMed

    Ni, Wang; Li, Miaomiao; Kan, Bin; Liu, Feng; Wan, Xiangjian; Zhang, Qian; Zhang, Hongtao; Russell, Thomas P; Chen, Yongsheng

    2016-01-11

    A new small molecule named DTBTF with thiobarbituric acid as a terminal group was designed and synthesized as an acceptor for organic photovoltaic applications. DTBTF exhibits strong absorption in the visible region, and a relatively high lying LUMO energy level (-3.62 eV). All-small-molecule organic solar cells based on DR3TSBDT:DTBTF blend films show a considerable PCE of 3.84% with a high V(oc) of 1.15 V.

  16. Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules.

    PubMed

    Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Adamo, Carlo

    2009-09-08

    Extensive Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out in order to obtain a statistically meaningful analysis of the merits of a large number of functionals. To reach this goal, a very extended set of molecules (∼500 compounds, >700 excited states) covering a broad range of (bio)organic molecules and dyes have been investigated. Likewise, 29 functionals including LDA, GGA, meta-GGA, global hybrids, and long-range-corrected hybrids have been considered. Comparisons with both theoretical references and experimental measurements have been carried out. On average, the functionals providing the best match with reference data are, one the one hand, global hybrids containing between 22% and 25% of exact exchange (X3LYP, B98, PBE0, and mPW1PW91) and, on the other hand, a long-range-corrected hybrid with a less-rapidly increasing HF ratio, namely LC-ωPBE(20). Pure functionals tend to be less consistent, whereas functionals incorporating a larger fraction of exact exchange tend to underestimate significantly the transition energies. For most treated cases, the M05 and CAM-B3LYP schemes deliver fairly small deviations but do not outperform standard hybrids such as X3LYP or PBE0, at least within the vertical approximation. With the optimal functionals, one obtains mean absolute deviations smaller than 0.25 eV, though the errors significantly depend on the subset of molecules or states considered. As an illustration, PBE0 and LC-ωPBE(20) provide a mean absolute error of only 0.14 eV for the 228 states related to neutral organic dyes but are completely off target for cyanine-like derivatives. On the basis of comparisons with theoretical estimates, it also turned out that CC2 and TD-DFT errors are of the same order of magnitude, once the above-mentioned hybrids are selected.

  17. The Laboratory Production of Complex Organic Molecules in Simulated Interstellar Ices

    NASA Technical Reports Server (NTRS)

    Dworkin, J. P.; Sandford, S. A.; Bernstein, M. P.; Allamandola, L. J.

    2002-01-01

    Much of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. Their low temperatures preclude most chemical reactions, but ionizing radiation can drive reactions that produce a suite of new species, many of which are complex organics. The Astrochemistry Lab at NASA Ames studies the UV radiation processing of interstellar ice analogs to better identify the resulting products and establish links between interstellar chemistry, the organics in meteorites, and the origin of life on Earth. Once identified, the spectral properties of the products can be quantified to assist with the search for these species in space. Of particular interest are findings that UV irradiation of interstellar ice analogs produces molecules of importance in current living organisms, including quinones, amphiphiles, and amino acids.

  18. A new interstellar molecule - Tricarbon monoxide

    NASA Technical Reports Server (NTRS)

    Matthews, H. E.; Irvine, W. M.; Friberg, P.; Brown, R. D.; Godfrey, P. D.

    1984-01-01

    The C3O molecule, whose pure rotational spectrum has only recently been studied in the laboratory, has been detected in the cold, dark interstellar Taurus Molecular Cloud 1. Since C3O is the first interstelar carbon chain molecule to contain oxygen, its existence places an important new constraint on chemical schemes for cold interstellar clouds. The abundance of C3O can be understood in terms of purely gas-phase ion-molecule chemistry.

  19. Radio Observations of Organics in Comets

    NASA Technical Reports Server (NTRS)

    Milam, Stefanie N.; Charnley, Steven B.; Kuan, Yi-Jehng; Chuang, Yo-Ling; Villanueva, Geronimo; Coulson, Iain; Remijan, Anthony J.

    2012-01-01

    A major observational challenge in cometary science is to quantify the extent to which chemical compounds can be linked to either interstellar or nebular chemistry. Recently, there have been complimentary observations from multiple facilities to try to unravel the chemical complexity of comets and their origins. Incorporating results from various techniques can gain further insight into the abundances, production rates, distributions, and formation mechanisms of molecules in these objects [I]. Such studies have provided great detail towards molecules with a-typical chemistries, such as H2CO [2]. We report multiwavelength spectral observations of comets from two dynamical families including the JFC 103P/Hartley 2 and a long period comet C/2009 PI (Garradd) with the Arizona Radio Observatory's SMT and 12-m telescopes, as well as the NRAO Greenbank telescope, and the James Clerk Maxwell Telescope. Multiple parent volatiles (e.g. HCN, CH30H, CO) as well as daughter products (e.g, CS and 01-1) have been detected in these objects. We will present a comparison of molecular abundances in these comets to those observed in others, supporting a long-term effort of building a comet taxonomy based on composition. Previous work has revealed a range of abundances of parent species (from "organics-poor" to "organics-rich") with respect to water among comets [3,4,5], however the statistics are not well constrained.

  20. On the Teneurin track: a new synaptic organization molecule emerges

    PubMed Central

    Mosca, Timothy J.

    2015-01-01

    To achieve proper synaptic development and function, coordinated signals must pass between the pre- and postsynaptic membranes. Such transsynaptic signals can be comprised of receptors and secreted ligands, membrane associated receptors, and also pairs of synaptic cell adhesion molecules. A critical open question bridging neuroscience, developmental biology, and cell biology involves identifying those signals and elucidating how they function. Recent work in Drosophila and vertebrate systems has implicated a family of proteins, the Teneurins, as a new transsynaptic signal in both the peripheral and central nervous systems. The Teneurins have established roles in neuronal wiring, but studies now show their involvement in regulating synaptic connections between neurons and bridging the synaptic membrane and the cytoskeleton. This review will examine the Teneurins as synaptic cell adhesion molecules, explore how they regulate synaptic organization, and consider how some consequences of human Teneurin mutations may have synaptopathic origins. PMID:26074772

  1. On the SIMS Ionization Probability of Organic Molecules.

    PubMed

    Popczun, Nicholas J; Breuer, Lars; Wucher, Andreas; Winograd, Nicholas

    2017-06-01

    The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α + ) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10 -5 . Our lab has developed a method for the direct determination of α + in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C 24 H 12 ), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C 60 cluster projectiles is of the order of 10 -3 , with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. Graphical Abstract .

  2. Simulated Raman Spectral Analysis of Organic Molecules

    NASA Astrophysics Data System (ADS)

    Lu, Lu

    The advent of the laser technology in the 1960s solved the main difficulty of Raman spectroscopy, resulted in simplified Raman spectroscopy instruments and also boosted the sensitivity of the technique. Up till now, Raman spectroscopy is commonly used in chemistry and biology. As vibrational information is specific to the chemical bonds, Raman spectroscopy provides fingerprints to identify the type of molecules in the sample. In this thesis, we simulate the Raman Spectrum of organic and inorganic materials by General Atomic and Molecular Electronic Structure System (GAMESS) and Gaussian, two computational codes that perform several general chemistry calculations. We run these codes on our CPU-based high-performance cluster (HPC). Through the message passing interface (MPI), a standardized and portable message-passing system which can make the codes run in parallel, we are able to decrease the amount of time for computation and increase the sizes and capacities of systems simulated by the codes. From our simulations, we will set up a database that allows search algorithm to quickly identify N-H and O-H bonds in different materials. Our ultimate goal is to analyze and identify the spectra of organic matter compositions from meteorites and compared these spectra with terrestrial biologically-produced amino acids and residues.

  3. A "roller-wheel" Pt-containing small molecule that outperforms its polymer analogs in organic solar cells

    DOE PAGES

    He, Wenhan; Wu, Qin; Livshits, Maksim Y.; ...

    2016-05-23

    A novel Pt-bisacetylide small molecule (Pt-SM) featuring “roller-wheel” geometry was synthesized and characterized. When compared with conventional Pt-containing polymers and small molecules having “dumbbell” shaped structures, Pt-SM displays enhanced crystallinity and intermolecular π–π interactions, as well as favorable panchromatic absorption behaviors. Furthermore, organic solar cells (OSCs) employing Pt-SM achieve power conversion efficiencies (PCEs) up to 5.9%, the highest reported so far for Pt-containing polymers and small molecules.

  4. A "roller-wheel" Pt-containing small molecule that outperforms its polymer analogs in organic solar cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    He, Wenhan; Wu, Qin; Livshits, Maksim Y.

    A novel Pt-bisacetylide small molecule (Pt-SM) featuring “roller-wheel” geometry was synthesized and characterized. When compared with conventional Pt-containing polymers and small molecules having “dumbbell” shaped structures, Pt-SM displays enhanced crystallinity and intermolecular π–π interactions, as well as favorable panchromatic absorption behaviors. Furthermore, organic solar cells (OSCs) employing Pt-SM achieve power conversion efficiencies (PCEs) up to 5.9%, the highest reported so far for Pt-containing polymers and small molecules.

  5. Enzymatic activities and prokaryotic abundance in relation to organic matter along a West-East Mediterranean transect (TRANSMED cruise).

    PubMed

    Zaccone, R; Boldrin, A; Caruso, G; La Ferla, R; Maimone, G; Santinelli, C; Turchetto, M

    2012-07-01

    The distribution of extracellular enzymatic activities (EEA) [leucine aminopeptidase (LAP), ß-glucosidase (GLU), alkaline phosphatase (AP)], as well as that of prokaryotic abundance (PA) and biomass (PB), dissolved organic carbon (DOC), particulate organic carbon and particulate total nitrogen (POC, PTN), was determined in the epi-, meso-, and bathypelagic waters of the Mediterranean Sea along a West-East transect and at one Atlantic station located outside the Strait of Gibraltar. This study represents a synoptical evaluation of the microbial metabolism during early summer. Decreasing trends with depth were observed for most of the parameters (PA, PB, AP, DOC, POC, PTN). Significant differences between the western and eastern basins of the Mediterranean Sea were found, displaying higher rates of LAP and GLU and lower C/N ratios more in the eastern than in the western areas. Conversely, in the epipelagic layer, PA and PB were found to be higher in the western than in the eastern basins. PB was significantly related to DOC concentration (all data, n = 145, r = 0.53, P < 0.01), while significant correlations of EEA with POC and PTN were found in the epipelagic layer, indicating an active response of microbial metabolism to organic substrates. Specific enzyme activities normalized to cell abundance pointed out high values of LAP and GLU in the bathypelagic layer, especially in the eastern basin, while cell-specific AP was high in the epi- and bathypelagic zone of the eastern basin indicating a rapid regeneration of inorganic P for both prokaryotes and phytoplankton needs. Low activity and abundance characterized the Atlantic station, while opposite trends of these parameters were observed along the Mediterranean transect, showing the uncoupling between abundance and activity data. In the east Mediterranean Sea, decomposition processes increased probably in response to mesoscale structures which lead to organic matter downwelling.

  6. Cometary delivery of organic molecules to the early earth

    NASA Technical Reports Server (NTRS)

    Chyba, Christopher F.; Thomas, Paul J.; Sagan, Carl; Brookshaw, Leigh

    1990-01-01

    It has long been speculated that earth accreted prebiotic organic molecules important for the origins of life from impacts of carbonaceous asteroids and comets during the period of heavy bombardment 4.5 x 10 to the 9th to 3.8 x 10 to the 9th years ago. A comprehensive treatment of comet-asteroid interaction with the atmosphere, surface impact, and resulting organic pyrolysis demonstrates that organics will not survive impacts at velocities greater than about 10 kilometers per second and that even comets and asteroids as small as 100 meters in radius cannot be aerobraked to below this velocity in 1-bar atmospheres. However, for plausible dense (10-bar carbon dioxide) early atmospheres, it is found that 4.5 x 10 to the 9th years ago earth was accreting intact cometary organics at a rate of at least about 10 to the 6th to 10 to the 7th kilograms per year, a flux that thereafter declined with a half-life of about 10 to the 8th years. These results may be put in context by comparison with terrestrial oceanic and total biomasses, about 3 x 10 to the 12th kilograms and about 6 x 10 to the 14th kilograms, respectively.

  7. Atomic-Resolution Transmission Electron Microscopic Movies for Study of Organic Molecules, Assemblies, and Reactions: The First 10 Years of Development.

    PubMed

    Nakamura, Eiichi

    2017-06-20

    A molecule is a quantum mechanical entity. "Watching motions and reactions of a molecule with our eyes" has therefore been a dream of chemists for a century. This dream has come true with the aid of the movies of atomic-resolution transmission electron microscopic (AR-TEM) molecular images through real-time observation of dynamic motions of single organic molecules (denoted hereafter as single-molecule atomic-resolution real-time (SMART) TEM imaging). Since 2007, we have reported movies of a variety of single organic molecules, organometallic molecules, and their assemblies, which are rotating, stretching, and reacting. Like movies in the theater, the atomic-resolution molecular movies provide us information on the 3-D structures of the molecules and also their time evolution. The success of the SMART-TEM imaging crucially depends on the development of "chemical fishhooks" with which fish (organic molecules) in solution can be captured on a single-walled carbon nanotube (CNT, serving as a "fishing rod"). The captured molecules are connected to a slowly vibrating CNT, and their motions are displayed on a monitor in real time. A "fishing line" connecting the fish and the rod may be a σ-bond, a van der Waals force, or other weak connections. Here, the molecule/CNT system behaves as a coupled oscillator, where the low-frequency anisotropic vibration of the CNT is transmitted to the molecules via the weak chemical connections that act as an energy filter. Interpretation of the observed motions of the molecules at atomic resolution needs us to consider the quantum mechanical nature of electrons as well as bond rotation, letting us deviate from the conventional statistical world of chemistry. What new horizons can we explore? We have so far carried out conformational studies of individual molecules, assigning anti or gauche conformations to each C-C bond in conformers that we saw. We can also determine the structures of van der Waals assemblies of organic molecules

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

    PubMed Central

    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.

    2013-01-01

    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 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. PMID:24101502

  9. Supramolecular organization of pi-conjugated molecules monitored by single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Alvarez, Laurent; Almadori, Yann; Belhboub, Anouar; Le Parc, Rozenn; Aznar, Raymond; Dieudonné-George, Philippe; Rahmani, Abdelali; Hermet, Patrick; Fossard, Frédéric; Loiseau, Annick; Jousselme, Bruno; Campidelli, Stéphane; Saito, Takeshi; Wang, Guillaume; Bantignies, Jean-Louis

    2016-03-01

    Photoactive pi-conjugated molecules (quaterthiophene and phthalocyanine) are either encapsulated into the hollow core of single-walled carbon nanotubes or noncovalently stacked at their outer surface in order to elaborate hybrid nanosystems with new physical properties, providing practical routes to fit different requirements for potential applications. We are interested in the relationship between the structure and the optoelectronic properties. The structural properties are investigated mainly by x-ray diffraction and/or transmission electron microscopy and Raman spectroscopy. We show that the supramolecular organizations of confined quaterthiophenes depend on the nanocontainer size, whereas phthalocyanine encapsulation leads to the formation of a one-dimensional phase for which the angle between the molecule ring and the nanotube axis is close to 32 deg. Confined phthalocyanine molecules display Raman spectra hardly altered with respect to the bulk phase, suggesting a rather weak interaction with the tubes. In contrast, the vibrational properties of the molecules stacked at the outer surface of tubes display important modifications. We assume a significant curvature of the phthalocyanine induced by the interaction with the tube walls and a change of the central atom position within the molecular ring, in good agreement with our density functional theory calculations.

  10. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  11. Self-assembly of amphiphilic molecules in organic liquids

    NASA Astrophysics Data System (ADS)

    Tung, Shih-Huang

    2007-12-01

    Amphiphilic molecules are well-known for their ability to self-assemble in water to form structures such as micelles and vesicles. In comparison, much less is known about amphiphilic self-assembly in nonpolar organic liquids. Such "reverse" self assembly can produce many of the counterparts to structures found in water. In this dissertation, we focus on the formation and dynamics of such reverse structures. We seek to obtain fundamental insight into the driving forces for reverse self-assembly processes. Three specific types of reverse structures are studied: (a) reverse wormlike micelles, i.e., long, flexible micellar chains; (b) reverse vesicles, i.e., hollow containers enclosed by reverse bilayers; and (c) organogel networks. While our focus is on the fundamentals, we note that reverse structures can be useful in a variety of applications ranging from drug delivery, controlled release, hosts for enzymatic reactions, and templates for nanomaterials synthesis. In the first part of this study, we describe a new route for forming reverse wormlike micelles in nonpolar organic liquids. This route involves the addition of trace amounts of a bile salt to solutions of the phospholipid, lecithin. We show that bile salts, due to their unique "facially amphiphilic" structure, can promote the aggregation of lecithin molecules into these reverse micellar chains. The resulting samples are viscoelastic and show interesting rheological properties. Unusual trends are seen in the temperature dependence of their rheology, which indicates the importance of hydrogen-bonding interactions in the formation of these micelles. Another remarkable feature of their rheology is the presence of strain-stiffening, where the material becomes stiffer at high deformations. Strain-stiffening has been seen before for elastic gels of biopolymers; here, we demonstrate the same properties for viscoelastic micellar solutions. The second reverse aggregate we deal with is the reverse vesicle. We present a

  12. Parametrization and Benchmark of Long-Range Corrected DFTB2 for Organic Molecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vuong, Van Quan; Akkarapattiakal Kuriappan, Jissy; Kubillus, Maximilian

    In this paper, we present the parametrization and benchmark of long-range corrected second-order density functional tight binding (DFTB), LC-DFTB2, for organic and biological molecules. The LC-DFTB2 model not only improves fundamental orbital energy gaps but also ameliorates the DFT self-interaction error and overpolarization problem, and further improves charge-transfer excited states significantly. Electronic parameters for the construction of the DFTB2 Hamiltonian as well as repulsive potentials were optimized for molecules containing C, H, N, and O chemical elements. We use a semiautomatic parametrization scheme based on a genetic algorithm. With the new parameters, LC-DFTB2 describes geometries and vibrational frequencies of organicmore » molecules similarly well as third-order DFTB3/3OB, the de facto standard parametrization based on a GGA functional. Finally, LC-DFTB2 performs well also for atomization and reaction energies, however, slightly less satisfactorily than DFTB3/3OB.« less

  13. Parametrization and Benchmark of Long-Range Corrected DFTB2 for Organic Molecules

    DOE PAGES

    Vuong, Van Quan; Akkarapattiakal Kuriappan, Jissy; Kubillus, Maximilian; ...

    2017-12-12

    In this paper, we present the parametrization and benchmark of long-range corrected second-order density functional tight binding (DFTB), LC-DFTB2, for organic and biological molecules. The LC-DFTB2 model not only improves fundamental orbital energy gaps but also ameliorates the DFT self-interaction error and overpolarization problem, and further improves charge-transfer excited states significantly. Electronic parameters for the construction of the DFTB2 Hamiltonian as well as repulsive potentials were optimized for molecules containing C, H, N, and O chemical elements. We use a semiautomatic parametrization scheme based on a genetic algorithm. With the new parameters, LC-DFTB2 describes geometries and vibrational frequencies of organicmore » molecules similarly well as third-order DFTB3/3OB, the de facto standard parametrization based on a GGA functional. Finally, LC-DFTB2 performs well also for atomization and reaction energies, however, slightly less satisfactorily than DFTB3/3OB.« less

  14. The Effects of Perchlorate and its Precursors on Organic Molecules under Simulated Mars Conditions

    NASA Astrophysics Data System (ADS)

    Carrier, B. L.; Beegle, L. W.; Bhartia, R.; Abbey, W. J.

    2016-12-01

    Perchlorate (ClO4-) was first detected on Mars by the Phoenix Lander in 2008 [1] and has subsequently been detected by Curiosity in Gale Crater [2], in Mars meteorite EETA79001 [3], and has been proposed as a possible explanation for results obtained by Viking [4]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [5]. The discovery of perchlorate on Mars has raised important questions about its effects on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [2, 4], few studies have been conducted on the potential effects of perchlorate and its precursors on organic molecules prior to analysis. Perchlorate is typically inert under Mars temperatures and pressures, but it has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-), hypochlorite (ClO-) and chlorine dioxide (ClO2) when exposed to Mars conditions including ionizing radiation [6]. The oxidation of chloride to perchlorate also results in the formation of reactive oxychlorine species such as chlorate (ClO3-) [5]. Here we investigate the effects of perchlorate and its oxychlorine precursors on organic molecules. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of Mojave Mars Simulant (MMS) [7] and each organic, as well as varying concentrations of perchlorate and/or chloride salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination

  15. First Detection of Non-Chlorinated Organic Molecules Indigenous to a Martian Sample

    NASA Technical Reports Server (NTRS)

    Freissinet, C.; Glavin, D. P.; Buch, A.; Szopa, C.; Summons, R. E.; Eigenbrode, J. L.; Archer, P. D., Jr.; Brinckerhoff, W. B.; Brunner, A. E.; Cabane, M.; hide

    2016-01-01

    The Sample Analysis at Mars (SAM) instrument onboard Curiosity can perform pyrolysis of martian solid samples, and analyze the volatiles by direct mass spectrometry in evolved gas analysis (EGA) mode, or separate the components in the GCMS mode (coupling the gas chromatograph and the mass spectrometer instruments). In addition, SAM has a wet chemistry laboratory designed for the extraction and identification of complex and refractory organic molecules in the solid samples. The chemical derivatization agent used, N-methyl-N-tert-butyldimethylsilyl- trifluoroacetamide (MTBSTFA), was sealed inside seven Inconel metal cups present in SAM. Although none of these foil-capped derivatization cups have been punctured on Mars for a full wet chemistry experiment, an MTBSTFA leak was detected and the resultant MTBSTFA vapor inside the instrument has been used for a multi-sol MTBSTFA derivatization (MD) procedure instead of direct exposure to MTBSTFA liquid by dropping a solid sample directly into a punctured wet chemistry cup. Pyr-EGA, Pyr-GCMS and Der-GCMS experiments each led to the detection and identification of a variety of organic molecules in diverse formations of Gale Crater.

  16. Guest molecules as a design element for metal–organic frameworks

    DOE PAGES

    Allendorf, Mark D.; Medishetty, Raghavender; Fischer, Roland A.

    2016-11-07

    The well-known synthetic versatility of MOFs is rooted in the ability to predict the metal ion coordination geometry and the vast possibilities to use organic chemistry to modify the linker groups. However, the use of “non-innocent” guest molecules as a component of framework design has been largely ignored. Nevertheless, recent reports show that the presence of guest molecules can have dramatic effects, even when these are seemingly innocuous species such as water or polar solvents. Advantages of using guests to impart new properties to MOFs include the relative ease of introducing new functionalities, the ability to modify the properties materialmore » at will by removing the guest or inserting different ones, and avoidance of the difficulties associated with synthesizing new frameworks, which can be challenging even when the basic topology remains constant. In this article we describe the “Guest@MOF” concept and provide examples illustrating its potential as a new MOF design element.« less

  17. Organic synthesis: the art and science of replicating the molecules of living nature and creating others like them in the laboratory.

    PubMed

    Nicolaou, K C

    2014-03-08

    Synthetic organic chemists have the power to replicate some of the most intriguing molecules of living nature in the laboratory and apply their developed synthetic strategies and technologies to construct variations of them. Such molecules facilitate biology and medicine, as they often find uses as biological tools and drug candidates for clinical development. In addition, by employing sophisticated catalytic reactions and appropriately designed synthetic processes, they can synthesize not only the molecules of nature and their analogues, but also myriad other organic molecules for potential applications in many areas of science, technology and everyday life. After a short historical introduction, this article focuses on recent advances in the field of organic synthesis with demonstrative examples of total synthesis of complex bioactive molecules, natural or designed, from the author's laboratories, and their impact on chemistry, biology and medicine.

  18. Organic synthesis: the art and science of replicating the molecules of living nature and creating others like them in the laboratory

    PubMed Central

    Nicolaou, K. C.

    2014-01-01

    Synthetic organic chemists have the power to replicate some of the most intriguing molecules of living nature in the laboratory and apply their developed synthetic strategies and technologies to construct variations of them. Such molecules facilitate biology and medicine, as they often find uses as biological tools and drug candidates for clinical development. In addition, by employing sophisticated catalytic reactions and appropriately designed synthetic processes, they can synthesize not only the molecules of nature and their analogues, but also myriad other organic molecules for potential applications in many areas of science, technology and everyday life. After a short historical introduction, this article focuses on recent advances in the field of organic synthesis with demonstrative examples of total synthesis of complex bioactive molecules, natural or designed, from the author’s laboratories, and their impact on chemistry, biology and medicine. PMID:24611027

  19. Application of terahertz spectroscopy for characterization of biologically active organic molecules in natural environment

    NASA Astrophysics Data System (ADS)

    Karaliūnas, Mindaugas; Jakštas, Vytautas; Nasser, Kinan E.; Venckevičius, Rimvydas; Urbanowicz, Andrzej; Kašalynas, Irmantas; Valušis, Gintaras

    2016-09-01

    In this work, a comparative research of biologically active organic molecules in its natural environment using the terahertz (THz) time domain spectroscopy (TDS) and Fourier transform spectroscopy (FTS) systems is carried out. Absorption coefficient and refractive index of Nicotiana tabacum L. leaves containing nicotine, Cannabis sativa L. leaves containing tetrahydrocannabinol, and Humulu lupulus L. leaves containing α-acids, active organic molecules that obtain in natural environment, were measured in broad frequency range from 0.1 to 13 THz at room temperature. In the spectra of absorption coefficient the features were found to be unique for N. tabacum, C. sativa and H. lupulus. Moreover, those features can be exploited for identification of C. sativa sex and N. tabacum origin. The refractive index can be also used to characterize different species.

  20. Predicting Complex Organic Molecule Emission from TW Hya

    NASA Astrophysics Data System (ADS)

    Vissapragada, Shreyas; Walsh, Catherine

    2017-01-01

    The Atacama Large Millimeter/submillimeter Array (ALMA) has significantly increased our ability to observe the rich chemical inventory of star and planet formation. ALMA has recently been used to detect CH3OH (methanol) and CH3CN (methyl cyanide) in protoplanetary disks; these molecules may be vital indicators of the complex organic ice reservoir in the comet-forming zone. We have constructed a physiochemical model of TW Hya, a well-studied protoplanetary disk, to explore the different formation mechanisms of complex ices. By running our model through a radiative transfer code and convolving with beam sizes appropriate for ALMA, we have obtained synthetic observations of methanol and methyl cyanide. Here, we compare and comment on these synthetic observations, and provide astrochemical justification for their spatial distributions.

  1. Guest–host interactions of a rigid organic molecule in porous silica frameworks

    PubMed Central

    Wu, Di; Hwang, Son-Jong; Zones, Stacey I.; Navrotsky, Alexandra

    2014-01-01

    Molecular-level interactions at organic–inorganic interfaces play crucial roles in many fields including catalysis, drug delivery, and geological mineral precipitation in the presence of organic matter. To seek insights into organic–inorganic interactions in porous framework materials, we investigated the phase evolution and energetics of confinement of a rigid organic guest, N,N,N-trimethyl-1-adamantammonium iodide (TMAAI), in inorganic porous silica frameworks (SSZ-24, MCM-41, and SBA-15) as a function of pore size (0.8 nm to 20.0 nm). We used hydrofluoric acid solution calorimetry to obtain the enthalpies of interaction between silica framework materials and TMAAI, and the values range from −56 to −177 kJ per mole of TMAAI. The phase evolution as a function of pore size was investigated by X-ray diffraction, IR, thermogravimetric differential scanning calorimetry, and solid-state NMR. The results suggest the existence of three types of inclusion depending on the pore size of the framework: single-molecule confinement in a small pore, multiple-molecule confinement/adsorption of an amorphous and possibly mobile assemblage of molecules near the pore walls, and nanocrystal confinement in the pore interior. These changes in structure probably represent equilibrium and minimize the free energy of the system for each pore size, as indicated by trends in the enthalpy of interaction and differential scanning calorimetry profiles, as well as the reversible changes in structure and mobility seen by variable temperature NMR. PMID:24449886

  2. Spectrophotometric and electrical properties of imperatorin: an organic molecule

    NASA Astrophysics Data System (ADS)

    Mir, Feroz A.

    2015-09-01

    Imperatorin (molecular formula = C16H14O4, molecular mass = 270) an organic molecule was isolated from ethyl acetate extract of the root parts of the plant Prangos pabularia. The optical study was carried out by ultraviolet-visible spectroscopy, and this compound showed an indirect allowed transition. The optical band gap ( E g ) was found around 3.75 eV. Photoluminescence shows various good emission bands. The frequency-dependent real part of the complex ac conductivity was found to follow the universal dielectric response: σ ac ( ω) α ω s [where σ ac ( ω) is the frequency-dependent total conductivity, ω is the frequency, and s is the frequency exponent]. From ac conductivity data analysis, correlated barrier hopping charge-transport mechanism is the dominant electrical transport process shown by this compound. The good emission, less absorption, wide band gap and good electrical properties shown by this compound project them as a bright choice for organic electronic devices.

  3. An All-Organic Composite System for Resistive Change Memory via the Self-Assembly of Plastic-Crystalline Molecules.

    PubMed

    Cha, An-Na; Lee, Sang-A; Bae, Sukang; Lee, Sang Hyun; Lee, Dong Su; Wang, Gunuk; Kim, Tae-Wook

    2017-01-25

    An all-organic composite system was introduced as an active component for organic resistive memory applications. The active layer was prepared by mixing a highly polar plastic-crystalline organic molecule (succinonitrile, SN) into an insulating polymer (poly(methyl methacrylate), PMMA). As increasing concentrations of SN from 0 to 3.0 wt % were added to solutions of different concentrations of PMMA, we observed distinguishable microscopic surface structures on blended films of SN and PMMA at certain concentrations after the spin-casting process. The structures were organic dormant volcanos composed of micron-scale PMMA craters and disk type SN lava. Atomic force microscopy (AFM), cross-sectional transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy dispersive X-ray spectrometer (EDX) analysis showed that these structures were located in the middle of the film. Self-assembly of the plastic-crystalline molecules resulted in the phase separation of the SN:PMMA mixture during solvent evaporation. The organic craters remained at the surface after the spin-casting process, indicative of the formation of an all-organic composite film. Because one organic crater contains one SN disk, our system has a coplanar monolayer disk composite system, indicative of the simplest composite type of organic memory system. Current-voltage (I-V) characteristics of the composite films with organic craters revealed that our all-organic composite system showed unipolar type resistive switching behavior. From logarithmic I-V characteristics, we found that the current flow was governed by space charge limited current (SCLC). From these results, we believe that a plastic-crystalline molecule-polymer composite system is one of the most reliable ways to develop organic composite systems as potential candidates for the active components of organic resistive memory applications.

  4. Dynamic Control of Synaptic Adhesion and Organizing Molecules in Synaptic Plasticity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rudenko, Gabby

    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 affectmore » 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.« less

  5. Dynamic Control of Synaptic Adhesion and Organizing Molecules in Synaptic Plasticity

    PubMed Central

    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, forming trans-complexes spanning the synaptic cleft or cis-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. PMID:28255461

  6. Metal-organic and supramolecular architectures based on mechanically interlocked molecules

    NASA Astrophysics Data System (ADS)

    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

  7. Exploiting single photon vacuum ultraviolet photoionization to unravel the synthesis of complex organic molecules in interstellar ices

    NASA Astrophysics Data System (ADS)

    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. Multiscale Molecular Simulation of Solution Processing of SMDPPEH: PCBM Small-Molecule Organic Solar Cells.

    PubMed

    Lee, Cheng-Kuang; Pao, Chun-Wei

    2016-08-17

    Solution-processed small-molecule organic solar cells are a promising renewable energy source because of their low production cost, mechanical flexibility, and light weight relative to their pure inorganic counterparts. In this work, we developed a coarse-grained (CG) Gay-Berne ellipsoid molecular simulation model based on atomistic trajectories from all-atom molecular dynamics simulations of smaller system sizes to systematically study the nanomorphology of the SMDPPEH/PCBM/solvent ternary blend during solution processing, including the blade-coating process by applying external shear to the solution. With the significantly reduced overall system degrees of freedom and computational acceleration from GPU, we were able to go well beyond the limitation of conventional all-atom molecular simulations with a system size on the order of hundreds of nanometers with mesoscale molecular detail. Our simulations indicate that, similar to polymer solar cells, the optimal blending ratio in small-molecule organic solar cells must provide the highest specific interfacial area for efficient exciton dissociation, while retaining balanced hole/electron transport pathway percolation. We also reveal that blade-coating processes have a significant impact on nanomorphology. For given donor/acceptor blending ratios, applying an external shear force can effectively promote donor/acceptor phase segregation and stacking in the SMDPPEH domains. The present study demonstrated the capability of an ellipsoid-based coarse-grained model for studying the nanomorphology evolution of small-molecule organic solar cells during solution processing/blade-coating and provided links between fabrication protocols and device nanomorphologies.

  9. Matrix-Isolation Spectroscopy of Reactive Organic Molecules of Relevance to Interstellar Space

    NASA Astrophysics Data System (ADS)

    Kopff, Laura A.; Nolan, Alex M.; Kreifels, Terese A.; Draxler, Thomas W.; Esselman, Brian J.; Burrmann, Nicola J.; McMahon, Robert J.

    2010-11-01

    Matrix isolation, the process of trapping a molecule in an inert gas at low temperature, provides a means for studying highly reactive intermediates, such as carbenes or radicals. Reactive species can be characterized by IR, UV-vis and/or EPR spectroscopy. Comparison of experimental and computed spectral data, as well as chemical reactivity, is used for structural assignment Triplet propynylidene is proposed to exist in the interstellar medium (ISM), due to the detection of a higher-energy isomers via rotational spectroscopy. Currently, we are exploring the structural and photochemical effects of varying substituents on the propynylidne system. A diazo precursor has been synthesized and photolyzed to produce dimethylpropynylidene in an argon matrix. A photochemical hydrogen shift to produce 1-penten-3-yne has been observed through infrared spectroscopy. Cyanocarbons are known to be abundant in the ISM and the atmosphere of Titan, however matrixisolation studies have not yet been carried out for a significant number of these compounds. Photolysis of 3-cyano-3-methyldiazirine should yield methylcyanocarbene, one of the simplest species in this family. Another molecule of interest is l-HC4N, which has been detected in the ISM, but has not yet been matrix-isolated and characterized. The study of arylcarbenes is vital to understanding the chemistry of carbon-rich environments, such as discharges, interstellar clouds, and circumstellar envelopes. The identification of small, sulfur containing molecules, and the identification of aromatics in the ISM make future thiophene and benzothiophene detections a real possibility. Studies on 2- and 3-diazomethyl substituted benzothiophenes are underway to assess their photochemical reactivity and potential for forming benzothiophene carbenes. Macrocylic polyynes are proposed to be involved in carbon condensation via the ring coalescence and annealing model to produce graphitic sheets or fullerenes. To simplify a complex system we

  10. Mechanisms and time-resolved dynamics for trihydrogen cation (H 3 +) formation from organic molecules in strong laser fields

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ekanayake, Nagitha; Nairat, Muath; Kaderiya, Balram

    Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. Here, we present evidence for the existence of two different reaction pathways for H 3 + formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followedmore » by the abstraction of a proton from the remaining CHOH 2+ fragment by the roaming H 2 molecule. This reaction has similarities to the H 2+H 2 + mechanism leading to formation of H 3 + in the universe. These exotic chemical reaction mechanisms, involving roaming H 2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.« less

  11. Mechanisms and time-resolved dynamics for trihydrogen cation (H 3 +) formation from organic molecules in strong laser fields

    DOE PAGES

    Ekanayake, Nagitha; Nairat, Muath; Kaderiya, Balram; ...

    2017-07-05

    Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. Here, we present evidence for the existence of two different reaction pathways for H 3 + formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followedmore » by the abstraction of a proton from the remaining CHOH 2+ fragment by the roaming H 2 molecule. This reaction has similarities to the H 2+H 2 + mechanism leading to formation of H 3 + in the universe. These exotic chemical reaction mechanisms, involving roaming H 2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.« less

  12. "Molecules-in-Medicine": Peer-Evaluated Presentations in a Fast-Paced Organic Chemistry Course for Medical Students

    ERIC Educational Resources Information Center

    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…

  13. The fabrication of small molecule organic light-emitting diode pixels by laser-induced forward transfer

    NASA Astrophysics Data System (ADS)

    Shaw-Stewart, J. R. H.; Mattle, T.; Lippert, T. K.; Nagel, M.; Nüesch, F. A.; Wokaun, A.

    2013-01-01

    Laser-induced forward transfer (LIFT) is a versatile organic light-emitting diode (OLED) pixel deposition process, but has hitherto been applied exclusively to polymeric materials. Here, a modified LIFT process has been used to fabricate small molecule Alq3 organic light-emitting diodes (SMOLEDs). Small molecule thin films are considerably more mechanically brittle than polymeric thin films, which posed significant challenges for LIFT of these materials. The LIFT process presented here uses a polymeric dynamic release layer, a reduced environmental pressure, and a well-defined receiver-donor gap. The Alq3 pixels demonstrate good morphology and functionality, even when compared to conventionally fabricated OLEDs. The Alq3 SMOLED pixel performances show a significant amount of fluence dependence, not observed with polymerical OLED pixels made in previous studies. A layer of tetrabutyl ammonium hydroxide has been deposited on top of the aluminium cathode, as part of the donor substrate, to improve electron injection to the Alq3, by over 600%. These results demonstrate that this variant of LIFT is applicable for the deposition of functional small molecule OLEDs as well as polymeric OLEDs.

  14. The survival of large organic molecules during hypervelocity impacts with water ice: implications for sampling the icy surfaces of moons

    NASA Astrophysics Data System (ADS)

    Hurst, A.; Bowden, S. A.; Parnell, J.; Burchell, M. J.; Ball, A. J.

    2007-12-01

    There are a number of measurements relevant to planetary geology that can only be adequately performed by physically contacting a sample. This necessitates landing on the surface of a moon or planetary body or returning samples to earth. The need to physically contact a sample is particularly important in the case of measurements that could detect medium to low concentrations of large organic molecules present in surface materials. Large organic molecules, although a trace component of many meteoritic materials and rocks on the surface of earth, carry crucial information concerning the processing of meteoritic material in the surface and subsurface environments, and can be crucial indicators for the presence of life. Unfortunately landing on the surface of a small planetary body or moon is complicated, particularly if surface topography is only poorly characterised and the atmosphere thin thus requiring a propulsion system for a soft landing. One alternative to a surface landing may be to use an impactor launched from an orbiting spacecraft to launch material from the planets surface and shallow sub-surface into orbit. Ejected material could then be collected by a follow-up spacecraft and analyzed. The mission scenario considered in the Europa-Ice Clipper mission proposal included both sample return and the analysis of captured particles. Employing such a sampling procedure to analyse large organic molecules is only viable if large organic molecules present in ices survive hypervelocity impacts (HVIs). To investigate the survival of large organic molecules in HVIs with icy bodies a two stage light air gas gun was used to fire steel projectiles (1-1.5 mm diameter) at samples of water ice containing large organic molecules (amino acids, anthracene and beta-carotene a biological pigment) at velocities > 4.8 km/s.UV-VIS spectroscopy of ejected material detected beta-carotene indicating large organic molecules can survive hypervelocity impacts. These preliminary results

  15. Exploring Charge Transport in Guest Molecule Infiltrated Cu 3(BTC) 2 Metal Organic Framework

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Leonard, Francois Leonard; Stavila, Vitalie; Allendorf, Mark D.

    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 Cu 3(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@Cu 3(BTC) 2 revealed a positive Seebeck coefficient of ~400 μV/k, indicating that holesmore » 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.« less

  16. Detection of a new interstellar molecule, H2CN

    NASA Technical Reports Server (NTRS)

    Ohishi, Masatoshi; Mcgonagle, Douglas; Irvine, William M.; Yamamoto, Satoshi; Saito, Shuji

    1994-01-01

    We have detected a new interstellar molecule, H2CN (methylene amidogen), in the cold, dark molecular cloud TMC-1. The column density of H2CN is estimated to be approximately 1.5 x 10(exp 11) cm(exp -2) by assuming an excitation temperature of 5 K. This column density corresponds to a fractional abundance relative to H2 of approximately 1.5 x 10(exp -11). This value is more than three orders of magnitude less than the abundance of the related molecule HCN in TMC-1. We also report a tentative detection of H2CN in Sgr B2(N). The formation mechanism of H2CN is discussed. Our detection of the N2CN molecule may suggest the existence of a new series of carbon-chain molecules, CH2C(n)N (N = 0, 1, 2, ...).

  17. "Trampoline" ejection of organic molecules from graphene and graphite via keV cluster ions impacts.

    PubMed

    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

  18. "Trampoline" ejection of organic molecules from graphene and graphite via keV cluster ions impacts

    NASA Astrophysics Data System (ADS)

    Verkhoturov, Stanislav V.; Gołuński, Mikołaj; Verkhoturov, Dmitriy S.; Geng, Sheng; Postawa, Zbigniew; Schweikert, Emile A.

    2018-04-01

    We present the data on ejection of molecules and emission of molecular ions caused by single impacts of 50 keV C602+ 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 tunneling of

  19. [Influences of long-term application of organic and inorganic fertilizers on the composition and abundance of nirS-type denitrifiers in black soil].

    PubMed

    Yin, Chang; Fan, Fen-Liang; Li, Zhao-Jun; Song, A-Lin; Zhu, Ping; Peng, Chang; Liang, Yong-Chao

    2012-11-01

    The objectives of this study were to explore the effects of long-term organic and inorganic fertilizations on the composition and abundance of nirS-type denitrifiers in black soil. Soil samples were collected from 4 treatments (i. e. no fertilizer treatment, CK; organic manure treatment, OM; chemical fertilizer treatment (NPK) and combination of organic and chemical fertilizers treatment (MNPK)) in Gongzhuling Long-term Fertilization Experiment Station. Composition and abundance of nirS-type denitrifiers were analyzed with terminal restriction fragment length polymorphism (T-RFLP) and real-time quantitative PCR (Q-PCR), respectively. Denitrification enzyme activity (DEA) and soil properties were also measured. Application of organic fertilizers (OM and MNPK) significantly increased the DEAs of black soil, with the DEAs in OM and MNPK being 5.92 and 6.03 times higher than that in CK treatment, respectively, whereas there was no significant difference between NPK and CK. OM and MNPK treatments increased the abundances of nirS-type denitrifiers by 2.73 and 3.83 times relative to that of CK treatment, respectively. The abundance of nirS-type denitrifiers in NPK treatment was not significantly different from that of CK. The T-RFLP analysis of nirS genes showed significant differences in community composition between organic and inorganic treatments, with the emergence of a 79 bp T-RF, a significant decrease in relative abundance of the 84 bp T-RF and a loss of the 99 bp T-RF in all organic treatments. Phylogenetic analysis indicated that the airS-type denitrifiers in the black soil were mainly composed of alpha, beta and gamma-Proteobacteria. The 79 bp-type denitrifiers inhabiting exclusively in organic treatments (OM and MNPK) were affiliated to Pseudomonadaceae in gamma-Proteobacteria and Burkholderiales in beta-Proteobacteria. The 84 bp-types were related to Burkholderiales and Rhodocyclales. Correlation analysis indicated that pH, concentrations of total nitrogen

  20. Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars.

    PubMed

    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; Franz, H B; Atreya, S K; Brinckerhoff, W B; Cabane, M; Coll, P; Conrad, P G; Des Marais, D J; Dworkin, J P; Fairén, A G; François, P; Grotzinger, J P; Kashyap, S; Ten Kate, I L; Leshin, L A; Malespin, C A; Martin, M G; Martin-Torres, F J; McAdam, A C; Ming, D W; Navarro-González, R; Pavlov, A A; Prats, B D; Squyres, S W; Steele, A; Stern, J C; Sumner, D Y; Sutter, B; Zorzano, M-P

    2015-03-01

    The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150-300 parts per billion by weight (ppbw)) and C 2 to C 4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition.

  1. Detection of a new carbon-chain molecule, CCO

    NASA Technical Reports Server (NTRS)

    Ohishi, Masatoshi; Ishikawa, Shin-Ichi; Yamada, Chikashi; Kanamori, Hideto; Irvine, William M.; Brown, Ronald D.; Godfrey, Peter D.; Kaifu, Norio; Suzuki, Hiroko

    1991-01-01

    A new carbon-chain molecule, CCO 3Sigma(-), has been detected in the cold dark molecular cloud TMC-1. The excitation temperature and the column density of CCO are, respectively, about 6 K and about 6 x 10 to the 11th/sq cm. This column density corresponds to a fractional abundance relative to H2 of about 6 x 10 to the -11th. This value is two orders of magnitude less than the abundance of the related carbon-chain molecule CCS, and about half that of C3O. The formation mechanism for CCO is discussed.

  2. Organic molecules on metal and oxide semiconductor substrates: Adsorption behavior and electronic energy level alignment

    NASA Astrophysics Data System (ADS)

    Ruggieri, Charles M.

    Modern devices such as organic light emitting diodes use organic/oxide and organic/metal interfaces for crucial processes such as charge injection and charge transfer. Understanding fundamental physical processes occurring at these interfaces is essential to improving device performance. The ultimate goal of studying such interfaces is to form a predictive model of interfacial interactions, which has not yet been established. To this end, this thesis focuses on obtaining a better understanding of fundamental physical interactions governing molecular self-assembly and electronic energy level alignment at organic/metal and organic/oxide interfaces. This is accomplished by investigating both the molecular adsorption geometry using scanning tunneling microscopy, as well as the electronic structure at the interface using direct and inverse photoemission spectroscopy, and analyzing the results in the context of first principles electronic structure calculations. First, we study the adsorption geometry of zinc tetraphenylporphyrin (ZnTPP) molecules on three noble metal surfaces: Au(111), Ag(111), and Ag(100). These surfaces were chosen to systematically compare the molecular self-assembly and adsorption behavior on two metals of the same surface symmetry and two surface symmetries of one metal. From this investigation, we improve the understanding of self-assembly at organic/metal interfaces and the relative strengths of competing intermolecular and molecule-substrate interactions that influence molecular adsorption geometry. We then investigate the electronic structure of the ZnTPP/Au(111), Ag(111), and Ag(100) interfaces as examples of weakly-interacting systems. We compare these cases to ZnTPP on TiO2(110), a wide-bandgap oxide semiconductor, and explain the intermolecular and molecule-substrate interactions that determine the electronic energy level alignment at the interface. Finally we study tetracyanoquinodimethane (TCNQ), a strong electron acceptor, on TiO2

  3. Mixing Behavior in Small Molecule: Fullerene Organic Photovoltaics [On the Mixing Behavior in Small Molecule: Fullerene Organic Photovoltaics

    DOE PAGES

    Oosterhout, Stefan D.; Savikhin, Victoria; Zhang, Junxiang; ...

    2017-02-22

    Here, we report a novel method to determine the amount of pure, aggregated phase of donor and acceptor in organic photovoltaic (OPV) bulk heterojunctions. By determination of the diffraction intensity per unit volume for both donor and acceptor, the volume content of pure, aggregated donor and acceptor in the blend can be determined. We find that for the small molecule X2:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) system, in contrast to most polymer systems, all the PCBM is aggregated, indicating there is negligible miscibility of PCBM with X2. This provides an explanation why the performance of OPV devices of X2:PCBM are highmore » over a large range of PCBM concentrations. This is in contrast to many other OPV blends, where PCBM forms a mixed phase with the donor and does not provide sufficient transport for electrons when the PCBM concentration is low. This study demonstrates that a mixed phase is not necessarily a requirement for good OPV device performance.« less

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

    NASA Astrophysics Data System (ADS)

    Collis, Gavin E.

    2015-12-01

    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.

  5. Submillimeter-wave Observations of Complex Organic Molecules in Southern Massive Star Forming Regions

    NASA Astrophysics Data System (ADS)

    Kamegai, Kazuhisa; Sakai, Takeshi; Sakai, Nami; Hirota, Tomoya; Yamamoto, Satoshi

    2013-03-01

    Submillimeter-wave observations of complex organic molecules toward southern massive star forming regions were carried out with ASTE 10m telescope. Methyl formate (HCOOCH3) and dimethyl ether (CH3OCH3) were detected in some molecular cloud cores with young protostars. Differences in chemical composition among neighboring cores were also found.

  6. Complex Organic Molecules tracing shocks along the outflow cavity in the high-mass protostar IRAS 20126+4104.

    PubMed

    Palau, Aina; Walsh, Catherine; Sánchez-Monge, Álvaro; Girart, Josep M; Cesaroni, Riccardo; Jiménez-Serra, Izaskun; Fuente, Asunción; Zapata, Luis A; Neri, Roberto

    2017-06-01

    We report on subarcsecond observations of complex organic molecules (COMs) in the high-mass protostar IRAS 20126+4104 with the Plateau de Bure Interferometer in its most extended configurations. In addition to the simple molecules SO, HNCO and H 2 13 CO, we detect emission from CH 3 CN, CH 3 OH, HCOOH, HCOOCH 3 , CH 3 OCH 3 , CH 3 CH 2 CN, CH 3 COCH 3 , NH 2 CN, and (CH 2 OH) 2 . SO and HNCO present a X-shaped morphology consistent with tracing the outflow cavity walls. Most of the COMs have their peak emission at the putative position of the protostar, but also show an extension towards the south(east), coinciding with an H 2 knot from the jet at about 800-1000 au from the protostar. This is especially clear in the case of H 2 13 CO and CH 3 OCH 3 . We fitted the spectra at representative positions for the disc and the outflow, and found that the abundances of most COMs are comparable at both positions, suggesting that COMs are enhanced in shocks as a result of the passage of the outflow. By coupling a parametric shock model to a large gas-grain chemical network including COMs, we find that the observed COMs should survive in the gas phase for ∼ 2000 yr, comparable to the shock lifetime estimated from the water masers at the outflow position. Overall, our data indicate that COMs in IRAS 20126+4104 may arise not only from the disc, but also from dense and hot regions associated with the outflow.

  7. Complex Organic Molecules tracing shocks along the outflow cavity in the high-mass protostar IRAS 20126+4104

    PubMed Central

    Palau, Aina; Walsh, Catherine; Sánchez-Monge, Álvaro; Girart, Josep M.; Cesaroni, Riccardo; Jiménez-Serra, Izaskun; Fuente, Asunción; Zapata, Luis A.; Neri, Roberto

    2017-01-01

    We report on subarcsecond observations of complex organic molecules (COMs) in the high-mass protostar IRAS 20126+4104 with the Plateau de Bure Interferometer in its most extended configurations. In addition to the simple molecules SO, HNCO and H213CO, we detect emission from CH3CN, CH3OH, HCOOH, HCOOCH3, CH3OCH3, CH3CH2CN, CH3COCH3, NH2CN, and (CH2OH)2. SO and HNCO present a X-shaped morphology consistent with tracing the outflow cavity walls. Most of the COMs have their peak emission at the putative position of the protostar, but also show an extension towards the south(east), coinciding with an H2 knot from the jet at about 800–1000 au from the protostar. This is especially clear in the case of H213CO and CH3OCH3. We fitted the spectra at representative positions for the disc and the outflow, and found that the abundances of most COMs are comparable at both positions, suggesting that COMs are enhanced in shocks as a result of the passage of the outflow. By coupling a parametric shock model to a large gas-grain chemical network including COMs, we find that the observed COMs should survive in the gas phase for ∼ 2000 yr, comparable to the shock lifetime estimated from the water masers at the outflow position. Overall, our data indicate that COMs in IRAS 20126+4104 may arise not only from the disc, but also from dense and hot regions associated with the outflow. PMID:28579644

  8. Nonlinear Transport in Organic Thin Film Transistors with Soluble Small Molecule Semiconductor.

    PubMed

    Kim, Hyeok; Song, Dong-Seok; Kwon, Jin-Hyuk; Jung, Ji-Hoon; Kim, Do-Kyung; Kim, SeonMin; Kang, In Man; Park, Jonghoo; Tae, Heung-Sik; Battaglini, Nicolas; Lang, Philippe; Horowitz, Gilles; Bae, Jin-Hyuk

    2016-03-01

    Nonlinear transport is intensively explained through Poole-Frenkel (PF) transport mechanism in organic thin film transistors with solution-processed small molecules, which is, 6,13-bis(triisopropylsilylethynyl) (TIPS) pentacene. We outline a detailed electrical study that identifies the source to drain field dependent mobility. Devices with diverse channel lengths enable the extensive exhibition of field dependent mobility due to thermal activation of carriers among traps.

  9. Molecular and structural characterization of dissolved organic matter from the deep ocean by FTICR-MS, including hydrophilic nitrogenous organic molecules

    USGS Publications Warehouse

    Reemtsma, T.; These, A.; Linscheid, M.; Leenheer, J.; Spitzy, A.

    2008-01-01

    Dissolved organic matter isolated from the deep Atlantic Ocean and fractionated into a so-called hydrophobic (HPO) fraction and a very hydrophilic (HPI) fraction was analyzed for the first time by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) to resolve the molecular species, to determine their exact masses, and to calculate their molecular formulas. The elemental composition of about 300 molecules was identified. Those in the HPO fraction (14C age of 5100 year) are very similar to much younger freshwater fulvic acids, but less aromatic and more oxygenated molecules are more frequent. This trend continues toward the HPI fraction and may indicate biotic and abiotic aging processes that this material experienced since its primary production thousands of years ago. In the HPI fraction series of nitrogenous molecules containing one, two, or three nitrogens were identified by FTICR-MS. Product ion spectra of the nitrogenous molecules suggest that the nitrogen atoms in these molecules are included in the (alicyclic) backbone of these molecules, possibly in reduced form. These mass spectrometric data suggest that a large set of stable fulvic acids is ubiquitous in all aquatic compartments. Although sources may differ, their actual composition and structure appears to be quite similar and largely independent from their source, because they are the remainder of intensive oxidative degradation processes. ?? 2008 American Chemical Society.

  10. Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 2: 2D NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Deshmukh, Ashish P.; Pacheco, Carlos; Hay, Michael B.; Myneni, Satish C. B.

    2007-07-01

    Carboxyl groups are abundant in natural organic molecules (NOM) and play a major role in their reactivity. The structural environments of carboxyl groups in IHSS soil and river humic samples were investigated using 2D NMR (heteronuclear and homonuclear correlation) spectroscopy. Based on the 1H- 13C heteronuclear multiple-bond correlation (HMBC) spectroscopy results, the carboxyl environments in NOM were categorized as Type I (unsubstituted and alkyl-substituted aliphatic/alicyclic), Type II (functionalized carbon substituted), Type IIIa, b (heteroatom and olefin substituted), and Type IVa, b (5-membered heterocyclic aromatic and 6-membered aromatic). The most intense signal in the HMBC spectra comes from the Type I carboxyl groups, including the 2JCH and 3JCH couplings of unsubstituted aliphatic and alicyclic acids, though this spectral region also includes the 3JCH couplings of Type II and III structures. Type II and III carboxyls have small but detectable 2JCH correlations in all NOM samples except for the Suwannee River humic acid. Signals from carboxyls bonded to 5-membered aromatic heterocyclic fragments (Type IVa) are observed in the soil HA and Suwannee River FA, while correlations to 6-membered aromatics (Type IVb) are only observed in Suwannee River HA. In general, aromatic carboxylic acids may be present at concentrations lower than previously imagined in these samples. Vibrational spectroscopy results for these NOM samples, described in an accompanying paper [Hay M. B. and Myneni S. C. B. (2007) Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: Infrared spectroscopy. Geochim. Cosmochim. Acta (in press)], suggest that Type II and Type III carboxylic acids with α substituents (e.g., -OH, -OR, or -CO 2H) constitute the majority of carboxyl structures in all humic substances examined. Furoic and salicylic acid structures (Type IV) are also feasible fragments, albeit as minor constituents. The

  11. A potentiometric titration method for the crystallization of drug-like organic molecules.

    PubMed

    Du-Cuny, Lei; Huwyler, Jörg; Fischer, Holger; Kansy, Manfred

    2007-09-05

    It is generally accepted, that crystalline solids representing a low energy polymorph should be selected for development of oral dosage forms. As a consequence, efficient and robust procedures are needed at an early stage during drug discovery to prepare crystals from drug-like organic molecules. In contrast to the use of supersaturated solutions, we present a potentiometric crystallization procedure where saturated solutions are prepared in a controlled manner by pH-titration. Crystallization is carried out under defined conditions using the sample concentration and experimental pK(a) values as input parameters. Crystals of high quality were obtained for 11 drugs selected to demonstrate the efficiency and applicability of the new method. Technical improvements are suggested to overcome practical limitations and to enhance the possibility of obtaining crystals from molecules in their uncharged form.

  12. Formation of highly oxygenated organic molecules from aromatic compounds

    NASA Astrophysics Data System (ADS)

    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.

  13. Electron Transfer as a Probe of the Interfacial Quantum Dot-Organic Molecule Interaction

    NASA Astrophysics Data System (ADS)

    Peterson, Mark D.

    This dissertation describes a set of experimental and theoretical studies of the interaction between small organic molecules and the surfaces of semiconductor nanoparticles, also called quantum dots (QDs). Chapter 1 reviews the literature on the influence of ligands on exciton relaxation dynamics following photoexcitation of semiconductor QDs, and describes how ligands promote or inhibit processes such as emission, nonradiative relaxation, and charge transfer to redox active adsorbates. Chapter 2 investigates the specific interaction of alkylcarboxylated viologen derivatives with CdS QDs, and shows how a combination of steady-state photoluminescence (PL) and transient absorption (TA) experiments can be used to reveal the specific binding geometry of redox active organic molecules on QD surfaces. Chapter 3 expands on Chapter 2 by using PL and TA to provide information about the mechanisms through which methyl viologen (MV 2+) associates with CdS QDs to form a stable QD/MV2+ complex, suggesting two chemically distinct reactions. We use our understanding of the QD/molecule interaction to design a drug delivery system in Chapter 4, which employs PL and TA experiments to show that conformational changes in a redox active adsorbate may follow electron transfer, "activating" a biologically inert Schiff base to a protein inhibitor form. The protein inhibitor limits cell motility and may be used to prevent tumor metastasis in cancer patients. Chapter 5 discusses future applications of QD/molecule redox couples with an emphasis on efficient multiple charge-transfer reactions -- a process facilitated by the high degeneracy of band-edge states in QDs. These multiple charge-transfer reactions may potentially increase the thermodynamic efficiency of solar cells, and may also facilitate the splitting of water into fuel. Multiple exciton generation procedures, multi-electron transfer experiments, and future directions are discussed.

  14. Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

    PubMed

    Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

    2017-06-06

    With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

  15. Fluorination-enabled optimal morphology leads to over 11% efficiency for inverted small-molecule organic solar cells

    PubMed Central

    Deng, Dan; Zhang, Yajie; Zhang, Jianqi; Wang, Zaiyu; Zhu, Lingyun; Fang, Jin; Xia, Benzheng; Wang, Zhen; Lu, Kun; Ma, Wei; Wei, Zhixiang

    2016-01-01

    Solution-processable small molecules for organic solar cells have attracted intense attention for their advantages of definite molecular structures compared with their polymer counterparts. However, the device efficiencies based on small molecules are still lower than those of polymers, especially for inverted devices, the highest efficiency of which is <9%. Here we report three novel solution-processable small molecules, which contain π-bridges with gradient-decreased electron density and end acceptors substituted with various fluorine atoms (0F, 1F and 2F, respectively). Fluorination leads to an optimal active layer morphology, including an enhanced domain purity, the formation of hierarchical domain size and a directional vertical phase gradation. The optimal morphology balances charge separation and transfer, and facilitates charge collection. As a consequence, fluorinated molecules exhibit excellent inverted device performance, and an average power conversion efficiency of 11.08% is achieved for a two-fluorine atom substituted molecule. PMID:27991486

  16. Organic molecules in the Sheepbed Mudstone, Gale Crater, Mars

    PubMed Central

    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; Franz, H B; Atreya, S K; Brinckerhoff, W B; Cabane, M; Coll, P; Conrad, P G; Des Marais, D J; Dworkin, J P; Fairén, A G; François, P; Grotzinger, J P; Kashyap, S; ten Kate, I L; Leshin, L A; Malespin, C A; Martin, M G; Martin-Torres, F J; McAdam, A C; Ming, D W; Navarro-González, R; Pavlov, A A; Prats, B D; Squyres, S W; Steele, A; Stern, J C; Sumner, D Y; Sutter, B; Zorzano, M-P

    2015-01-01

    The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150–300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles. Key Points First in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition PMID:26690960

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

    PubMed

    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.

  18. A flexible metal–organic framework: Guest molecules controlled dynamic gas adsorption

    DOE PAGES

    Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; ...

    2015-04-13

    A flexible metal–organic framework (MOF) of [Zn 3(btca) 2(OH) 2]·(guest) n (H 2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N 2, He, and Ar induce a structural transition with a corresponding appearance of additional steps in the isotherms. Physical insights into the dynamic adsorption behaviors of flexible compound 1 were detected by gas adsorption at different temperatures and different pressures and confirmed by Fourier transform infrared spectroscopy and molecular simulations. Interestingly, by taking advantage of the flexible nature inherent to the framework, this MOF material enables highlymore » selective adsorption of CO 2/N 2, CO 2/Ar, and CO 2/He of 36.3, 32.6, and 35.9, respectively, at 298 K. Furthermore, this class of flexible MOFs has potential applications for controlled release, molecular sensing, noble gas separation, smart membranes, and nanotechnological devices.« less

  19. Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2012-01-01

    More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphous carbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert

  20. Organization of 'nanocrystal molecules' using DNA

    NASA Astrophysics Data System (ADS)

    Alivisatos, A. Paul; Johnsson, Kai P.; Peng, Xiaogang; Wilson, Troy E.; Loweth, Colin J.; Bruchez, Marcel P.; Schultz, Peter G.

    1996-08-01

    PATTERNING matter on the nanometre scale is an important objective of current materials chemistry and physics. It is driven by both the need to further miniaturize electronic components and the fact that at the nanometre scale, materials properties are strongly size-dependent and thus can be tuned sensitively1. In nanoscale crystals, quantum size effects and the large number of surface atoms influence the, chemical, electronic, magnetic and optical behaviour2-4. 'Top-down' (for example, lithographic) methods for nanoscale manipulation reach only to the upper end of the nanometre regime5; but whereas 'bottom-up' wet chemical techniques allow for the preparation of mono-disperse, defect-free crystallites just 1-10 nm in size6-10, ways to control the structure of nanocrystal assemblies are scarce. Here we describe a strategy for the synthesis of'nanocrystal molecules', in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions. We attach single-stranded DNA oligonucleotides of defined length and sequence to individual nanocrystals, and these assemble into dimers and trimers on addition of a complementary single-stranded DNA template. We anticipate that this approach should allow the construction of more complex two-and three-dimensional assemblies.

  1. Chemical abundances in cold, dark interstellar clouds

    NASA Technical Reports Server (NTRS)

    Irvine, William M.; Kaifu, Norio; Ohishi, Masatoshi

    1991-01-01

    Current tabulations are presented of the entire range of known interstellar molecules, giving attention to that subset which has been identified in the cold, dark interstellar clouds out of which the sun has been suggested to have formed. The molecular abundances of two such clouds, Taurus Molecular Cloud 1 and Lynd's 134N, exhibit prepossessing chemical differences despite considerable physical similarities. This discrepancy may be accounted for by the two clouds' differing evolutionary stages. Two novel classes of interstellar molecules are noted: sulfur-terminated carbon chains and silicon-terminated ones.

  2. Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

    NASA Astrophysics Data System (ADS)

    Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

    2016-11-01

    Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.

  3. Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

    PubMed Central

    Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

    2016-01-01

    Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow. PMID:27830697

  4. Approaches for optimizing the first electronic hyperpolarizability of conjugated organic molecules

    NASA Technical Reports Server (NTRS)

    Marder, S. R.; Beratan, D. N.; Cheng, L.-T.

    1991-01-01

    Conjugated organic molecules with electron-donating and -accepting moieties can exhibit large electronic second-order nonlinearities, or first hyperpolarizabilities, beta. The present two-state, four-orbital independent-electron analysis of beta leads to the prediction that its absolute value will be maximized at a combination of donor and acceptor strengths for a given conjugated bridge. Molecular design strategies for beta optimization are proposed which give attention to the energetic manipulations of the bridge states. Experimental results have been obtained which support the validity of this approach.

  5. A Complex Organic Slushy Bathing Low-Mass Protostars

    NASA Astrophysics Data System (ADS)

    Drozdovskaya, Maria; Walsh, Catherine; Visser, Ruud; Harsono, Daniel; van Dishoeck, Ewine

    2015-08-01

    Complex organic molecules are ubiquitous companions of young forming stars. They were first observed in hot cores surrounding high-mass protostars [e.g., 1], but have since also been detected in the environs of several low-mass counterparts [e.g., 2]. Recent studies have shown that colder envelopes and positions with impinging outflows may also glow with emission from complex organic species [e.g., 3, 4]. For this meeting, I would like to present physicochemical modeling results on the synthesis of complex organics in an envelope-cavity system that is subject to non-thermal processing. This includes wavelength-dependent radiative transfer calculations with RADMC [5] and a comprehensive gas-grain chemical network [6]. The results show that the morphology of such a system delineates three distinct regions: the cavity wall layer with time-dependent and species-variant enhancements; a torus rich in complex organic ices, but not reflected in gas-phase abundances; and the remaining outer envelope abundant in simpler solid and gaseous molecules. Within the adopted paradigm, complex organic molecules are demonstrated to have unique lifetimes and be grouped into early and late species [7]. Key chemical processes for forming and destroying complex organic molecules will be discussed. In addition, the results of adding newly experimentally verified routes [8] into the existing chemical networks will be shown.[1] Blake G. A., Sutton E. C., Masson C. R., Phillips T. G., 1987, ApJ, 315, 621[2] Jørgensen J. K., Favre C., Bisschop S. E., Bourke T. L., van Dishoeck E. F., Schmalzl M., 2012, ApJ, 757, L4[3] Arce H. G., Santiago-García J., Jørgensen J. K., Tafalla M., Bachiller R., 2008, ApJ, 681, L21[4] Öberg K. I., Bottinelli S., Jørgensen J. K., van Dishoeck E. F., 2010, ApJ, 716, 825[5] Dullemond C. P., Dominik C., 2004, A&A, 417, 159[6] Walsh C., Millar T. J., Nomura H., Herbst E., Widicus Weaver S., Aikawa Y., Laas J. C., Vasyunin A. I., 2014, A&A, 563, A33[7] Drozdovskaya

  6. Employing exciton transfer molecules to increase the lifetime of phosphorescent red organic light emitting diodes

    NASA Astrophysics Data System (ADS)

    Lindla, Florian; Boesing, Manuel; van Gemmern, Philipp; Bertram, Dietrich; Keiper, Dietmar; Heuken, Michael; Kalisch, Holger; Jansen, Rolf H.

    2011-04-01

    The lifetime of phosphorescent red organic light emitting diodes (OLEDs) is investigated employing either N,N'-diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine (NPB), TMM117, or 4,4',4″-tris(N-carbazolyl)-triphenylamine (TCTA) as hole-conducting host material (mixed with an electron conductor). All OLED (organic vapor phase deposition-processed) show similar efficiencies around 30 lm/W but strongly different lifetimes. Quickly degrading OLED based on TCTA can be stabilized by doping exciton transfer molecules [tris-(phenyl-pyridyl)-Ir (Ir(ppy)3)] to the emission layer. At a current density of 50 mA/cm2 (12 800 cd/m2), a lifetime of 387 h can be achieved. Employing exciton transfer molecules is suggested to prevent the degradation of the red emission layer in phosphorescent white OLED.

  7. On the nucleation and initial film growth of rod-like organic molecules

    NASA Astrophysics Data System (ADS)

    Winkler, Adolf

    2016-10-01

    In this article, some fundamental topics related to the initial steps of organic film growth are reviewed. General conclusions will be drawn based on experimental results obtained for the film formation of oligophenylene and pentacene molecules on gold and mica substrates. Thin films were prepared via physical vapor deposition under ultrahigh-vacuum conditions and characterized in-situ mainly by thermal desorption spectroscopy, and ex-situ by X-ray diffraction and atomic force microscopy. In this short review article the following topics will be discussed: What are the necessary conditions to form island-like films which are either composed of flat-lying or of standing molecules? Does a wetting layer exist below and in between the islands? What is the reason behind the occasionally observed bimodal island size distribution? Can one describe the nucleation process with the diffusion-limited aggregation model? Do the impinging molecules directly adsorb on the surface or rather via a hot-precursor state? Finally, it will be described how the critical island size can be determined by an independent measurement of the deposition rate dependence of the island density and the capture-zone distribution via a universal relationship.

  8. Mars Organic Matter Revealed by the Detection of Organo-chlorinated Molecules from Pyro-GCMS Analyses of Yellowknife Bay Mudstone

    NASA Astrophysics Data System (ADS)

    Szopa, C.; Freissinet, C.; Glavin, D. P.; Buch, A.; Coll, P. J.; Cabane, M.; Millan, M.; Belmahadi, I.; Navarro-Gonzalez, R.; Steele, A.; Summons, R. E.; Eigenbrode, J. L.; Mahaffy, P. R.

    2015-12-01

    Mudstones collected on the Yellowknife Bay site in Gale crater by the Curiosity rover, were analyzed with the Sample Analysis at Mars (SAM) chemical laboratory with the aim (among others) to detect and identify organic molecules in the Martian reglith [1]. The pyrolysis (to 900°C)-gas chromatography-mass spectrometry (Pyro-GCMS) analytical mode was systematically used to reach that goal. It revealed the existence of complex interactions between compounds present in the soil sample (e.g. oxychlorines [2]) and internal components of the SAM experiment (e.g. derivatization reactant) resulting in signals complex to interpret [3]. By comparing these results with those obtained for the other Mars samples analysed with SAM, and by carefully identifying, from laboratory work, the possible SAM internal contributions to the organic molecules detected [4], chlorobenzene has already been identified as mainly originating from organics present in the mudstone [5]. Since this discovery, we did additional studies of the chromatograms that reveal the presence of dichlorobenzene originating from an organic source endogenous to the sample. Even if the exact original source of these organic molecules cannot be strictly identified, the detection of several chlorinated aromatic molecules suggests the presence of a significant amount of aromatized materials which are in an oxidized state involving oxygen in the mudstone. We present here the corresponding results and the implication it can have on the origin of these organic materials References: [1] Mahaffy, P. et al. (2012) Space Sci Rev, 170, 401-478. [2] Glavin, D. et al. (2013), JGR. [3] Ming D. et al. (2013), Science 32, 64, [4] Miller K. et al. (In press), JGR, [5] Freissinet et al., (2015), JGR Pla. 120, 495.

  9. Effects of multiple levels of social organization on survival and abundance.

    PubMed

    Ward, Eric J; Semmens, Brice X; Holmes, Elizabeth E; Balcomb Iii, Ken C

    2011-04-01

    Identifying how social organization shapes individual behavior, survival, and fecundity of animals that live in groups can inform conservation efforts and improve forecasts of population abundance, even when the mechanism responsible for group-level differences is unknown. We constructed a hierarchical Bayesian model to quantify the relative variability in survival rates among different levels of social organization (matrilines and pods) of an endangered population of killer whales (Orcinus orca). Individual killer whales often participate in group activities such as prey sharing and cooperative hunting. The estimated age-specific survival probabilities and survivorship curves differed considerably among pods and to a lesser extent among matrilines (within pods). Across all pods, males had lower life expectancy than females. Differences in survival between pods may be caused by a combination of factors that vary across the population's range, including reduced prey availability, contaminants in prey, and human activity. Our modeling approach could be applied to demographic rates for other species and for parameters other than survival, including reproduction, prey selection, movement, and detection probabilities. Conservation Biology ©2010 Society for Conservation Biology. No claim to original US government works.

  10. Fluorescence detection of organic molecules in the Jovian atmosphere

    NASA Technical Reports Server (NTRS)

    Levine, J. S.; Rogowski, R. S.

    1975-01-01

    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 precipitating 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.

  11. Manipulating the dipole layer of polar organic molecules on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Wang, Chin-Yung; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

    The key properties of organic films such as energy level alignment (ELA), work functions, and injection barriers are closely linked to this dipole layer. Using angle resolved photoemission spectroscopy (ARPES), we systemically investigate the coverage-dependent work functions and spectra line shapes of occupied molecular orbital states of a polar molecule, chloroaluminium phthalocyanine (ClAlPc), grown on Ag(111) to show that the orientations of the first ClAlPc layer can be manipulated via the molecule deposition rate and post annealing, causing ELA at organic-metal interface to differ for about 0.3 eV between Cl-up and Cl-down configuration. Moreover, by comparing the experimental results with the calculations based on both gas-phase model and realistic model of ClAlPc on Ag(111) , we evidence that the different orientations of ClAlPc dipole layers lead to different charge-transfer channels between ClAlPc and Ag, a key factor that controls the ELA at organic-metal interface.

  12. A scale-bridging modeling approach for anisotropic organic molecules at patterned semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Kleppmann, Nicola; Klapp, Sabine H. L.

    2015-02-01

    Hybrid systems consisting of organic molecules at inorganic semiconductor surfaces are gaining increasing importance as thin film devices for optoelectronics. The efficiency of such devices strongly depends on the collective behavior of the adsorbed molecules. In the present paper, we propose a novel, coarse-grained model addressing the condensed phases of a representative hybrid system, that is, para-sexiphenyl (6P) at zinc-oxide (ZnO). Within our model, intermolecular interactions are represented via a Gay-Berne potential (describing steric and van-der-Waals interactions) combined with the electrostatic potential between two linear quadrupoles. Similarly, the molecule-substrate interactions include a coupling between a linear molecular quadrupole to the electric field generated by the line charges characterizing ZnO(10-10). To validate our approach, we perform equilibrium Monte Carlo simulations, where the lateral positions are fixed to a 2D lattice, while the rotational degrees of freedom are continuous. We use these simulations to investigate orientational ordering in the condensed state. We reproduce various experimentally observed features such as the alignment of individual molecules with the line charges on the surface, the formation of a standing uniaxial phase with a herringbone structure, as well as the formation of a lying nematic phase.

  13. Intracellular delivery of peptide nucleic acid and organic molecules using zeolite-L nanocrystals.

    PubMed

    Bertucci, Alessandro; Lülf, Henning; Septiadi, Dedy; Manicardi, Alex; Corradini, Roberto; De Cola, Luisa

    2014-11-01

    The design and synthesis of smart nanomaterials can provide interesting potential applications for biomedical purposes from bioimaging to drug delivery. Manufacturing multifunctional systems in a way to carry bioactive molecules, like peptide nucleic acids able to recognize specific targets in living cells, represents an achievement towards the development of highly selective tools for both diagnosis and therapeutics. This work describes a very first example of the use of zeolite nanocrystals as multifunctional nanocarriers to deliver simultaneously PNA and organic molecules into living cells. Zeolite-L nanocrystals are functionalized by covalently attaching the PNA probes onto the surface, while the channel system is filled with fluorescent guest molecules. The cellular uptake of the PNA/Zeolite-L hybrid material is then significantly increased by coating the whole system with a thin layer of biodegradable poly-L-lysine. The delivery of DAPI as a model drug molecule, inserted into the zeolite pores, is also demonstrated to occur in the cells, proving the multifunctional ability of the system. Using this zeolite nanosystem carrying PNA probes designed to target specific RNA sequences of interest in living cells could open new possibilities for theranostic and gene therapy applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Semiempirical evaluation of post-Hartree-Fock diagonal-Born-Oppenheimer corrections for organic molecules.

    PubMed

    Mohallem, José R

    2008-04-14

    Recent post-Hartree-Fock calculations of the diagonal-Born-Oppenheimer correction empirically show that it behaves quite similar to atomic nuclear mass corrections. An almost constant contribution per electron is identified, which converges with system size for specific series of organic molecules. This feature permits pocket-calculator evaluation of the corrections within thermochemical accuracy (10(-1) mhartree or kcal/mol).

  15. Abundance of Soil-Borne Entomopathogenic Fungi in Organic and Conventional Fields in the Midwestern USA with an Emphasis on the Effect of Herbicides and Fungicides on Fungal Persistence.

    PubMed

    Clifton, Eric H; Jaronski, Stefan T; Hodgson, Erin W; Gassmann, Aaron J

    2015-01-01

    Entomopathogenic fungi (EPF) are widespread in agricultural fields and help suppress crop pests. These natural enemies may be hindered by certain agronomic practices associated with conventional agriculture including the use of pesticides. We tested whether the abundance of EPF differed between organic and conventional fields, and whether specific cropping practices and soil properties were correlated with their abundance. In one year of the survey, soil from organic fields and accompanying margins had significantly more EPF than conventional fields and accompanying margins. Regression analysis revealed that the percentage of silt and the application of organic fertilizer were positively correlated with EPF abundance; but nitrogen concentration, tillage, conventional fields, and margins of conventional fields were negatively correlated with EPF abundance. A greenhouse experiment in which fungicides and herbicides were applied to the soil surface showed no significant effect on EPF. Though organic fields were perceived to be more suitable environments for EPF, abiotic factors and cropping practices such as tillage may have greater impacts on the abundance of EPF. Also, fungicides and herbicides may not be as toxic to soil-borne EPF as originally thought.

  16. Molecules for organic electronics studied one by one.

    PubMed

    Meyer, Jörg; Wadewitz, Anja; Lokamani; Toher, Cormac; Gresser, Roland; Leo, Karl; Riede, Moritz; Moresco, Francesca; Cuniberti, Gianaurelio

    2011-08-28

    The electronic and geometrical structure of single difluoro-bora-1,3,5,7-tetraphenyl-aza-dipyrromethene (aza-BODIPY) molecules adsorbed on the Au(111) surface is investigated by low temperature scanning tunneling microscopy and spectroscopy in conjunction with ab initio density functional theory simulations of the density of states and of the interaction with the substrate. Our DFT calculations indicate that the aza-bodipy molecule forms a chemical bond with the Au(111) substrate, with distortion of the molecular geometry and significant charge transfer between the molecule and the substrate. Nevertheless, most likely due to the low corrugation of the Au(111) surface, diffusion of the molecule is observed for applied bias in excess of 1 V.

  17. Exploration of organic-inorganic hybrid perovskites for surface-enhanced infrared spectroscopy of small molecules.

    PubMed

    Chen, Jia; Mo, Zhi-Hong; Yang, Xiao; Zhou, Hai-Ling; Gao, Qin

    2017-06-22

    The organic-inorganic hybrid perovskites efficiently enhance the infrared absorption of small molecules. It is suggested that the quantum wells of perovskites enable the electrons of the perovskites to be excited by light in the infrared region. The exploration has opened a new path for chemical sensing through infrared spectroscopy.

  18. High Abundance of Ions in Cosmic Ices

    NASA Technical Reports Server (NTRS)

    Gudipati, Murthy S.; Allamandola, Louis J.; Fonda, Mark (Technical Monitor)

    2002-01-01

    Water-rich, mixed molecular ices and polycyclic aromatic hydrocarbons (PAHs) are common throughout interstellar molecular clouds and the Solar System. Vacuum ultraviolet (VUV) irradiation and particle bombardment of these abiotic ices produces complex organic species, including important biogenic molecules such as amino acids and functionalized PAHs which may have played a role in the origin of life. This ability of such water-rich, oxygen dominated ices to promote production of complex organic species is surprising and points to an important, unusual, but previously overlooked mechanism at play within the ice. Here we report the nature of this mechanism using electronic spectroscopy. VUV-irradiation of PAH/H2O ices leads to an unprecedented and efficient (greater than 70 %) conversion of the neutral PAHs to their cation form (PAH+). Further, these H2O/PAH+ ices are stabile at temperatures below 50 K, a temperature domain common throughout interstellar clouds and the Solar System. Between 50 and 125 K they react to form the complex organics. In view of this, we conclude that charged PAHs and other molecular ions should be common and abundant in many cosmic ices. The chemical, spectroscopic and physical properties of these ion-rich ices can be of fundamental importance for objects as diverse as comets, planets, and molecular clouds and may account for several poorly understood phenomena associated with each of these object classes.

  19. Formation, Detection and the Distribution of Complex Organic Molecules with the Atacama Large Millimeter/submillimeter Array (ALMA)

    NASA Astrophysics Data System (ADS)

    Remijan, Anthony John

    2015-08-01

    The formation and distribution of complex organic material in astronomical environments continues to be a focused research area in astrochemistry. For several decades now, emphasis has been placed on the millimeter/submillimeter regime of the radio spectrum for trying to detect new molecular species and to constrain the chemical formation route of complex molecules by comparing and contrasting their relative distributions towards varying astronomical environments. This effort has been extremely laborious as millimeter/submillimeter facilities have been only able to detect and map the distribution of the strongest transition(s) of the simplest organic molecules. Even then, these single transition "chemical maps" have been very low spatial resolution because early millimeter/submillimeter facilities did not have access to broadband spectral coverage or the imaging capabilities to truly ascertain the morphology of the molecular emission. In the era of ALMA, these limitations have been greatly lifted. Broadband spectral line surveys now hold the key to uncovering the full molecular complexity in astronomical environments. In addition, searches for complex organic material is no longer limited to investigating the strongest lines of the simplest molecules toward the strongest sources of emission in the Galaxy. ALMA is issuing a new era of exploration as the search for complex molecules will now be available to an increased suite of sources in the Galaxy and our understanding of the formation of this complex material will be greatly increased as a result. This presentation will highlight the current and future ALMA capabilities in the search for complex molecules towards astronomical environments, highlight the recent searches that ALMA scientists have conducted from the start of ALMA Early Science and provide the motivation for the next suite of astronomical searches to investigate our pre-biotic origins in the universe.

  20. The Rotational Spectrum of Complex Organic Molecules: 2(N)-METHYLAMINOETHANOL

    NASA Astrophysics Data System (ADS)

    Melandri, S.; Maris, A.; Calabrese, C.

    2013-06-01

    The detection of molecules in space, is based on their spectroscopic features and high resolution spectral data is needed to allow an unambiguous identification of them. Many of the molecules detected in space are complex organic molecules containing chains of carbon atoms and which therefore show a high degree of molecular flexibility. The high number of low energy conformations and the presence of large amplitude motions on shallow potential energy surfaces are peculiar to this kind of systems. The presence of a high number of stable conformers - often interconverting through small energy barriers - usually gives rise to very complex spectra, which represent a challenge for spectroscopic and computational methods. We report the rotational study of methylaminoethanol (MAE) performed by Free Jet Absorption Microwave Spectrocopy (FJAMW). For this species it has proved essential to compute the complete potential energy surfaces related to the low amplitude modes. This has been calculated at the B3LYP/6-311++G** level of theory while the stable geometries have been characterized MP2/6-311++G**. The interest in the conformational properties of MAE is twofold: in the first place, aminoethanol and thus also MAE can be considered precursors of aminoacids in the interstellar medium and secondly, the MAE side chain is present in important biological molecules such as adrenaline. The conformational preferences of MAE are dominated by the intramolecular hydrogen bond between the OH and NH2 groups and its flexibility and asymmetry generate a very high number of conformers. 24 stable conformations have been predicted and two conformers were observed by FJAMW spectroscopy with our 60-72 GHz spectrometer. With respect to a previous study we have extended the observed frequency range, partly reassigned the rotational spectrum of one of the conformers and determined the nuclear quadrupole constants. The search for higher energy conformers has also been undertaken. S. Charnley, in

  1. Characterization of the Hole Transport and Electrical Properties in the Small-Molecule Organic Semiconductors

    NASA Astrophysics Data System (ADS)

    Wang, L. G.; Zhu, J. J.; Liu, X. L.; Cheng, L. F.

    2017-10-01

    In this paper, we investigate the hole transport and electrical properties in a small-molecule organic material N, N'-bis(1-naphthyl)- N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (NPB), which is frequently used in organic light-emitting diodes. It is shown that the thickness-dependent current density versus voltage ( J- V) characteristics of sandwich-type NPB-based hole-only devices cannot be described well using the conventional mobility model without carrier density or electric field dependence. However, a consistent and excellent description of the thickness-dependent and temperature-dependent J- V characteristics of NPB hole-only devices can be obtained with a single set of parameters by using our recently introduced improved model that take into account the temperature, carrier density, and electric field dependence of the mobility. For the small-molecule organic semiconductor studied, we find that the width of the Gaussian distribution of density of states σ and the lattice constant a are similar to the values reported for conjugated polymers. Furthermore, we show that the boundary carrier density has an important effect on the J- V characteristics. Both the maximum of carrier density and the minimum of electric field appear near the interface of NPB hole-only devices.

  2. Formation and Atmosphere of Complex Organic Molecules of the HH 212 Protostellar Disk

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Chin-Fei; Ho, Paul T. P.; Hirano, Naomi

    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 methanolmore » (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.« less

  3. Theoretical study of anisotropic mobility in ladder-type molecule organic semiconductors

    NASA Astrophysics Data System (ADS)

    Wei, Hui-Ling; Liu, Yu-Fang

    2014-09-01

    The properties of two ladder-type semiconductors {M1: 2,2'-(2,7-dihexy1-4,9-dihydro- s-indaceno[1,2- b:5,6- b']dithiophene-4,9-diylidene) dimalononitrile and M2: 2,7-dihexy1-4,9-dihydro- s-indaceno[1,2- b:5,6- b']dithiophene-4,9-dione} as the n-type and ambipolar organic materials are systematically investigated using the first-principle density functional theory combined with the Marcus-Hush electron transfer theory. It is found that the substitution of M1 induces large changes in its electron-transfer mobility of 1.370 cm2 V-1 s-1. M2 has both large electron- and hole-transfer mobility of 0.420 and 0.288 cm2 V-1 s-1, respectively, which indicates that M2 is potentially a high efficient ambipolar organic semiconducting material. Both the M1 and M2 crystals show remarkable anisotropic behavior. A proper design of the n-type and ambipolar organic electronic materials, which may have high mobility performance, is suggested based on the investigated two molecules.

  4. Gas-phase spectra of MgO molecules: a possible connection from gas-phase molecules to planet formation

    NASA Astrophysics Data System (ADS)

    Kloska, Katherine A.; Fortenberry, Ryan C.

    2018-02-01

    A more fine-tuned method for probing planet-forming regions, such as protoplanetary discs, could be rovibrational molecular spectroscopy observation of particular premineral molecules instead of more common but ultimately less related volatile organic compounds. Planets are created when grains aggregate, but how molecules form grains is an ongoing topic of discussion in astrophysics and planetary science. Using the spectroscopic data of molecules specifically involved in mineral formation could help to map regions where planet formation is believed to be occurring in order to examine the interplay between gas and dust. Four atoms are frequently associated with planetary formation: Fe, Si, Mg and O. Magnesium, in particular, has been shown to be in higher relative abundance in planet-hosting stars. Magnesium oxide crystals comprise the mineral periclase making it the chemically simplest magnesium-bearing mineral and a natural choice for analysis. The monomer, dimer and trimer forms of (MgO)n with n = 1-3 are analysed in this work using high-level quantum chemical computations known to produce accurate results. Strong vibrational transitions at 12.5, 15.0 and 16.5 μm are indicative of magnesium oxide monomer, dimer and trimer making these wavelengths of particular interest for the observation of protoplanetary discs and even potentially planet-forming regions around stars. If such transitions are observed in emission from the accretion discs or absorptions from stellar spectra, the beginning stages of mineral and, subsequently, rocky body formation could be indicated.

  5. The Composition of Comet C 2012 K1 (PanSTARRS) and the Distribution of Primary Volatile Abundances Among Comets

    NASA Technical Reports Server (NTRS)

    Roth, Nathan X.; Gibb, Erika; Bonev, Boncho P.; Disanti, Michael A.; Mumma, Michael J.; Villanueva, Geronimo L.; Paganini, Lucas

    2017-01-01

    On 2014 May 22 and 24 we characterized the volatile composition of the dynamically new Oort cloud comet C2012 K1 (PanSTARRS) using the long-slit, high resolution ( lambda/delta lambda is approximately or equal to 25,000) near-infrared echelle spectrograph (NIRSPEC) at the 10 m Keck II telescope on Maunakea, Hawaii. We detected fluorescent emission from six primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, and CO). Upper limits were derived for C2H2, NH3, and H2CO. We report rotational temperatures, production rates, and mixing ratios (relative to water). Compared with median abundance ratios for primary volatiles in other sampled Oort cloud comets, trace gas abundance ratios in C2012 K1 (PanSTARRS) for CO and HCN are consistent, but CH3OH and C2H6 are enriched while H2CO, CH4, and possibly C2H2 are depleted. When placed in context with comets observed in the near- infrared to date, the data suggest a continuous distribution of abundances of some organic volatiles (HCN, C2H6, CH3OH, CH4) among the comet population. The level of enrichment or depletion in a given comet does not necessarily correlate across all molecules sampled, suggesting that chemical diversity among comets may be more complex than the simple organics-enriched, organics-normal, and organics-depleted framework.

  6. Effect of organic small-molecule hole injection materials on the performance of inverted organic solar cells

    NASA Astrophysics Data System (ADS)

    Li, Jie; Zheng, Yifan; Zheng, Ding; Yu, Junsheng

    2016-07-01

    In this study, the influence of small-molecule organic hole injection materials on the performance of organic solar cells (OSCs) as the hole transport layer (HTL) with an architecture of ITO/ZnO/P3HT:PC71BM/HTL/Ag has been investigated. A significant enhancement on the performance of OSCs from 1.06% to 2.63% is obtained by using N, N‧-bis(1-naphthalenyl)-N, N‧-bis-phenyl-(1, 1‧-biphenyl)-4, 4‧-diamine (NPB) HTL. Through the resistance simulation and space-charge limited current analysis, we found that NPB HTL cannot merely improve the hole mobility of the device but also form the Ohmic contact between the active layer and anode. Besides, when we apply mix HTL by depositing the NPB on the surface of molybdenum oxide, the power conversion efficiency of OSC are able to be further improved to 2.96%.

  7. Anisotropic charge transport in large single crystals of π-conjugated organic molecules.

    PubMed

    Hourani, Wael; Rahimi, Khosrow; Botiz, Ioan; Koch, Felix Peter Vinzenz; Reiter, Günter; Lienerth, Peter; Heiser, Thomas; Bubendorff, Jean-Luc; Simon, Laurent

    2014-05-07

    The electronic properties of organic semiconductors depend strongly on the nature of the molecules, their conjugation and conformation, their mutual distance and the orientation between adjacent molecules. Variations of intramolecular distances and conformation disturb the conjugation and perturb the delocalization of charges. As a result, the mobility considerably decreases compared to that of a covalently well-organized crystal. Here, we present electrical characterization of large single crystals made of the regioregular octamer of 3-hexyl-thiophene (3HT)8 using a conductive-atomic force microscope (C-AFM) in air. We find a large anisotropy in the conduction with charge mobility values depending on the crystallographic orientation of the single crystal. The smaller conduction is in the direction of π-π stacking (along the long axis of the single crystal) with a mobility value in the order of 10(-3) cm(2) V(-1) s(-1), and the larger one is along the molecular axis (in the direction normal to the single crystal surface) with a mobility value in the order of 0.5 cm(2) V(-1) s(-1). The measured current-voltage (I-V) curves showed that along the molecular axis, the current followed an exponential dependence corresponding to an injection mode. In the π-π stacking direction, the current exhibits a space charge limited current (SCLC) behavior, which allows us to estimate the charge carrier mobility.

  8. Abundance of Soil-Borne Entomopathogenic Fungi in Organic and Conventional Fields in the Midwestern USA with an Emphasis on the Effect of Herbicides and Fungicides on Fungal Persistence

    PubMed Central

    Clifton, Eric H.; Jaronski, Stefan T.; Hodgson, Erin W.; Gassmann, Aaron J.

    2015-01-01

    Entomopathogenic fungi (EPF) are widespread in agricultural fields and help suppress crop pests. These natural enemies may be hindered by certain agronomic practices associated with conventional agriculture including the use of pesticides. We tested whether the abundance of EPF differed between organic and conventional fields, and whether specific cropping practices and soil properties were correlated with their abundance. In one year of the survey, soil from organic fields and accompanying margins had significantly more EPF than conventional fields and accompanying margins. Regression analysis revealed that the percentage of silt and the application of organic fertilizer were positively correlated with EPF abundance; but nitrogen concentration, tillage, conventional fields, and margins of conventional fields were negatively correlated with EPF abundance. A greenhouse experiment in which fungicides and herbicides were applied to the soil surface showed no significant effect on EPF. Though organic fields were perceived to be more suitable environments for EPF, abiotic factors and cropping practices such as tillage may have greater impacts on the abundance of EPF. Also, fungicides and herbicides may not be as toxic to soil-borne EPF as originally thought. PMID:26191815

  9. Structural Ordering of Semiconducting Polymers and Small-Molecules for Organic Electronics

    NASA Astrophysics Data System (ADS)

    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

  10. Coupling between diffusion and orientation of pentacene molecules on an organic surface.

    PubMed

    Rotter, Paul; Lechner, Barbara A J; Morherr, Antonia; Chisnall, David M; Ward, David J; Jardine, Andrew P; Ellis, John; Allison, William; Eckhardt, Bruno; Witte, Gregor

    2016-04-01

    The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.

  11. Linking species abundance distributions in numerical abundance and biomass through simple assumptions about community structure.

    PubMed

    Henderson, Peter A; Magurran, Anne E

    2010-05-22

    Species abundance distributions (SADs) are widely used as a tool for summarizing ecological communities but may have different shapes, depending on the currency used to measure species importance. We develop a simple plotting method that links SADs in the alternative currencies of numerical abundance and biomass and is underpinned by testable predictions about how organisms occupy physical space. When log numerical abundance is plotted against log biomass, the species lie within an approximately triangular region. Simple energetic and sampling constraints explain the triangular form. The dispersion of species within this triangle is the key to understanding why SADs of numerical abundance and biomass can differ. Given regular or random species dispersion, we can predict the shape of the SAD for both currencies under a variety of sampling regimes. We argue that this dispersion pattern will lie between regular and random for the following reasons. First, regular dispersion patterns will result if communities are comprised groups of organisms that use different components of the physical space (e.g. open water, the sea bed surface or rock crevices in a marine fish assemblage), and if the abundance of species in each of these spatial guilds is linked to the way individuals of varying size use the habitat. Second, temporal variation in abundance and sampling error will tend to randomize this regular pattern. Data from two intensively studied marine ecosystems offer empirical support for these predictions. Our approach also has application in environmental monitoring and the recognition of anthropogenic disturbance, which may change the shape of the triangular region by, for example, the loss of large body size top predators that occur at low abundance.

  12. Linking species abundance distributions in numerical abundance and biomass through simple assumptions about community structure

    PubMed Central

    Henderson, Peter A.; Magurran, Anne E.

    2010-01-01

    Species abundance distributions (SADs) are widely used as a tool for summarizing ecological communities but may have different shapes, depending on the currency used to measure species importance. We develop a simple plotting method that links SADs in the alternative currencies of numerical abundance and biomass and is underpinned by testable predictions about how organisms occupy physical space. When log numerical abundance is plotted against log biomass, the species lie within an approximately triangular region. Simple energetic and sampling constraints explain the triangular form. The dispersion of species within this triangle is the key to understanding why SADs of numerical abundance and biomass can differ. Given regular or random species dispersion, we can predict the shape of the SAD for both currencies under a variety of sampling regimes. We argue that this dispersion pattern will lie between regular and random for the following reasons. First, regular dispersion patterns will result if communities are comprised groups of organisms that use different components of the physical space (e.g. open water, the sea bed surface or rock crevices in a marine fish assemblage), and if the abundance of species in each of these spatial guilds is linked to the way individuals of varying size use the habitat. Second, temporal variation in abundance and sampling error will tend to randomize this regular pattern. Data from two intensively studied marine ecosystems offer empirical support for these predictions. Our approach also has application in environmental monitoring and the recognition of anthropogenic disturbance, which may change the shape of the triangular region by, for example, the loss of large body size top predators that occur at low abundance. PMID:20071388

  13. Molecular size-dependent abundance and composition of dissolved organic matter in river, lake and sea waters.

    PubMed

    Xu, Huacheng; Guo, Laodong

    2017-06-15

    Dissolved organic matter (DOM) is ubiquitous in natural waters. The ecological role and environmental fate of DOM are highly related to the chemical composition and size distribution. To evaluate size-dependent DOM quantity and quality, water samples were collected from river, lake, and coastal marine environments and size fractionated through a series of micro- and ultra-filtrations with different membranes having different pore-sizes/cutoffs, including 0.7, 0.4, and 0.2 μm and 100, 10, 3, and 1 kDa. Abundance of dissolved organic carbon, total carbohydrates, chromophoric and fluorescent components in the filtrates decreased consistently with decreasing filter/membrane cutoffs, but with a rapid decline when the filter cutoff reached 3 kDa, showing an evident size-dependent DOM abundance and composition. About 70% of carbohydrates and 90% of humic- and protein-like components were measured in the <3 kDa fraction in freshwater samples, but these percentages were higher in the seawater sample. Spectroscopic properties of DOM, such as specific ultraviolet absorbance, spectral slope, and biological and humification indices also varied significantly with membrane cutoffs. In addition, different ultrafiltration membranes with the same manufacture-rated cutoff also gave rise to different DOM retention efficiencies and thus different colloidal abundances and size spectra. Thus, the size-dependent DOM properties were related to both sample types and membranes used. Our results here provide not only baseline data for filter pore-size selection when exploring DOM ecological and environmental roles, but also new insights into better understanding the physical definition of DOM and its size continuum in quantity and quality in aquatic environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Blending crystalline/liquid crystalline small molecule semiconductors: A strategy towards high performance organic thin film transistors

    NASA Astrophysics Data System (ADS)

    He, Chao; He, Yaowu; Li, Aiyuan; Zhang, Dongwei; Meng, Hong

    2016-10-01

    Solution processed small molecule polycrystalline thin films often suffer from the problems of inhomogeneity and discontinuity. Here, we describe a strategy to solve these problems through deposition of the active layer from a blended solution of crystalline (2-phenyl[1]benzothieno[3,2-b][1]benzothiophene, Ph-BTBT) and liquid crystalline (2-(4-dodecylphenyl) [1]benzothieno[3,2-b]benzothiophene, C12-Ph-BTBT) small molecule semiconductors with the hot spin-coating method. Organic thin film transistors with average hole mobility approaching 1 cm2/V s, much higher than that of single component devices, have been demonstrated, mainly due to the improved uniformity, continuity, crystallinity, and stronger intermolecular π-π stacking in blend thin films. Our results indicate that the crystalline/liquid crystalline semiconductor blend method is an effective way to enhance the performance of organic transistors.

  15. Carbon molecules in space: from astrochemistry to astrobiology.

    PubMed

    Ehrenfreund, Pascale; Sephton, Mark A

    2006-01-01

    How complex carbonaceous molecules in space are, what their abundance is and on what timescales they form are crucial questions within cosmochemistry. Despite the large heterogeneity of galactic and interstellar regions the organic chemistry in the universe seems to follow common pathways. The largest fraction of carbon in the universe is incorporated into aromatic molecules (gaseous polycyclic aromatic hydrocarbon as well as solid macromolecular aromatic structures). Macromolecular carbon constitutes more than half of the interstellar carbon, approximately 80% of the carbon in meteorites, and is likely to be present in comets. Molecules of high astrobiological relevance such as N-heterocycles, amino acids and pre-sugars have all been identified in trace quantities (ppb) in extracts of carbonaceous meteorites. Their presence in inter- and circumstellar regions is either unknown or contentious. In any event such fragile species are easily destroyed by UV radiation, shocks and thermal processing and are unlikely to survive incorporation into Solar System material without some degradation. The more refractory material, in particular macromolecular carbon may retain an interstellar heritage more faithfully. We present laboratory measurements on the photostability of organic compounds and discuss their survival in regions with elevated UV radiation. We also show recent observations of diffuse interstellar bands indicating the presence of fullerenes. We investigate the link between the carbon chemistry in interstellar space and in the Solar System by analyzing the carbonaceous fraction of meteorites and by reviewing stable isotopic data. It also seems evident that both volatile and refractory material from carbonaceous meteoritic has been substantially altered owing to thermal and aqueous processing within the Solar System.

  16. SYSTEMATIC THEORETICAL STUDY ON THE INTERSTELLAR CARBON CHAIN MOLECULES

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Etim, Emmanuel E.; Arunan, Elangannan; Gorai, Prasanta

    2016-12-01

    In an effort to further our interest in understanding the basic chemistry of interstellar molecules, here we carry out an extensive investigation of the stabilities of interstellar carbon chains; C{sub n}, H{sub 2}C{sub n}, HC{sub n}N and C{sub n}X (X = N, O, Si, S, H, P, H{sup −}, N{sup −}). These sets of molecules account for about 20% of all the known interstellar and circumstellar molecules. Their high abundances, therefore, demand serious attention. High-level ab initio quantum chemical calculations are employed to accurately estimate the enthalpy of formation, chemical reactivity indices, global hardness and softness, and other chemical parametersmore » of these molecules. Chemical modeling of the abundances of these molecular species has also been performed. Of the 89 molecules considered from these groups, 47 have been astronomically observed, and these observed molecules are found to be more stable with respect to other members of the group. Of the 47 observed molecules, 60% are odd-numbered carbon chains. Interstellar chemistry is not actually driven by thermodynamics, but it is primarily dependent on various kinetic parameters. However, we found that the detectability of the odd-numbered carbon chains could be correlated due to the fact that they are more stable than the corresponding even-numbered carbon chains. Based on this aspect, the next possible carbon chain molecule for astronomical observation in each group is proposed. The effect of kinetics in the formation of some of these carbon chain molecules is also discussed.« less

  17. Interplay between efficiency and device architecture for small molecule organic solar cells.

    PubMed

    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.

  18. Diels-Alder Trapping of Photochemically Generated o-Xylenols: Application in the Synthesis of Novel Organic Molecules and Polymers

    NASA Technical Reports Server (NTRS)

    Meador, Michael A.

    2003-01-01

    Bis(o-xylenol) equivalents are useful synthetic intermediates in the construction of polymers and hydroxyl substituted organic molecules which can organize by hydrogen bonded self-assembly into unique supramolecular structures. These polymers and supramolecular materials have potential use as coatings and thin films in aerospace, electronic and biomedical applications.

  19. Photoautotrophic organisms control microbial abundance and diversity in biological soil crusts

    NASA Astrophysics Data System (ADS)

    Tamm, Alexandra; Maier, Stefanie; Wu, Dianming; Caesar, Jennifer; Hoffman, Timm; Grube, Martin; Weber, Bettina

    2017-04-01

    Vascular vegetation is typically quite sparse or even absent in dryland ecosystems all over the world, but the ground surface is not bare and largely covered by biological soil crusts (referred to as biocrusts hereafter). These biocrust communities generally comprise poikilohydric organisms. They are usually dominated by photoautotrophic cyanobacteria, lichens and mosses, growing together with heterotrophic fungi, bacteria and archaea in varying composition. Cyanobacteria-, lichen- and moss-dominated biocrusts are known to stabilize the soil and to influence the water budgets and plant establishment. The autotrophic organisms take up atmospheric CO2, and (cyano-)bacteria fix atmospheric nitrogen. The intention of the present project was to study the relevance of the dominating photoautotrophic organisms for biocrust microbial composition and physiology. High-throughput sequencing revealed that soil microbiota of biocrusts largely differ from the bacterial community in bare soil. We observed that bacterial and fungal abundance (16S and 18S rRNA gene copy numbers) as well as alpha diversity was lowest in bare soil, and increasing from cyanobacteria-, and chlorolichen- to moss-dominated biocrusts. CO2 gas exchange measurements revealed large respiration rates of the soil in moss-dominated biocrusts, which was not observed for cyanobacteria- and chlorolichen-dominated biocrusts. Thus, soil respiration of moss-dominated biocrusts is mainly due to the activity of the microbial communities, whereas the microorganisms in the other biocrust types are either dormant or feature functionally different microbial communities. Our results indicate that biocrust type determines the pattern of microbial communities in the underlying soil layer.

  20. Self-Assembling Amphiphilic Molecules: A Possible Relationship Between Interstellar Chemistry and Meteoritic Organics

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Dworkin, Jason P.; Deamer, David W.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Interstellar gas and dust comprise the primary material from which the solar system formed. Evidence that some of this material was organic in nature and survived incorporation into the protosolar nebula is provided by the presence of deuterium-enriched organics in meteorites and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall of meteoroids and cosmic dust must have seeded them with some of these complex organic compounds. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by ultraviolet (UV) photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

  1. Array Formatting of the Heat-Transfer Method (HTM) for the Detection of Small Organic Molecules by Molecularly Imprinted Polymers

    PubMed Central

    Wackers, Gideon; Vandenryt, Thijs; Cornelis, Peter; Kellens, Evelien; Thoelen, Ronald; De Ceuninck, Ward; Losada-Pérez, Patricia; van Grinsven, Bart; Peeters, Marloes; Wagner, Patrick

    2014-01-01

    In this work we present the first steps towards a molecularly imprinted polymer (MIP)-based biomimetic sensor array for the detection of small organic molecules via the heat-transfer method (HTM). HTM relies on the change in thermal resistance upon binding of the target molecule to the MIP-type receptor. A flow-through sensor cell was developed, which is segmented into four quadrants with a volume of 2.5 μL each, allowing four measurements to be done simultaneously on a single substrate. Verification measurements were conducted, in which all quadrants received a uniform treatment and all four channels exhibited a similar response. Subsequently, measurements were performed in quadrants, which were functionalized with different MIP particles. Each of these quadrants was exposed to the same buffer solution, spiked with different molecules, according to the MIP under analysis. With the flow cell design we could discriminate between similar small organic molecules and observed no significant cross-selectivity. Therefore, the MIP array sensor platform with HTM as a readout technique, has the potential to become a low-cost analysis tool for bioanalytical applications. PMID:24955945

  2. A Solution-Processable Molecule using Thieno[3,2-b]thiophene as Building Block for Efficient Organic Solar Cells.

    PubMed

    Wei, Huan; Chen, Weichao; Han, Liangliang; Wang, Ting; Bao, Xichang; Li, Xiaoyun; Liu, Jie; Zhou, Yuanhang; Yang, Renqiang

    2015-08-01

    A solution-processed acceptor-π-donor-π-acceptor (A-π-D-π-A) type small molecule, namely DCATT, has been designed and synthesized for the application as donor material in organic solar cells. The fused aromatic unit thieno[3,2-b]thiophene (TT) flanked with thiophene is applied as π bridge, while 4,8-bisthienyl substituted benzodithiophene (BDT) and 2-ethylhexyl cyanoacetate are chosen as the central building block and end group, respectively. Introduction of fused ring to the small molecule enhances the conjugation length of the main chain, and gives a strong tendency to form π-π stacking with a large overlapping area which favors to high charge carrier transport. Small-molecule organic solar cells based on blends of DCATT and fullerene acceptor exhibit power conversion efficiencies as high as 5.20 % under the illumination of AM 1.5G, 100 mW cm(-2) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Ambipolar Small-Molecule:Polymer Blend Semiconductors for Solution-Processable Organic Field-Effect Transistors.

    PubMed

    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.

  4. Time scales for molecule formation by ion-molecule reactions

    NASA Technical Reports Server (NTRS)

    Langer, W. D.; Glassgold, A. E.

    1976-01-01

    Analytical solutions are obtained for nonlinear differential equations governing the time-dependence of molecular abundances in interstellar clouds. Three gas-phase reaction schemes are considered separately for the regions where each dominates. The particular case of CO, and closely related members of the Oh and CH families of molecules, is studied for given values of temperature, density, and the radiation field. Nonlinear effects and couplings with particular ions are found to be important. The time scales for CO formation range from 100,000 to a few million years, depending on the chemistry and regime. The time required for essentially complete conversion of C(+) to CO in the region where the H3(+) chemistry dominates is several million years. Because this time is longer than or comparable to dynamical time scales for dense interstellar clouds, steady-state abundances may not be observed in such clouds.

  5. Linear Ion Trap for the Mars Organic Molecule Analyzer

    NASA Astrophysics Data System (ADS)

    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. Benchmarking density functional tight binding models for barrier heights and reaction energetics of organic molecules.

    PubMed

    Gruden, Maja; Andjeklović, Ljubica; Jissy, Akkarapattiakal Kuriappan; Stepanović, Stepan; Zlatar, Matija; Cui, Qiang; Elstner, Marcus

    2017-09-30

    Density Functional Tight Binding (DFTB) models are two to three orders of magnitude faster than ab initio and Density Functional Theory (DFT) methods and therefore are particularly attractive in applications to large molecules and condensed phase systems. To establish the applicability of DFTB models to general chemical reactions, we conduct benchmark calculations for barrier heights and reaction energetics of organic molecules using existing databases and several new ones compiled in this study. Structures for the transition states and stable species have been fully optimized at the DFTB level, making it possible to characterize the reliability of DFTB models in a more thorough fashion compared to conducting single point energy calculations as done in previous benchmark studies. The encouraging results for the diverse sets of reactions studied here suggest that DFTB models, especially the most recent third-order version (DFTB3/3OB augmented with dispersion correction), in most cases provide satisfactory description of organic chemical reactions with accuracy almost comparable to popular DFT methods with large basis sets, although larger errors are also seen for certain cases. Therefore, DFTB models can be effective for mechanistic analysis (e.g., transition state search) of large (bio)molecules, especially when coupled with single point energy calculations at higher levels of theory. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  7. Novel Flourescent Sensors for the Detection of Organic Molecules in Extraterrestrial Samples

    NASA Astrophysics Data System (ADS)

    Adkin, Roy C.; Bruce, James I.; Pearson, Victoria K.

    2015-04-01

    Organic compounds in extraterrestrial samples have mostly been elucidated by destructive analytical techniques therefore information regarding spatial relationships between minerals and organic species is lost. Minerals form under specific chemical and physical conditions so organic compounds associated with these minerals are likely to have formed under the same conditions. It is therefore possible to infer in which cosmological provinces their chemical evolution took place. We will describe progress towards developing fluorescent sensors that may resolve spatial discrimination. Lanthanide elements such as europium and terbium produce well defined line-like, high intensity and long lived fluorescent emissions. Interactions with organic molecules may alter the luminescent emission characteristics. The lanthanide atom needs to be rendered chemically inert but must remain susceptible to these organic molecule interactions. An organic ligand must be employed to attain this. DOTA (1,4,7,10-tetraazacyclododecanetetracetic acid) was chosen as a plausible organic ligand because its structure, a tetra-substituted cyclen ring, and ability to chelate are well characterized. It is also commercially available. Fluorescent lanthanide-DOTA complexes are used in many biological and analytical imaging applications so it is logical to investigate their applicability to fluorimetric analysis of extraterrestrial organics. Lanthanide-DOTA complexes are very stable because the lanthanide metal atom is enveloped within the DOTA structure. Experimental procedures were designed to investigate lanthanide/analyte interactions and their effect upon fluorescent emissions. A range of compounds were chosen giving a good representation of the organics identified in extraterrestrial samples and whether they may to interact with the lanthanide metal ion. An Europium-DOTA baseline fluorescent spectrum was obtained and compared against Europium-DOTA/analyte mixtures of a range of concentrations

  8. Sol-gel method for encapsulating molecules

    DOEpatents

    Brinker, C. Jeffrey; Ashley, Carol S.; Bhatia, Rimple; Singh, Anup K.

    2002-01-01

    A method for encapsulating organic molecules, and in particular, biomolecules using sol-gel chemistry. A silica sol is prepared from an aqueous alkali metal silicate solution, such as a mixture of silicon dioxide and sodium or potassium oxide in water. The pH is adjusted to a suitably low value to stabilize the sol by minimizing the rate of siloxane condensation, thereby allowing storage stability of the sol prior to gelation. The organic molecules, generally in solution, is then added with the organic molecules being encapsulated in the sol matrix. After aging, either a thin film can be prepared or a gel can be formed with the encapsulated molecules. Depending upon the acid used, pH, and other processing conditions, the gelation time can be from one minute up to several days. In the method of the present invention, no alcohols are generated as by-products during the sol-gel and encapsulation steps. The organic molecules can be added at any desired pH value, where the pH value is generally chosen to achieve the desired reactivity of the organic molecules. The method of the present invention thereby presents a sufficiently mild encapsulation method to retain a significant portion of the activity of the biomolecules, compared with the activity of the biomolecules in free solution.

  9. The organic inventory of primitive meteorites

    NASA Astrophysics Data System (ADS)

    Martins, Zita

    Carbonaceous meteorites are primitive samples that provide crucial information about the solar system genesis and evolution. This class of meteorites has also a rich organic inventory, which may have contributed the first prebiotic building blocks of life to the early Earth. We have studied the soluble organic inventory of several CR and CM meteorites, using high performance liquid chromatography with UV fluorescence detection (HPLC-FD), gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Our target organic molecules include amino acids, nucleobases and polycyclic aromatic hydrocarbons (PAHs), among others. CR chondrites contain the highest amino acids concentration ever detected in a meteorite. The degree of aqueous alteration amongst this class of meteorites seems to be responsible for the amino acid distribution. Pioneering compound-specific carbon isotope measurements of nucleobases present in carbonaceous chondrites show that these compounds have a non-terrestrial origin. This suggests that components of the ge-netic code may have had a crucial role in life's origin. Investigating the abundances, distribution and isotopic composition of organic molecules in primitive meteorites significantly improves our knowledge of the chemistry of the early solar system, and the resources available for the first living organisms on Earth.

  10. Trapping and desorption of complex organic molecules in water at 20 K

    NASA Astrophysics Data System (ADS)

    Burke, Daren J.; Puletti, Fabrizio; Woods, Paul M.; Viti, Serena; Slater, Ben; Brown, Wendy A.

    2015-10-01

    The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices.

  11. Flash pyrolysis of adsorbed aromatic organic acids on carbonate minerals: Assessing the impact of mineralogy for the identification of organic compounds in extraterrestrial bodies

    NASA Astrophysics Data System (ADS)

    Zafar, R.

    2017-12-01

    The relationship between minerals and organics is an essential factor in comprehending the origin of life on extraterrestrial bodies. So far organic molecules have been detected on meteorites, comets, interstellar medium and interplanetary dust particles. While on Mars, organic molecules may also be present as indicated by the Sample Analysis at Mars (SAM) instrument suite on the Curiosity Rover in Martian sediments. Minerals including hydrated phyllosilicate, carbonate, and sulfate minerals have been confirmed in carbonaceous chondrites. The presence of phyllosilicate minerals on Mars has been indicated by in situ elemental analysis by the Viking Landers, remote sensing infrared observations and the presence of smectites in meteorites. Likewise, the presence of carbonate minerals on the surface of Mars has been indicated by both Phoenix Lander and Spirit Rover. Considering the fact that both mineral and organic matter are present on the surface of extraterrestrial bodies including Mars, a comprehensive work is required to understand the interaction of minerals with specific organic compounds. The adsorption of the organic molecule at water/mineral surface is a key process of concentrating organic molecules on the surface of minerals. Carboxylic acids are abundantly observed in extraterrestrial material such as meteorites and interstellar space. It is highly suspected that carboxylic acids are also present on Mars due to the average organic carbon infall rate of 108 kg/yr. Further aromatic organic acids have also been observed in carbonaceous chondrite meteorites. This work presents the adsorption of an aromatic carboxylic acid at the water/calcite interface and characterization of the products formed after adsorption via on-line pyrolysis. Adsorption and online pyrolysis results are used to gain insight into adsorbed aromatic organic acid-calcite interaction. Adsorption and online pyrolysis results are related to the interpretation of organic compounds identified

  12. Visualizing electron dynamics in organic materials: Charge transport through molecules and angular resolved photoemission

    NASA Astrophysics Data System (ADS)

    Kümmel, Stephan

    Being able to visualize the dynamics of electrons in organic materials is a fascinating perspective. Simulations based on time-dependent density functional theory allow to realize this hope, as they visualize the flow of charge through molecular structures in real-space and real-time. We here present results on two fundamental processes: Photoemission from organic semiconductor molecules and charge transport through molecular structures. In the first part we demonstrate that angular resolved photoemission intensities - from both theory and experiment - can often be interpreted as a visualization of molecular orbitals. However, counter-intuitive quantum-mechanical electron dynamics such as emission perpendicular to the direction of the electrical field can substantially alter the picture, adding surprising features to the molecular orbital interpretation. In a second study we calculate the flow of charge through conjugated molecules. The calculations show in real time how breaks in the conjugation can lead to a local buildup of charge and the formation of local electrical dipoles. These can interact with neighboring molecular chains. As a consequence, collections of ''molecular electrical wires'' can show distinctly different characteristics than ''classical electrical wires''. German Science Foundation GRK 1640.

  13. Advances in ultrasensitive mass spectrometry of organic molecules.

    PubMed

    Kandiah, Mathivathani; Urban, Pawel L

    2013-06-21

    Ultrasensitive mass spectrometric analysis of organic molecules is important for various branches of chemistry, and other fields including physics, earth and environmental sciences, archaeology, biomedicine, and materials science. It finds applications--as an enabling tool--in systems biology, biological imaging, clinical analysis, and forensics. Although there are a number of technical obstacles associated with the analysis of samples by mass spectrometry at ultratrace level (for example analyte losses during sample preparation, insufficient sensitivity, ion suppression), several noteworthy developments have been made over the years. They include: sensitive ion sources, loss-free interfaces, ion optics components, efficient mass analyzers and detectors, as well as "smart" sample preparation strategies. Some of the mass spectrometric methods published to date can achieve sensitivity which is by several orders of magnitude higher than that of alternative approaches. Femto- and attomole level limits of detection are nowadays common, while zepto- and yoctomole level limits of detection have also been reported. We envision that the ultrasensitive mass spectrometric assays will soon contribute to new discoveries in bioscience and other areas.

  14. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100kHz MAS

    DOE PAGES

    Nishiyama, Y.; Kobayashi, T.; Malon, M.; ...

    2015-02-16

    Two-dimensional 1H{ 13C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in 1H dimensionmore » without resorting to 1H– 1H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. As a result, the HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone.« less

  15. Trap density of states in small-molecule organic semiconductors: A quantitative comparison of thin-film transistors with single crystals

    NASA Astrophysics Data System (ADS)

    Kalb, Wolfgang L.; Haas, Simon; Krellner, Cornelius; Mathis, Thomas; Batlogg, Bertram

    2010-04-01

    We show that it is possible to reach one of the ultimate goals of organic electronics: producing organic field-effect transistors with trap densities as low as in the bulk of single crystals. We studied the spectral density of localized states in the band gap [trap density of states (trap DOS)] of small-molecule organic semiconductors as derived from electrical characteristics of organic field-effect transistors or from space-charge-limited current measurements. This was done by comparing data from a large number of samples including thin-film transistors (TFT’s), single crystal field-effect transistors (SC-FET’s) and bulk samples. The compilation of all data strongly suggests that structural defects associated with grain boundaries are the main cause of “fast” hole traps in TFT’s made with vacuum-evaporated pentacene. For high-performance transistors made with small-molecule semiconductors such as rubrene it is essential to reduce the dipolar disorder caused by water adsorbed on the gate dielectric surface. In samples with very low trap densities, we sometimes observe a steep increase in the trap DOS very close (<0.15eV) to the mobility edge with a characteristic slope of 10-20 meV. It is discussed to what degree band broadening due to the thermal fluctuation of the intermolecular transfer integral is reflected in this steep increase in the trap DOS. Moreover, we show that the trap DOS in TFT’s with small-molecule semiconductors is very similar to the trap DOS in hydrogenated amorphous silicon even though polycrystalline films of small-molecules with van der Waals-type interaction on the one hand are compared with covalently bound amorphous silicon on the other hand.

  16. 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

    NASA Technical Reports Server (NTRS)

    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.

  17. Organics and other molecules in the surfaces of Callisto and Ganymede

    USGS Publications Warehouse

    McCord, T.B.; Carlson, R.W.; Smythe, W.D.; Hansen, G.B.; Clark, R.N.; Hibbitts, C.A.; Fanale, F.P.; Granahan, J.C.; Segura, M.; Matson, D.L.; Johnson, T.V.; Martin, P.D.

    1997-01-01

    Five absorption features are reported at wavelengths of 3.4, 3.88, 4.05, 4.25, and 4.57 micrometers in the surface materials of the Galilean satellites Callisto and Ganymede from analysis of reflectance spectra returned by the Galileo mission near-infrared mapping spectrometer. Candidate materials include CO2, organic materials (such as tholins containing C???N and C-H), SO2, and compounds containing an SH-functional group; CO2, SO2, and perhaps cyanogen [(CN)2] may be present within the surface material itself as collections of a few molecules each. The spectra indicate that the primary surface constituents are water ice and hydrated minerals.

  18. Organics and other molecules in the surfaces of Callisto and Ganymede.

    PubMed

    McCord, T B; Carlson, R W; Smythe, W D; Hansen, G B; Clark, R N; Hibbitts, C A; Fanale, F P; Granahan, J C; Segura, M; Matson, D L; Johnson, T V; Martin, P D

    1997-10-10

    Five absorption features are reported at wavelengths of 3.4, 3.88, 4. 05, 4.25, and 4.57 micrometers in the surface materials of the Galilean satellites Callisto and Ganymede from analysis of reflectance spectra returned by the Galileo mission near-infrared mapping spectrometer. Candidate materials include CO2, organic materials (such as tholins containing C(triple bond)N and C-H), SO2, and compounds containing an SH-functional group; CO2, SO2, and perhaps cyanogen [(CN)2] may be present within the surface material itself as collections of a few molecules each. The spectra indicate that the primary surface constituents are water ice and hydrated minerals.

  19. Making More-Complex Molecules Using Superthermal Atom/Molecule Collisions

    NASA Technical Reports Server (NTRS)

    Shortt, Brian; Chutjian, Ara; Orient, Otto

    2008-01-01

    A method of making more-complex molecules from simpler ones has emerged as a by-product of an experimental study in outer-space atom/surface collision physics. The subject of the study was the formation of CO2 molecules as a result of impingement of O atoms at controlled kinetic energies upon cold surfaces onto which CO molecules had been adsorbed. In this study, the O/CO system served as a laboratory model, not only for the formation of CO2 but also for the formation of other compounds through impingement of rapidly moving atoms upon molecules adsorbed on such cold interstellar surfaces as those of dust grains or comets. By contributing to the formation of increasingly complex molecules, including organic ones, this study and related other studies may eventually contribute to understanding of the origins of life.

  20. Modeling Stretching Modes of Common Organic Molecules with the Quantum Mechanical Harmonic Oscillator: An Undergraduate Vibrational Spectroscopy Laboratory Exercise

    ERIC Educational Resources Information Center

    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.

  1. Band-selective excited ultrahigh resolution PSYCHE-TOCSY: fast screening of organic molecules and complex mixtures.

    PubMed

    Kakita, Veera Mohana Rao; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

    2016-04-01

    Precise assignments of (1) H atomic sites and establishment of their through-bond COSY or TOCSY connectivity are crucial for molecular structural characterization by using (1) H NMR spectroscopy. However, this exercise is often hampered by signal overlap, primarily because of (1) H-(1) H scalar coupling multiplets, even at typical high magnetic fields. The recent developments in homodecoupling strategies for effectively suppressing the coupling multiplets into nice singlets (pure-shift), particularly, Morris's advanced broadband pure-shift yielded by chirp excitation (PSYCHE) decoupling and ultrahigh resolution PSYCHE-TOCSY schemes, have shown new possibilities for unambiguous structural elucidation of complex organic molecules. The superior broadband PSYCHE-TOCSY exhibits enhanced performance over the earlier TOCSY methods, which however warrants prolonged experimental times due to the requirement of large number of dwell increments along the indirect dimension. Herein, we present fast and band-selective analog of the broadband PSYCHE-TOCSY, which is useful for analyzing complex organic molecules that exhibit characteristic yet crowded spectral regions. The simple pulse scheme relies on band-selective excitation (BSE) followed by PSYCHE homodecoupling in the indirect dimension. The BSE-PSYCHE-TOCSY has been exemplified for Estradiol and a complex carbohydrate mixture comprised of six constituents of closely comparable molecular weights. The experimental times are greatly reduced viz., ~20 fold for Estradiol and ~10 fold for carbohydrate mixture, with respect to the broadband PSYCHE-TOCSY. Furthermore, unlike the earlier homonuclear band-selective decoupling, the BSE-PSYCHE-decoupling provides fully decoupled pure-shift spectra for all the individual chemical sites within the excited band. The BSE-PSYCHE-TOCSY is expected to have significant potential for quick screening of complex organic molecules and mixtures at ultrahigh resolution. Copyright © 2015 John Wiley

  2. New Solid-Phase IR Spectra of Solar-System Molecules: Methanol, Ethanol, and Methanethiol

    NASA Astrophysics Data System (ADS)

    Hudson, Reggie L.; Gerakines, Perry A.; Ferrante, Robert F.

    2017-10-01

    The presence and abundances of organic molecules in extraterrestrial environments, such as on TNOs, can be determined with infrared (IR) spectroscopy, but significant challenges exist. Reference IR spectra for organics under relevant conditions are vital for such work, yet for many compounds such data either are lacking or fragmentary. In this presentation we describe new laboratory results for methanol (CH3OH), the simplest alcohol, which has been reported to exist in planetary and interstellar ices. Our new results include near- and mid-IR spectra, band strengths, and optical constants at various ice temperatures. Moreover, the influence of H2O-ice is examined. In addition to CH3OH, we also have new results for the related cometary molecules CH3SH and CH3CH2OH. Although IR spectra of such molecules have been reported by many groups over the past 60 years, our work appears to be the first to cover densities, refractive indices, band strengths and optical constants of both the amorphous and crystalline phases. Our results are compared to earlier work, the influence of literature assumptions is explored, and possible revisions to the literature are described. Support from the following is acknowledged: (a) NASA-SSERVI's DREAM2 program, (b) the NASA Astrobiology Institute's Goddard Center for Astrobiology, and (c) a NASA-APRA award.

  3. Abundances and Excitation of H2, H3+ & CO in Star-Forming Regions

    NASA Astrophysics Data System (ADS)

    Kulesa, Craig A.

    Although most of the 123 reported interstellar molecules to date have been detected through millimeter-wave emission-line spectroscopy, this technique is inapplicable to non-polar molecules like H2 and H3+, which are central to our understanding of interstellar chemistry. Thus high resolution infrared absorption-line spectroscopy bears an important role in interstellar studies: chemically important non-polar molecules can be observed, and their abundances and excitation conditions can be referred to the same ``pencil beam'' absorbing column. In particular, through a weak quadrupole absorption line spectrum at near-infrared wavelengths, the abundance of cold H2 in dark molecular clouds and star forming regions can now be accurately measured and compared along the same ``pencil beam'' line of sight with the abundance of its most commonly cited surrogate, CO, and its rare isotopomers. Also detected via infrared line absorption is the pivotal molecular ion H3+, whose abundance provides the most direct measurement of the cosmic ray ionization rate in dark molecular clouds, a process that initiates the formation of many other observed molecules there. Our growing sample of H2 and CO detections now includes detailed multi-beam studies of the ρ Ophiuchi molecular cloud and NGC 2024 in Orion. We explore the excitation and degree of ortho- and para-H2 thermalization in dark clouds, variation of the CO abundance over a cloud, and the relation of H2 column density to infrared extinction mapping, far-infrared/submillimeter dust continuum emission, and large scale submillimeter CO, [C I] and HCO+ line emission -- all commonly invoked to indirectly trace H2 during the past 30+ years. For each of the distinct velocity components seen toward some embedded young stellar objects, we are also able to determine the temperature, density, and a CO/H2 abundance ratio, thus unraveling some of the internal structure of a star-forming cloud. H2 and H3+ continue to surprise and delight us

  4. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  5. Morphological study on small molecule acceptor-based organic solar cells with efficiencies beyond 7% (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Ma, Wei; Yan, He

    2015-10-01

    Despite the essential role of fullerenes in achieving best-performance organic solar cells (OSCs), fullerene acceptors have several drawbacks including poor light absorption, high-cost production and purification. For this reason, small molecule acceptor (SMA)-based OSCs have attracted much attention due to the easy tunability of electronic and optical properties of SMA materials. In this study, polymers with temperature dependent aggregation behaviors are combined with various small molecule acceptor materials, which lead to impressive power conversion efficiencies of up to 7.3%. The morphological and aggregation properties of the polymer:small molecule blends are studied in details. It is found that the temperature-dependent aggregation behavior of polymers allows for the processing of the polymer solutions at moderately elevated temperature, and more importantly, controlled aggregation and strong crystallization of the polymer during the film cooling and drying process. This results in a well-controlled and near-ideal polymer:small molecule morphology that is controlled by polymer aggregation during warm casting and thus insensitive to the choice of small molecules. As a result, several cases of highly efficient (PCE between 6-7.3%) SMA OSCs are achieved. The second part of this presentation will describe the morphology of a new small molecule acceptor with a unique 3D structure. The relationship between molecular structure and morphology is revealed.

  6. Ion-molecule calculation of the abundance ratio of CCD to CCH in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Herbst, Eric; Adams, Nigel G.; Smith, David; Defrees, D. J.

    1987-01-01

    Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2(+) (HD)=C2HD(+)(H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.0l-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.

  7. Pre-biotic molecules in shocks: the case of L1157

    NASA Astrophysics Data System (ADS)

    Mendoza, Edgar; Lefloch, Bertrand; López-Sepulcre, Ana; Ceccarelli, Cecilia; Codella, Claudio; Boechat-Roberty, Heloisa M.; Bachiller, Rafael

    2015-08-01

    Interstellar molecules with a peptide link -NH-C(=O)-, like formamide (NH2CHO) and isocyanic acid (HNCO) are notably interesting for their potential role in pre-biotic chemistry. For first time, we report the detection of both molecules towards the protostellar shock L1157-B1 and L1157-B2, with the IRAM 30m telescope. Analysis of the line profiles shows that the emission arises from the outflow cavities associated with B1 and B2. From a simple rotational diagram analysis, molecular abundance of ≈ (0.4-1.1)×10-8 and (3.3-8.8)×10-8 are derived for NH2CHO and HNCO, respectively. The shock regions B1 and B2 appear to be among the richest Galactic sources of HNCO and NH2CHO molecules. We have observed a narrow linear correlation between their abundances, suggesting that the two species are chemically related. Comparison with astrochemical models favours molecule formation on ice grain mantles, with NH2CHO generated from hydrogenation of HNCO.

  8. Formation and processing of organics in the early solar system.

    PubMed

    Kerridge, J F

    1999-01-01

    Until pristine samples can be returned from cometary nuclei, primitive meteorites represent our best source of information about organic chemistry in the early solar system. However, this material has been affected by secondary processing on asteroidal parent bodies which probably did not affect the material now present in cometary nuclei. Production of meteoritic organic matter apparently involved the following sequence of events: Molecule formation by a variety of reaction pathways in dense interstellar clouds; Condensation of those molecules onto refractory interstellar grains; Irradiation of organic-rich interstellar-grain mantles producing a range of molecular fragments and free radicals; Inclusion of those interstellar grains into the protosolar nebula with probable heating of at least some grain mantles during passage through the shock wave bounding the solar accretion disc; Agglomeration of residual interstellar grains and locally produced nebular condensates into asteroid-sized planetesimals; Heating of planetesimals by decay of extinct radionuclides; Melting of ice to produce liquid water within asteroidal bodies; Reaction of interstellar molecules, fragments and radicals with each other and with the aqueous environment, possibly catalysed by mineral grains; Loss of water and other volatiles to space yielding a partially hydrated lithology containing a complex suite of organic molecules; Heating of some of this organic matter to generate a kerogen-like complex; Mixing of heated and unheated material to yield the meteoritic material now observed. Properties of meteoritic organic matter believed to be consistent with this scenario include: Systematic decrease of abundance with increasing C number in homologous series of characterisable molecules; Complete structural diversity within homologous series; Predominance of branched-chain isomers; Considerable isotopic variability among characterisable molecules and within kerogen-like material; Substantial

  9. Biological response of HeLa cells to gold nanoparticles coated with organic molecules.

    PubMed

    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.

  10. Density Functional Theory Investigations of D-A-D' Structural Molecules as Donor Materials in Organic Solar Cell.

    PubMed

    Chen, Junxian; Liu, Qingyu; Li, Hao; Zhao, Zhigang; Lu, Zhiyun; Huang, Yan; Xu, Dingguo

    2018-01-01

    Squaraine core based small molecules in bulk heterojunction organic solar cells have received extensive attentions due to their distinguished photochemical properties in far red and infrared domain. In this paper, combining theoretical simulations and experimental syntheses and characterizations, three major factors (fill factor, short circuit and open-cirvuit voltage) have been carried out together to achieve improvement of power conversion efficiencies of solar cells. As model material systems with D-A-D' framework, two asymmetric squaraines (CNSQ and CCSQ-Tol) as donor materials in bulk heterojunction organic solar cell were synthesized and characterized. Intensive density functional theory computations were applied to identify some direct connections between three factors and corresponding molecular structural properties. It then helps us to predict one new molecule of CCSQ'-Ox that matches all the requirements to improve the power conversion efficiency.

  11. Organic and inorganic molecules as probes of mineral surfaces (Invited)

    NASA Astrophysics Data System (ADS)

    Sverjensky, D. A.

    2010-12-01

    Although the multi-site nature of mineral surfaces is to be expected based on the underlying crystal structure, definitive evidence of the need to use more than one site in modelling proton surface charge or adsorption of a single adsorbate at the mineral-water interface is lacking. Instead, a single-site approach affords a practical way of averaging over all possible crystal planes and sites in a powdered mineral sample. Extensive analysis of published proton surface charge and adsorption of metals on oxide mineral surfaces can be undertaken with a single site density for each mineral based on tritium exchange or estimation from averages of the site densities of likely exposed surfaces. Even in systems with competing metals (e.g. Cu and Pb on hematite), the same site density as used for proton surface charge can be employed depending on the reaction stoichiometry. All of this indicates that protons and metals can bind to a great variety of sites with the same overall site density. However, simple oxyanions such as carbonate, sulfate, selenate, arsenate and arsenite require a much lower site density for a given mineral. For example, on goethite these oxyanions utilize a site density that correlates with the BET surface area of the goethite. In this way, the oxyanions can be thought of as selectively probing the available sites on the mineral. The correlation probably arises because goethites with different BET surface areas have different proportions of singly and multiply-bonded oxygens, and only the singly-bonded oxygens are useful for inner-sphere surface complexation by the ligand exchange mechanism. Small organic molecules behave in a remarkably similar way. For example, adsorption of oxalate on goethite, and aspartate, glutamate, dihydroxyphenylalanine, lysine and arginine on rutile are all consistent with a much smaller site density than those required for metals such as calcium or neodymium. Overall, these results suggest that both inorganic oxyanions and

  12. Chemistry of the organic-rich hot core G327.3-0.6

    NASA Technical Reports Server (NTRS)

    Gibb, E.; Nummelin, A.; Irvine, W. M.; Whittet, D. C.; Bergman, P.; Ferris, J. P. (Principal Investigator)

    2000-01-01

    We present gas-phase abundances of species found in the organic-rich hot core G327.3-0.6. The data were taken with the Swedish-ESO Submillimetre Telescope (SEST). The 1-3 mm spectrum of this source is dominated by emission features of nitrile species and saturated organics, with abundances greater than those found in many other hot cores, including Sgr B2 and OMC-1. Population diagram analysis indicates that many species (CH3CN, C2H3CN, C2H5CN, CH3OH, etc.) have hot components that originate in a compact (2") region. Gas-phase chemical models cannot reproduce the high abundances of these molecules found in hot cores, and we suggest that they originate from processing and evaporation of icy grain mantle material. In addition, we report the first detection of vibrationally excited ethyl cyanide and the first detection of methyl mercaptan (CH3SH) outside the Galactic center.

  13. The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Vincenzi, Donald (Technical Monitor)

    2002-01-01

    One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR studies (telescopic and laboratory) have demonstrated that much of the carbon in the interstellar medium (ISM) is in complex organic species of a variety of types, but the distribution, abundance, and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEAST mission concept designed to conduct IR spectroscopic observations to detect and identify these materials to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. Systematic studies include the observation of planetary nebulae and stellar outflows, protostellar objects, Solar System Objects, and galaxies, and multiple lines of sight through dense molecular clouds and the diffuse ISM. ABE will also search for evidence of D enrichment in complex molecules in all these environments. The mission is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cryogenic cross-dispersed spectrographs that share a single common slit. The 3 spectrometers each measure single spectral octaves (2.5-5, 5-10, 10-20 microns) and together cover the entire 2.5 - 20 micron region simultaneously. The spectrometers use state-of-the-art 1024x1024 pixel detectors, with a single InSb array for the 2.5-5 micron region and two Si:As arrays for the 5-10 and 10-20 micron regions. The spectral resolution is wavelength dependent but is greater than 2000 across the entire spectral range. ABE would operate in a heliocentric, Earth drift-away orbit and is designed to take maximum advantage of this environment for cooling, thermal stability, and mission lifetime. ABE would have a core science mission lasting approximately 1.5 years.

  14. Synthesis of an A-D-A type of molecule used as electron acceptor for improving charge transfer in organic solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Chao-Zhi; Gu, Shu-Duo; Shen, Dan; Yuan, Yang; Zhang, Mingdao

    2016-08-01

    Electron-accepting molecules play an important role in developing organic solar cells. A new type of A-D-A molecule, 3,6-di([7-(5-bromothiophen-2-yl)-1,5,2,4,6,8-dithiotetrazocin-3-yl]thiophen-2-yl)-9-(2-ethylhexyl)carbazole, was synthesized. The lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels are -3.55 and -5.85 eV, respectively. Therefore, the A-D-A type of compound could be used as electron acceptor for fabricating organic solar cell with a high open circuit voltage. Gibbs free energy (-49.2 kJ/mol) reveals that the process of A-D-A acceptor accepting an electron from poly(3-hexylthiophene) at excited state is spontaneous. The value of entropy (118 J/mol) in the process of an electron transferring from P3HT to the A-D-A acceptor at organic interface suggests that electrons generated from separation of electron-hole pairs at donor/acceptor interface would be delocalized efficiently. Therefore, the A-D-A molecule would be a potential acceptor for efficient organic BHJ solar cells.

  15. Superposed Redox Chemistry of Fused Carbon Rings in Cyclooctatetraene-Based Organic Molecules for High-Voltage and High-Capacity Cathodes.

    PubMed

    Zhao, Xiaolin; Qiu, Wujie; Ma, Chao; Zhao, Yingqin; Wang, Kaixue; Zhang, Wenqing; Kang, Litao; Liu, Jianjun

    2018-01-24

    Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N-O, C═X (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C 8 H 8 ) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C 8 -C 4 -C 8 (C 16 H 12 ) and C 8 -C 4 -C 8 -C 4 -C 8 (C 24 H 16 ) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C 16 H 12 and C 24 H 16 exhibit discharge capacities of 525.3 and 357.2 mA h g -1 at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na + /Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C 24 H 16 -based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C 4 ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.

  16. Structure-Property Relationships of Small Organic Molecules as a Prelude to the Teaching of Polymer Science

    ERIC Educational Resources Information Center

    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…

  17. Introducing Bond-Line Organic Structures in High School Biology: An Activity that Incorporates Pleasant-Smelling Molecules

    ERIC Educational Resources Information Center

    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…

  18. Study on detection of terrestrial and marine fractions in marine organic molecules by spectrophoto- and spectrofluorometric methods

    NASA Astrophysics Data System (ADS)

    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

  19. Indirect observation of unobservable interstellar molecules

    NASA Technical Reports Server (NTRS)

    Herbst, E.; Green, S.; Thaddeus, P.; Klemperer, W.

    1977-01-01

    It is suggested that the abundances of neutral non-polar interstellar molecules unobservable by radio astronomy can be systematically determined by radio observation of the protonated ions. As an example, observed N2H(+) column densities are analyzed to infer molecular nitrogen abundances in dense interstellar clouds. The chemistries and expected densities of the protonated ions of O2, C2, CO2, C2H2 and CH4 are then discussed. Microwave transition frequencies fo HCO2(+) and C2H3(+) are estimated, and a preliminary astronomical search for HCO2(+) is described.

  20. Identifying Organic Molecules in Space: The AstroBiology Explorer (ABE) MIDEX Mission Concept

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis; Bregman, Jesse; Ennico, Kimberly; Greene, Thomas; Hudgins, Douglas; Strecker, Donald; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds are detected and identified in space. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to H II regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. The technical considerations of achieving these science objectives in a MIDEX-sized mission will be described.

  1. Chlorine isn't Just for Swimming Pools Anymore... Chlorination of Organic Compounds in the Arctic

    NASA Astrophysics Data System (ADS)

    Han, A.; Raab, T. K.

    2013-12-01

    The cycling of chlorine between its organic and inorganic forms is known to occur in forest soils, but little is known about the generality of this mechanism, which soil components chlorine attaches to, and at what rate chlorination occurs. The study uses peat-rich tundra soils from Barrow, Alaska varying in age since formation of 50 yrs - 5500 yrs BP, and seeks to measure the rate at which organic molecules are chlorinated and to understand what changes those molecules undergo once chlorinated. Soil abundance of chlorine and bromine was estimated in soils of varying age using X-ray fluorescence, and org-Cl levels were measured using pyro-hydrolysis [Table 1]. We considered activity of the enzyme Chloroperoxidase, and data was gathered using absorbance scans of the organic molecule monochlorodimedone to determine whether it had been chlorinated and if so, at what rate. Additional information was gathered from the chlorination of small organic components of the macromolecule lignin, whose constituent molecules make up a large portion of humic materials critical to soil health, through emission scans and fluorescence scans. The results showed that the enzyme chloroperoxidase, which is found in nature and is associated with fungi or bacteria, attaches a chlorine atom to monochlorodimedone and that similar enzymes found in Arctic soils act on it, as well as the lignin model subunits cinnamaldehyde ((2E)-3-phenylprop-2-enal) and naringenin-7-rhamnoglucoside. The results may provide more information on chlorination rates in the Arctic and may contribute to an understanding of how and at what rate chlorine changes form in nature, and answer questions about ozone deterioration or anthropogenic chlorine impact(s) on the environment.Average Halogen Abundance in Arctic Soils xrf=Energy Dispersive X-Ray Fluorescencepyro= TOX Pyro-Hydrolysis

  2. Predicting the Dynamics of Protein Abundance

    PubMed Central

    Mehdi, Ahmed M.; Patrick, Ralph; Bailey, Timothy L.; Bodén, Mikael

    2014-01-01

    Protein synthesis is finely regulated across all organisms, from bacteria to humans, and its integrity underpins many important processes. Emerging evidence suggests that the dynamic range of protein abundance is greater than that observed at the transcript level. Technological breakthroughs now mean that sequencing-based measurement of mRNA levels is routine, but protocols for measuring protein abundance remain both complex and expensive. This paper introduces a Bayesian network that integrates transcriptomic and proteomic data to predict protein abundance and to model the effects of its determinants. We aim to use this model to follow a molecular response over time, from condition-specific data, in order to understand adaptation during processes such as the cell cycle. With microarray data now available for many conditions, the general utility of a protein abundance predictor is broad. Whereas most quantitative proteomics studies have focused on higher organisms, we developed a predictive model of protein abundance for both Saccharomyces cerevisiae and Schizosaccharomyces pombe to explore the latitude at the protein level. Our predictor primarily relies on mRNA level, mRNA–protein interaction, mRNA folding energy and half-life, and tRNA adaptation. The combination of key features, allowing for the low certainty and uneven coverage of experimental observations, gives comparatively minor but robust prediction accuracy. The model substantially improved the analysis of protein regulation during the cell cycle: predicted protein abundance identified twice as many cell-cycle-associated proteins as experimental mRNA levels. Predicted protein abundance was more dynamic than observed mRNA expression, agreeing with experimental protein abundance from a human cell line. We illustrate how the same model can be used to predict the folding energy of mRNA when protein abundance is available, lending credence to the emerging view that mRNA folding affects translation

  3. Predicting the dynamics of protein abundance.

    PubMed

    Mehdi, Ahmed M; Patrick, Ralph; Bailey, Timothy L; Bodén, Mikael

    2014-05-01

    Protein synthesis is finely regulated across all organisms, from bacteria to humans, and its integrity underpins many important processes. Emerging evidence suggests that the dynamic range of protein abundance is greater than that observed at the transcript level. Technological breakthroughs now mean that sequencing-based measurement of mRNA levels is routine, but protocols for measuring protein abundance remain both complex and expensive. This paper introduces a Bayesian network that integrates transcriptomic and proteomic data to predict protein abundance and to model the effects of its determinants. We aim to use this model to follow a molecular response over time, from condition-specific data, in order to understand adaptation during processes such as the cell cycle. With microarray data now available for many conditions, the general utility of a protein abundance predictor is broad. Whereas most quantitative proteomics studies have focused on higher organisms, we developed a predictive model of protein abundance for both Saccharomyces cerevisiae and Schizosaccharomyces pombe to explore the latitude at the protein level. Our predictor primarily relies on mRNA level, mRNA-protein interaction, mRNA folding energy and half-life, and tRNA adaptation. The combination of key features, allowing for the low certainty and uneven coverage of experimental observations, gives comparatively minor but robust prediction accuracy. The model substantially improved the analysis of protein regulation during the cell cycle: predicted protein abundance identified twice as many cell-cycle-associated proteins as experimental mRNA levels. Predicted protein abundance was more dynamic than observed mRNA expression, agreeing with experimental protein abundance from a human cell line. We illustrate how the same model can be used to predict the folding energy of mRNA when protein abundance is available, lending credence to the emerging view that mRNA folding affects translation efficiency

  4. Primitive bodies - Molecular abundances in Comet Halley as probes of cometary formation environments

    NASA Technical Reports Server (NTRS)

    Lunine, Jonathan I.

    1989-01-01

    The most recent results on abundances of molecules in Halley's comet are examined in the context of various models for the environment in which comets formed. These environments include molecular clouds associated with star-forming regions, the solar nebula, gaseous disks around proto-planets, and combinations of these. Of all constituents in a cometary nucleus, the highly volatile molecules such as methane, ammonia, molecular nitrogen, and carbon monoxide are most sensitive to the final episode of cometary grain formation and incorporation in the comet's nucleus; hence they likely reflect at least some chemical processing in the solar nebula. Proper interpretation requires modeling of a number of physical processes including gas phase chemistry, chemistry on grain surfaces, and fractionation effects resulting from preferential incorporation of certain gases in proto-cometary grains. The abundance of methane in Halley's comet could be a key indicator of where that comet formed, provided the methane abundance on grains in star-forming regions can be observationally constrained.

  5. Shocks and Molecules in Protostellar Outflows

    NASA Astrophysics Data System (ADS)

    Arce, Héctor

    2014-06-01

    As protostars form through the gravitational infall of material from their parent molecular cloud, they power energetic bipolar outflows that interact with the surrounding medium. Protostellar outflows are important to the chemical evolution of star forming regions, as the shocks produced by the interaction of the high-velocity protostellar wind and the ambient cloud can heat the surrounding medium and trigger chemical and physical processes that would otherwise not take place in a quiescent molecular cloud. Protostellar outflows, are therefore a great laboratory to study shock physics and shock-induced chemistry. I will present results from millimeter-wave observations of a small sample of outflow shocks. The spectra show clear evidence of the existence of complex organic molecules (e.g., methyl formate, ethanol, acetaldehyde) and high abundance of certain simple molecules (e.g., HCO^+, HCN, H_2O) in outflows. Results indicate that, most likely, the complex species formed on the surface of grains and were then ejected from the grain mantles by the shock. Spectral surveys of shocked regions using ALMA could therefore be used to probe the composition of dust in molecular clouds. Our results demonstrate that outflows modify the chemical composition of the surrounding gaseous environment and that this needs to be considered when using certain species to study active star forming regions.

  6. Electronegativity Equalization Method: Parameterization and Validation for Large Sets of Organic, Organohalogene and Organometal Molecule

    PubMed Central

    Vařeková, Radka Svobodová; Jiroušková, Zuzana; Vaněk, Jakub; Suchomel, Šimon; Koča, Jaroslav

    2007-01-01

    The Electronegativity Equalization Method (EEM) is a fast approach for charge calculation. A challenging part of the EEM is the parameterization, which is performed using ab initio charges obtained for a set of molecules. The goal of our work was to perform the EEM parameterization for selected sets of organic, organohalogen and organometal molecules. We have performed the most robust parameterization published so far. The EEM parameterization was based on 12 training sets selected from a database of predicted 3D structures (NCI DIS) and from a database of crystallographic structures (CSD). Each set contained from 2000 to 6000 molecules. We have shown that the number of molecules in the training set is very important for quality of the parameters. We have improved EEM parameters (STO-3G MPA charges) for elements that were already parameterized, specifically: C, O, N, H, S, F and Cl. The new parameters provide more accurate charges than those published previously. We have also developed new parameters for elements that were not parameterized yet, specifically for Br, I, Fe and Zn. We have also performed crossover validation of all obtained parameters using all training sets that included relevant elements and confirmed that calculated parameters provide accurate charges.

  7. Organic molecules as tools to control the growth, surface structure, and redox activity of colloidal quantum dots.

    PubMed

    Weiss, Emily A

    2013-11-19

    In order to achieve efficient and reliable technology that can harness solar energy, the behavior of electrons and energy at interfaces between different types or phases of materials must be understood. Conversion of light to chemical or electrical potential in condensed phase systems requires gradients in free energy that allow the movement of energy or charge carriers and facilitate redox reactions and dissociation of photoexcited states (excitons) into free charge carriers. Such free energy gradients are present at interfaces between solid and liquid phases or between inorganic and organic materials. Nanostructured materials have a higher density of these interfaces than bulk materials. Nanostructured materials, however, have a structural and chemical complexity that does not exist in bulk materials, which presents a difficult challenge: to lower or eliminate energy barriers to electron and energy flux that inevitably result from forcing different materials to meet in a spatial region of atomic dimensions. Chemical functionalization of nanostructured materials is perhaps the most versatile and powerful strategy for controlling the potential energy landscape of their interfaces and for minimizing losses in energy conversion efficiency due to interfacial structural and electronic defects. Colloidal quantum dots are semiconductor nanocrystals synthesized with wet-chemical methods and coated in organic molecules. Chemists can use these model systems to study the effects of chemical functionalization of nanoscale organic/inorganic interfaces on the optical and electronic properties of a nanostructured material, and the behavior of electrons and energy at interfaces. The optical and electronic properties of colloidal quantum dots have an intense sensitivity to their surface chemistry, and their organic adlayers make them dispersible in solvent. This allows researchers to use high signal-to-noise solution-phase spectroscopy to study processes at interfaces. In this

  8. Inkjet-Printed Small-Molecule Organic Light-Emitting Diodes: Halogen-Free Inks, Printing Optimization, and Large-Area Patterning.

    PubMed

    Zhou, Lu; Yang, Lei; Yu, Mengjie; Jiang, Yi; Liu, Cheng-Fang; Lai, Wen-Yong; Huang, Wei

    2017-11-22

    Manufacturing small-molecule organic light-emitting diodes (OLEDs) via inkjet printing is rather attractive for realizing high-efficiency and long-life-span devices, yet it is challenging. In this paper, we present our efforts on systematical investigation and optimization of the ink properties and the printing process to enable facile inkjet printing of conjugated light-emitting small molecules. Various factors on influencing the inkjet-printed film quality during the droplet generation, the ink spreading on the substrates, and its solidification processes have been systematically investigated and optimized. Consequently, halogen-free inks have been developed and large-area patterning inkjet printing on flexible substrates with efficient blue emission has been successfully demonstrated. Moreover, OLEDs manufactured by inkjet printing the light-emitting small molecules manifested superior performance as compared with their corresponding spin-cast counterparts.

  9. Molecular Abundances in the Circumstellar Envelope of Oxygen-Rich Supergiant VY Canis Majoris

    NASA Astrophysics Data System (ADS)

    Edwards, Jessica L.; Ziurys, Lucy

    2014-06-01

    A complete set of molecular abundances have been established for the Oxygen-rich circumstellar envelope (CSE) surrounding the supergiant star VY Canis Majoris (VY CMa). These data were obtained from The Arizona Radio Observatory (ARO) 1-mm spectral line survey of this object using the ARO Sub-millimeter Telescope (SMT), as well as complimentary transitions taken with the ARO 12-meter. The non-LTE radiative transfer code ESCAPADE has been used to obtain the molecular abundances and distributions in VY CMa, including modeling of the various asymmetric outflow geometries in this source. For example, SO and SO2 were determined to arise from five distinct outflows, four of which are asymmetric with respect to the central star. Abundances of these two sulfur-bearing molecules range from 3 x 10-8 - 2.5 x 10-7 for the various outflows. Similar results will be presented for molecules like CS, SiS, HCN, and SiO, as well as more exotic species like NS, PO, AlO, and AlOH. The molecular abundances between the various outflows will be compared and implications for supergiant chemistry will be discussed.

  10. Human Heart Mitochondrial DNA Is Organized in Complex Catenated Networks Containing Abundant Four-way Junctions and Replication Forks*

    PubMed Central

    Pohjoismäki, Jaakko L. O.; Goffart, Steffi; Tyynismaa, Henna; Willcox, Smaranda; Ide, Tomomi; Kang, Dongchon; Suomalainen, Anu; Karhunen, Pekka J.; Griffith, Jack D.; Holt, Ian J.; Jacobs, Howard T.

    2009-01-01

    Analysis of human heart mitochondrial DNA (mtDNA) by electron microscopy and agarose gel electrophoresis revealed a complete absence of the θ-type replication intermediates seen abundantly in mtDNA from all other tissues. Instead only Y- and X-junctional forms were detected after restriction digestion. Uncut heart mtDNA was organized in tangled complexes of up to 20 or more genome equivalents, which could be resolved to genomic monomers, dimers, and linear fragments by treatment with the decatenating enzyme topoisomerase IV plus the cruciform-cutting T7 endonuclease I. Human and mouse brain also contained a population of such mtDNA forms, which were absent, however, from mouse, rabbit, or pig heart. Overexpression in transgenic mice of two proteins involved in mtDNA replication, namely human mitochondrial transcription factor A or the mouse Twinkle DNA helicase, generated abundant four-way junctions in mtDNA of heart, brain, and skeletal muscle. The organization of mtDNA of human heart as well as of mouse and human brain in complex junctional networks replicating via a presumed non-θ mechanism is unprecedented in mammals. PMID:19525233

  11. Profiling protein function with small molecule microarrays

    PubMed Central

    Winssinger, Nicolas; Ficarro, Scott; Schultz, Peter G.; Harris, Jennifer L.

    2002-01-01

    The regulation of protein function through posttranslational modification, local environment, and protein–protein interaction is critical to cellular function. The ability to analyze on a genome-wide scale protein functional activity rather than changes in protein abundance or structure would provide important new insights into complex biological processes. Herein, we report the application of a spatially addressable small molecule microarray to an activity-based profile of proteases in crude cell lysates. The potential of this small molecule-based profiling technology is demonstrated by the detection of caspase activation upon induction of apoptosis, characterization of the activated caspase, and inhibition of the caspase-executed apoptotic phenotype using the small molecule inhibitor identified in the microarray-based profile. PMID:12167675

  12. A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bruneval, Fabien; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720; Department of Physics, University of California, Berkeley, California 94720

    2015-06-28

    The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green’s function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for neutral electronic excitations of organic molecules exist. Here, we study the performance of the BSE for the 28 small molecules in Thiel’s widely used time-dependent density functional theory benchmark setmore » [Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. We observe that the BSE produces results that depend critically on the mean-field starting point employed in the perturbative approach. We find that this starting point dependence is mainly introduced through the quasiparticle energies obtained at the intermediate GW step and that with a judicious choice of starting mean-field, singlet excitation energies obtained from BSE are in excellent quantitative agreement with higher-level wavefunction methods. The quality of the triplet excitations is slightly less satisfactory.« less

  13. THE SPATIAL DISTRIBUTION OF COMPLEX ORGANIC MOLECULES IN THE L1544 PRE-STELLAR CORE

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jiménez-Serra, Izaskun; Vasyunin, Anton I.; Caselli, Paola

    The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T < 10 K) has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modeling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly extinguished continuum peak with A{sub V}≥ 30 mag within the inner 2700 au; and a low-densitymore » shell with average A{sub V}∼ 7.5–8 mag located at 4000 au from the core’s center and bright in CH{sub 3}OH. Our observations show that CH{sub 3}O, CH{sub 3}OCH{sub 3}, and CH{sub 3}CHO are more abundant (by factors of ∼2–10) toward the low-density shell than toward the continuum peak. Other COMs such as CH{sub 3}OCHO, c-C{sub 3}H{sub 2}O, HCCCHO, CH{sub 2}CHCN, and HCCNC show slight enhancements (by factors ≤3), but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modeling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because (i) CO starts freezing out onto dust grains driving an active surface chemistry; (ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and (iii) the density is still moderate to prevent severe depletion of COMs onto grains.« less

  14. The Spatial Distribution of Complex Organic Molecules in the L1544 Pre-stellar Core.

    PubMed

    Jiménez-Serra, Izaskun; Vasyunin, Anton I; Caselli, Paola; Marcelino, Nuria; Billot, Nicolas; Viti, Serena; Testi, Leonardo; Vastel, Charlotte; Lefloch, Bertrand; Bachiller, Rafael

    2016-10-10

    The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T<10 K), has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modelling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly-extinguished continuum peak with A V ≥30 mag within the inner 2700 au; and a low-density shell with average A V ~7.5-8 mag located at 4000 au from the core's center and bright in CH 3 OH. Our observations show that CH 3 O, CH 3 OCH 3 and CH 3 CHO are more abundant (by factors ~2-10) toward the low-density shell than toward the continuum peak. Other COMs such as CH 3 OCHO, c-C 3 H 2 O, HCCCHO, CH 2 CHCN and HCCNC show slight enhancements (by factors ≤3) but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modelling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because i) CO starts freezing out onto dust grains driving an active surface chemistry; ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and iii) the density is still moderate to prevent severe depletion of COMs onto grains.

  15. The Spatial Distribution of Complex Organic Molecules in the L1544 Pre-stellar Core

    PubMed Central

    Jiménez-Serra, Izaskun; Vasyunin, Anton I.; Caselli, Paola; Marcelino, Nuria; Billot, Nicolas; Viti, Serena; Testi, Leonardo; Vastel, Charlotte; Lefloch, Bertrand; Bachiller, Rafael

    2016-01-01

    The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T<10 K), has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modelling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly-extinguished continuum peak with AV ≥30 mag within the inner 2700 au; and a low-density shell with average AV ~7.5-8 mag located at 4000 au from the core’s center and bright in CH3OH. Our observations show that CH3O, CH3OCH3 and CH3CHO are more abundant (by factors ~2-10) toward the low-density shell than toward the continuum peak. Other COMs such as CH3OCHO, c-C3H2O, HCCCHO, CH2CHCN and HCCNC show slight enhancements (by factors ≤3) but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modelling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because i) CO starts freezing out onto dust grains driving an active surface chemistry; ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and iii) the density is still moderate to prevent severe depletion of COMs onto grains. PMID:27733899

  16. Ultrahigh-efficiency solution-processed simplified small-molecule organic light-emitting diodes using universal host materials

    PubMed Central

    Han, Tae-Hee; Choi, Mi-Ri; Jeon, Chan-Woo; Kim, Yun-Hi; Kwon, Soon-Ki; Lee, Tae-Woo

    2016-01-01

    Although solution processing of small-molecule organic light-emitting diodes (OLEDs) has been considered as a promising alternative to standard vacuum deposition requiring high material and processing cost, the devices have suffered from low luminous efficiency and difficulty of multilayer solution processing. Therefore, high efficiency should be achieved in simple-structured small-molecule OLEDs fabricated using a solution process. We report very efficient solution-processed simple-structured small-molecule OLEDs that use novel universal electron-transporting host materials based on tetraphenylsilane with pyridine moieties. These materials have wide band gaps, high triplet energy levels, and good solution processabilities; they provide balanced charge transport in a mixed-host emitting layer. Orange-red (~97.5 cd/A, ~35.5% photons per electron), green (~101.5 cd/A, ~29.0% photons per electron), and white (~74.2 cd/A, ~28.5% photons per electron) phosphorescent OLEDs exhibited the highest recorded electroluminescent efficiencies of solution-processed OLEDs reported to date. We also demonstrate a solution-processed flexible solid-state lighting device as a potential application of our devices. PMID:27819053

  17. Probabilisitc Geobiological Classification Using Elemental Abundance Distributions and Lossless Image Compression in Recent and Modern Organisms

    NASA Technical Reports Server (NTRS)

    Storrie-Lombardi, Michael C.; Hoover, Richard B.

    2005-01-01

    Last year we presented techniques for the detection of fossils during robotic missions to Mars using both structural and chemical signatures[Storrie-Lombardi and Hoover, 2004]. Analyses included lossless compression of photographic images to estimate the relative complexity of a putative fossil compared to the rock matrix [Corsetti and Storrie-Lombardi, 2003] and elemental abundance distributions to provide mineralogical classification of the rock matrix [Storrie-Lombardi and Fisk, 2004]. We presented a classification strategy employing two exploratory classification algorithms (Principal Component Analysis and Hierarchical Cluster Analysis) and non-linear stochastic neural network to produce a Bayesian estimate of classification accuracy. We now present an extension of our previous experiments exploring putative fossil forms morphologically resembling cyanobacteria discovered in the Orgueil meteorite. Elemental abundances (C6, N7, O8, Na11, Mg12, Ai13, Si14, P15, S16, Cl17, K19, Ca20, Fe26) obtained for both extant cyanobacteria and fossil trilobites produce signatures readily distinguishing them from meteorite targets. When compared to elemental abundance signatures for extant cyanobacteria Orgueil structures exhibit decreased abundances for C6, N7, Na11, All3, P15, Cl17, K19, Ca20 and increases in Mg12, S16, Fe26. Diatoms and silicified portions of cyanobacterial sheaths exhibiting high levels of silicon and correspondingly low levels of carbon cluster more closely with terrestrial fossils than with extant cyanobacteria. Compression indices verify that variations in random and redundant textural patterns between perceived forms and the background matrix contribute significantly to morphological visual identification. The results provide a quantitative probabilistic methodology for discriminating putatitive fossils from the surrounding rock matrix and &om extant organisms using both structural and chemical information. The techniques described appear applicable

  18. Complex organics in IRAS 4A revisited with ALMA and PdBI: Striking contrast between two neighbouring protostellar cores

    NASA Astrophysics Data System (ADS)

    López-Sepulcre, A.; Sakai, N.; Neri, R.; Imai, M.; Oya, Y.; Ceccarelli, C.; Higuchi, A. E.; Aikawa, Y.; Bottinelli, S.; Caux, E.; Hirota, T.; Kahane, C.; Lefloch, B.; Vastel, C.; Watanabe, Y.; Yamamoto, S.

    2017-10-01

    Context. Hot corinos are extremely rich in complex organic molecules (COMs). Accurate abundance measurements of COMs in such objects are crucial to constrain astrochemical models. In the particular case of close binary systems this can only be achieved through high angular resolution imaging. Aims: We aim to perform an interferometric study of multiple COMs in NGC 1333 IRAS 4A, which is a protostellar binary hosting hot corino activity, at an angular resolution that is sufficient to distinguish easily the emission from the two cores separated by 1.8''. Methods: We used the Atacama Large (sub-)Millimeter Array (ALMA) in its 1.2 mm band and the IRAM Plateau de Bure Interferometer (PdBI) at 2.7 mm to image, with an angular resolution of 0.5'' (120 au) and 1'' (235 au), respectively, the emission from 11 different organic molecules in IRAS 4A. This allowed us to clearly disentangle A1 and A2, the two protostellar cores. For the first time, we were able to derive the column densities and fractional abundances simultaneously for the two objects, allowing us to analyse the chemical differences between them. Results: Molecular emission from organic molecules is concentrated exclusively in A2, while A1 appears completely devoid of COMs or even simpler organic molecules, such as HNCO, even though A1 is the strongest continuum emitter. The protostellar core A2 displays typical hot corino abundances and its deconvolved size is 70 au. In contrast, the upper limits we placed on COM abundances for A1 are extremely low, lying about one order of magnitude below prestellar values. The difference in the amount of COMs present in A1 and A2 ranges between one and two orders of magnitude. Our results suggest that the optical depth of dust emission at these wavelengths is unlikely to be sufficiently high to completely hide a hot corino in A1 similar in size to that in A2. Thus, the significant contrast in molecular richness found between the two sources is most probably real. We estimate

  19. Measurement of the conductance properties of single organic molecules using gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Gordin, Yoav

    In this work we describe the development and application of a new method for the electrical conductance measurement of single molecules. The issue of reliable theoretical modeling of molecular electronic transport is still very much in debate. The experimental methods used in the field are difficult to realize and interpret; most have very low yield, preventing proper statistical analysis and many have problems in the researchers' ability to characterize the system properly. We address this issue by using self assembly of gold nanoparticle-molecule-gold nanoparticle objects called dimers. This method allows fabrication of molecular junctions with greater ease; moreover it allows individual characterization of the various elements of the junction, removing much of the uncertainties that exist in this kind of measurements. We make use of home grown gold nanoparticles with a few tens of nanometer diameter to form the hybrid dimers. The dimers are large enough to connect between electrodes fabricated using electron beam lithography and to measure the electric properties of the molecule. We have invested significant effort in the characterization of the system, ensuring that the dimers are indeed bridged by the molecules, and that the chances that more than a single molecule exists in a dimer are negligibly small. We have made measurements on single gold nanoparticles, to characterize their properties separately from those of the molecule. These measurements have allowed us to observe single electron transistor (SET) behavior, resulting from the requirement that electrons charge the nanoparticle during transport. We have shown that the energy associated with this charging scales with nanoparticle size as expected. We have performed measurements on single organic molecules, showing that there is a very strong influence of molecular conjugation (the way electronic orbitals are spread along the molecular backbone) on its conductance. The molecules with broken conjugation

  20. Geochemical Origin of Biological Molecules

    NASA Astrophysics Data System (ADS)

    Bassez, Marie-Paule

    2013-04-01

    A model for the geochemical origin of biological molecules is presented. Rocks such as peridotites and basalts, which contain ferromagnesian minerals, evolve in the presence of water. Their hydrolysis is an exothermic reaction which generates heat and a release of H2 and of minerals with modified structures. The hydrogen reacts with the CO2 embedded inside the rock or with the CO2 of the environment to form CO in an hydrothermal process. With the N2 of the environment, and with an activation source arising from cosmic radiation, ferromagnesian rocks might evolve towards the abiotic formation of biological molecules, such as peptide like macromolecules which produce amino acids after acid hydrolysis. The reactions concerned are described. The production of hydrothermal CO is discussed in geological sites containing ferromagnesian silicate minerals and the low intensity of the Earth's magnetic field during Paleoarchaean Era is also discussed. It is concluded that excitation sources arising from cosmic radiation were much more abundant during Paleoarchaean Era and that macromolecular structures of biological relevance might consequently form during Archaean Eon, as a product of the chemical evolution of the rocks and of their mineral contents. This synthesis of abiotically formed biological molecules is consecutively discussed for meteorites and other planets such as Mars. This model for the geochemical origin of biological molecules has first been proposed in 2008 in the context of reactions involving catalysers such as kaolinite [Bassez 2008a] and then presented in conferences and articles [Bassez 2008b, 2009, 2012; Bassez et al. 2009a to 2012b]. BASSEZ M.P. 2008a Synthèse prébiotique dans les conditions hydrothermales, CNRIUT'08, Lyon 29-30/05/2008, Conf. and open access article:http://liris.cnrs.fr/~cnriut08/actes/ 29 mai 11h-12h40. BASSEZ M.P. 2008b Prebiotic synthesis under hydrothermal conditions, ISSOL'08, P2-6, Firenze-Italy, 24-29/08/2008. Poster at the

  1. Factors controlling the abundance of organic sulfur in flash pyrolyzates of Upper Cretaceous kerogens from Sergipe Basin, Brazil

    USGS Publications Warehouse

    Carmo, A.M.; Stankiewicz, B.A.; Mastalerz, Maria; Pratt, L.M.

    1997-01-01

    The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene + dec-1-ene) in the pyrolyzates is variable and may be related to changes in the type of primary organic input and/or to variations in rates of bacterial sulfate reduction. A concomitant increase in S/C and O/C ratios determined in situ using the electron microprobe is observed in AOM and alginites and may be related to a progressive oxidation of the organic matter during sulfurization. The S/C ratio of the AOM is systematically higher than the S C ratio of the alginites. Combined with a thiophene distribution characteristic of pyrolyzates of Type II organic matter, the higher S/C of AOM in Sergipe kerogens suggests that sulfurization and incorporation of low-molecular weight lipids derived from normal marine organic matter into the kerogen structure predominated over direct sulfurization of highly aliphatic algal biomacromolecules.The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene+dec-1-ene) in the pyrolyzates is variable and may be related to changes in

  2. One-pot synthesis of amino acid precursors with insoluble organic matter in planetesimals with aqueous activity.

    PubMed

    Kebukawa, Yoko; Chan, Queenie H S; Tachibana, Shogo; Kobayashi, Kensei; Zolensky, Michael E

    2017-03-01

    The exogenous delivery of organic molecules could have played an important role in the emergence of life on the early Earth. Carbonaceous chondrites are known to contain indigenous amino acids as well as various organic compounds and complex macromolecular materials, such as the so-called insoluble organic matter (IOM), but the origins of the organic matter are still subject to debate. We report that the water-soluble amino acid precursors are synthesized from formaldehyde, glycolaldehyde, and ammonia with the presence of liquid water, simultaneously with macromolecular organic solids similar to the chondritic IOM. Amino acid products from hydrothermal experiments after acid hydrolysis include α-, β-, and γ-amino acids up to five carbons, for which relative abundances are similar to those extracted from carbonaceous chondrites. One-pot aqueous processing from simple ubiquitous molecules can thus produce a wide variety of meteoritic organic matter from amino acid precursors to macromolecular IOM in chondrite parent bodies.

  3. Single molecule fluorescence microscopy for ultra-sensitive RNA expression profiling

    NASA Astrophysics Data System (ADS)

    Hesse, Jan; Jacak, Jaroslaw; Regl, Gerhard; Eichberger, Thomas; Aberger, Fritz; Schlapak, Robert; Howorka, Stefan; Muresan, Leila; Frischauf, Anna-Maria; Schütz, Gerhard J.

    2007-02-01

    We developed a microarray analysis platform for ultra-sensitive RNA expression profiling of minute samples. It utilizes a novel scanning system for single molecule fluorescence detection on cm2 size samples in combination with specialized biochips, optimized for low autofluorescence and weak unspecific adsorption. 20 μg total RNA was extracted from 10 6 cells of a human keratinocyte cell line (HaCaT) and reversely transcribed in the presence of Alexa647-aha-dUTP. 1% of the resulting labeled cDNA was used for complex hybridization to a custom-made oligonucleotide microarray representing a set of 125 different genes. For low abundant genes, individual cDNA molecules hybridized to the microarray spots could be resolved. Single cDNA molecules hybridized to the chip surface appeared as diffraction limited features in the fluorescence images. The à trous wavelet method was utilized for localization and counting of the separated cDNA signals. Subsequently, the degree of labeling of the localized cDNA molecules was determined by brightness analysis for the different genes. Variations by factors up to 6 were found, which in conventional microarray analysis would result in a misrepresentation of the relative abundance of mRNAs.

  4. Extraterrestrial Organic Chemistry: From the Interstellar Medium to the Origins of Life

    NASA Technical Reports Server (NTRS)

    Pohorille, Andrew; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Extraterrestrially delivered organics in the origin of cellular life. Various processes leading to the emergence of cellular life from organics delivered from space to earth or other planetary bodies in the solar system will be reviewed. The focus will be on: (1) self-assembly of amphiphilic material to vesicles and other structures, such as micelles and multilayers, and its role in creating environments suitable for chemical catalysis, (2) a possible role of extraterrestrial delivery of organics in the formation of the simplest bioenergetics (3) mechanisms leading from amino acids or their precursors to simple peptides and, subsequently, to the evolution of metabolism. These issues will be discussed from two opposite points of view: (1) Which molecules could have been particularly useful in the protobiological evolution; this may provide focus for searching for these molecules in interstellar media. (2) Assuming that a considerable part of the inventory of organic matter on the early earth was delivered extraterrestrially, what does relative abundance of different organics in space tell us about the scenario leading to the origin of life.

  5. Tracing the Origins of Nitrogen Bearing Organics Toward Orion KL with Alma

    NASA Astrophysics Data System (ADS)

    Carroll, Brandon; Crockett, Nathan; Wilkins, Olivia H.; Bergin, Edwin; Blake, Geoffrey

    2017-06-01

    A comprehensive analysis of a broadband 1.2 THz wide spectral survey of the Orion Kleinmann-Low nebula (Orion KL) has shown that nitrogen bearing complex organics trace systematically hotter gas than O-bearing organics toward this source. The origin of this O/N dichotomy remains a mystery. If complex molecules originate from grain surfaces, N-bearing species may be more difficult to remove from grain surfaces than O-bearing organics. Theoretical studies, however, have shown that hot (T=300 K) gas phase chemistry can produce high abundances of N-bearing organics while suppressing the formation of O-bearing complex molecules. In order to distinguish these distinct formation pathways we have obtained extremely high angular resolution observations of methyl cyanide (CH_3CN) using the Atacama Large Millimeter/Submillimeter Array (ALMA) toward Orion KL. By simultaneously imaging ^{13}CH_3CN and CH_2DCN we map the temperature structure and D/H ratio of CH_3CN. We will present updated results of these observations and discuss their implications for the formation of N-bearing organics in the interstellar medium.

  6. Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry.

    PubMed

    Feng, Dan; Xia, Yan

    2018-07-19

    Covalent organic framework (COF) was explored as a novel matrix with a high desorption/ionization efficiency for direct detection of small molecules by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). By using COF as an LDI MS matrix, we could detect not only biological micro molecules such as amino acids and fatty acids, but also emerging environmental pollutants like bisphenol S (BPS) and pyrene. With COF as the matrix, higher desorption/ionization efficiency, and less background interference were achieved than the conventional organic matrices. Good salt tolerance (as high as 500 mM NaCl) and repeatability allowed the detection limit of amino acids was 90 fmol. In addition, COF matrix performed well for amino acids analysis in the honey sample. The ionization mechanism was also discussed. These results demonstrate that COF is a powerful matrix for small molecules analysis in real samples by MS. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Photo-electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation.

    PubMed

    Reichert, Robert; Zambrzycki, Christian; Jusys, Zenonas; Behm, R Jürgen

    2015-11-01

    To better understand organic-molecule-assisted photo-electrochemical water splitting, photo-electrochemistry and on-line mass spectrometry measurements are used to investigate the photo-electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2 (+) and CO2 (+) ion currents show that water oxidation is strongly suppressed by the organic species. Photo-electro-oxidation of formic acid is dominated by formation of CO2 , whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo-electro-oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Probing the emitter site of Renilla luciferase using small organic molecules; an attempt to understand the molecular architecture of the emitter site.

    PubMed

    Salehi, Farajollah; Emamzadeh, Rahman; Nazari, Mahboobeh; Rasa, Seyed Mohammad Mahdi

    2016-12-01

    Renilla luciferase is a sensitive enzyme and has wide applications in biotechnology such as drug screening. Previous studies have tried to show the catalytic residues, nevertheless, the accurate architecture and molecular behavior of its emitter site remains uncharacterized. In this study, the activity of Renilla luciferase, in the presence of two small organic molecules including dimethyl sulfoxide (DMSO) and isopropanol was considered and the structure was studied by circular dichroism (CD) and fluorescence spectroscopy. Moreover, the interaction of small organic molecules with the Renilla luciferase was studied using molecular dynamics simulations. Kinetics studies showed that at low concentration of DMSO (16.6-66mM) and isopropanol (19.3-76mM) the K m changed and a competitive inhibition pattern was observed. Moreover, spectroscopy studies reveled that the changes of activity of Renilla luciferase in the presence of low concentrations of small organic molecules was not associated with structural collapse or severe changes in the enzyme conformation. Molecular dynamics simulations indicated that DMSO and isopropanol, as probing molecules, were both able to bind to the emitter site and remained with the residues of the emitter site. Based on the probing data, the architecture of the emitter site in the "non-binding" model was proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Strategy to discover diverse optimal molecules in the small molecule universe.

    PubMed

    Rupakheti, Chetan; Virshup, Aaron; Yang, Weitao; Beratan, David N

    2015-03-23

    The small molecule universe (SMU) is defined as a set of over 10(60) synthetically feasible organic molecules with molecular weight less than ∼500 Da. Exhaustive enumerations and evaluation of all SMU molecules for the purpose of discovering favorable structures is impossible. We take a stochastic approach and extend the ACSESS framework ( Virshup et al. J. Am. Chem. Soc. 2013 , 135 , 7296 - 7303 ) to develop diversity oriented molecular libraries that can generate a set of compounds that is representative of the small molecule universe and that also biases the library toward favorable physical property values. We show that the approach is efficient compared to exhaustive enumeration and to existing evolutionary algorithms for generating such libraries by testing in the NKp fitness landscape model and in the fully enumerated GDB-9 chemical universe containing 3 × 10(5) molecules.

  10. Strategy To Discover Diverse Optimal Molecules in the Small Molecule Universe

    PubMed Central

    2015-01-01

    The small molecule universe (SMU) is defined as a set of over 1060 synthetically feasible organic molecules with molecular weight less than ∼500 Da. Exhaustive enumerations and evaluation of all SMU molecules for the purpose of discovering favorable structures is impossible. We take a stochastic approach and extend the ACSESS framework (Virshup et al. J. Am. Chem. Soc.2013, 135, 7296–730323548177) to develop diversity oriented molecular libraries that can generate a set of compounds that is representative of the small molecule universe and that also biases the library toward favorable physical property values. We show that the approach is efficient compared to exhaustive enumeration and to existing evolutionary algorithms for generating such libraries by testing in the NKp fitness landscape model and in the fully enumerated GDB-9 chemical universe containing 3 × 105 molecules. PMID:25594586

  11. Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars.

    PubMed

    Rix, Catherine S; Sims, Mark R; Cullen, David C

    2011-11-01

    The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from

  12. Perylene-Diimide Based Donor-Acceptor-Donor Type Small-Molecule Acceptors for Solution-Processable Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    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 <2 eV. The energy levels of small molecules SM-1 to SM-4 were suitable for use as electron-accepting materials. The small molecules showed good thermal stability up to 300°C. BHJ-OSCs with SM-1 and 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.

  13. Induction of Syndecan-4 by Organic-Inorganic Hybrid Molecules with a 1,10-Phenanthroline Structure in Cultured Vascular Endothelial Cells.

    PubMed

    Hara, Takato; Kojima, Takayuki; Matsuzaki, Hiroka; Nakamura, Takehiro; Yoshida, Eiko; Fujiwara, Yasuyuki; Yamamoto, Chika; Saito, Shinichi; Kaji, Toshiyuki

    2017-02-08

    Organic-inorganic hybrid molecules constitute analytical tools used in biological systems. Vascular endothelial cells synthesize and secrete proteoglycans, which are macromolecules consisting of a core protein and glycosaminoglycan side chains. Although the expression of endothelial proteoglycans is regulated by several cytokines/growth factors, there may be alternative pathways for proteoglycan synthesis aside from downstream pathways activated by these cytokines/growth factors. Here, we investigated organic-inorganic hybrid molecules to determine a variant capable of analyzing the expression of syndecan-4, a transmembrane heparan-sulfate proteoglycan, and identified 1,10-phenanthroline ( o -Phen) with or without zinc (Zn-Phen) or rhodium (Rh-Phen). Bovine aortic endothelial cells in culture were treated with these compounds, and the expression of syndecan-4 mRNA and core proteins was determined by real-time reverse transcription polymerase chain reaction and Western blot analysis, respectively. Our findings indicated that o -Phen and Zn-Phen specifically and strongly induced syndecan-4 expression in cultured vascular endothelial cells through activation of the hypoxia-inducible factor-1α/β pathway via inhibition of prolyl hydroxylase-domain-containing protein 2. These results demonstrated an alternative pathway involved in mediating induction of endothelial syndecan-4 expression and revealed organic-inorganic hybrid molecules as effective tools for analyzing biological systems.

  14. Small molecules as tracers in atmospheric secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    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

  15. Constraints on hydrocarbon and organic acid abundances in hydrothermal fluids at the Von Damm vent field, Mid-Cayman Rise (Invited)

    NASA Astrophysics Data System (ADS)

    McDermott, J. M.; Seewald, J.; German, C. R.; Sylva, S. P.

    2013-12-01

    The generation of organic compounds in vent fluids has been of interest since the discovery of seafloor hydrothermal systems, due to implications for the sustenance of present-day microbial populations and their potential role in the origin of life on early Earth. Possible sources of organic compounds in hydrothermal systems include microbial production, thermogenic degradation of organic material, and abiotic synthesis. Abiotic organic synthesis reactions may occur during active circulation of seawater-derived fluids through the oceanic crust or within olivine-hosted fluid inclusions containing carbon-rich magmatic volatiles. H2-rich end-member fluids at the Von Damm vent field on the Mid-Cayman Rise, where fluid temperatures reach 226°C, provide an exciting opportunity to examine the extent of abiotic carbon transformations in a highly reducing system. Our results indicate multiple sources of carbon compounds in vent fluids at Von Damm. An ultramafic-influenced hydrothermal system located on the Mount Dent oceanic core complex at 2350 m depth, Von Damm vent fluids contain H2, CH4, and C2+ hydrocarbons in high abundance relative to basalt-hosted vent fields, and in similar abundance to other ultramafic-hosted systems, such as Rainbow and Lost City. The CO2 content and isotopic composition in end-member fluids are virtually identical to bottom seawater, suggesting that seawater DIC is unchanged during hydrothermal circulation of seawater-derived fluids. Accordingly, end-member CH4 that is present in slightly greater abundance than CO2 cannot be generated from reduction of aqueous CO2 during hydrothermal circulation. We postulate that CH4 and C2+ hydrocarbons that are abundantly present in Von Damm vent fluids reflect leaching of fluids from carbon- and H2-rich fluid inclusions hosted in plutonic rocks. Geochemical modeling of carbon speciation in the Von Damm fluids suggests that the relative abundances of CH4, C2+ hydrocarbons, and CO2 are consistent with

  16. Study on environmental stability of a Zn based metal chelate organic small molecule in powder and thin films

    NASA Astrophysics Data System (ADS)

    Shukla, Vivek Kumar; Maitra, Jaya

    2013-06-01

    The organic small molecules like Bis (8-hydroxy quinoline) Zinc, (Znq2), used in organic light emitting diodes (OLEDs) are sensitive to environment species like moisture and air. Using characterization tools like photoluminescence (PL), FTIR and DSC, we investigated that as deposited films of Znq2 have a significant component of Znq2 tetramer and less dihydrate component. The stability of films deposited at higher deposition rates may be due to higher component of tetramer.

  17. Self-organization across scales: from molecules to organisms.

    PubMed

    Saha, Tanumoy; Galic, Milos

    2018-05-26

    Creating ordered structures from chaotic environments is at the core of biological processes at the subcellular, cellular and organismic level. In this perspective, we explore the physical as well as biological features of two prominent concepts driving self-organization, namely phase transition and reaction-diffusion, before closing with a discussion on open questions and future challenges associated with studying self-organizing systems.This article is part of the theme issue 'Self-organization in cell biology'. © 2018 The Author(s).

  18. Photobleaching dynamics in small molecule vs.  polymer organic photovoltaic blends with 1,7-bis-trifluoromethylfullerene

    DOE PAGES

    Garner, Logan E.; Nellissery Viswanathan, Vinila; Arias, Dylan H.; ...

    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 PC 70BM and the bistrifluoromethylfullerene 1,7-C 60(CF 3) 2. For both the polymer and small molecule blends, C 60(CF 3) 2 stabilizes the initial rate of photobleaching by a factor of 15 relative to PC70BM. However, once the small molecule:C 60(CF 3) 2 blend bleaches to ~80% of its initial optical density, themore » rate of photobleaching dramatically accelerates, which is not observed in the analagous polymer blend. We probe that phenomenon using time-resovled photoluminescence (TRPL) to measure PL quenching efficiencies at defined intervals during the photobleaching experiments. The data indicates the small molecule donor and C 60(CF 3) 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.« less

  19. Photobleaching dynamics in small molecule vs.  polymer organic photovoltaic blends with 1,7-bis-trifluoromethylfullerene

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Garner, Logan E.; Nellissery Viswanathan, Vinila; Arias, Dylan H.

    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 PC 70BM and the bistrifluoromethylfullerene 1,7-C 60(CF 3) 2. For both the polymer and small molecule blends, C 60(CF 3) 2 stabilizes the initial rate of photobleaching by a factor of 15 relative to PC70BM. However, once the small molecule:C 60(CF 3) 2 blend bleaches to ~80% of its initial optical density, themore » rate of photobleaching dramatically accelerates, which is not observed in the analagous polymer blend. We probe that phenomenon using time-resovled photoluminescence (TRPL) to measure PL quenching efficiencies at defined intervals during the photobleaching experiments. The data indicates the small molecule donor and C 60(CF 3) 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.« less

  20. The Identification of Complex Organic Molecules in the Interstellar Medium: Using Lasers and Matrix Isolation Spectroscopy to Simulate the Interstellar Environment

    NASA Technical Reports Server (NTRS)

    Stone, Bradley M.

    1998-01-01

    The Astrochemistry Group at NASA Ames Research Center is interested in the identification of large organic molecules in the interstellar medium Many smaller organic species (e.g. hydrocarbons, alcohols, etc.) have been previously identified by their radiofrequency signature due to molecular rotations. However, this becomes increasingly difficult to observe as the size of the molecule increases. Our group in interested in the identification of the carriers of the Diffuse Interstellar Bands (absorption features observed throughout the visible and near-infrared in the spectra of stars, due to species in the interstellar medium). Polycyclic Aromatic Hydrocarbons (PAHs) and related molecules are thought to be good candidates for these carriers. Laboratory experiments am performed at Ames to simulate the interstellar environment, and to compare spectra obtained from molecules in the laboratory to those derived astronomically. We are also interested in PAHs with respect to their possible connection to the UIR (Unidentified infrared) and ERE (Extended Red Emission) bands - emission features found to emanate from particular regions of our galaxy (e.g. Orion nebula, Red Rectangle, etc.). An old, "tried and proven spectroscopic technique, matrix isolation spectroscopy creates molecular conditions ideal for performing laboratory astrophysics.

  1. Molecules from Clouds to Planets: Sweet Results from Alma

    NASA Astrophysics Data System (ADS)

    van Dishoeck, Ewine

    2017-06-01

    One of the most exciting developments in astronomy is the discovery of thousands of planets around stars other than our Sun. But how do these exo-planets form, and which chemical ingredients are available to build them? Thanks to powerful new telescopes, especially the Atacama Large Millimeter/submillimeter Array (ALMA), astronomers are starting to address these age-old questions scientifically. Stars and planets are born in the cold and tenuous clouds between the stars in the Milky Way. In spite of the extremely low temperatures and densities, a surprisingly rich and interesting chemistry occurs in these interstellar clouds, as evidenced by the detection of more than 180 different molecules. Highly accurate spectroscopic data are key to their identification, and examples of the continued need and close interaction between laboratory work and astronomical observations will be given. ALMA now allows us to zoom in on solar system construction for the first time. Spectral scans of the birth sites of young stars contain tens of thousands of rotational lines. Water and a surprisingly rich variety of organic materials are found, including simple sugars and high abundances of deuterated species. How are these molecules formed? Can these pre-biotic molecules end up on new planets and form the basis for life elsewhere in the universe? Stay tuned for the latest analyses and also a comparison with recent results from the Rosetta mission to comet 67 P/C-G in our own Solar System.

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

    PubMed Central

    2014-01-01

    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. PMID:24501431

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

    PubMed

    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.

  4. Rock samples analysis with the pyrolysis system of the Mars Organic Molecule Analyzer (MOMA)

    NASA Astrophysics Data System (ADS)

    Steininger, H.; Goetz, W.; Goesmann, F.

    2012-12-01

    The Mars Organic Molecule Analyzer (MOMA) is a combined pyrolysis gas chromatograph mass spectrometer (GC-MS) and laser desorption mass spectrometer (LD-MS). It will be the key instrument of the ESA/Roscosmos ExoMars 2018 mission to search for extinct and extant life. Additionally the instrument will be able to detect the organic background which has possibly been delivered to Mars by meteorites. Several samples containing a wide range of organic molecules have been tested with a flight analog injection system. The results of the tests were compared to results obtained by a commercial pyrolysis system, the Pyrola pyrolysis unit. The first experimental setup (Pyrola unit) consists of a small quartz tube with an electrically heated platinum filament. A constant helium flow transports the volatilized compounds through an injection needle directly into the injector of the GC. The whole system is heated to 175°C. The second experimental setup (flight analog injection system) consists of a 6 mm diameter platinum oven connected to a microvalve plate to route the gas from the oven to the GC. The microvalves can be switched electrically. The volatiles are subsequently trapped in a cold trap consisting of a Tenax filed tube. Heating this tube releases the volatiles and injects them through an injection needle into the GC. A Varian 4000 GC-MS with RTX-5 column was used to separate and analyze the volatiles generated from both experimental setups. During the experiments several natural rock samples with a broad content of organic material have been analyzed. The sample material was crushed and ground. To obtain comparable results the same amount of sample was used in both setups. Lower temperatures were used in the flight analog injection system due to restrictions of the reusable oven. Lower temperatures normally lead to only a slight decrease in the very heavy and non-volatile compounds but do not change the overall appearance of the chromatogram. Significant differences in

  5. Synthetic fermentation of bioactive molecules.

    PubMed

    Stepek, Iain A; Bode, Jeffrey W

    2018-04-05

    The concept of synthetic fermentation is to 'grow' complex organic molecules in a controlled and predictable manner by combining small molecule building blocks in water-without the need for reagents, enzymes, or organisms. This approach mimics the production of small mixtures of structurally related natural products by living organisms, particularly microbes, under conditions compatible with direct screening of the cultures for biological activity. This review discusses the development and implementation of this concept, its use for the discovery of protease inhibitors, its basis as a chemistry outreach program allowing non-specialists to make and discover new antibiotics, and highlights of related approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Deep, Broadband Spectral Line Surveys of Molecule-rich Interstellar Clouds

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Widicus Weaver, Susanna L.; Laas, Jacob C.; Zou, Luyao

    2017-09-01

    Spectral line surveys are an indispensable tool for exploring the physical and chemical evolution of astrophysical environments due to the vast amount of data that can be obtained in a relatively short amount of time. We present deep, broadband spectral line surveys of 30 interstellar clouds using two broadband λ  = 1.3 mm receivers at the Caltech Submillimeter Observatory. This information can be used to probe the influence of physical environment on molecular complexity. We observed a wide variety of sources to examine the relative abundances of organic molecules as they relate to the physical properties of the source (i.e., temperature,more » density, dynamics, etc.). The spectra are highly sensitive, with noise levels ≤25 mK at a velocity resolution of ∼0.35 km s{sup −1}. In the initial analysis presented here, column densities and rotational temperatures have been determined for the molecular species that contribute significantly to the spectral line density in this wavelength regime. We present these results and discuss their implications for complex molecule formation in the interstellar medium.« less

  7. Differences in leukocyte differentiation molecule abundances on domestic sheep (Ovis aries) and bighorn sheep (Ovis canadensis) neutrophils identified by flow cytometry.

    PubMed

    Highland, Margaret A; Schneider, David A; White, Stephen N; Madsen-Bouterse, Sally A; Knowles, Donald P; Davis, William C

    2016-06-01

    Although both domestic sheep (DS) and bighorn sheep (BHS) are affected by similar respiratory bacterial pathogens, experimental and field data indicate BHS are more susceptible to pneumonia. Cross-reactive monoclonal antibodies (mAbs) for use in flow cytometry (FC) are valuable reagents for interspecies comparative immune system analyses. This study describes cross-reactive mAbs that recognize leukocyte differentiation molecules (LDMs) and major histocompatibility complex antigens on DS and BHS leukocytes. Characterization of multichannel eosinophil autofluorescence in this study permitted cell-type specific gating of granulocytes for evaluating LDMs, specifically on neutrophils, by single-label FC. Evaluation of relative abundances of LDMs by flow cytometry revealed greater CD11a, CD11b, CD18 (β2 integrins) and CD 172a (SIRPα) on DS neutrophils and greater CD14 (lipopolysaccharide receptor) on BHS neutrophils. Greater CD25 (IL-2) was identified on BHS lymphocytes following Concavalin A stimulation. While DS and BHS have similar total peripheral blood leukocyte counts, BHS have proportionately more neutrophils. Published by Elsevier Ltd.

  8. Export of Terrestrially-Derived Organic Matter from the Mississippi River to the Gulf of Mexico Sediments as Determined by Ultrahigh Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Hatcher, P.; Ware, S. A.; Vaughn, D.; Waggoner, D. C.; Bianchi, T. S.

    2017-12-01

    Sediment samples extending from the main channel of the Mississippi River to edge of the continental shelf of the Gulf of Mexico were extracted to recover humic acids from the organic matter and subjected to molecular level characterization by electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The data show that sedimentary organic matter at the river mouth contains humic substances with a predominantly terrestrial signature resembling those obtained from soils. Condensed aromatic molecules and carboxyl rich alicyclic molecules (CRAM) typify the major structures observed. The CRAM-like molecules persist progressing seaward into the Gulf while the condensed aromatic molecules diminish in relative abundance. This trend is characteristic of traditional mixing of allochthonous terrestrial with autochthonous source materials, consistent with published isotope and lignin phenol biomarker data. Alternatively, the trend could also be explained by oxidative degradation of mainly terrestrial organic matter whereby the condensed aromatic molecules would be selectively oxidized. CRAM molecules would then become selectively enriched as one progresses from the channel to the continental shelf. Laboratory studies show that aromatic molecules (like those in lignin) subjected to oxidative degradation mainly by hydroxyl radical attack, either biologically or non-biologically, undergo molecular rearrangement via ring-opening to form reactive species. These can interact with nucleophilic molecules such as peptides and sulfur-containing species and/or can undergo cycloaddition reactions to produce CRAM-like species. This latter explanation suggests that the main source of organic matter in this coastal depocenter is terrestrial and that autochthonous organic matter contributes little to sedimentary organic matter.

  9. Results of the First Mars Organic Molecule Analyzer (MOMA) GC-MS Coupling

    NASA Astrophysics Data System (ADS)

    Buch, Arnaud; Pinnick, Veronica; Szopa, Cyril; Danell, Ryan; Grand, Noel; Van Amerom, Friso; Glavin, Daniel; Freissinet, Caroline; Humeau, Olivier; Coll, Patrice; Arevalo, Ricardo; Stalport, Fabien; Brinckerhoff, William; Steininger, Harald; Goesmann, Fred; Mahaffy, Paul; Raulin, Francois

    2014-11-01

    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 collected by the rover, with a particular focus on the char-acterization of the organic content. The core of the MOMA instrument is a gas chromatograph coupled with a mass spectrometer (GC-MS) which provides the unique capability to characterize a broad range of compounds, including both of volatile and non-volatile species. Samples will be crushed and deposited into sample cups seated in a rotating carousel. Soil samples will be analyzed either by UV laser desorption / ionization (LDI) or pyrolysis gas chromatography ion trap mass spectrometry (pyr-GC-ITMS).The French GC brassboard was coupled to the US ion trap mass spectrometer brassboard in a flight-like con-figuration for several coupling campains. The MOMA GC setup is based on the SAM heritage design with a He reservoir and 4 separate analytical modules including traps, columns and Thermal Conductivity Detectors. Solid samples are sealed and heated in this setup using a manual tapping station, designed and built at MPS in Germany, for GC-MS analysis. The gaseous species eluting from the GC are then ionized by an electron impact ionization source in the MS chamber and analyzed by the linear ion trap mass spectrometer. Volatile and non-volatile compounds were injected in the MOMA instrumental suite. Both of these compounds classes were detected by the TCD and by the MS. MS signal (total ion current) and single mass spectra by comparison with the NIST library, gave us an unambiguous confirmation of these identifications. The mass spectra arise from an average of 10 mass spectra averaged around a given time point in the total ion chromatogram.Based on commercial instrument, the MOMA requirement for sensitivity in the GC-MS mode for organic molecules is 1 pmol. In this test, sensitivity was determined for the GC TCD and MS response to a dilution

  10. Thermal Reactivity of Organic Molecules in the Presence of Chlorates and Perchlorates and the Quest for Organics on Mars with the SAM Experiment Onboard the Curiostiy Rover

    NASA Astrophysics Data System (ADS)

    Szopa, Cyril; Millan, Maeva; Buch, Arnaud; Belmahdi, Imene; Coll, Patrice; Glavin, Daniel P.; Freissinet, Caroline; Eigenbrode, Jennifer; archer, doug; sutter, brad; Summons, Roger; Navarro-Gonzalez, Rafael; Mahaffy, Paul; cabane, Michel

    2016-10-01

    One of the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples collected by Curiosity when they are heated up to ~850°C. With this aim SAM uses a gas-chromatograph coupled to a mass spectrometer (GC-MS) able to detect and identify both inorganic and organic molecules released by the samples.During the pyrolysis, chemical reactions occur between oxychlorines, probably homogeneously distributed at Mars's surface, and organic compounds SAM seeks for. This was confirmed by the first chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM that were entirely attributed to reaction products occurring between these oxychlorines and organics from instrument background. But SAM also detected in the Sheepbed mudstone of Gale crater, chloroalkanes produced by reaction between oxychlorines and Mars indigenous organics, proving for the first time the presence of organics in the soil of Mars. However, the identification of the molecules at the origin of these chloroalkanes is much more difficult due to the complexity of the reactivity occurring during the sample pyrolysis. If a first study has already been done recently with this aim, it was relatively limited in terms of parameters investigated.This is the reason why, we performed a systematic study in the laboratory to help understanding the influence of oxychlorines on organic matter during pyrolysis. With this aim, different organic compounds from various chemical families (e.g. amino and carboxylic acids) mixed with different perchlorates and chlorates, in concentrations compatible with the Mars soil from estimations done with SAM measurements, were pyrolyzed under SAM like conditions. The products of reaction were analyzed and identified by GC-MS in order to show a possible correlation between them and the parent molecule. Different parameters were tested for the pyrolysis to evaluate their potential influence on the

  11. In Situ Oxidation Synthesis of p-Type Composite with Narrow-Bandgap Small Organic Molecule Coating on Single-Walled Carbon Nanotube: Flexible Film and Thermoelectric Performance.

    PubMed

    Gao, Caiyan; Chen, Guangming

    2018-03-01

    Although composites of organic polymers or n-type small molecule/carbon nanotube (CNT) have achieved significant advances in thermoelectric (TE) applications, p-type TE composites of small organic molecules as thick surface coating layers on the surfaces of inorganic nanoparticles still remain a great challenge. Taking advantage of in situ oxidation reaction of thieno[3,4-b]pyrazine (TP) into TP di-N-oxide (TPNO) on single-walled CNT (SWCNT) surface, a novel synthesis strategy is proposed to achieve flexible films of TE composites with narrow-bandgap (1.19 eV) small molecule coating on SWCNT surface. The TE performance can be effectively enhanced and conveniently tuned by poly(sodium-p-styrenesulfonate) content, TPNO/SWCNT mass ratio, and posttreatment by various polar solvents. The maximum of the composite power factor at room temperature is 29.4 ± 1.0 µW m -1 K -2 . The work presents a way to achieve flexible films of p-type small organic molecule/inorganic composites with clear surface coating morphology for TE application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. First principles investigations of vinazene molecule and molecular crystal: a prospective candidate for organic photovoltaic applications.

    PubMed

    Mohamad, Mazmira; Ahmed, Rashid; Shaari, Amirudin; Goumri-Said, Souraya

    2015-02-01

    Escalating demand for sustainable energy resources, because of the rapid exhaustion of conventional energy resources as well as to maintain the environmental level of carbon dioxide (CO2) to avoid its adverse effect on the climate, has led to the exploitation of photovoltaic technology manifold more than ever. In this regard organic materials have attracted great attention on account of demonstrating their potential to harvest solar energy at an affordable rate for photovoltaic technology. 2-vinyl-4,5-dicyanoimidazole (vinazene) is considered as a suitable material over the fullerenes for photovoltaic applications because of its particular chemical and physical nature. In the present study, DFT approaches are employed to provide an exposition of optoelectronic properties of vinazene molecule and molecular crystal. To gain insight into its properties, different forms of exchange correlation energy functional/potential such as LDA, GGA, BLYP, and BL3YP are used. Calculated electronic structure of vinazene molecule has been displayed via HOMO-LUMO isosurfaces, whereas electronic structure of the vinazene molecular crystal, via electronic band structure, is presented. The calculated electronic and optical properties were analyzed and compared as well. Our results endorse vinazene as a suitable material for organic photovoltaic applications.

  13. Functionalized organic semiconductor molecules to enhance charge carrier injection in electroluminescent cell

    NASA Astrophysics Data System (ADS)

    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.

  14. Electronegativity equalization method: parameterization and validation for organic molecules using the Merz-Kollman-Singh charge distribution scheme.

    PubMed

    Jirousková, Zuzana; Vareková, Radka Svobodová; Vanek, Jakub; Koca, Jaroslav

    2009-05-01

    The electronegativity equalization method (EEM) was developed by Mortier et al. as a semiempirical method based on the density-functional theory. After parameterization, in which EEM parameters A(i), B(i), and adjusting factor kappa are obtained, this approach can be used for calculation of average electronegativity and charge distribution in a molecule. The aim of this work is to perform the EEM parameterization using the Merz-Kollman-Singh (MK) charge distribution scheme obtained from B3LYP/6-31G* and HF/6-31G* calculations. To achieve this goal, we selected a set of 380 organic molecules from the Cambridge Structural Database (CSD) and used the methodology, which was recently successfully applied to EEM parameterization to calculate the HF/STO-3G Mulliken charges on large sets of molecules. In the case of B3LYP/6-31G* MK charges, we have improved the EEM parameters for already parameterized elements, specifically C, H, N, O, and F. Moreover, EEM parameters for S, Br, Cl, and Zn, which have not as yet been parameterized for this level of theory and basis set, we also developed. In the case of HF/6-31G* MK charges, we have developed the EEM parameters for C, H, N, O, S, Br, Cl, F, and Zn that have not been parameterized for this level of theory and basis set so far. The obtained EEM parameters were verified by a previously developed validation procedure and used for the charge calculation on a different set of 116 organic molecules from the CSD. The calculated EEM charges are in a very good agreement with the quantum mechanically obtained ab initio charges. 2008 Wiley Periodicals, Inc.

  15. Inorganic bromine in organic molecular crystals: Database survey and four case studies

    NASA Astrophysics Data System (ADS)

    Nemec, Vinko; Lisac, Katarina; Stilinović, Vladimir; Cinčić, Dominik

    2017-01-01

    We present a Cambridge Structural Database and experimental study of multicomponent molecular crystals containing bromine. The CSD study covers supramolecular behaviour of bromide and tribromide anions as well as halogen bonded dibromine molecules in crystal structures of organic salts and cocrystals, and a study of the geometries and complexities in polybromide anion systems. In addition, we present four case studies of organic structures with bromide, tribromide and polybromide anions as well as the neutral dibromine molecule. These include the first observed crystal with diprotonated phenazine, a double salt of phenazinium bromide and tribromide, a cocrystal of 4-methoxypyridine with the neutral dibromine molecule as a halogen bond donor, as well as bis(4-methoxypyridine)bromonium polybromide. Structural features of the four case studies are in the most part consistent with the statistically prevalent behaviour indicated by the CSD study for given bromine species, although they do exhibit some unorthodox structural features and in that indicate possible supramolecular causes for aberrations from the statistically most abundant (and presumably most favourable) geometries.

  16. Organic Chemistry of Southern Sources: Microwave Spectroscopy of Cha-MMS1 and IRAS 15194-5115

    NASA Technical Reports Server (NTRS)

    Cordiner, Martin; Charnley, Steven

    2011-01-01

    We report new spectra of molecule-rich sources in the southern hemisphere obtained using the 22-meter Mopra telescope. Spectra and maps are presented of organic molecules detected between 30 and 50 GHz in the young Class 0 protostar Chamaeleon MMS-1. The large abundances of polyynes, cyanopolyynes and methanol may be indicative of a warm carbon chemistry in the dense gas surrounding this protostar. Spectra are also presented from a 78-96 GHz scan of the carbon-rich AGB star IRAS 15194-5115, including new detections of HC5N, CCS and C13CH.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Thermodynamic characteristics of the adsorption of organic molecules on modified MCM-41 adsorbents

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Sukhareva, D. A.; Salikhova, G. R.; Karpov, S. I.; Kudasheva, F. Kh.; Roessner, F.; Borodina, E. V.

    2017-07-01

    The adsorption of a number of organic molecules on samples of MCM-41 adsorbent modified with dichloromethylphenylsilane and subsequently treated with sulfuric acid (MDCS) and N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride (MNM) is studied. Specific retention volumes equal to the Henry constant are determined by means of inverse gas chromatography at infinite dilution. The thermodynamic characteristics of adsorption, the dispersive and specific components of the Helmholtz energy of adsorption, and the increment of the methyl group to the heat of adsorption are calculated. It is shown that the grafting of aminosilane and phenylsilane groups enhances the forces of dispersion and reduces specific interactions. A greater drop in polarity is observed for MDCS than for MNM, due to the stronger polarity of amoinosilane; the enthalpy factor makes the main contribution to the adsorption of organic compounds on the investigated adsorbents. It is found that the MNM sample is capable of the irreversible adsorption of alcohols.

  19. The synthesis and properties of linear A-π-D-π-A type organic small molecule containing diketopyrrolopyrrole terminal units.

    PubMed

    Zhang, Shanshan; Niu, Qingfen; Sun, Tao; Li, Yang; Li, Tianduo; Liu, Haixia

    2017-08-05

    A novel linear A-π-D-π-A-type organic small molecule Ph2(PDPP) 2 consisting diketopyrrolopyrrole (DPP) as acceptor unit, biphenylene as donor unit and acetylene unit as π-linkage has been successfully designed and synthesized. Its corresponding thermal, photophysical and electrochemical properties as well as the photoinduced charge-separation process were investigated. Ph2(PDPP) 2 exhibits high thermal stability and it can be soluble in common organic solvents such as chloroform and tetrahydrofuran. The photophysical properties show that DPP 2 Ph 2 harvests sunlight over the entire visible spectrum range in the thin-film state (300-800nm). DPP 2 Ph 2 has lower band gaps and appropriate energy levels to satisfy the requirement of solution-processable organic solar cells. The efficient photoinduced charge separation process was clearly observed between DPP 2 Ph 2 with PC 61 BM and the K sv value was found to be as high as 2.13×10 4 M -1 . Therefore, these excellent properties demonstrate that the designed A-π-D-π-A-type small molecule Ph2(PDPP) 2 is the prospective candidate as donor material for organic photovoltaic material. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Tracing the Origins of Nitrogen Bearing Organics Toward Orion KL with Alma

    NASA Astrophysics Data System (ADS)

    Carroll, Brandon; Crockett, Nathan; Bergin, Edwin; Blake, Geoffrey

    2016-06-01

    A comprehensive analysis of a broadband 1.2 THz wide spectral survey of the Orion Kleinmann-Low nebula (Orion KL) from the Herschel Space Telescope has shown that nitrogen bearing complex organics trace systematically hotter gas than O-bearing organics toward this source. The origin of this O/N dichotomy remains a mystery. If complex molecules originate from grain surfaces, N-bearing species may be more difficult to remove from grain surfaces than O-bearing organics. Theoretical studies, however, have shown that hot (T=300 K) gas phase chemistry can produce high abundances of N-bearing organics while suppressing the formation of O-bearing complex molecules. In order to distinguish these distinct formation pathways we have obtained extremely high angular resolution observations of methyl cyanide (CH_3CN) using the Atacama Large Millimeter/Submillimeter Array (ALMA) toward Orion KL. By simultaneously imaging 13CH_3CN and CH_2DCN we map the temperature structure and D/H ratio of CH_3CN. We will present the initial results of these observations and discuss their implications for the formation of N-bearing organics in the interstellar medium.

  2. Melt-processing of small molecule organic photovoltaics via bulk heterojunction compatibilization.

    PubMed

    Rahmanudin, Aiman; Yao, Liang; Jeanbourquin, Xavier A; Liu, Yongpeng; Sekar, Arvindh; Ripaud, Emilie; Sivula, Kevin

    2018-05-21

    Melt-processing of organic semiconductors (OSCs) is a promising environmentally-friendly technique that can alleviate dependence on toxic chlorinated solvents. While melt-processed single-component OSC devices ( e.g. field-effect-transistors) have been demonstrated, multi-component bulk heterojunctions (BHJs) for organic photovoltaics (OPVs) remain a challenge. Herein, we demonstrate a strategy that affords tunable BHJ phase segregation and domain sizes from a single-phase homogeneous melt by employing strongly-crystalline small-molecule OSCs together with a customized molecular compatibilizing (MCP) additive. An optimized photoactive BHJ with 50 wt% MCP achieved a device power conversion efficiency of ca. 1% after melting the active layer at 240 °C (15 min, followed by slow cooling) before deposition of the top electrode. BHJ morphology characterization using atomic force and Kelvin probe microscopy, X-ray diffraction, and photo-luminescence measurements further demonstrate the trade-off between free charge generation and transport with respect to MCP loading in the BHJ. In addition, a functional OPV was also obtained from the melt-processing of dispersed micron-sized solid BHJ particles into a smooth and homogeneous thin-film by using the MCP approach. These results demonstrate that molecular compatibilization is a key prerequisite for further developments towards true solvent-free melt-processed BHJ OPV systems.

  3. Modeling CO, CO2, and H2O Ice Abundances in the Envelopes of Young Stellar Objects in the Magellanic Clouds

    NASA Astrophysics Data System (ADS)

    Pauly, Tyler; Garrod, Robin T.

    2018-02-01

    Massive young stellar objects (MYSOs) in the Magellanic Clouds show infrared absorption features corresponding to significant abundances of CO, CO2, and H2O ice along the line of sight, with the relative abundances of these ices differing between the Magellanic Clouds and the Milky Way. CO ice is not detected toward sources in the Small Magellanic Cloud, and upper limits put its relative abundance well below sources in the Large Magellanic Cloud and the Milky Way. We use our gas-grain chemical code MAGICKAL, with multiple grain sizes and grain temperatures, and further expand it with a treatment for increased interstellar radiation field intensity to model the elevated dust temperatures observed in the MCs. We also adjust the elemental abundances used in the chemical models, guided by observations of H II regions in these metal-poor satellite galaxies. With a grid of models, we are able to reproduce the relative ice fractions observed in MC MYSOs, indicating that metal depletion and elevated grain temperature are important drivers of the MYSO envelope ice composition. Magellanic Cloud elemental abundances have a subgalactic C/O ratio, increasing H2O ice abundances relative to the other ices; elevated grain temperatures favor CO2 production over H2O and CO. The observed shortfall in CO in the Small Magellanic Cloud can be explained by a combination of reduced carbon abundance and increased grain temperatures. The models indicate that a large variation in radiation field strength is required to match the range of observed LMC abundances. CH3OH abundance is found to be enhanced in low-metallicity models, providing seed material for complex organic molecule formation in the Magellanic Clouds.

  4. viral abundance distribution in deep waters of the Northern of South China Sea

    NASA Astrophysics Data System (ADS)

    He, Lei; Yin, Kedong

    2017-04-01

    Little is known about the vertical distribution and interaction of viruses and bacteria in the deep ocean water column. The vertical distribution of viral-like particles and bacterial abundance was investigated in the deep water column in the South China Sea during September 2005 along with salinity, temperature and dissolved oxygen. There were double maxima in the ratio of viral to bacterial abundance (VBR) in the water column: the subsurface maximum located at 50-100 m near the pycnocline layer, and the deep maximum at 800-1000 m. At the subsurface maximum of VBR, both viral and bacterial abundance were maximal in the water column, and at the deep maximum of VBR, both viral and bacterial abundance were low, but bacterial abundance was relatively lower than viral abundance. The subsurface VBR maximum coincided with the subsurface chlorophyll maximum while the deep VBR maximum coincided with the minimum in dissolved oxygen (2.91mg L-1). Therefore, we hypothesize that the two maxima were formed by different mechanisms. The subsurface VBR maximum was formed due to an increase in bacterial abundance resulting from the stimulation of abundant organic supply at the subsurface chlorophyll maximum, whereas the deep VBR maximum was formed due to a decrease in bacterial abundance caused by more limitation of organic matter at the oxygen minimum. The evidence suggests that viruses play an important role in controlling bacterial abundance in the deep water column due to the limitation of organic matter supply. In turn, this slows down the formation of the oxygen minimum in which oxygen may be otherwise lower. The mechanism has a great implication that viruses could control bacterial decomposition of organic matter, oxygen consumption and nutrient remineralization in the deep oceans.

  5. Measuring molecular abundances in comet C/2014 Q2 (Lovejoy) using the APEX telescope

    NASA Astrophysics Data System (ADS)

    de Val-Borro, M.; Milam, S. N.; Cordiner, M. A.; Charnley, S. B.; Coulson, I. M.; Remijan, A. J.; Villanueva, G. L.

    2018-02-01

    Comet composition provides critical information on the chemical and physical processes that took place during the formation of the Solar system. We report here on millimetre spectroscopic observations of the long-period bright comet C/2014 Q2 (Lovejoy) using the Atacama Pathfinder Experiment (APEX) band 1 receiver between 2015 January UT 16.948 and 18.120, when the comet was at heliocentric distance of 1.30 au and geocentric distance of 0.53 au. Bright comets allow for sensitive observations of gaseous volatiles that sublimate in their coma. These observations allowed us to detect HCN, CH3OH (multiple transitions), H2CO and CO, and to measure precise molecular production rates. Additionally, sensitive upper limits were derived on the complex molecules acetaldehyde (CH3CHO) and formamide (NH2CHO) based on the average of the strongest lines in the targeted spectral range to improve the signal-to-noise ratio. Gas production rates are derived using a non-LTE molecular excitation calculation involving collisions with H2O and radiative pumping that becomes important in the outer coma due to solar radiation. We find a depletion of CO in C/2014 Q2 (Lovejoy) with a production rate relative to water of 2.0 per cent, and relatively low abundances of Q(HCN)/Q(H2O), 0.1 per cent, and Q(H2CO)/Q(H2O), 0.2 per cent. In contrast, the CH3OH relative abundance Q(CH3OH)/Q(H2O), 2.2 per cent, is close to the mean value observed in other comets. The measured production rates are consistent with values derived for this object from other facilities at similar wavelengths taking into account the difference in the fields of view. Based on the observed mixing ratios of organic molecules in four bright comets including C/2014 Q2, we find some support for atom addition reactions on cold dust being the origin of some of the molecules.

  6. Robust and Porous β-Diketiminate-Functionalized Metal–Organic Frameworks for Earth-Abundant-Metal-Catalyzed C–H Amination and Hydrogenation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Thacker, Nathan C.; Lin, Zekai; Zhang, Teng

    We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp 3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp 3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity.more » Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.« less

  7. Distribution and Abundance of Hopanoid Producers in Low-Oxygen Environments of the Eastern Pacific Ocean.

    PubMed

    Kharbush, Jenan J; Kejriwal, Kanchi; Aluwihare, Lihini I

    2016-02-01

    Hopanoids are bacterial membrane lipid biomarker molecules that feature prominently in the molecular fossil record. In the modern marine water column, recent reports implicate bacteria inhabiting low-oxygen environments as important sources of hopanoids to marine sediments. However, the preliminary biogeography reported by recent studies and the environmental conditions governing such distributions can only be confirmed when the numerical abundance of these organisms is known with more certainty. In this study, we employ two different approaches to examine the quantitative significance of phylogenetically distinct hopanoid producers in low-oxygen environments. First, we develop a novel quantitative PCR (qPCR) assay for the squalene hopene cyclase (sqhC) gene, targeting a subset of hopanoid producers previously identified to be important in the eastern North Pacific Ocean. The results represent the first quantitative gene abundance data of any kind for hopanoid producers in the marine water column and show that these putative alphaproteobacterial hopanoid producers are rare, comprising at most 0.2 % of the total bacterial community in our samples. Second, a complementary analysis of existing low-oxygen metagenomic datasets further examined the generality of the qPCR observation. We find that the dominant sqhC sequences in these metagenomic datasets are associated with phyla such as Nitrospinae rather than Proteobacteria, consistent with the qPCR finding that alphaproteobacterial hopanoid producers are not very abundant in low-oxygen environments. In fact, positive correlations between sqhC gene abundance and environmental parameters in these samples identify nitrite availability as a potentially important factor in the ecology of hopanoid producers that dominate low-oxygen environments.

  8. Electrochemical Detection of the Molecules of Life

    NASA Technical Reports Server (NTRS)

    Thomson, Seamus; Quinn, Richard; Koehne, Jessica

    2017-01-01

    All forms of life on Earth contain cellular machinery that can transform and regulate chemical energy through metabolic pathways. These processes are oxidation-reduction reactions that are performed by four key classes of molecules: flavins, nicotinamaides, porphyrins, and quinones. By detecting the electrochemical interaction of these redox-active molecules with an electrode, a method of differentiating them by their class could be established and incorporated into future life-detecting missions. This body of work investigates the electrochemistry of ubiquitous molecules found in life and how they may be detected. Molecules can oxidise or reduce the surface of an electrode - giving or receiving electrons - and these interactions are represented by changes in current with respect to an applied voltage. This relationship varies with: electrolyte type and concentration, working electrode material, the redox-active molecule itself, and scan rate. Flavin adenine dinucleotide (FAD), riboflavin, nicotinamide adenine dinucleotide (NADH), and anthraquinone are all molecules found intracellularly in almost all living organisms. An organism-synthesised extracellular redox-active molecule, Plumbagin, was also selected as part of this study. The goal of this work is to detect these molecules in seawater and assess its application in searching for life on Ocean Worlds.

  9. Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks.

    PubMed

    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. Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal–Organic Frameworks

    PubMed Central

    2017-01-01

    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 I2 adsorption in a series of robust porous metal–organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g–1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 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–I2 and I2–I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H–O = 2.263(9) Å] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) Å]. I2II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm–3 in MFM-300(Sc). PMID:29020767

  11. Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal–Organic Frameworks

    DOE PAGES

    Zhang, Xinran; da Silva, Ivan; Godfrey, Harry G. W.; ...

    2017-10-11

    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 andmore » 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).« less

  12. Solar Coronal and photospheric abundances from solar energetic particle measurements

    NASA Technical Reports Server (NTRS)

    Breneman, H.; Stone, E. C.

    1985-01-01

    Solar energetic particle (SEP) elemental abundance data from the cosmic ray subsystem (CRS) aboard the Voyager 1 and 2 spacecraft are used to derive unfractionated coronal and photospheric abundances for elements with 3 Z or = 30. It is found that the ionic charge-to-mass ratio (Q/M) is the principal organizing parameter for the fractionation of SEPs by acceleration and propagation processes and for flare-to-flare variability, making possible a single-parameter Q/M-dependent correction to the average SEP abundances to obtain unfractionated coronal abundances. A further correction based on first ionization potential allows the determination of unfractionated photospheric abundances.

  13. Solar coronal and photospheric abundances from solar energetic particle measurements

    NASA Technical Reports Server (NTRS)

    Breneman, H. H.; Stone, E. C.

    1985-01-01

    Solar energetic particle (SEP) elemental abundance data from the cosmic ray subsystem (CRS) aboard the Voyager 1 and 2 spacecraft are used to derive unfractionated coronal and photospheric abundances for elements with Z = 6-30. It is found that the ionic charge-to-mass ratio (Q/M) is the principal organizing parameter for the fractionation of SEPs by acceleration and propagation processes and for flare-to-flare variability, making possible a single-parameter Q/M-dependent correction to the average SEP abundances to obtain unfractionated coronal abundances. A further correction based on first ionization potential allows the determination of unfractionated photospheric abundances.

  14. Solar coronal and photospheric abundances from solar energetic particle measurements

    NASA Technical Reports Server (NTRS)

    Breneman, H.; Stone, E. C.

    1985-01-01

    Solar energetic particle (SEP) elemental abundance data from the Cosmic Ray Subsystem (CRS) aboard the Voyager 1 and 2 spacecraft are used to derive unfractionated coronal and photospheric abundances for elements with 3 = or Z or = 30. The ionic charge-to-mass ratio (Q/M) is the principal organizing parameter for the fractionation of SEPs by acceleration and propagation processes and for flare-to-flare variability, making possible a single-parameter Q/M-dependent correction to the average SEP abundances to obtain unfractionated coronal abundances. A further correction based on first ionization potential allows the determination of unfractionated photospheric abundances.

  15. Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules

    PubMed Central

    Kee, Terence P.; Bryant, David E.; Herschy, Barry; Marriott, Katie E. R.; Cosgrove, Nichola E.; Pasek, Matthew A.; Atlas, Zachary D.; Cousins, Claire R.

    2013-01-01

    The emergence of mechanisms for phosphorylating organic and inorganic molecules is a key step en route to the earliest living systems. At the heart of all contemporary biochemical systems reside reactive phosphorus (P) molecules (such as adenosine triphosphate, ATP) as energy currency molecules to drive endergonic metabolic processes and it has been proposed that a predecessor of such molecules could have been pyrophosphate [P2O74−; PPi(V)]. Arguably the most geologically plausible route to PPi(V) is dehydration of orthophosphate, Pi(V), normally a highly endergonic process in the absence of mechanisms for activating Pi(V). One possible solution to this problem recognizes the presence of reactive-P containing mineral phases, such as schreibersite [(Fe,Ni)3P] within meteorites whose abundance on the early Earth would likely have been significant during a putative Hadean-Archean heavy bombardment. Here, we propose that the reduced oxidation state P-oxyacid, H-phosphite [HPO32−; Pi(III)] could have activated Pi(V) towards condensation via the intermediacy of the condensed oxyacid pyrophosphite [H2P2O52−; PPi(III)]. We provide geologically plausible provenance for PPi(III) along with evidence of its ability to activate Pi(V) towards PPi(V) formation under mild conditions (80 °C) in water. PMID:25369812

  16. Organic Nanoflowers from a Wide Variety of Molecules Templated by a Hierarchical Supramolecular Scaffold.

    PubMed

    Negrón, Luis M; Díaz, Tanya L; Ortiz-Quiles, Edwin O; Dieppa-Matos, Diómedes; Madera-Soto, Bismark; Rivera, José M

    2016-03-15

    Nanoflowers (NFs) are flowered-shaped particles with overall sizes or features in the nanoscale. Beyond their pleasing aesthetics, NFs have found a number of applications ranging from catalysis, to sensing, to drug delivery. Compared to inorganic based NFs, their organic and hybrid counterparts are relatively underdeveloped mostly because of the lack of a reliable and versatile method for their construction. We report here a method for constructing NFs from a wide variety of biologically relevant molecules (guests), ranging from small molecules, like doxorubicin, to biomacromolecules, like various proteins and plasmid DNA. The method relies on the encapsulation of the guests within a hierarchically structured particle made from supramolecular G-quadruplexes. The size and overall flexibility of the guests dictate the broad morphological features of the resulting NFs, specifically, small and rigid guests favor the formation of NFs with spiky petals, while large and/or flexible guests promote NFs with wide petals. The results from experiments using confocal fluorescence microscopy, and scanning electron microscopy provides the basis for the proposed mechanism for the NF formation.

  17. Controlling the Morphology of BDTT-DPP-Based Small Molecules via End-Group Functionalization for Highly Efficient Single and Tandem Organic Photovoltaic Cells.

    PubMed

    Kim, Ji-Hoon; Park, Jong Baek; Yang, Hoichang; Jung, In Hwan; Yoon, Sung Cheol; Kim, Dongwook; Hwang, Do-Hoon

    2015-11-04

    A series of narrow-band gap, π-conjugated small molecules based on diketopyrrolopyrrole (DPP) electron acceptor units coupled with alkylthienyl-substituted-benzodithiophene (BDTT) electron donors were designed and synthesized for use as donor materials in solution-processed organic photovoltaic cells. In particular, by end-group functionalization of the small molecules with fluorine derivatives, the nanoscale morphologies of the photoactive layers of the photovoltaic cells were successfully controlled. The influences of different fluorine-based end-groups on the optoelectronic and morphological properties, carrier mobilities, and the photovoltaic performances of these materials were investigated. A high power conversion efficiency (PCE) of 6.00% under simulated solar light (AM 1.5G) illumination has been achieved for organic photovoltaic cells based on a small-molecule bulk heterojunction system consisting of a trifluoromethylbenzene (CF3) end-group-containing oligomer (BDTT-(DPP)2-CF3) as the donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor. As a result, the introduction of CF3 end-groups has been found to enhance both the short circuit current density (JSC) and fill factor (FF). A tandem photovoltaic device comprising an inverted BDTT-(DPP)2-CF3:PC71BM cell and a poly(3-hexylthiophene) (P3HT):indene-C60-bisadduct (IC60BA)-based cell as the top and bottom cell components, respectively, showed a maximum PCE of 8.30%. These results provide valuable guidelines for the rational design of conjugated small molecules for applications in high-performance organic photovoltaic cells. Furthermore, to the best of our knowledge, this is the first report on the design of fluorine-functionalized BDTT-DPP-based small molecules, which have been shown to be a viable candidate for use in inverted tandem cells.

  18. Investigating the Crystallization Propensity of Structurally Similar Organic Molecules From Amorphous State

    NASA Astrophysics Data System (ADS)

    Kalra, Arjun

    Combinatorial chemistry and high-throughput screening approaches utilized during drug discovery have resulted in many potent pharmacologically active molecules with low aqueous solubility and consequently poor bioavailability. Enabling technologies, such as amorphous solid dispersions (ASD's), can obviate these challenges and provide an efficient route to formulate the drug as an oral solid dosage form. However, high-energy amorphous materials have an inherent tendency to crystallize and in doing so can negate the apparent solubility advantage achieved by using such formulations. Crystallization can occur during (1) cooling the drug molecule from the melt state (such as during hot melt extrusion); (2) during storage of an amorphous formulation; (3) during pharmaceutical processing unit operations such as compression, granulation etc. Current knowledge with regards to the relationship between crystallization propensity of an active pharmaceutical ingredient (API) from the amorphous state (supercooled liquid and glass) and its thermodynamic, kinetic and molecular properties is limited. Furthermore, examining the mechanistic steps involved in crystallization of organic molecules under conditions of supercooling provides an opportunity to examine supramolecular aggregation events occurring during early stages of crystallization. Studying crystallization mechanism from amorphous state is important for pharmaceutical formulation development because a molecular-level understanding of the crystallization process would provide clues regarding the intermolecular interactions at the early stages of nucleation and help in rational selection of polymeric excipients to hinder such events. The primary goal of this research is to develop an understanding of phase transition from amorphous pharmaceuticals, specifically focusing on the role of thermodynamic, kinetic and molecular properties of a series of structurally similar compounds. It is hypothesized that the there exists a

  19. Comparative Study of Human and Mouse Postsynaptic Proteomes Finds High Compositional Conservation and Abundance Differences for Key Synaptic Proteins

    PubMed Central

    Bayés, Àlex; Collins, Mark O.; Croning, Mike D. R.; van de Lagemaat, Louie N.; Choudhary, Jyoti S.; Grant, Seth G. N.

    2012-01-01

    Direct comparison of protein components from human and mouse excitatory synapses is important for determining the suitability of mice as models of human brain disease and to understand the evolution of the mammalian brain. The postsynaptic density is a highly complex set of proteins organized into molecular networks that play a central role in behavior and disease. We report the first direct comparison of the proteome of triplicate isolates of mouse and human cortical postsynaptic densities. The mouse postsynaptic density comprised 1556 proteins and the human one 1461. A large compositional overlap was observed; more than 70% of human postsynaptic density proteins were also observed in the mouse postsynaptic density. Quantitative analysis of postsynaptic density components in both species indicates a broadly similar profile of abundance but also shows that there is higher abundance variation between species than within species. Well known components of this synaptic structure are generally more abundant in the mouse postsynaptic density. Significant inter-species abundance differences exist in some families of key postsynaptic density proteins including glutamatergic neurotransmitter receptors and adaptor proteins. Furthermore, we have identified a closely interacting set of molecules enriched in the human postsynaptic density that could be involved in dendrite and spine structural plasticity. Understanding synapse proteome diversity within and between species will be important to further our understanding of brain complexity and disease. PMID:23071613

  20. Inorganic and organic fertilizers impact the abundance and proportion of antibiotic resistance and integron-integrase genes in agricultural grassland soil.

    PubMed

    Nõlvak, Hiie; Truu, Marika; Kanger, Kärt; Tampere, Mailiis; Espenberg, Mikk; Loit, Evelin; Raave, Henn; Truu, Jaak

    2016-08-15

    Soil fertilization with animal manure or its digestate may facilitate an important antibiotic resistance dissemination route from anthropogenic sources to the environment. This study examines the effect of mineral fertilizer (NH4NO3), cattle slurry and cattle slurry digestate amendment on the abundance and proportion dynamics of five antibiotic resistance genes (ARGs) and two classes of integron-integrase genes (intI1 and intI2) in agricultural grassland soil. Fertilization was performed thrice throughout one vegetation period. The targeted ARGs (sul1, tetA, blaCTX-M, blaOXA2 and qnrS) encode resistance to several major antibiotic classes used in veterinary medicine such as sulfonamides, tetracycline, cephalosporins, penicillin and fluoroquinolones, respectively. The non-fertilized grassland soil contained a stable background of tetA, blaCTX-M and sul1 genes. The type of applied fertilizer significantly affected ARGs and integron-integrase genes abundances and proportions in the bacterial community (p<0.001 in both cases), explaining 67.04% of the abundance and 42.95% of the proportion variations in the grassland soil. Both cattle slurry and cattle slurry digestate proved to be considerable sources of ARGs, especially sul1, as well as integron-integrases. Sul1, intI1 and intI2 levels in grassland soil were elevated in response to each organic fertilizer's application event, but this increase was followed by a stage of decrease, suggesting that microbes possessing these genes were predominantly entrained into soil via cattle slurry or its digestate application and had somewhat limited survival potential in a soil environment. However, the abundance of these three target genes did not decrease to a background level by the end of the study period. TetA was most abundant in mineral fertilizer treated soil and blaCTX-M in cattle slurry digestate amended soil. Despite significantly different abundances, the abundance dynamics of bacteria possessing these genes were

  1. Soil compaction and organic matter affect conifer seedling nonmycorrhizal and ectomycorrhizal root tip abundance and diversity. Forest Service research paper

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Amaranthus, M.P.; Page-Dumroese, D.; Harvey, A.

    1996-05-01

    Three levels of organic matter removal (bole only; bole and crowns; and bole, crowns, and forest floor) and three levels of mechanical soil compaction (no compaction, moderate compaction, and severe soil compaction) were studied as they influence Douglas-fir (Pseudotsuga menziesii var. glauca (Beissn.) Franco) and western white pine (Pinus monticola Dougl. ex D. Don) seedlings following outplanting. Moderate and severe soil compaction significantly reduced nonmycorrhizal root tip abundance on both Douglas-fir and western white pine seedlings (p less than or equal to 0.05). Ectomycorrhizal root tip abundance was significantly reduced on Douglas-fir seedlings in severely compacted areas with bole andmore » crowns and bole, crowns, and forest floor removed. Ectomycorrhizal diversity also was significantly reduced on Douglas-fir seedlings in all severely compacted areas.« less

  2. Stability of metal organic frameworks and interaction of small gas molecules in these materials

    NASA Astrophysics Data System (ADS)

    Tan, Kui

    The work in this dissertation combines spectroscopy ( in-situ infrared absorption and Raman), powder X-ray diffraction and DFT calculations to study the stability of metal organic frameworks materials (MOFs) in the presence of water vapor and other corrosive gases (e.g., SO 2, NO2 NO), and the interaction and competitive co-adsorption of several gases within MOFs by considering two types of prototypical MOFs: 1) a MOF with saturated metal centers based on paddlewheel secondary building units: M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co, bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine], and 2) a MOF with unsaturated metal centers: M2(dobdc) [M=Mg2+, Zn2+, Ni2+, Co2+ and dobdc = 2,5-dihydroxybenzenedicarboxylate]. We find that the stability of MOFs to water vapor critically depends on their structure and the specific metal cation in the building units. For M(bdc)(ted)0.5, the metal-bdc bond is the most vulnerable for Cu(bdc)(ted)0.5, while the metal-ted bond is first attacked for the Zn and Co analogs. In contrast, Ni(bdc)(ted)0.5 remains stable under the same conditions. For M2(dobdc), or MOF-74, the weak link is the dobdc-metal bond. The water molecule is dissociatively adsorbed at the metal-oxygen group with OH adsorption directly on the metal center and H adsorption on the bridging O of the phenolate group in the dobdc linker. Other technologically important molecules besides water, such as NO, NO2, SO2, tend to poison M2(dobdc) through dissociative or molecular adsorption onto the open metal sites. A high uptake SO2 capacity was measured in M(bdc)(ted)0.5, attributed to multipoint interactions between the guest SO2 molecule and the MOF host. In the case of competitive co-adsorption between CO2 and other small molecules, we find that binding energy alone is not a good indicator of molecular site occupation within the MOF (i.e., it cannot successfully predict and evaluate the displacement of CO2 by other molecules). Instead, we show that the kinetic barrier for the

  3. Structural interaction fingerprints: a new approach to organizing, mining, analyzing, and designing protein-small molecule complexes.

    PubMed

    Singh, Juswinder; Deng, Zhan; Narale, Gaurav; Chuaqui, Claudio

    2006-01-01

    The combination of advances in structure-based drug design efforts in the pharmaceutical industry in parallel with structural genomics initiatives in the public domain has led to an explosion in the number of structures of protein-small molecule complexes structures. This information has critical importance to both the understanding of the structural basis for molecular recognition in biological systems and the design of better drugs. A significant challenge exists in managing this vast amount of data and fully leveraging it. Here, we review our work to develop a simple, fast way to store, organize, mine, and analyze large numbers of protein-small molecule complexes. We illustrate the utility of the approach to the management of inhibitor complexes from the protein kinase family. Finally, we describe our recent efforts in applying this method to the design of target-focused chemical libraries.

  4. Linear Ion Traps in Space: The Mars Organic Molecule Analyzer (MOMA) Instrument and Beyond

    NASA Astrophysics Data System (ADS)

    Arevalo, Ricardo; Brinckerhoff, William; Mahaffy, Paul; van Amerom, Friso; Danell, Ryan; Pinnick, Veronica; Li, Xiang; Hovmand, Lars; Getty, Stephanie; Grubisic, Andrej; Goesmann, Fred; Cottin, Hervé

    2015-11-01

    Historically, quadrupole mass spectrometer (QMS) instruments have been used to explore a wide survey of planetary targets in our solar system, from Venus (Pioneer Venus) to Saturn (Cassini-Huygens). However, linear ion trap (LIT) mass spectrometers have found a niche as smaller, versatile alternatives to traditional quadrupole analyzers.The core astrobiological experiment of ESA’s ExoMars Program is the Mars Organic Molecule Analyzer (MOMA) onboard the ExoMars 2018 rover. The MOMA instrument is centered on a linear (or 2-D) ion trap mass spectrometer. As opposed to 3-D traps, LIT-based instruments accommodate two symmetrical ion injection pathways, enabling two complementary ion sources to be used. In the case of MOMA, these two analytical approaches are laser desorption mass spectrometry (LDMS) at Mars ambient pressures, and traditional gas chromatography mass spectrometry (GCMS). The LIT analyzer employed by MOMA also offers: higher ion capacity compared to a 3-D trap of the same volume; redundant detection subassemblies for extended lifetime; and, a link to heritage QMS designs and assembly logistics. The MOMA engineering test unit (ETU) has demonstrated the detection of organics in the presence of wt.%-levels of perchlorate, effective ion enhancement via stored waveform inverse Fourier transform (SWIFT), and derivation of structural information through tandem mass spectrometry (MS/MS).A more progressive linear ion trap mass spectrometer (LITMS), funded by the NASA ROSES MatISSE Program, is being developed at NASA GSFC and promises to augment the capabilities of the MOMA instrument by way of: an expanded mass range (i.e., 20 - 2000 Da); detection of both positive and negative ions; spatially resolved (<1 mm) characterization of individual rock core layers; and, evolved gas analysis and GCMS with pyrolysis up to 1300° C (enabling breakdown of refractory phases). The Advanced Resolution Organic Molecule Analyzer (AROMA) instrument, being developed through NASA

  5. High mobility high efficiency organic films based on pure organic materials

    DOEpatents

    Salzman, Rhonda F [Ann Arbor, MI; Forrest, Stephen R [Ann Arbor, MI

    2009-01-27

    A method of purifying small molecule organic material, performed as a series of operations beginning with a first sample of the organic small molecule material. The first step is to purify the organic small molecule material by thermal gradient sublimation. The second step is to test the purity of at least one sample from the purified organic small molecule material by spectroscopy. The third step is to repeat the first through third steps on the purified small molecule material if the spectroscopic testing reveals any peaks exceeding a threshold percentage of a magnitude of a characteristic peak of a target organic small molecule. The steps are performed at least twice. The threshold percentage is at most 10%. Preferably the threshold percentage is 5% and more preferably 2%. The threshold percentage may be selected based on the spectra of past samples that achieved target performance characteristics in finished devices.

  6. When 2D Materials Meet Molecules: Opportunities and Challenges of Hybrid Organic/Inorganic van der Waals Heterostructures.

    PubMed

    Gobbi, Marco; Orgiu, Emanuele; Samorì, Paolo

    2018-05-01

    van der Waals heterostructures, composed of vertically stacked inorganic 2D materials, represent an ideal platform to demonstrate novel device architectures and to fabricate on-demand materials. The incorporation of organic molecules within these systems holds an immense potential, since, while nature offers a finite number of 2D materials, an almost unlimited variety of molecules can be designed and synthesized with predictable functionalities. The possibilities offered by systems in which continuous molecular layers are interfaced with inorganic 2D materials to form hybrid organic/inorganic van der Waals heterostructures are emphasized. Similar to their inorganic counterpart, the hybrid structures have been exploited to put forward novel device architectures, such as antiambipolar transistors and barristors. Moreover, specific molecular groups can be employed to modify intrinsic properties and confer new capabilities to 2D materials. In particular, it is highlighted how molecular self-assembly at the surface of 2D materials can be mastered to achieve precise control over position and density of (molecular) functional groups, paving the way for a new class of hybrid functional materials whose final properties can be selected by careful molecular design. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Separation of rare gases and chiral molecules by selective binding in porous organic cages

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Linjiang; Reiss, Paul S.; Chong, Samantha Y.

    2014-10-31

    Abstract: The rare gases krypton, xenon, and radon pose both an economic opportunity and a potential environmental hazard. Xenon is used in commercial lighting, medical imaging, and anesthesia, and can sell for $5,000 per kilogram. Radon, by contrast, Is naturally radioactive and the second largest cause of lung cancer, and radioactive xenon, 133Xe, was a major pollutant released In the Fukushima Daiichi Nuclear Power Plant disaster. We describe an organic cage molecule that can capture xenon and radon with unprecedented selectivity, suggesting new technologies for environmental monitoring, removal of pollutants, or the recovery of rare, valuable elements from air.

  8. CAL3JHH: a Java program to calculate the vicinal coupling constants (3J H,H) of organic molecules.

    PubMed

    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.

  9. Inclusion of Ti and Zr species on clay surfaces and their effect on the interaction with organic molecules

    NASA Astrophysics Data System (ADS)

    Rangel-Rivera, Pedro; Bachiller-Baeza, María Belén; Galindo-Esquivel, Ignacio; Rangel-Porras, Gustavo

    2018-07-01

    The interactions between the clay surface and the organic molecules play an important role in the efficient of these materials in adsorption and catalytic processes. These materials are often modified with the inclusion of other catalytic particles for the purpose of enhancing the activity. In this study, commercial clay K10 was modified with the particles inclusion of titanium and zirconium. The solid surfaces were examined by infrared spectroscopy, scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectroscopy device (EDS), and X-ray photoelectron spectroscopy (XPS). Temperature programmed desorption of ammonia (TPD-NH3) and propan-2-ol decomposition test reaction were performed to probe the acid properties. The adsorption of acetic acid, ethanol, and propan-2-ol on the surface of each solid and their thermal stability were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). Finally, these materials were used in the esterification of acetic acid with penta-1-ol. The real effect over the incorporation of titanium species and zirconium species on clay surface for interacting with the organic molecules was discussed.

  10. Comparison of meiofaunal abundance in two mangrove wetlands in Tong'an Bay, Xiamen, China

    NASA Astrophysics Data System (ADS)

    Zhou, Xiping; Cai, Lizhe; Fu, Sujing

    2015-10-01

    To compare meiofaunal community in the two mangrove wetlands in Tong'an Bay, Xiamen, China, and probe the response of meiofauna to high organic matter, sampling was carried out in Fenglin and Xiang'an mangrove wetlands in the bay. The results showed that the Ne/Co ratio (nematode to benthic copepod) and organic matter in Fenglin mangrove wetland were higher than those in Xiang'an mangrove wetland. The meiofaunal abundance in Fenglin mangrove was all lower than that in Xiang'an mangrove wetland in summer, autumn and spring, while the meiofaunal abundance in Fenglin mangrove was higher than that in Xiang'an mangrove wetland in winter. Two-way ANOVA results showed that the meiofaunal abundance and nematode abundance were significantly different between regions, seasons and region×season. With all the results in the present study, we confirmed that the positive response of meiofaunal and nematode abundance were only detected for medium organic matter contents according to the Xiang'an wetland's level, and that the distribution of meiofaunal abundance would be influenced by sand content. Higher copepod abundance and lower N/C value usually suggest better environmental quality.

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

    PubMed

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

    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 100-6000mgcarbonL(-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). Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Conjugated-Backbone Effect of Organic Small Molecules for n-Type Thermoelectric Materials with ZT over 0.2.

    PubMed

    Huang, Dazhen; Yao, Huiying; Cui, Yutao; Zou, Ye; Zhang, Fengjiao; Wang, Chao; Shen, Hongguang; Jin, Wenlong; Zhu, Jia; Diao, Ying; Xu, Wei; Di, Chong-An; Zhu, Daoben

    2017-09-20

    Conjugated backbones play a fundamental role in determining the electronic properties of organic semiconductors. On the basis of two solution-processable dihydropyrrolo[3,4-c]pyrrole-1,4-diylidenebis(thieno[3,2-b]thiophene) derivatives with aromatic and quinoid structures, we have carried out a systematic study of the relationship between the conjugated-backbone structure and the thermoelectric properties. In particular, a combination of UV-vis-NIR spectra, photoemission spectroscopy, and doping optimization are utilized to probe the interplay between energy levels, chemical doping, and thermoelectric performance. We found that a moderate change in the conjugated backbone leads to varied doping mechanisms and contributes to dramatic changes in the thermoelectric performance. Notably, the chemically doped A-DCV-DPPTT, a small molecule with aromatic structure, exhibits an electrical conductivity of 5.3 S cm -1 and a high power factor (PF 373 K ) up to 236 μW m -1 K -2 , which is 50 times higher than that of Q-DCM-DPPTT with a quinoid structure. More importantly, the low thermal conductivity enables A-DCV-DPPTT to possess a figure of merit (ZT) of 0.23 ± 0.03, which is the highest value reported to date for thermoelectric materials based on organic small molecules. These results demonstrate that the modulation of the conjugated backbone represents a powerful strategy for tuning the electronic structure and mobility of organic semiconductors toward a maximum thermoelectric performance.

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

    PubMed Central

    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.

    2015-01-01

    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) × 1010 cm−2 in TMC-1 and (3.9 ± 1.8) × 1010 cm−2 in L483, which translate to fairly low fractional abundances relative to H2, 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 H2, i.e., comparable to that of other abundant nitriles such as HCN, HNC, and HC3N. PMID:26543239

  14. Sample Analysis at Mars (SAM) and Mars Organic Molecule Analyzer (MOMA) as Critical In Situ Investigation for Targeting Mars Returned Samples

    NASA Astrophysics Data System (ADS)

    Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Szopa, C.; Buch, A.; Goesmann, F.; Goetz, W.; Raulin, F.; SAM Science Team; MOMA Science Team

    2018-04-01

    SAM (Curiosity) and MOMA (ExoMars) Mars instruments, seeking for organics and biosignatures, are essential to establish taphonomic windows of preservation of molecules, in order to target the most interesting samples to return from Mars.

  15. Organic molecules and nanoparticles in inorganic crystals: Vitamin C in CaCO3 as an ultraviolet absorber

    NASA Astrophysics Data System (ADS)

    Sato, H.; Ikeya, M.

    2004-03-01

    Organic molecules and nanoparticles embedded in inorganic crystalline lattices have been studied to add different properties and functions to composite materials. Calcium carbonate was precipitated by dropping an aqueous solution of CaCl2 into that of Na2CO3 containing dissolved vitamin C (ascorbic acid). The optical absorption ascribed to divalent ascorbate anions in the lattice was observed in the ultraviolet B (wavelength: 280-315 nm) region, while solid vitamin C exhibited absorption in the ultraviolet C (100-280 nm) region. The divalent ascorbate anion is only stable in CaCO3 due to the absence of oxygen molecules. Doping CaCO3 with nanoparticles of ZnO also enhanced the absorption in the ultraviolet A (315-380 nm) region. These composite materials are suggested for use as UV absorbers.

  16. A Dual Source Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer of ExoMars 2018

    NASA Technical Reports Server (NTRS)

    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.

  17. Detecting and Identifying Organic Molecules in Space - The AstroBiology Explorer (ABE) MIDEX Mission Concept

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.

    2001-01-01

    Infrared spectroscopy in the 2.5-16 micron (4000-625/cm) range is a principle means by which organic compounds are detected and identified in space. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX (Medium-class Explorer) mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to H II regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. Both the scientific goals of the mission and how they would be achieved will be discussed.

  18. Detecting and Identifying Organic Molecules in Space: The AstroBiology Explorer (ABE) MIDEX Mission Concept

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Infrared spectroscopy in the 2.5-16 microns (4000-625/cm) range is a principle means by which organic compounds are detected and identified in space. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX (Medium-class Explorer) mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to H II regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. Both the scientific goals of the mission and how they would be achieved will be discussed.

  19. Mycosporine-like amino acids are multifunctional molecules in sea hares and their marine community

    PubMed Central

    Kicklighter, Cynthia E.; Kamio, Michiya; Nguyen, Linh; Germann, Markus W.; Derby, Charles D.

    2011-01-01

    Molecules of keystone significance are relatively rare, yet mediate a variety of interactions between organisms. They influence the distribution and abundance of species, the transfer of energy across multiple trophic levels, and thus they play significant roles in structuring ecosystems. Despite their potential importance in facilitating our understanding of ecological systems, only three molecules thus far have been proposed as molecules of keystone significance: saxitoxin and dimethyl sulfide in marine communities and tetrodotoxin in riparian communities. In the course of studying the neuroecology of chemical defenses, we identified three mycosporine-like amino acids (MAAs)—N-ethanol palythine (= asterina-330), N-isopropanol palythine (= aplysiapalythine A), and N-ethyl palythine (= aplysiapalythine B)—as intraspecific alarm cues for sea hares (Aplysia californica). These alarm cues are released in the ink secretion of sea hares and cause avoidance behaviors in neighboring conspecifics. Further, we show that these three bioactive MAAs, two [aplysiapalythine A (APA) and -B (APB)] being previously unknown molecules, are present in the algal diet of sea hares and are concentrated in their defensive secretion as well as in their skin. MAAs are known to be produced by algae, fungi, and cyanobacteria and are acquired by many aquatic animals through trophic interactions. MAAs are widely used as sunscreens, among other uses, but sea hares modify their function to serve a previously undocumented role, as intraspecific chemical cues. Our findings highlight the multifunctionality of MAAs and their role in ecological connectivity, suggesting that they may function as molecules of keystone significance in marine ecosystems. PMID:21709250

  20. Complex molecules in the W51 North region

    NASA Astrophysics Data System (ADS)

    Rong, Jialei; Qin, Sheng-Li; Zapata, Luis A.; Wu, Yuefang; Liu, Tie; Zhang, Chengpeng; Peng, Yaping; Zhang, Li; Liu, Ying

    2016-01-01

    We present Submillimeter Array (SMA) molecular-line observations in two 2-GHz wide bands centred at 217.5 and 227.5 GHz, towards the massive star-forming region W51 North. We identified 84 molecular-line transitions from 17 species and their isotopologues. The molecular gas distribution of these lines mainly peaks in the continuum position of W51 North, and has a small tail extending to the west, probably associated with W51 d2. In addition to the commonly detected nitrogen- and oxygen-bearing species, we detected a large number of transitions of acetone (CH3COCH3) and methyl formate (CH3OCHO), which might suggest that these molecules are present in an early evolutionary stage of massive stars. We have also found that W51 North is an ethanol-rich source. There is no obvious difference in the molecular gas distributions between the oxygen-bearing and nitrogen-bearing molecules. Under the assumption of local thermodynamic equilibrium, with the XCLASS tool, the molecular column densities and rotation temperatures are estimated. We have found that the oxygen-bearing molecules have considerably higher column densities and fractional abundances than the nitrogen-bearing molecules. The rotation temperatures range from 100 to 200 K, suggesting that the molecular emission could originate from a warm environment. Finally, based on the gas distributions, fractional abundances and the rotation temperatures, we conclude that CH3OH, C2H5OH, CH3COCH3 and CH3CH2CN might be synthesized on the grain surface, while gas phase chemistry is responsible for the production of CH3OCH3, CH3OCHO and CH2CHCN.

  1. Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation.

    PubMed

    Feng, Dawei; Liu, Tian-Fu; Su, Jie; Bosch, Mathieu; Wei, Zhangwen; Wan, Wei; Yuan, Daqiang; Chen, Ying-Pin; Wang, Xuan; Wang, Kecheng; Lian, Xizhen; Gu, Zhi-Yuan; Park, Jihye; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-19

    Enzymatic catalytic processes possess great potential in chemical manufacturing, including pharmaceuticals, fuel production and food processing. However, the engineering of enzymes is severely hampered due to their low operational stability and difficulty of reuse. Here, we develop a series of stable metal-organic frameworks with rationally designed ultra-large mesoporous cages as single-molecule traps (SMTs) for enzyme encapsulation. With a high concentration of mesoporous cages as SMTs, PCN-333(Al) encapsulates three enzymes with record-high loadings and recyclability. Immobilized enzymes that most likely undergo single-enzyme encapsulation (SEE) show smaller Km than free enzymes while maintaining comparable catalytic efficiency. Under harsh conditions, the enzyme in SEE exhibits better performance than free enzyme, showing the effectiveness of SEE in preventing enzyme aggregation or denaturation. With extraordinarily large pore size and excellent chemical stability, PCN-333 may be of interest not only for enzyme encapsulation, but also for entrapment of other nanoscaled functional moieties.

  2. Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation

    NASA Astrophysics Data System (ADS)

    Feng, Dawei; Liu, Tian-Fu; Su, Jie; Bosch, Mathieu; Wei, Zhangwen; Wan, Wei; Yuan, Daqiang; Chen, Ying-Pin; Wang, Xuan; Wang, Kecheng; Lian, Xizhen; Gu, Zhi-Yuan; Park, Jihye; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-01

    Enzymatic catalytic processes possess great potential in chemical manufacturing, including pharmaceuticals, fuel production and food processing. However, the engineering of enzymes is severely hampered due to their low operational stability and difficulty of reuse. Here, we develop a series of stable metal-organic frameworks with rationally designed ultra-large mesoporous cages as single-molecule traps (SMTs) for enzyme encapsulation. With a high concentration of mesoporous cages as SMTs, PCN-333(Al) encapsulates three enzymes with record-high loadings and recyclability. Immobilized enzymes that most likely undergo single-enzyme encapsulation (SEE) show smaller Km than free enzymes while maintaining comparable catalytic efficiency. Under harsh conditions, the enzyme in SEE exhibits better performance than free enzyme, showing the effectiveness of SEE in preventing enzyme aggregation or denaturation. With extraordinarily large pore size and excellent chemical stability, PCN-333 may be of interest not only for enzyme encapsulation, but also for entrapment of other nanoscaled functional moieties.

  3. Discovery of interstellar ketenyl (HCCO), a surprisingly abundant radical

    NASA Astrophysics Data System (ADS)

    Agúndez, Marcelino; Cernicharo, José; Guélin, Michel

    2015-05-01

    We conducted radioastronomical observations of 9 dark clouds with the IRAM 30 m telescope. We present the first identification in space of the ketenyl radical (HCCO) toward the starless core Lupus-1A and the molecular cloud L483 and the detection of the related molecules ketene (H2CCO) and acetaldehyde (CH3CHO) in these two sources and 3 additional dark clouds. We also report the detection of the formyl radical (HCO) in the 9 targeted sources and of propylene (CH2CHCH3) in 4 of the observed sources, which significantly extends the number of dark clouds where these molecules are known to be present. We have derived a beam-averaged column density of HCCO of ~5 × 1011 cm-2 in both Lupus-1A and L483, which means that the ketenyl radical is just ~10 times less abundant than ketene in these sources. The non-negligible abundance of HCCO found implies that there must be a powerful formation mechanism able to counterbalance the efficient destruction of this radical through reactions with neutral atoms. The column densities derived for HCO, (0.5-2.7) ×1012 cm-2, and CH2CHCH3, (1.9-4-2) ×1013 cm-2, are remarkably uniform across the sources where these species are detected, confirming their ubiquity in dark clouds. Gas phase chemical models of cold dark clouds can reproduce the observed abundances of HCO, but cannot explain the presence of HCCO in Lupus-1A and L483 and the high abundances derived for propylene. The chemistry of cold dark clouds needs to be revised in light of these new observational results. Based on observations carried out with the IRAM 30 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).Tables 3-6 are available in electronic form at http://www.aanda.org

  4. High abundances of presolar grains and 15N-rich organic matter in CO3.0 chondrite Dominion Range 08006

    NASA Astrophysics Data System (ADS)

    Nittler, Larry R.; Alexander, Conel M. O'D.; Davidson, Jemma; Riebe, My E. I.; Stroud, Rhonda M.; Wang, Jianhua

    2018-04-01

    NanoSIMS C-, N-, and O-isotopic mapping of matrix in CO3.0 chondrite Dominion Range (DOM) 08006 revealed it to have in its matrix the highest abundance of presolar O-rich grains (257 +76/-96 ppm, 2σ) of any meteorite. It also has a matrix abundance of presolar SiC of 35 (+25/-17, 2σ) ppm, similar to that seen across primitive chondrite classes. This provides additional support to bulk isotopic and petrologic evidence that DOM 08006 is the most primitive known CO meteorite. Transmission electron microscopy of five presolar silicate grains revealed one to have a composite mineralogy similar to larger amoeboid olivine aggregates and consistent with equilibrium condensation, two non-stoichiometric amorphous grains, and two olivine grains, though one is identified as such solely based on its composition. We also found insoluble organic matter (IOM) to be present primarily as sub-micron inclusions with ranges of C- and N-isotopic anomalies similar to those seen in primitive CR chondrites and interplanetary dust particles. In contrast to other primitive extraterrestrial materials, H isotopic imaging showed normal and homogeneous D/H. Most likely, DOM 08006 and other CO chondrites accreted a similar complement of primitive and isotopically anomalous organic matter to that found in other chondrite classes and IDPs, but the very limited amount of thermal metamorphism experienced by DOM 08006 has caused loss of D-rich organic moieties, while not substantially affecting either the molecular carriers of C and N anomalies or most inorganic phases in the meteorite. One C-rich grain that was highly depleted in 13C and 15N was identified; we propose it originated in the Sun's parental molecular cloud.

  5. Bringing abundance into environmental politics: Constructing a Zionist network of water abundance, immigration, and colonization.

    PubMed

    Alatout, Samer

    2009-06-01

    For more than five decades, resource scarcity has been the lead story in debates over environmental politics. More importantly, and whenever environmental politics implies conflict, resource scarcity is constructed as the culprit. Abundance of resources, if at all visited in the literature, holds less importance. Resource abundance is seen, at best, as the other side of scarcity--maybe the successful conclusion of multiple interventions that may turn scarcity into abundance. This paper reinstates abundance as a politico-environmental category in its own right. Rather than relegating abundance to a second-order environmental actor that matters only on occasion, this paper foregrounds it as a crucial element in modern environmental politics. On the substantive level, and using insights from science and technology studies, especially a slightly modified actor-network framework, I describe the emergence and consolidation of a Zionist network of abundance, immigration, and colonization in Palestine between 1918 and 1948. The essential argument here is that water abundance was constructed as fact, and became a political rallying point around which a techno-political network emerged that included a great number of elements. To name just a few, the following were enrolled in the service of such a network: geologists, geophysicists, Zionist settlement experts, Zionist organizations, political and technical categories of all sorts, Palestinians as the negated others, Palestinian revolts in search of political rights, the British Mandate authorities, the hydrological system of Palestine, and the absorptive capacity of Palestine, among others. The point was to successfully articulate these disparate elements into a network that seeks opening Palestine for Jewish immigration, redefining Palestinian geography and history through Judeo-Christian Biblical narratives, and, in the process, de-legitimizing political Palestinian presence in historic Palestine.

  6. Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities

    PubMed Central

    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. PMID:26136731

  7. Adsorption of Organic Molecules to van der Waals Materials: Comparison of Fluorographene and Fluorographite with Graphene and Graphite

    PubMed Central

    2017-01-01

    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. PMID:28145699

  8. Simple and advanced ferromagnet/molecule spinterfaces

    NASA Astrophysics Data System (ADS)

    Gruber, M.; Ibrahim, F.; Djedhloul, F.; Barraud, C.; Garreau, G.; Boukari, S.; Isshiki, H.; Joly, L.; Urbain, E.; Peter, M.; Studniarek, M.; Da Costa, V.; Jabbar, H.; Bulou, H.; Davesne, V.; Halisdemir, U.; Chen, J.; Xenioti, D.; Arabski, J.; Bouzehouane, K.; Deranlot, C.; Fusil, S.; Otero, E.; Choueikani, F.; Chen, K.; Ohresser, P.; Bertran, F.; Le Fèvre, P.; Taleb-Ibrahimi, A.; Wulfhekel, W.; Hajjar-Garreau, S.; Wetzel, P.; Seneor, P.; Mattana, R.; Petroff, F.; Scheurer, F.; Weber, W.; Alouani, M.; Beaurepaire, E.; Bowen, M.

    2016-10-01

    Spin-polarized charge transfer between a ferromagnet and a molecule can promote molecular ferromagnetism 1, 2 and hybridized interfacial states3, 4. Observations of high spin-polarization of Fermi level states at room temperature5 designate such interfaces as a very promising candidate toward achieving a highly spin-polarized, nanoscale current source at room temperature, when compared to other solutions such as half-metallic systems and solid-state tunnelling over the past decades. We will discuss three aspects of this research. 1) Does the ferromagnet/molecule interface, also called an organic spinterface, exhibit this high spin-polarization as a generic feature? Spin-polarized photoemission experiments reveal that a high spin-polarization of electronics states at the Fermi level also exist at the simple interface between ferromagnetic cobalt and amorphous carbon6. Furthermore, this effect is general to an array of ferromagnetic and molecular candidates7. 2) Integrating molecules with intrinsic properties (e.g. spin crossover molecules) into a spinterface toward enhanced functionality requires lowering the charge transfer onto the molecule8 while magnetizing it1,2. We propose to achieve this by utilizing interlayer exchange coupling within a more advanced organic spinterface architecture. We present results at room temperature across the fcc Co(001)/Cu/manganese phthalocyanine (MnPc) system9. 3) Finally, we discuss how the Co/MnPc spinterface's ferromagnetism stabilizes antiferromagnetic ordering at room temperature onto subsequent molecules away from the spinterface, which in turn can exchange bias the Co layer at low temperature10. Consequences include tunnelling anisotropic magnetoresistance across a CoPc tunnel barrier11. This augurs new possibilities to transmit spin information across organic semiconductors using spin flip excitations12.

  9. The interstellar N2 abundance towards HD 124314 from far-ultraviolet observations.

    PubMed

    Knauth, David C; Andersson, B-G; McCandliss, Stephan R; Moos, H Warren

    2004-06-10

    The abundance of interstellar molecular nitrogen (N2) is of considerable importance: models of steady-state gas-phase interstellar chemistry, together with millimetre-wavelength observations of interstellar N2H+ in dense molecular clouds predict that N2 should be the most abundant nitrogen-bearing molecule in the interstellar medium. Previous attempts to detect N2 absorption in the far-ultraviolet or infrared (ice features) have hitherto been unsuccessful. Here we report the detection of interstellar N2 at far-ultraviolet wavelengths towards the moderately reddened star HD 124314 in the constellation of Centaurus. The N2 column density is larger than expected from models of diffuse clouds and significantly smaller than expected for dense molecular clouds. Moreover, the N2 abundance does not explain the observed variations in the abundance of atomic nitrogen (N I) towards high-column-density sightlines, implying that the models of nitrogen chemistry in the interstellar medium are incomplete.

  10. Observing Organic Molecules in Interstellar Gases: Non Equilibrium Excitation.

    NASA Astrophysics Data System (ADS)

    Wiesenfeld, Laurent; Faure, Alexandre; Remijan, Anthony; Szalewicz, Krzysztof

    2014-06-01

    In order to observe quantitatively organic molecules in interstellar gas, it is necessary to understand the relative importance of photonic and collisional excitations. In order to do so, collisional excitation transfer rates have to be computed. We undertook several such studies, in particular for H_2CO and HCOOCH_3. Both species are observed in many astrochemical environments, including star-forming regions. We found that those two molecules behave in their low-lying rotational levels in an opposite way. For cis methyl-formate, a non-equilibrium radiative transfer treatment of rotational lines is performed, using a new set of theoretical collisional rate coefficients. These coefficients have been computed in the temperature range 5 to 30 K by combining coupled-channel scattering calculations with a high accuracy potential energy surface for HCOOCH_3 -- He. The results are compared to observations toward the Sagittarius B2(N) molecular cloud. A total of 2080 low-lying transitions of methyl formate, with upper levels below 25 K, were treated. These lines are found to probe a cold (30 K), moderately dense (n ˜ 104 cm-3) interstellar gas. In addition, our calculations indicate that all detected emission lines with a frequency below 30 GHz are collisionally pumped weak masers amplifying the background of Sgr B2(N). This result demonstrates the generality of the inversion mechanism for the low-lying transitions of methyl formate. For formaldehyde, we performed a similar non-equilibrium treatment, with H_2 as the collisional partner, thanks to the accurate H_2CO - H_2 potential energy surface . We found very different energy transfer rates for collisions with para-H_2 (J=0) and ortho-H_2 (J=1). The well-known absorption against the cosmological background of the 111→ 101 line is shown to depend critically on the difference of behaviour between para and ortho-H_2, for a wide range of H_2 density. We thank the CNRS-PCMI French national program for continuous support

  11. Hierarchical Self-Organization of AB n Dendron-like Molecules into a Supramolecular Lattice Sequence

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Feng, Xueyan; Zhang, Ruimeng; Li, Yiwen

    To understand the hierarchical self-organization behaviors of soft materials as well as their dependence on molecular geometry, a series of ABn dendron-type giant molecules based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles were designed and synthesized. The apex of these molecules is a hydrophilic POSS cage with fourteen hydroxyl groups (denoted DPOSS). At its periphery, there are different numbers (n = 1–8) of hydrophobic POSS cages with seven isobutyl groups (denoted BPOSS), connected to the apical DPOSS via flexible dendron type linker(s). With varying the BPOSS number from one to seven, a supramolecular lattice formation sequence ranging from lamella (DPOSS-BPOSS), doublemore » gyroid (space group of Ia3d, DPOSS-BPOSS2), hexagonal cylinder (space group of P6mm, DPOSS-BPOSS3), Frank-Kasper A15 (space group of Pm3n, DPOSS-BPOSS4, DPOSS-BPOSS5, and DPOSS-BPOSS6), to Frank-Kasper sigma (space group of P42/mnm, DPOSS-BPOSS7) phases can be observed. The nanostructure formations in this series of ABn dendron-type giant molecules are mainly directed by the macromolecular geometric shapes. Furthermore, within each spherical motif, the soft spherical core is consisted of hydrophilic DPOSS cages with flexible linkages, while the hydrophobic BPOSS cages form the relative rigid shell and contact with neighbors to provide decreased interfaces among the spherical motifs for constructing final polyhedral motifs in these Frank-Kasper lattices. This study provides the design principle of macromolecules with specific geometric shapes and functional groups to achieve anticipated structures and macroscopic properties.« less

  12. The δ18O of Atmospheric Water Vapour is Recorded in the Oxygen Isotope Ratios of Leaf water and Organic Molecules at High Relative Humidity

    NASA Astrophysics Data System (ADS)

    Lehmann, M. M.; Goldsmith, G. R.; Schmid, L.; Siegwolf, R. T.; Gessler, A.; Saurer, M.

    2016-12-01

    The oxygen stable isotope ratios (δ18O) of water and organic molecules in plants hold information about plant physiology, ecohydrology, and environmental conditions. For instance, the δ18O ratio of leaf water reflects both the δ18O ratios of water in the soil and in the atmosphere. This water, which is incorporated into organic molecules at the time of synthesis, thus serves to record the environment in which the plant was growing. However, how δ18O of atmospheric water vapour affects the δ18O ratio of organic molecules remains poorly understood. In order to investigate the effects of fog and rain (e.g. high atmospheric water availability) on δ18O ratios of leaf water and organic molecules, we exposed oak tree saplings (Quercus robur) in wet and dry soil treatments to 18O-depleted water vapour at ca. 90% relative humidity for 5 h. We harvested plant material over 24 h to trace the movement of the isotopic label in water and organics throughout the plant from the leaves to the stem. The atmospheric water vapour caused a strong 18O-depletion in leaf and xylem water, as well as in leaf carbohydrates, with the most negative ratios observed at the end of the fogging. Moreover, the label was clearly observed in twig and stem phloem carbohydrates following a short delay. A detailed compound-specific isotope analysis of the leaf carbohydrates revealed that the label caused an 18O-depletion in fructose, glucose, and sucrose. Quercitol, an oak-specific alditol, did not show 18O-depletion. Clear soil moisture treatment effects were only observed for twig phloem carbohydrates, with a stronger 18O-depletion in wet plants than in dry plants, suggesting retarded leaf-to-phloem sugar export in trees under drought. We demonstrate that labelling with 18O-depleted water is a potential tool to trace the movement and incorporation of oxygen stable isotopes in plants. We clearly show that changes in δ18O of atmospheric water vapour are quickly imprinted on leaf water and

  13. Abundances of Neutral and Ionized PAH Along The Lines-of-Sight of Diffuse and Translucent Interstellar Clouds

    NASA Technical Reports Server (NTRS)

    Salama, Farid; Galazutdinov, Gazinur; Krewloski, Jacek; Biennier, Ludovic; Beletsky, Yuri; Song, In-Ok

    2013-01-01

    The spectra of neutral and ionized PAHs isolated in the gas phase at low temperature have been measured in the laboratory under conditions that mimic interstellar conditions and are compared with a set of astronomical spectra of reddened, early type stars. The comparisons of astronomical and laboratory data provide upper limits for the abundances of neutral PAH molecules and ions along specific lines-of-sight. Something that is not attainable from infrared observations. We present the characteristics of the laboratory facility (COSmIC) that was developed for this study and discuss the findings resulting from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. COSmIC combines a supersonic jet expansion with discharge plasma and cavity ringdown spectroscopy and provides experimental conditions that closely mimic the interstellar conditions. The column densities of the individual PAH molecules and ions probed in these surveys are derived from the comparison of the laboratory data with high resolution, high S/N ratio astronomical observations. The comparisons of astronomical and laboratory data lead to clear conclusions regarding the expected abundances for PAHs in the interstellar environments probed in the surveys. Band profile comparisons between laboratory and astronomical spectra lead to information regarding the molecular structures and characteristics associated with the DIB carriers in the corresponding lines-of-sight. These quantitative surveys of neutral and ionized PAHs in the optical range open the way for quantitative searches of PAHs and complex organics in a variety of interstellar and circumstellar environments.

  14. Molecular Spectroscopy in Space: Discovering New Molecules from Line Surveys and Laboratory Spectroscopy

    NASA Astrophysics Data System (ADS)

    Cernicharo, Jose

    2016-06-01

    The increasing sensitivity offered by the new generation of radio astronomical receivers and radio telescopes (single dishes and radio interferometers) has provided an enormous impact in our capacity to study the molecular content of interstellar and circumstellar clouds. Astronomers face now the challenging problem of interpreting the thousands of lines detected in hot cores which arise from isotopologues and vibrationally excited states of most known molecules. Although all strong features have been already assigned to abundant species, many of the lines still pending to be assigned could arise from very abundant molecular species having low dipole moment and/or very large partition functions. The only way to address this problem in astrophysics is through a close collaboration between astrophysicists and laboratory spectroscopists. In this talk I am going to present the results obtained over the last 10 years in interpreting the line surveys of Orion gathered with the 30m IRAM radio telescope and with ALMA. The most recent molecule found in this cloud is methyl isocyanate, CH3NCO, for which near 400 lines have been found in Oriona in the 80-280 GHz domain. This molecule has an abundance only a factor 5-20 below that of the well-known species HNCO and CH3CN. The molecule has been also found towards the giant cloud SgrB2b in the galactic center. Finally, I will present the case of the submillimeter spectrum of the carbon-rich evolved star IRC+10216 in which we have recently found Si2C with an abundance similar to SiC2. Our recent ALMA observations in a narrow band of 20 GHz around 265 GHz show near 200 features corresponding to the J=3-2 transition of hot HCN (vibrational levels up to 11000 cm-1). In addition to HCN lines, a forest of several hundreds of U lines dominates the spectrum. Most of these lines arise from molecules that condensate very quickly into dust grainsc. aJ. Cernicharo, Z.Kisiel, B.Tercero, et al., A&A 587, L4 (2016). bD.T. Halfen, V

  15. Inter- and intra-organ spatial distributions of sea star saponins by MALDI imaging.

    PubMed

    Demeyer, Marie; Wisztorski, Maxence; Decroo, Corentin; De Winter, Julien; Caulier, Guillaume; Hennebert, Elise; Eeckhaut, Igor; Fournier, Isabelle; Flammang, Patrick; Gerbaux, Pascal

    2015-11-01

    Saponins are secondary metabolites that are abundant and diversified in echinoderms. Mass spectrometry is increasingly used not only to identify saponin congeners within animal extracts but also to decipher the structure/biological activity relationships of these molecules by determining their inter-organ and inter-individual variability. The usual method requires extensive purification procedures to prepare saponin extracts compatible with mass spectrometry analysis. Here, we selected the sea star Asterias rubens as a model animal to prove that direct analysis of saponins can be performed on tissue sections. We also demonstrated that carboxymethyl cellulose can be used as an embedding medium to facilitate the cryosectioning procedure. Matrix-assisted laser desorption/ionization (MALDI) imaging was also revealed to afford interesting data on the distribution of saponin molecules within the tissues. We indeed highlight that saponins are located not only inside the body wall of the animals but also within the mucus layer that probably protects the animal against external aggressions. Graphical Abstract Saponins are the most abundant secondary metabolites in sea stars. They should therefore participate in important biological activities. Here, MALDI imaging is presented as a powerful method to determine the spatial distribution of saponins within the animal tissues. The inhomogeneity of the intra-organ saponin distribution is highlighted, paving the way for future elegant structure/activity relationship investigations.

  16. Crossing borders to bind proteins--a new concept in protein recognition based on the conjugation of small organic molecules or short peptides to polypeptides from a designed set.

    PubMed

    Baltzer, Lars

    2011-06-01

    A new concept for protein recognition and binding is highlighted. The conjugation of small organic molecules or short peptides to polypeptides from a designed set provides binder molecules that bind proteins with high affinities, and with selectivities that are equal to those of antibodies. The small organic molecules or peptides need to bind the protein targets but only with modest affinities and selectivities, because conjugation to the polypeptides results in molecules with dramatically improved binder performance. The polypeptides are selected from a set of only sixteen sequences designed to bind, in principle, any protein. The small number of polypeptides used to prepare high-affinity binders contrasts sharply with the huge libraries used in binder technologies based on selection or immunization. Also, unlike antibodies and engineered proteins, the polypeptides have unordered three-dimensional structures and adapt to the proteins to which they bind. Binder molecules for the C-reactive protein, human carbonic anhydrase II, acetylcholine esterase, thymidine kinase 1, phosphorylated proteins, the D-dimer, and a number of antibodies are used as examples to demonstrate that affinities are achieved that are higher than those of the small molecules or peptides by as much as four orders of magnitude. Evaluation by pull-down experiments and ELISA-based tests in human serum show selectivities to be equal to those of antibodies. Small organic molecules and peptides are readily available from pools of endogenous ligands, enzyme substrates, inhibitors or products, from screened small molecule libraries, from phage display, and from mRNA display. The technology is an alternative to established binder concepts for applications in drug development, diagnostics, medical imaging, and protein separation.

  17. Ice photochemistry as a source of amino acids and other organic molecules in meteorites, and implications for the origin of life and the search for life in the Solar System

    NASA Technical Reports Server (NTRS)

    Bernstein, Max

    2005-01-01

    The tons of extraterrestrial organic material that come to the Earth every day probably helped to made the Earth habitable, and possibly played a role in the origin of life. At the astrochemistry lab (http://www.astrochem.orq) we investigate the formation and distribution of organic molecules in space and consider the impact such molecules may have on the habitability of planets and the search for life in the Solar System. The organic compounds in meteorites include amino acids, aromatics of various sorts including purine and pyrimidine bases, and fatty acids that form bi-layer vesicles. The origin of many of these species remains mysterious, but in recent years we and others have performed experiments that suggest low temperature radiation chemistry could account for the presence and deuterium enrichment of many of these molecules. . I will present our laboratory experiments that show the viability of low temperature radiation chemistry as a source of organic molecules such as;amino acids (Nature, 2002, 416, 401-403), amphiphiles (Astrobiology, 2003, 2, 371, Proc. Nat. Acad. Sci. 2001, 98, 815), quinones (Science, 1999, 283, 1135) and other functionalized aromatic compounds (Meteoritics, 2001, 36, 351 ; Astrophysical Journal., 2003, 582, L25), some of which were invoked as potential biomarkers in the Alan Hills 84001 Martian meteorite. Understanding how components of proteins and DNA could form in sterile space environments is also of relevance to our search for life elsewhere in the Solar System, the great task now ahead of NASA. If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While most people think of molecules such as amino acids, and nucleo-bases as good candidate biomarkers, these molecules are produced non-biotically in space and are expected to be present on the surface of other planets even in the absence of

  18. Medium-Bandgap Small-Molecule Donors Compatible with Both Fullerene and Nonfullerene Acceptors.

    PubMed

    Huo, Yong; Yan, Cenqi; Kan, Bin; Liu, Xiao-Fei; Chen, Li-Chuan; Hu, Chen-Xia; Lau, Tsz-Ki; Lu, Xinhui; Sun, Chun-Lin; Shao, Xiangfeng; Chen, Yongsheng; Zhan, Xiaowei; Zhang, Hao-Li

    2018-03-21

    Much effort has been devoted to the development of new donor materials for small-molecule organic solar cells due to their inherent advantages of well-defined molecular weight, easy purification, and good reproducibility in photovoltaic performance. Herein, we report two small-molecule donors that are compatible with both fullerene and nonfullerene acceptors. Both molecules consist of an (E)-1,2-di(thiophen-2-yl)ethane-substituted (TVT-substituted) benzo[1,2-b:4,5-b']dithiophene (BDT) as the central unit, and two rhodanine units as the terminal electron-withdrawing groups. The central units are modified with either alkyl side chains (DRBDT-TVT) or alkylthio side chains (DRBDT-STVT). Both molecules exhibit a medium bandgap with complementary absorption and proper energy level offset with typical acceptors like PC 71 BM and IDIC. The optimized devices show a decent power conversion efficiency (PCE) of 6.87% for small-molecule organic solar cells and 6.63% for nonfullerene all small-molecule organic solar cells. Our results reveal that rationally designed medium-bandgap small-molecule donors can be applied in high-performance small-molecule organic solar cells with different types of acceptors.

  19. Search for biochemical fossils on earth and non-biological organic molecules on Jupiter, Saturn and Titan

    NASA Astrophysics Data System (ADS)

    Nagy, Bartholomew

    1982-07-01

    Recognizable remnants of ancient biochemicals may survive under mild/moderate geological environments. Acyclic isoprenoid hydrocarbons, cyclic hydrocarbons with terpenoid carbon skeletons (e.g. hopanes) and vanadyl and nickel porphyrins have been isolated from organic matter, including petroleum, in Phanerozoic sedimentary rocks. Remnants of lignin have also been found. Usually, carbohydrates do not survive long; they degrade and/or react with other organic substances to form macromolecular matter. Proteins, e.g. apparently those in dinosaur bone collagen, break down relatively rapidly. Life arose during the Precambrian and potential biochemical fossils, e.g. n-alkanes, 2,5-dimethylfuran have been isolated from Precambrian kerogens. Traces of hydrocarbons, NH3, PH3 occur on Jupiter and Saturn. Hydrocarbons, N2 and HCN, the latter a key intermediary in the laboratory abiological syntheses of amino acids and nucleic acid bases, are present on Titan where life could not have evolved. Precursor abiological organic molecules of some complexity may have been synthesized on Titan and the Jovian planets.

  20. Functional Amyloids Keep Quorum-sensing Molecules in Check*

    PubMed Central

    Seviour, Thomas; Hansen, Susan Hove; Yang, Liang; Yau, Yin Hoe; Wang, Victor Bochuan; Stenvang, Marcel R.; Christiansen, Gunna; Marsili, Enrico; Givskov, Michael; Chen, Yicai; Otzen, Daniel E.; Nielsen, Per Halkjær; Geifman-Shochat, Susana; Kjelleberg, Staffan; Dueholm, Morten S.

    2015-01-01

    The mechanism by which extracellular metabolites, including redox mediators and quorum-sensing signaling molecules, traffic through the extracellular matrix of biofilms is poorly explored. We hypothesize that functional amyloids, abundant in natural biofilms and possessing hydrophobic domains, retain these metabolites. Using surface plasmon resonance, we demonstrate that the quorum-sensing (QS) molecules, 2-heptyl-3-hydroxy-4(1H)-quinolone and N-(3-oxododecanoyl)-l-homoserine lactone, and the redox mediator pyocyanin bind with transient affinity to functional amyloids from Pseudomonas (Fap). Their high hydrophobicity predisposes them to signal-amyloid interactions, but specific interactions also play a role. Transient interactions allow for rapid association and dissociation kinetics, which make the QS molecules bioavailable and at the same time secure within the extracellular matrix as a consequence of serial bindings. Retention of the QS molecules was confirmed using Pseudomonas aeruginosa PAO1-based 2-heptyl-3-hydroxy-4(1H)-quinolone and N-(3-oxododecanoyl)-l-homoserine lactone reporter assays, showing that Fap fibrils pretreated with the QS molecules activate the reporters even after sequential washes. Pyocyanin retention was validated by electrochemical analysis of pyocyanin-pretreated Fap fibrils subjected to the same washing process. Results suggest that QS molecule-amyloid interactions are probably important in the turbulent environments commonly encountered in natural habitats. PMID:25586180

  1. A solution-doped small molecule hole transport layer for efficient ITO-free organic solar cells (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Bormann, Ludwig; Selzer, Franz; Leo, Karl; Mueller-Meskamp, Lars

    2015-10-01

    Indium-tin-oxide-free (ITO-free) organic solar cells are an important, emerging research field because ITO transparent electrodes are a bottleneck for cheap large area devices on flexible substrates. Among highly conductive PEDOT:PSS and metal grids, percolation networks made of silver nanowires (AgNW) with a diameter in the nanoscale show a huge potential due to easy processing (e.g. spray coating), high aspect ratios and excellent electrical and optical properties like 15 Ohm/sq with a transmission of 83.5 % including the substrate. However, the inherent surface roughness of the AgNW film impedes the implementation as bottom electrode in organic devices, especially fully vacuum deposited ones, where often shunts are obtained. Here, we report about the solution processing of a small molecule hole transport layer (s-HTL) comprising N,N'-((Diphenyl-N,N'-bis)9,9,-dimethyl-fluoren-2-yl)-benzidine (BF-DPB, host material) and the proprietary NDP9 (p-dopant) deposited from tetrahydrofuran (THF) as non-halogenated, "green" solvent. We show, that the doping process already takes place in solution and that conductivities, achieved with this process at high doping efficiencies (4 * 10^-4 S/cm at 10 wt% doping concentration), are comparable to thermal co-evaporation of BF-DPB:NDP9 under high vacuum, which is the proven deposition method for doped small molecule films. Applying this s-HTL to AgNW films leads to well smoothened electrodes, ready for application in organic devices. Vacuum-deposited organic p-i-n solar cells with DCV2-5T-Me(3:3):C60 as active layer show a power conversion efficiency of 4.4% and 3.7% on AgNW electrode with 35nm and 90 nm wire diameter, compared to 4.1% on ITO with the s-HTL.

  2. Inorganics in Organics: Tracking down the Intrinsic Equilibriums between Organic Molecules and Trace Elements in Oceanic Waters

    NASA Astrophysics Data System (ADS)

    Lechtenfeld, O. J.; Koch, B. P.; Kattner, G.

    2010-12-01

    Recent developments in analytical instrumentation enable to describe biogeochemical processes in oceanic waters on a molecular level. This is the prerequisite to integrate biological and geochemical parameters and to develop chemical cycles on a global perspective. The state-of-the-art Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) applications for dissolved organic matter (DOM) focus mainly on carbon, hydrogen, oxygen and nitrogen isotopes. Implementation of sulfur and especially phosphorus in the molecular formula assignment has been questionable because of ambiguous calculated elemental formulas. On the other hand, many compounds bearing these elements are well known to occur in the dissolved state as part of the permanent recycling processes (e.g. phospholipids, phosphonates) but analytics of dissolved organic phosphorus (DOP) and sulfur (DOS) are often hampered by the large inorganic P and S pools. Even less is known about complexation characteristics of the DOM moieties. Although electrochemical methods provide some information about trace metal speciation, the high amount of organic molecules and its insufficient description as chemical functional classes prevent the assignment of trace metals to ligand classes. Nevertheless, it is undoubtful that a varying but extensive amount of transition metals is bond in form of organic complexes. Hyphenation of reversed phase high performance liquid chromatography (RP-HPLC) with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) is a valuable tool to study these metal-organic interactions in a qualitative and quantitative approach. We established a desolvation method that allows direct transfer of high organic solvent loads into the plasma. Thus, in combination with internal standardization and external calibration, the investigation of a broad polarity scale was possible. This approach overcomes previous restrictions to non-organic solvent separation techniques like size

  3. Extraterrestrial organic matter: a review

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.

    1998-01-01

    We review the nature of the widespread organic material present in the Milky Way Galaxy and in the Solar System. Attention is given to the links between these environments and between primitive Solar System objects and the early Earth, indicating the preservation of organic material as an interstellar cloud collapsed to form the Solar System and as the Earth accreted such material from asteroids, comets and interplanetary dust particles. In the interstellar medium of the Milky Way Galaxy more than 100 molecular species, the bulk of them organic, have been securely identified, primarily through spectroscopy at the highest radio frequencies. There is considerable evidence for significantly heavier organic molecules, particularly polycyclic aromatics, although precise identification of individual species has not yet been obtained. The so-called diffuse interstellar bands are probably important in this context. The low temperature kinetics in interstellar clouds leads to very large isotopic fractionation, particularly for hydrogen, and this signature is present in organic components preserved in carbonaceous chondritic meteorites. Outer belt asteroids are the probable parent bodies of the carbonaceous chondrites, which may contain as much as 5% organic material, including a rich variety of amino acids, purines, pyrimidines, and other species of potential prebiotic interest. Richer in volatiles and hence less thermally processed are the comets, whose organic matter is abundant and poorly characterized. Cometary volatiles, observed after sublimation into the coma, include many species also present in the interstellar medium. There is evidence that most of the Earth's volatiles may have been supplied by a 'late' bombardment of comets and carbonaceous meteorites, scattered into the inner Solar System following the formation of the giant planets. How much in the way of intact organic molecules of potential prebiotic interest survived delivery to the Earth has become an

  4. Accuracy or precision: Implications of sample design and methodology on abundance estimation

    USGS Publications Warehouse

    Kowalewski, Lucas K.; Chizinski, Christopher J.; Powell, Larkin A.; Pope, Kevin L.; Pegg, Mark A.

    2015-01-01

    Sampling by spatially replicated counts (point-count) is an increasingly popular method of estimating population size of organisms. Challenges exist when sampling by point-count method, and it is often impractical to sample entire area of interest and impossible to detect every individual present. Ecologists encounter logistical limitations that force them to sample either few large-sample units or many small sample-units, introducing biases to sample counts. We generated a computer environment and simulated sampling scenarios to test the role of number of samples, sample unit area, number of organisms, and distribution of organisms in the estimation of population sizes using N-mixture models. Many sample units of small area provided estimates that were consistently closer to true abundance than sample scenarios with few sample units of large area. However, sample scenarios with few sample units of large area provided more precise abundance estimates than abundance estimates derived from sample scenarios with many sample units of small area. It is important to consider accuracy and precision of abundance estimates during the sample design process with study goals and objectives fully recognized, although and with consequence, consideration of accuracy and precision of abundance estimates is often an afterthought that occurs during the data analysis process.

  5. Detection of interstellar N2O: A new molecule containing an N-O bond

    NASA Astrophysics Data System (ADS)

    Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

    1994-12-01

    A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is Ntot approx. 1015/sq. cm, which corresponds to a fractional abundance of approx. 10-9, relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

  6. Detection of interstellar N2O: A new molecule containing an N-O bond

    NASA Technical Reports Server (NTRS)

    Ziurys, L. M.; Apponi, A. J.; Hollis, J. M.; Snyder, L. E.

    1994-01-01

    A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is N(sub tot) approx. 10(exp 15)/sq. cm, which corresponds to a fractional abundance of approx. 10(exp -9), relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

  7. Continuously Adjustable, Molecular-Sieving “Gate” on 5A Zeolite for Distinguishing Small Organic Molecules by Size

    PubMed Central

    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

  8. Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm2/Vs.

    PubMed

    Smith, Jeremy; Zhang, Weimin; Sougrat, Rachid; Zhao, Kui; Li, Ruipeng; Cha, Dongkyu; Amassian, Aram; Heeney, Martin; McCulloch, Iain; Anthopoulos, Thomas D

    2012-05-08

    Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm(2) /Vs, current on/off ratio ≥10(6) and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Searching for Prebiotically Important Molecules in Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Gibb, Erika L.; Brown, L. R.; Sudholt, E.

    2012-05-01

    Understanding how prebiotic molecules form and are distributed around young stars is an important step in determining how and where life can form in planetary systems. In general, protoplanetary disks consist of a cold, dense midplane where, beyond the frost line, water and organic molecules will condense onto dust grains as icy coatings. The surface of the disk is exposed to stellar and interstellar radiation, giving rise to a photon-dominated region characterized by ionization and dissociation products. Between these two layers is a warm molecular layer where a rich molecular chemistry is predicted to occur. The warm molecular layer is somewhat protected from ionizing radiation by the dust and polycyclic aromatic hydrocarbons (PAHs) in the surface region. We present a high-resolution (λ / Δλ 25,000), near-infrared spectroscopic survey of the L-band toward T Tauri star GV Tau N. The data were acquired with the NIRSPEC instrument on the Keck II telescope, located on Mauna Kea, HI. We detected strong HCN absorption lines that we interpret to be located in the warm molecular layer of a nearly edge-on protoplanetary disk. We discuss significant differences in spectra acquired in 2006 and 2010 and implications for the material in the disk of GV Tau N, including rotational temperatures, abundances, and inferred location. This work was supported by the NSF Stellar Astronomy Program (Grant #0908230) and the NASA Exobiology program (NNX11AG44G).

  10. Resolving protein interactions and organization downstream the T cell antigen receptor using single-molecule localization microscopy: a review

    NASA Astrophysics Data System (ADS)

    Sherman, Eilon

    2016-06-01

    Signal transduction is mediated by heterogeneous and dynamic protein complexes. Such complexes play a critical role in diverse cell functions, with the important example of T cell activation. Biochemical studies of signalling complexes and their imaging by diffraction limited microscopy have resulted in an intricate network of interactions downstream the T cell antigen receptor (TCR). However, in spite of their crucial roles in T cell activation, much remains to be learned about these signalling complexes, including their heterogeneous contents and size distribution, their complex arrangements in the PM, and the molecular requirements for their formation. Here, we review how recent advancements in single molecule localization microscopy have helped to shed new light on the organization of signalling complexes in single molecule detail in intact T cells. From these studies emerges a picture where cells extensively employ hierarchical and dynamic patterns of nano-scale organization to control the local concentration of interacting molecular species. These patterns are suggested to play a critical role in cell decision making. The combination of SMLM with more traditional techniques is expected to continue and critically contribute to our understanding of multimolecular protein complexes and their significance to cell function.

  11. Cyclodextrin-supported organic matrix for application of MALDI-MS for forensics. Soft-ionization to obtain protonated molecules of low molecular weight compounds

    NASA Astrophysics Data System (ADS)

    Yonezawa, Tetsu; Asano, Takashi; Fujino, Tatsuya; Nishihara, Hiroshi

    2013-06-01

    A mass measurement technique for detecting low-molecular-weight drugs with a cyclodextrin-supported organic matrix was investigated. By using cyclodextrin-supported 2,4,6-trihydroxyacetophenone (THAP), the matrix-related peaks of drugs were suppressed. The peaks of protonated molecules of the sample and THAP were mainly observed, and small fragments were detected in a few cases. Despite the Na+ and K+ peaks were observed in the spectrum, Na+ or K+ adduct sample molecules were undetected, owing to the sugar units of cyclodextrin. The advantages of MALDI-MS with cyclodextrin-supported matrices as an analytical tool for forensic samples are discussed. The suppression of alkali adducted molecules and desorption process are also discussed.

  12. Clustering in the stellar abundance space

    NASA Astrophysics Data System (ADS)

    Boesso, R.; Rocha-Pinto, H. J.

    2018-03-01

    We have studied the chemical enrichment history of the interstellar medium through an analysis of the n-dimensional stellar abundance space. This work is a non-parametric analysis of the stellar chemical abundance space. The main goal is to study the stars from their organization within this abundance space. Within this space, we seek to find clusters (in a statistical sense), that is, stars likely to share similar chemo-evolutionary history, using two methods: the hierarchical clustering and the principal component analysis. We analysed some selected abundance surveys available in the literature. For each sample, we labelled the group of stars according to its average abundance curve. In all samples, we identify the existence of a main enrichment pattern of the stars, which we call chemical enrichment flow. This flow is set by the structured and well-defined mean rate at which the abundances of the interstellar medium increase, resulting from the mixture of the material ejected from the stars and stellar mass-loss and interstellar medium gas. One of the main results of our analysis is the identification of subgroups of stars with peculiar chemistry. These stars are situated in regions outside of the enrichment flow in the abundance space. These peculiar stars show a mismatch in the enrichment rate of a few elements, such as Mg, Si, Sc and V, when compared to the mean enrichment rate of the other elements of the same stars. We believe that the existence of these groups of stars with peculiar chemistry may be related to the accretion of planetary material on to stellar surfaces or may be due to production of the same chemical element by different nucleosynthetic sites.

  13. Insight into the molecular composition of laboratory organic residues produced from interstellar/pre-cometary ice analogues using very high resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Danger, G.; Fresneau, A.; Abou Mrad, N.; de Marcellus, P.; Orthous-Daunay, F.-R.; Duvernay, F.; Vuitton, V.; Le Sergeant d'Hendecourt, L.; Thissen, R.; Chiavassa, T.

    2016-09-01

    Experimental simulations in the laboratory may provide important information about the chemical evolution occurring in various astrophysical objects such as extraterrestrial ices. Interstellar or (pre)cometary ice analogues made of H2O, CH3OH, and NH3 at 77 K, when subjected to an energetic process (VUV photons, electrons or ions) and then warmed-up to room temperature, lead, in the laboratory, to the formation of an organic residue. In this paper we expand our previous analysis of the residues in order to obtain a better insight into their molecular content. Data analyses show that three different chemical groups are present in the residue in the negative electrospray ionization (ESI) mode: CHN, CHO and CHNOsbnd whereas only two groups are detected in the positive ESI mode: CHN and CHNO. In both cases, the CHNO group is the most abundant. The application of specific data treatment shows that residue mainly contains aliphatic linear molecules or cyclic structures connected to unsaturated chemical functions such as esters, carboxylic acids, amides or aldehydes. In lower abundances, some molecules do present aromatic structures. The comparison of our residue with organic compounds detected in the Murchison meteorite gives an interesting match, which suggests that laboratory simulation of interstellar ice chemistry is relevant to understand astrophysical organic matter evolution.

  14. Multicolor emission from large-area porous thin films constructed of nanowires of small organic molecules

    NASA Astrophysics Data System (ADS)

    Wang, Zhe-Chen; Xiao, Wen-Chang; Ding, Xun-Lei; Ma, Yan-Ping; Xue, Wei; He, Sheng-Gui

    2008-12-01

    We describe a facile low-temperature physical vapor deposition approach to fabricate porous network thin films constructed of nanowires of small organic molecules on a large area. Supermolecular assemblies of pyrene nanowires based on a combination of van der Waals forces and π-π stacking tend to hierarchically self-assemble to form uniform porous films using our techniques. The morphology of the films is studied and we also study several reasons influencing the process of assembly such as evaporation temperature, deposition temperature, and different kinds of substrate. The deposition temperature is determined to be the main reason for hierarchical aggregation. Typically prepared films exhibit unique optical properties, that is, multicolor red-green-blue emissions. This novel method can be applied to other organic molecular systems and may be potentially used to place nanoscaled building blocks directly on solid surfaces for fabricating large-area nanostructure-based flat screens.

  15. Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

    NASA Astrophysics Data System (ADS)

    Desai, R. T.; Coates, A. J.; Wellbrock, A.; Vuitton, V.; Crary, F. J.; González-Caniulef, D.; Shebanits, O.; Jones, G. H.; Lewis, G. R.; Waite, J. H.; Cordiner, M.; Taylor, S. A.; Kataria, D. O.; Wahlund, J.-E.; Edberg, N. J. T.; Sittler, E. C.

    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-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-1 and between 49.0-50.1 u q-1 which are identified as belonging to the carbon chain anions, CN-/C3N- and/or C2H-/C4H-, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73-74 u q-1 could be attributed to the further carbon chain anions C5N-/C6H- 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-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.

  16. Abundance models improve spatial and temporal prioritization of conservation resources.

    PubMed

    Johnston, Alison; Fink, Daniel; Reynolds, Mark D; Hochachka, Wesley M; Sullivan, Brian L; Bruns, Nicholas E; Hallstein, Eric; Merrifield, Matt S; Matsumoto, Sandi; Kelling, Steve

    2015-10-01

    Conservation prioritization requires knowledge about organism distribution and density. This information is often inferred from models that estimate the probability of species occurrence rather than from models that estimate species abundance, because abundance data are harder to obtain and model. However, occurrence and abundance may not display similar patterns and therefore development of robust, scalable, abundance models is critical to ensuring that scarce conservation resources are applied where they can have the greatest benefits. Motivated by a dynamic land conservation program, we develop and assess a general method for modeling relative abundance using citizen science monitoring data. Weekly estimates of relative abundance and occurrence were compared for prioritizing times and locations of conservation actions for migratory waterbird species in California, USA. We found that abundance estimates consistently provided better rankings of observed counts than occurrence estimates. Additionally, the relationship between abundance and occurrence was nonlinear and varied by species and season. Across species, locations prioritized by occurrence models had only 10-58% overlap with locations prioritized by abundance models, highlighting that occurrence models will not typically identify the locations of highest abundance that are vital for conservation of populations.

  17. Deep K-band Observations of TMC-1 with the Green Bank Telescope: Detection of HC7O, Nondetection of HC11N, and a Search for New Organic Molecules

    NASA Astrophysics Data System (ADS)

    Cordiner, M. A.; Charnley, S. B.; Kisiel, Z.; McGuire, B. A.; Kuan, Y.-J.

    2017-12-01

    The 100 m Robert C. Byrd Green Bank Telescope K-band (KFPA) receiver was used to perform a high-sensitivity search for rotational emission lines from complex organic molecules in the cold interstellar medium toward TMC-1 (cyanopolyyne peak), focussing on the identification of new carbon-chain-bearing species as well as molecules of possible prebiotic relevance. We report a detection of the carbon-chain oxide species HC7O and derive a column density of (7.8+/- 0.9)× {10}11 cm-2. This species is theorized to form as a result of associative electron detachment reactions between oxygen atoms and C7H-, and/or reaction of C6H2 + with CO (followed by dissociative electron recombination). Upper limits are given for the related HC6O, C6O, and C7O molecules. In addition, we obtained the first detections of emission from individual 13C isotopologues of HC7N, and derive abundance ratios HC7N/HCCC13CCCCN = 110 ± 16 and HC7N/HCCCC13CCCN = 96 ± 11, indicative of significant 13C depletion in this species relative to the local interstellar elemental 12C/13C ratio of 60-70. The observed spectral region covered two transitions of HC11N, but emission from this species was not detected, and the corresponding column density upper limit is 7.4× {10}10 {{cm}}-2 (at 95% confidence). This is significantly lower than the value of 2.8× {10}11 {{cm}}-2 previously claimed by Bell et al. and confirms the recent nondetection of HC11N in TMC-1 by Loomis et al. Upper limits were also obtained for the column densities of malononitrile and the nitrogen heterocycles quinoline, isoquinoline, and pyrimidine.

  18. Novel Design Strategies for Platinum-Containing Conjugated Polymers and Small Molecules for Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    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

  19. Patterns of rare and abundant marine microbial eukaryotes.

    PubMed

    Logares, Ramiro; Audic, Stéphane; Bass, David; Bittner, Lucie; Boutte, Christophe; Christen, Richard; Claverie, Jean-Michel; Decelle, Johan; Dolan, John R; Dunthorn, Micah; Edvardsen, Bente; Gobet, Angélique; Kooistra, Wiebe H C F; Mahé, Frédéric; Not, Fabrice; Ogata, Hiroyuki; Pawlowski, Jan; Pernice, Massimo C; Romac, Sarah; Shalchian-Tabrizi, Kamran; Simon, Nathalie; Stoeck, Thorsten; Santini, Sébastien; Siano, Raffaele; Wincker, Patrick; Zingone, Adriana; Richards, Thomas A; de Vargas, Colomban; Massana, Ramon

    2014-04-14

    Biological communities are normally composed of a few abundant and many rare species. This pattern is particularly prominent in microbial communities, in which most constituent taxa are usually extremely rare. Although abundant and rare subcommunities may present intrinsic characteristics that could be crucial for understanding community dynamics and ecosystem functioning, microbiologists normally do not differentiate between them. Here, we investigate abundant and rare subcommunities of marine microbial eukaryotes, a crucial group of organisms that remains among the least-explored biodiversity components of the biosphere. We surveyed surface waters of six separate coastal locations in Europe, independently considering the picoplankton, nanoplankton, and microplankton/mesoplankton organismal size fractions. Deep Illumina sequencing of the 18S rRNA indicated that the abundant regional community was mostly structured by organismal size fraction, whereas the rare regional community was mainly structured by geographic origin. However, some abundant and rare taxa presented similar biogeography, pointing to spatiotemporal structure in the rare microeukaryote biosphere. Abundant and rare subcommunities presented regular proportions across samples, indicating similar species-abundance distributions despite taxonomic compositional variation. Several taxa were abundant in one location and rare in other locations, suggesting large oscillations in abundance. The substantial amount of metabolically active lineages found in the rare biosphere suggests that this subcommunity constitutes a diversity reservoir that can respond rapidly to environmental change. We propose that marine planktonic microeukaryote assemblages incorporate dynamic and metabolically active abundant and rare subcommunities, with contrasting structuring patterns but fairly regular proportions, across space and time. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Molecular abundances and C/O ratios in chemically evolving planet-forming disk midplanes

    NASA Astrophysics Data System (ADS)

    Eistrup, Christian; Walsh, Catherine; van Dishoeck, Ewine F.

    2018-05-01

    Context. Exoplanet atmospheres are thought be built up from accretion of gas as well as pebbles and planetesimals in the midplanes of planet-forming disks. The chemical composition of this material is usually assumed to be unchanged during the disk lifetime. However, chemistry can alter the relative abundances of molecules in this planet-building material. Aims: We aim to assess the impact of disk chemistry during the era of planet formation. This is done by investigating the chemical changes to volatile gases and ices in a protoplanetary disk midplane out to 30 AU for up to 7 Myr, considering a variety of different conditions, including a physical midplane structure that is evolving in time, and also considering two disks with different masses. Methods: An extensive kinetic chemistry gas-grain reaction network was utilised to evolve the abundances of chemical species over time. Two disk midplane ionisation levels (low and high) were explored, as well as two different makeups of the initial abundances ("inheritance" or "reset"). Results: Given a high level of ionisation, chemical evolution in protoplanetary disk midplanes becomes significant after a few times 105 yr, and is still ongoing by 7 Myr between the H2O and the O2 icelines. Inside the H2O iceline, and in the outer, colder regions of the disk midplane outside the O2 iceline, the relative abundances of the species reach (close to) steady state by 7 Myr. Importantly, the changes in the abundances of the major elemental carbon and oxygen-bearing molecules imply that the traditional "stepfunction" for the C/O ratios in gas and ice in the disk midplane (as defined by sharp changes at icelines of H2O, CO2 and CO) evolves over time, and cannot be assumed fixed, with the C/O ratio in the gas even becoming smaller than the C/O ratio in the ice. In addition, at lower temperatures (<29 K), gaseous CO colliding with the grains gets converted into CO2 and other more complex ices, lowering the CO gas abundance between

  1. THE EFFECTS OF INITIAL ABUNDANCES ON NITROGEN IN PROTOPLANETARY DISKS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Schwarz, Kamber R.; Bergin, Edwin A.

    2014-12-20

    The dominant form of nitrogen provided to most solar system bodies is currently unknown, though available measurements show that the detected nitrogen in solar system rocks and ices is depleted with respect to solar abundances and the interstellar medium. We use a detailed chemical/physical model of the chemical evolution of a protoplanetary disk to explore the evolution and abundance of nitrogen-bearing molecules. Based on this model, we analyze how initial chemical abundances provided as either gas or ice during the early stages of disk formation influence which species become the dominant nitrogen bearers at later stages. We find that amore » disk with the majority of its initial nitrogen in either atomic or molecular nitrogen is later dominated by atomic and molecular nitrogen as well as NH{sub 3} and HCN ices, where the dominant species varies with disk radius. When nitrogen is initially in gaseous ammonia, it later becomes trapped in ammonia ice except in the outer disk where atomic nitrogen dominates. For a disk with the initial nitrogen in the form of ammonia ice, the nitrogen remains trapped in the ice as NH{sub 3} at later stages. The model in which most of the initial nitrogen is placed in atomic N best matches the ammonia abundances observed in comets. Furthermore, the initial state of nitrogen influences the abundance of N{sub 2}H{sup +}, which has been detected in protoplanetary disks. Strong N{sub 2}H{sup +} emission is found to be indicative of an N{sub 2} abundance greater than n{sub N{sub 2}}/n{sub H{sub 2}}>10{sup −6} in addition to tracing the CO snow line. Our models also indicate that NO is potentially detectable, with lower N gas abundances leading to higher NO abundances.« less

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

    PubMed Central

    Reisner, Walter; Larsen, Niels B.; Flyvbjerg, Henrik; Tegenfeldt, Jonas O.; Kristensen, Anders

    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 without additional chemical modification and achieve a high degree of control over local DNA conformation. DNA can be extended between two nanopits and in closely spaced arrays will self-assemble into “connect-the-dots” conformations consisting of locally pinned segments joined by fluctuating linkers. These results have broad implications for nanotechnology fields that require methods for the nanoscale positioning and manipulation of DNA. PMID:19122138

  3. Porous materials with pre-designed single-molecule traps for CO2 selective adsorption

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, JR; Yu, JM; Lu, WG

    2013-02-26

    Despite tremendous efforts, precise control in the synthesis of porous materials with pre-designed pore properties for desired applications remains challenging. Newly emerged porous metal-organic materials, such as metal-organic polyhedra and metal-organic frameworks, are amenable to design and property tuning, enabling precise control of functionality by accurate design of structures at the molecular level. Here we propose and validate, both experimentally and computationally, a precisely designed cavity, termed a 'single-molecule trap', with the desired size and properties suitable for trapping target CO2 molecules. Such a single-molecule trap can strengthen CO2-host interactions without evoking chemical bonding, thus showing potential for CO2 capture.more » Molecular single-molecule traps in the form of metal-organic polyhedra are designed, synthesised and tested for selective adsorption of CO2 over N-2 and CH4, demonstrating the trapping effect. Building these pre-designed single-molecule traps into extended frameworks yields metal-organic frameworks with efficient mass transfer, whereas the CO2 selective adsorption nature of single-molecule traps is preserved.« less

  4. Continuously adjustable, molecular-sieving “gate” on 5A zeolite for distinguishing small organic molecules by size

    DOE PAGES

    Song, Zhuonan; Huang, Yi; Xu, Weiwei L.; ...

    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 weremore » effectively distinguished via appropriate misalignment. Lastly, this novel concept may have great potential to fill the pore size gaps of the zeolite family and realize size-selective adsorption separation.« less

  5. Toward control of the metal-organic interfacial electronic structure in molecular electronics: a first-principles study on self-assembled monolayers of pi-conjugated molecules on noble metals.

    PubMed

    Heimel, Georg; Romaner, Lorenz; Zojer, Egbert; Brédas, Jean-Luc

    2007-04-01

    Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

  6. Intercalated Water and Organic Molecules for Electrode Materials of Rechargeable Batteries.

    PubMed

    Lee, Hyeon Jeong; Shin, Jaeho; Choi, Jang Wook

    2018-03-24

    The intrinsic limitations of lithium-ion batteries (LIBs) with regard to safety, cost, and the availability of raw materials have promoted research on so-called "post-LIBs". The recent intense research of post-LIBs provides an invaluable lesson that existing electrode materials used in LIBs may not perform as well in post-LIBs, calling for new material designs compliant with emerging batteries based on new chemistries. One promising approach in this direction is the development of materials with intercalated water or organic molecules, as these materials demonstrate superior electrochemical performance in emerging battery systems. The enlarged ionic channel dimensions and effective shielding of the electrostatic interaction between carrier ions and the lattice host are the origins of the observed electrochemical performance. Moreover, these intercalants serve as interlayer pillars to sustain the framework for prolonged cycles. Representative examples of such intercalated materials applied to batteries based on Li + , Na + , Mg 2+ , and Zn 2+ ions and supercapacitors are considered, along with their impact in materials research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Single-Molecule Fluorescence Imaging for Studying Organic, Organometallic, and Inorganic Reaction Mechanisms

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Blum, Suzanne A.

    2016-05-24

    The reactive behavior of individual molecules is seldom observed, because we usually measure the average properties of billions of molecules. What we miss is important: the catalytic activity of less than 1% of the molecules under observation can dominate the outcome of a chemical reaction seen at a macroscopic level. Currently available techniques to examine reaction mechanisms (such as nuclear magnetic resonance spectroscopy and mass spectrometry) study molecules as an averaged ensemble. These ensemble techniques are unable to detect minor components (under ~1%) in mixtures or determine which components in the mixture are responsible for reactivity and catalysis. In themore » field of mechanistic chemistry, there is a resulting heuristic device that if an intermediate is very reactive in catalysis, it often cannot be observed (termed “Halpern’s Rule” ). Ultimately, the development of single-molecule imaging technology could be a powerful tool to observe these “unobservable” intermediates and active catalysts. Single-molecule techniques have already transformed biology and the understanding of biochemical processes. The potential of single-molecule fluorescence microscopy to address diverse chemical questions, such as the chemical reactivity of organometallic or inorganic systems with discrete metal complexes, however, has not yet been realized. In this respect, its application to chemical systems lags significantly behind its application to biophysical systems. This transformative imaging technique has broad, multidisciplinary impact with the potential to change the way the chemistry community studies reaction mechanisms and reactivity distributions, especially in the core area of catalysis.« less

  8. Reducing dynamic disorder in small-molecule organic semiconductors by suppressing large-amplitude thermal motions

    PubMed Central

    Illig, Steffen; Eggeman, Alexander S.; Troisi, Alessandro; Jiang, Lang; Warwick, Chris; Nikolka, Mark; Schweicher, Guillaume; Yeates, Stephen G.; Henri Geerts, Yves; Anthony, John E.; Sirringhaus, Henning

    2016-01-01

    Thermal vibrations and the dynamic disorder they create can detrimentally affect the transport properties of van der Waals bonded molecular semiconductors. The low-energy nature of these vibrations makes it difficult to access them experimentally, which is why we still lack clear molecular design rules to control and reduce dynamic disorder. In this study we discuss the promising organic semiconductors rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothio-phene and 2,9-di-decyl-dinaphtho-[2,3-b:20,30-f]-thieno-[3,2-b]-thiophene in terms of an exceptionally low degree of dynamic disorder. In particular, we analyse diffuse scattering in transmission electron microscopy, to show that small molecules that have their side chains attached along the long axis of their conjugated core are better encapsulated in their crystal structure, which helps reduce large-amplitude thermal motions. Our work provides a general strategy for the design of new classes of very high mobility organic semiconductors with a low degree of dynamic disorder. PMID:26898754

  9. Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

    NASA Technical Reports Server (NTRS)

    Nuevo, Michel; Milam, Stefanie N.; Sandford, Scott

    2012-01-01

    Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

  10. Organic molecules as sorbing tracers for the assessment of surface areas in consolidated aquifer systems

    NASA Astrophysics Data System (ADS)

    Schaffer, Mario; Warner, Wiebke; Kutzner, Susann; Börnick, Hilmar; Worch, Eckhard; Licha, Tobias

    2017-03-01

    Based on the assumption that the specific surface area to volume ratio Asurf/V of consolidated rock materials is proportional to the surface area available for sorption, several inorganic cations were recently proposed as sorbing (cation exchanging) tracers for estimating these ratios in aquifers (e.g., for deriving the efficient heat exchange area of geothermal reservoirs). The main disadvantages of inorganic ions, however, are the limited number of suitable ions, their potential geogenic background, and their challenging online detection at trace concentrations. In this work, the spectrum of chemical substances used as sorbing tracers expands by considering fluorescent organic compounds that are cationic. They have the advantage of being highly water soluble and easy to measure online at very low concentrations. Results from systematic lab column experiments with seven selected organic cations under various conditions (different salinities and temperatures) are presented, emphasizing the potential of organic molecules as alternative sorbing tracers especially in consolidated aquifer systems. This work is a first stepping stone in identifying suitable molecular structures that can be selected or even individually adapted to the requirements of the tracer tests and prevailing aquifer conditions.

  11. Clean graphene electrodes on organic thin-film devices via orthogonal fluorinated chemistry.

    PubMed

    Beck, Jonathan H; Barton, Robert A; Cox, Marshall P; Alexandrou, Konstantinos; Petrone, Nicholas; Olivieri, Giorgia; Yang, Shyuan; Hone, James; Kymissis, Ioannis

    2015-04-08

    Graphene is a promising flexible, highly transparent, and elementally abundant electrode for organic electronics. Typical methods utilized to transfer large-area films of graphene synthesized by chemical vapor deposition on metal catalysts are not compatible with organic thin-films, limiting the integration of graphene into organic optoelectronic devices. This article describes a graphene transfer process onto chemically sensitive organic semiconductor thin-films. The process incorporates an elastomeric stamp with a fluorinated polymer release layer that can be removed, post-transfer, via a fluorinated solvent; neither fluorinated material adversely affects the organic semiconductor materials. We used Raman spectroscopy, atomic force microscopy, and scanning electron microscopy to show that chemical vapor deposition graphene can be successfully transferred without inducing defects in the graphene film. To demonstrate our transfer method's compatibility with organic semiconductors, we fabricate three classes of organic thin-film devices: graphene field effect transistors without additional cleaning processes, transparent organic light-emitting diodes, and transparent small-molecule organic photovoltaic devices. These experiments demonstrate the potential of hybrid graphene/organic devices in which graphene is deposited directly onto underlying organic thin-film structures.

  12. Accurate Induction Energies for Small Organic Molecules. 2. Development and Testing of Distributed Polarizability Models against SAPT(DFT) Energies.

    PubMed

    Misquitta, Alston J; Stone, Anthony J; Price, Sarah L

    2008-01-01

    In part 1 of this two-part investigation we set out the theoretical basis for constructing accurate models of the induction energy of clusters of moderately sized organic molecules. In this paper we use these techniques to develop a variety of accurate distributed polarizability models for a set of representative molecules that include formamide, N-methyl propanamide, benzene, and 3-azabicyclo[3.3.1]nonane-2,4-dione. We have also explored damping, penetration, and basis set effects. In particular, we have provided a way to treat the damping of the induction expansion. Different approximations to the induction energy are evaluated against accurate SAPT(DFT) energies, and we demonstrate the accuracy of our induction models on the formamide-water dimer.

  13. A SIFT study of the reactions of H2ONO+ ions with several types of organic molecules

    NASA Astrophysics Data System (ADS)

    Smith, David; Wang, Tianshu; Spanel, Patrik

    2003-11-01

    A selected ion flow tube (SIFT) study has been carried out of the reactions of hydrated nitrosonium ions, NO+H2O, which theory has equated to protonated nitrous acid ions, H2ONO+. One objective of this study was to investigate if this ion exhibits the properties of both a cluster ion and a protonated acid in their reactions with a variety of organic molecules. The chosen reactant molecules comprise two each of the following types--amines, terpenes, aromatic hydrocarbons, esters, carboxylic acids, ketones, aldehydes and alcohols. The reactant H2ONO+ (NO+H2O) ions are formed in a discharge ion source and injected into helium carrier gas where they are partially vibrationally excited and partially dissociated to NO+ ions. Hence, the reactions of the H2ONO+ ions had to be studies simultaneously with NO+ ions, the reactions of the latter ions readily being studied by selectively injecting NO+ ions into the carrier gas. The results of this study indicate that the H2ONO+ ions undergo a wide variety of reaction processes that depend on the properties of the reactant molecules such as their ionisation energies and proton affinities. These processes include charge transfer with compounds, M, that have low ionisation energies (producing M+), proton transfer with compounds possessing large proton affinities (MH+), hydride ion transfer (M---H+), alkyl radical (M---R+), alkoxide radical transfer (M---OR+), ion-molecule association (NO+H2OM) and ligand switching (NO+M), producing the ions given in parentheses.

  14. The relationship of metals, bifenthrin, physical habitat metrics, grain size, total organic carbon, dissolved oxygen and conductivity to Hyalella sp. abundance in urban California streams.

    PubMed

    Hall, Lenwood W; Anderson, Ronald D

    2013-01-01

    The objectives of this study were to determine the relationship between Hyalella sp. abundance in four urban California streams and the following parameters: (1) 8 bulk metals (As, Cd, Cr, Cu, Pb, Hg, Ni, and Zn) and their associated sediment Threshold Effect Levels (TELs); (2) bifenthrin sediment concentrations; (3) 10 habitat metrics and total score; (4) grain size (% sand, silt and clay); (5) Total Organic Carbon (TOC); (6) dissolved oxygen; and (7) conductivity. California stream data used for this study were collected from Kirker Creek (2006 and 2007), Pleasant Grove Creek (2006, 2007 and 2008), Salinas streams (2009 and 2010) and Arcade Creek (2009 and 2010). Hyalella abundance in the four California streams generally declined when metals concentrations were elevated beyond the TELs. There was also a statistically significant negative relationship between Hyalella abundance and % silt for these 4 California streams as Hyalella were generally not present in silt areas. No statistically significant relationships were reported between Hyalella abundance and metals concentrations, bifenthrin concentrations, habitat metrics, % sand, % clay, TOC, dissolved oxygen and conductivity. The results from this study highlight the complexity of assessing which factors are responsible for determining the abundance of amphipods, such as Hyalella sp., in the natural environment.

  15. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  16. Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Desai, R. T.; Coates, A. J.; Wellbrock, A.

    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 −},more » 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.« less

  17. Salting Constants of Small Organic Molecules in Aerosol-Relevant Salts and Application to Aerosol Formation in the Southeastern United States

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Carlton, A. M. G.; Ziemann, P. J.; Volkamer, R. M.

    2014-12-01

    Secondary organic aerosol (SOA) formation from small water-soluble molecules such as glyoxal and methyl glyoxal is a topic of emerging interest. Results from recent field campaigns, e.g. Waxman et al. (2013, GRL) and Knote et al. (2014, ACP), show that these molecules can form significant SOA mass as a result of 'salting-in'. Salting-in happens when a molecule's solubility increases with salt concentration and salting-out is the reverse. Salting effects modify the solubility exponentially with increasing salt concentration, and thus the effective Henry's law constant can strongly modify partitioning, and multiphase chemical reaction rates in aerosol water. Moreover, the solubility in aerosol water cannot easily inferred based on the solubility in cloud water, as the salting effects could change the solubility by a factor of 104 or more. In this work, we have devised and applied a novel experimental setup to measure salting constants using an ion trap mass spectrometer. We focus on small, water soluble molecules like methyl glyoxal and similar compounds and measure salting constants for aerosol-relevant salts including ammonium sulfate, ammonium nitrate, and sodium chloride. The Setschenow salting-constant values are then used to parameterize the effects of salting in CMAQ. We present a series of sensitivity studies of the effects that inorganic aerosols have on the SOA formation from small soluble molecules in the southeastern United States.

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

    NASA Technical Reports Server (NTRS)

    Engler, Charles; Canham, John

    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, non-magnetic 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.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    Engler, Charles D.; 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.