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Sample records for adjacent aromatic rings

  1. An electronic aromaticity index for large rings.

    PubMed

    Matito, Eduard

    2016-04-28

    We introduce a new electronic aromaticity index, AV1245, consisting of an average of the 4-center multicenter indices (MCI) along the ring that keeps a positional relationship of 1, 2, 4, 5. AV1245 measures the extent of transferability of the delocalized electrons between bonds 1-2 and 4-5, which is expected to be large in conjugated circuits and, therefore, in aromatic molecules. A new algorithm for the calculation of MCI for large rings is also introduced and used to produce the data for the calibration of the new aromaticity index. AV1245 does not rely on reference values, does not suffer from large numerical precision errors, and it does not present any limitation on the nature of atoms, the molecular geometry or the level of calculation. It is a size-extensive measure with low computational cost that grows linearly with the number of ring members. Therefore, it is especially suitable to study the aromaticity of large molecular rings such as those occurring in belt-shaped Möbius structures or porphyrins. The analysis of AV1245 in free-base and bis-metalated Pd [32]octaphyrins(1,0,1,0,1,0,1,0) completes this study. PMID:26878146

  2. Optimization of low ring polycylic aromatic biodegradation

    NASA Astrophysics Data System (ADS)

    Othman, N.; Abdul-Talib, S.; Tay, C. C.

    2016-07-01

    Polycyclic aromatic hydrocarbons (PAHs) are recalcitrance and persistence that finally turn into problematic environmental contaminants. Microbial degradation is considered to be the primary mechanism of PAHs removal from the environment due to its organic criteria. This study is carried out to optimize degradation process of low ring PAHs. Bacteria used in this study was isolated from sludge collected from Kolej Mawar, Universiti Teknologi MARA, Shah Alam, Selangor. Working condition namely, substrate concentration, bacteria concentration, pH and temperature were optimized. PAHs in the liquid sample was extracted by using solid phase microextractio equipped with a 7 µm polydimethylsiloxane (PDMS) SPME fibr. Removal of PAHs were assessed by measuring PAHs concentration using GC-FID. Results from the optimization study of biodegradation indicated that maximum rate of PAHs removal occurred at 100 mgL-1 of PAHs, 10% bacteria concentration, pH 7.0 and 30°C. These working condition had proved the effectiveness of using bacteria in biodegradation process of PAHs.

  3. Experimental measurement of noncovalent interactions between halogens and aromatic rings.

    PubMed

    Adams, Harry; Cockroft, Scott L; Guardigli, Claudio; Hunter, Christopher A; Lawson, Kevin R; Perkins, Julie; Spey, Sharon E; Urch, Christopher J; Ford, Rhonan

    2004-05-01

    Chemical double mutant cycles have been used to quantify the interactions of halogens with the faces of aromatic rings in chloroform. The halogens are forced over the face of an aromatic ring by an array of hydrogen-bonding interactions that lock the complexes in a single, well-defined conformation. These interactions can also be engineered into the crystal structures of simpler model compounds, but experiments in solution show that the halogen-aromatic interactions observed in the solid state are all unfavourable, regardless of whether the aromatic rings contain electron-withdrawing or electron-donating substituents. The halogen-aromatic interactions are repulsive by 1-3 kJ mol(-1). The interactions with fluorine are slightly less favourable than with chlorine and bromine.

  4. Redox shuttles having an aromatic ring fused to a 1,1,4,4-tetrasubstituted cyclohexane ring

    SciTech Connect

    Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

    2015-12-01

    An electrolyte includes an alkali metal salt; an aprotic solvent; and a redox shuttle additive including an aromatic compound having at least one aromatic ring fused with at least one non-aromatic ring, the aromatic ring having two or more oxygen or phosphorus-containing substituents.

  5. [Laser Induced Fluorescence Spectroscopic Analysis of Aromatics from One Ring to Four Rings].

    PubMed

    Zhang, Peng; Liu, Hai-feng; Yue, Zong-yu; Chen, Bei-ling; Yao, Ming-fa

    2015-06-01

    In order to distinguish small aromatics preferably, a Nd : YAG Laser was used to supply an excitation laser, which was adjusted to 0.085 J x cm(-2) at 266 nm. Benzene, toluene, naphthalene, phenanthrene, anthracene, pyrene and chrysene were used as the representative of different rings aromatics. The fluorescence emission spectra were researched for each aromatic hydrocarbon and mixtures by Laser induced fluorescence (LIF). Results showed that the rings number determined the fluorescence emission spectra, and the structure with same rings number did not affect the emission fluorescence spectrum ranges. This was due to the fact that the absorption efficiency difference at 266 nm resulted in that the fluorescence intensities of each aromatic hydrocarbon with same rings number were different and the fluorescence intensities difference were more apparently with aromatic ring number increasing. When the absorption efficiency was similar at 266 nm and the concentrations of each aromatic hydrocarbon were same, the fluorescence intensities were increased with aromatic ring number increasing. With aromatic ring number increasing, the fluorescence spectrum and emission peak wavelength were all red-shifted from ultraviolet to visible and the fluorescence spectrum range was also wider as the absorption efficiency was similar. The fluorescence emission spectra from one to four rings could be discriminated in the following wavelengths, 275 to 320 nm, 320 to 375 nm, 375 to 425 nm, 425 to 556 nm, respectively. It can be used for distinguish the type of the polycyclic aromatic hydrocarbons (PAHs) as it exists in single type. As PAHs are usually exist in a variety of different rings number at the same time, the results for each aromatic hydrocarbon may not apply to the aromatic hydrocarbon mixtures. For the aromatic hydrocarbon mixtures, results showed that the one- or two-ring PAHs in mixtures could not be detected by fluorescence as three- or four-ring PAHs existed in mixture

  6. Aromatic rings in chemical and biological recognition: energetics and structures.

    PubMed

    Salonen, Laura M; Ellermann, Manuel; Diederich, François

    2011-05-16

    This review describes a multidimensional treatment of molecular recognition phenomena involving aromatic rings in chemical and biological systems. It summarizes new results reported since the appearance of an earlier review in 2003 in host-guest chemistry, biological affinity assays and biostructural analysis, data base mining in the Cambridge Structural Database (CSD) and the Protein Data Bank (PDB), and advanced computational studies. Topics addressed are arene-arene, perfluoroarene-arene, S⋅⋅⋅aromatic, cation-π, and anion-π interactions, as well as hydrogen bonding to π systems. The generated knowledge benefits, in particular, structure-based hit-to-lead development and lead optimization both in the pharmaceutical and in the crop protection industry. It equally facilitates the development of new advanced materials and supramolecular systems, and should inspire further utilization of interactions with aromatic rings to control the stereochemical outcome of synthetic transformations. PMID:21538733

  7. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G.; Sims, R.C.

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  8. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G. ); Sims, R.C. . Dept. of Civil and Environmental Engineering)

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  9. Synthesis of Carbazole Alkaloids by Ring-Closing Metathesis and Ring Rearrangement-Aromatization.

    PubMed

    Dhara, Kalyan; Mandal, Tirtha; Das, Joydeb; Dash, Jyotirmayee

    2015-12-21

    Aprocess for the assembly of carbazole alkaloids has been developed on the basis of ring-closing metathesis (RCM) and ringrearrangement-aromatization (RRA) as the key steps. This method is based on allyl Grignard addition to isatin derivatives to provide smooth access to 2,2-diallyl 3-oxindole derivatives through a 1,2-allyl shift. The diallyl derivatives were used as RCM precursors to afford a novel class of spirocyclopentene-3-oxindole derivatives, which underwent a novel RRA reaction to afford carbazole derivatives. The synthetic sequence to carbazoles was shortened by combining the RCM and RRA steps in an orthogonal tandem catalytic process. The utility of this methodology was further demonstrated by the straightforward synthesis of carbazole alkaloids, including amukonal derivative, girinimbilol, heptaphylline, and bis(2-hydroxy-3-methylcarbazole).

  10. Synthesis of Carbazole Alkaloids by Ring-Closing Metathesis and Ring Rearrangement-Aromatization.

    PubMed

    Dhara, Kalyan; Mandal, Tirtha; Das, Joydeb; Dash, Jyotirmayee

    2015-12-21

    Aprocess for the assembly of carbazole alkaloids has been developed on the basis of ring-closing metathesis (RCM) and ringrearrangement-aromatization (RRA) as the key steps. This method is based on allyl Grignard addition to isatin derivatives to provide smooth access to 2,2-diallyl 3-oxindole derivatives through a 1,2-allyl shift. The diallyl derivatives were used as RCM precursors to afford a novel class of spirocyclopentene-3-oxindole derivatives, which underwent a novel RRA reaction to afford carbazole derivatives. The synthetic sequence to carbazoles was shortened by combining the RCM and RRA steps in an orthogonal tandem catalytic process. The utility of this methodology was further demonstrated by the straightforward synthesis of carbazole alkaloids, including amukonal derivative, girinimbilol, heptaphylline, and bis(2-hydroxy-3-methylcarbazole). PMID:26768698

  11. Polyimides with carbonyl and ether connecting groups between the aromatic rings

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Havens, Stephen J. (Inventor)

    1992-01-01

    New polyimides have been prepared from the reaction of aromatic dianhydrides with novel aromatic diamines containing carbonyl and ether connecting groups between the aromatic rings. Several of these polyimides are shown to be semi-crystalline as evidenced by wide angle x ray diffraction and differential scanning calorimetry. Most of the polyimides form tough solvent resistant films with high tensile properties. Several of these materials can be thermally processed to form solvent and base resistant moldings.

  12. A Multistep Synthesis Incorporating a Green Bromination of an Aromatic Ring

    ERIC Educational Resources Information Center

    Cardinal, Pascal; Greer, Brandon; Luong, Horace; Tyagunova, Yevgeniya

    2012-01-01

    Electrophilic aromatic substitution is a fundamental topic taught in the undergraduate organic chemistry curriculum. A multistep synthesis that includes a safer and greener method for the bromination of an aromatic ring than traditional bromination methods is described. This experiment is multifaceted and can be used to teach students about…

  13. The Misuse of the Circle Notation to Represent Aromatic Rings.

    ERIC Educational Resources Information Center

    Belloli, Robert C.

    1983-01-01

    Discusses the confusion and erroneous conclusions that can result from the overuse and misuse of the circle notation to represent aromaticity in polycylic aromatic hydrocarbons. Includes nature of the problem, textbook treatment, and a possible compromise method of representation. (Author/JN)

  14. No-carrier-added (NCA) aryl ([sup 18]F) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    DOEpatents

    Yushin Ding; Fowler, J.S.; Wolf, A.P.

    1993-10-19

    A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

  15. No-carrier-added (NCA) aryl (18E) fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    DOEpatents

    Ding, Yu-Shin; Fowler, Joanna S.; Wolf, Alfred P.

    1993-01-01

    A method for synthesizing no-carrier-added (NCA) aryl [.sup.18 F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method of the present invention includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substitutent on an electron rich ring. The reaction is The U.S. Government has rights in this invention pursuant to Contract Number DE-AC02-76CH00016, between the U.S. Department of Energy and Associated Universities Inc.

  16. σ-Aromaticity in an unsaturated ring: osmapentalene derivatives containing a metallacyclopropene unit.

    PubMed

    Zhu, Congqing; Zhou, Xiaoxi; Xing, Hongjie; An, Ke; Zhu, Jun; Xia, Haiping

    2015-03-01

    In general, aromaticity can be clarified as π- and σ-aromaticity according to the type of electrons with major contributions. The traditional π-aromaticity generally describes the π-conjugation in fully unsaturated rings whereas σ-aromaticity may stabilize fully saturated rings with delocalization caused by σ-electron conjugation. Reported herein is an example of σ-aromaticity in an unsaturated three-membered ring (3 MR), which is supported by experimental observations and theoretical calculations. Specifically, when the 3 MR in cyclopropaosmapentalene is cleaved by ethane through two isodesmic reactions, both of them are highly endothermic (+29.7 and +35.0 kcal mol(-1)). These positive values are in sharp contrast to the expected exothermicity, thus indicating aromaticity in the 3 MR. Further nucleus-independent chemical shift and anisotropy of the current-induced density calculations reveal the nature of σ-aromaticity in the unsaturated 3 MR. PMID:25656694

  17. Δg: The new aromaticity index based on g-factor calculation applied for polycyclic benzene rings

    NASA Astrophysics Data System (ADS)

    Ucun, Fatih; Tokatlı, Ahmet

    2015-02-01

    In this work, the aromaticity of polycyclic benzene rings was evaluated by the calculation of g-factor for a hydrogen placed perpendicularly at geometrical center of related ring plane at a distance of 1.2 Å. The results have compared with the other commonly used aromatic indices, such as HOMA, NICSs, PDI, FLU, MCI, CTED and, generally been found to be in agreement with them. So, it was proposed that the calculation of the average g-factor as Δg could be applied to study the aromaticity of polycyclic benzene rings without any restriction in the number of benzene rings as a new magnetic-based aromaticity index.

  18. A new aromatic probe - The ring stretching vibration Raman spectroscopy frequency

    NASA Astrophysics Data System (ADS)

    Guo, Yan-bo; Liu, Zi-zhong; Liu, Hong-xia; Zhang, Feng-ying; Yin, Jun-qing

    2016-07-01

    A new aromatic criterion is presented to determine the aromatic degree of the high symmetric molecules. Group theory is used to explain the correlation between the aromatic degree and the value of Ring Stretching Vibration Raman Spectroscopic Frequency (RSVRSF). The calculations of the geometrical optimization, nucleus-independent chemical shifts (NICS) and values of the Raman Spectroscopy for the aromatic molecules-LnHn (L = C, Si, Ge, n = 3, 5-8) were performed using the Density Functional Theory (DFT) Method, as well as the correlations between the values of their RSVRSF and NICS values by Statistic Package for Social Science (SPSS17.0). There are high positive correlations between the theoretical calculated the NICS values and the value of the RSVRSF (A1g/A1‧) of the LnHn (L = C, Si, Ge, n = 3, 5-8). The bigger the aromatic degree, the bigger the RSVRSF is. The value of the RSVRSF is a new probe of aromaticity. Expectedly, it is predicted that the experimental determination of the aromatic degree can be achieved by the determination of the ring stretching vibration (A1g/A1‧) Raman spectrum frequencies for the aromatic target molecules.

  19. A sharp thermal transition of fast aromatic ring dynamics in ubiquitin

    PubMed Central

    Kasinath, Vignesh; Fu, Yinan; Sharp, Kim A.

    2015-01-01

    Aromatic amino acid side chains have a rich role within proteins and are often central to their structure and function. Suitable isotopic labelling strategies enable studies of sub-nanosecond aromatic ring dynamics using solution NMR relaxation methods. Surprisingly, we find that the three aromatic side chains in human ubiquitin show a sharp thermal dynamical transition at ~312 K. Hydrostatic pressure has little effect on the low temperature behaviour but decreases somewhat the amplitude of motion in the high temperature regime. Thus below the transition temperature ring motion is largely librational. Above it complete ring rotation that is most consistent with a continuous rotational diffusion not requiring transient creation of a large activated free volume occurs. Molecular dynamics simulations qualitatively corroborate this view and reinforce the notion that the dynamical character of the protein interior has a much more liquid alkane-like properties than previously appreciated. PMID:25476230

  20. Synthesis of Aromatic Aza-metallapentalenes from Metallabenzene via Sequential Ring Contraction/Annulation

    PubMed Central

    Wang, Tongdao; Han, Feifei; Huang, Haiping; Li, Jinhua; Zhang, Hong; Zhu, Jun; Lin, Zhenyang; Xia, Haiping

    2015-01-01

    The concept of aromaticity has long played an important role in chemistry and continues to fascinate both experimentalists and theoreticians. Among the archetypal aromatic compounds, heteroaromatics are particularly attractive. Recently, substitution of a transition-metal fragment for a carbon atom in the anti-aromatic hydrocarbon pentalene has led to the new heteroaromatic osmapentalenes. However, construction of the aza-homolog of osmapentalenes cannot be accomplished by a similar synthetic manipulation. Here, we report the synthesis of aza-osmapentalenes by sequential ring contraction/annulation reactions of osmabenzenes via osmapentafulvenes. Nuclear magnetic resonance spectra, X-ray crystallographic analysis, and DFT calculations all suggest that these aza-osmapentalenes exhibit aromatic character. Thus, the stepwise transformation of metallabenzenes to metallapentafulvenes and then aza-metallapentalenes provides an efficient and facile synthetic route to these bicyclic heteroaromatics. PMID:25856747

  1. Argentation chromatography for the separation of polycyclic aromatic compounds according to ring number.

    PubMed

    Nocun, Margarete; Andersson, Jan T

    2012-01-01

    Crude oils are the most complex mixtures known and every speciation method relies on a simplification of their complexity. Argentation chromatography is shown to be superior to traditional liquid chromatographic ways of separating aromatic compounds based on the number of aromatic carbon atoms. A silver(I) mercaptopropano silica gel allows an efficient group separation of polycyclic aromatic compounds to be achieved. The usefulness of this phase is demonstrated for SRM 1582 Wilmington crude oil and a diesel fuel. Furthermore, the phase can also be used for semi-preparative purposes to collect fractions for further analysis with high resolution mass spectrometry. Orbitrap mass spectra are obtained here for the polycyclic aromatic sulfur heterocycles and it is demonstrated that they can contain one to five naphtheno rings.

  2. Competitive substituent effects on the reactivity of aromatic rings.

    PubMed

    Jaramillo, Cinthia; Guerra, Doris; Moreno, Luis Fernando; Restrepo, Albeiro

    2010-05-20

    We performed second order perturbation theory calculations of gas phase proton affinities for o, m, p-nitroaniline at all positions and attempted correlations of the thermodynamic stability of the products with several reactivity indices: inductive effects from resonance, partial charges, and frontier orbital related indices such as local nucleophilic and electron-donating powers, global hardness of the products, and the substituent push-pull effect. All protonation reactions at ring positions are predicted to be exothermic. Resonance and charge analysis give inconsistent correlations with proton affinities, while the condensed nucleophilic Fukui function, electron-donating power, global hardness, and push-pull effect show promising trends.

  3. Induction of an aromatic six-membered nitrogen ring via cation-pi interaction.

    PubMed

    Duan, Hongxia; Gong, Zhen; Cheng, Jiagao; Zhu, Weiliang; Chen, Kaixian; Jiang, Hualiang

    2006-11-01

    Nitrogen clusters have been intensively studied for their potential application as high-energy density materials, but a six-membered nitrogen ring (N6) was not found to be stable and aromatic. To explore the possibility of inducing an aromatic N6 ring via cation-pi interaction, quantum chemistry calculations were performed on the systems of Ca2N6, CaN6, CaN6(2-), N6, and N6(4-) at the B3LYP/6-311+G level. The optimized geometries reveal that the planar structure of the N6 ring is stable only in the Ca2N6 complex. The computed NBO and CHelpG charges demonstrate that the planar N6 moiety in the Ca2N6 complex is almost a 10pi-electron system. The predicted nucleus-independent chemical shift (NICS) values demonstrate that the N6 moiety is aromatic in comparison with the NICS values of benzene. The estimated enthalpy of formation for the Ca2N6 complex is 100.4 kcal/mol for the reaction of 2Ca and 3N2. The binding energy between the Ca2+ cation and the N6(4-) moiety is -1928.8 kcal/mol, with electrostatic interaction serving as the predominant component. When all the calculated results are taken into account, including the planar structure, 10pi-electron system, identical bond length, and negative NICS value of the N6(4-) moiety in the Ca2N6 complex, it is deduced that the alkaline earth metal Ca is capable of inducing an aromatic N6 ring through the cation-pi interaction formed by electron transfer from the Ca atom to the N6 ring.

  4. Hydrogen/deuterium exchange on aromatic rings during atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Davies, Noel W; Smith, Jason A; Molesworth, Peter P; Ross, John J

    2010-04-15

    It has been demonstrated that substituted indoles fully labelled with deuterium on the aromatic ring can undergo substantial exchange back to partial and even fully protonated forms during atmospheric pressure chemical ionisation (APCI) liquid chromatography/mass spectrometry (LC/MS). The degree of this exchange was strongly dependent on the absolute quantity of analyte, the APCI desolvation temperature, the nature of the mobile phase, the mobile phase flow rate and the instrument used. Hydrogen/deuterium (H/D) exchange on several other aromatic ring systems during APCI LC/MS was either undetectable (nitrobenzene, aniline) or extremely small (acetanilide) compared to the effect observed for substituted indoles. This observation has major implications for quantitative assays using deuterium-labelled internal standards and for the detection of deuterium-labelled products from isotopically labelled feeding experiments where there is a risk of back exchange to the protonated form during the analysis. PMID:20213724

  5. Secondary Structures in a Freeze-Dried Lignite Humic Acid Fraction Caused by Hydrogen-Bonding of Acidic Protons with Aromatic Rings.

    PubMed

    Cao, Xiaoyan; Drosos, Marios; Leenheer, Jerry A; Mao, Jingdong

    2016-02-16

    A lignite humic acid (HA) was separated from inorganic and non-HA impurities (i.e., aluminosilicates, metals) and fractionated by a combination of dialysis and XAD-8 resin. Fractionation revealed a more homogeneous structure of lignite HA. New and more specific structural information on the main lignite HA fraction is obtained by solid-state nuclear magnetic resonance (NMR) spectroscopy. Quantitative (13)C multiple cross-polarization (multiCP) NMR indicated oxidized phenyl propane structures derived from lignin. MultiCP experiments, conducted on potassium HA salts titrated to pH 10 and pH 12, revealed shifts consistent with carboxylate and phenolate formation, but structural changes associated with enolate formation from aromatic beta keto acids were not detected. Two-dimensional (1)H-(13)C heteronuclear correlation (2D HETCOR) NMR indicated aryl-aliphatic ketones, aliphatic and aromatic carboxyl groups, phenol, and methoxy phenyl ethers. Acidic protons from carboxyl groups in both the lignite HA fraction and a synthetic HA-like polycondensate were found to be hydrogen-bonded with electron-rich aromatic rings. Our results coupled with published infrared spectra provide evidence for the preferential hydrogen bonding of acidic hydrogens with electron-rich aromatic rings rather than adjacent carbonyl groups. These hydrogen-bonding interactions likely result from stereochemical arrangements in primary structures and folding. PMID:26836017

  6. Secondary Structures in a Freeze-Dried Lignite Humic Acid Fraction Caused by Hydrogen-Bonding of Acidic Protons with Aromatic Rings.

    PubMed

    Cao, Xiaoyan; Drosos, Marios; Leenheer, Jerry A; Mao, Jingdong

    2016-02-16

    A lignite humic acid (HA) was separated from inorganic and non-HA impurities (i.e., aluminosilicates, metals) and fractionated by a combination of dialysis and XAD-8 resin. Fractionation revealed a more homogeneous structure of lignite HA. New and more specific structural information on the main lignite HA fraction is obtained by solid-state nuclear magnetic resonance (NMR) spectroscopy. Quantitative (13)C multiple cross-polarization (multiCP) NMR indicated oxidized phenyl propane structures derived from lignin. MultiCP experiments, conducted on potassium HA salts titrated to pH 10 and pH 12, revealed shifts consistent with carboxylate and phenolate formation, but structural changes associated with enolate formation from aromatic beta keto acids were not detected. Two-dimensional (1)H-(13)C heteronuclear correlation (2D HETCOR) NMR indicated aryl-aliphatic ketones, aliphatic and aromatic carboxyl groups, phenol, and methoxy phenyl ethers. Acidic protons from carboxyl groups in both the lignite HA fraction and a synthetic HA-like polycondensate were found to be hydrogen-bonded with electron-rich aromatic rings. Our results coupled with published infrared spectra provide evidence for the preferential hydrogen bonding of acidic hydrogens with electron-rich aromatic rings rather than adjacent carbonyl groups. These hydrogen-bonding interactions likely result from stereochemical arrangements in primary structures and folding.

  7. Synthesis and antifungal activity of C-21 steroids with an aromatic D ring.

    PubMed

    Sonego, Juan M; Cirigliano, Adriana M; Cabrera, Gabriela M; Burton, Gerardo; Veleiro, Adriana S

    2013-07-01

    Six analogues of salpichrolides with a simplified side chain (6-11) were synthesized using a new methodology to obtain steroids with an aromatic D-ring. The key step was the elimination of HBr in a vicinal dibromo D-homosteroid by treatment with 1,4-diazabicyclo[2.2.2]octane (DABCO). All new compounds were completely characterized by 2D NMR techniques and tested on two fungal pathogenic species, Fusarium virguliforme and Fusarium solani.

  8. Aromaticity of rings-in-molecules (RIMs) from electron localization-delocalization matrices (LDMs)

    NASA Astrophysics Data System (ADS)

    Sumar, Ismat; Cook, Ronald; Ayers, Paul W.; Matta, Chérif F.

    2016-01-01

    A new and powerful molecular descriptor termed the LDM (localization-delocalization matrix) has recently been proposed as a molecular fingerprinting tool and has been shown to yield robust quantitative-structure-to-activity/property-relationships (QSAR/QSPR). An LDM lists the average number of electrons localized within an atom in a molecule along its diagonal while the off-diagonal elements are the pair-wise average number of electrons shared between every pair of atoms in the molecule, bonded or not. Hence, the LDM is a representation of a fuzzy molecular graph that accounts for the whereabouts of all electron(s) in the molecule and can be expected to encode for several facets of its chemistry at once. We show that the LDM captures the aromatic character of a ring-in-a-molecule by comparing the aromaticity ranking based on the LDMs and their eigenvalues of 6-membered carbon rings within (polycyclic) benzenoid hydrocarbons with the ranking based on four well-established local aromaticity measures (harmonic oscillator model of aromaticity, acromatic fluctuation index, para delocalization index, and nucleus independent chemical shift(0)). This paper is dedicated to the memory of Professor Paul von Ragué Schleyer (1930-2014).

  9. Differential Degradation of Bicyclics with Aromatic and Alicyclic Rings by Rhodococcus sp. Strain DK17 ▿

    PubMed Central

    Kim, Dockyu; Yoo, Miyoun; Choi, Ki Young; Kang, Beom Sik; Kim, Tai Kyoung; Hong, Soon Gyu; Zylstra, Gerben J.; Kim, Eungbin

    2011-01-01

    The metabolically versatile Rhodococcus sp. strain DK17 is able to grow on tetralin and indan but cannot use their respective desaturated counterparts, 1,2-dihydronaphthalene and indene, as sole carbon and energy sources. Metabolite analyses by gas chromatography-mass spectrometry and nuclear magnetic resonance spectrometry clearly show that (i) the meta-cleavage dioxygenase mutant strain DK180 accumulates 5,6,7,8-tetrahydro-1,2-naphthalene diol, 1,2-indene diol, and 3,4-dihydro-naphthalene-1,2-diol from tetralin, indene, and 1,2-dihydronaphthalene, respectively, and (ii) when expressed in Escherichia coli, the DK17 o-xylene dioxygenase transforms tetralin, indene, and 1,2-dihydronaphthalene into tetralin cis-dihydrodiol, indan-1,2-diol, and cis-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene, respectively. Tetralin, which is activated by aromatic hydroxylation, is degraded successfully via the ring cleavage pathway to support growth of DK17. Indene and 1,2-dihydronaphthalene do not serve as growth substrates because DK17 hydroxylates them on the alicyclic ring and further metabolism results in a dead-end metabolite. This study reveals that aromatic hydroxylation is a prerequisite for proper degradation of bicyclics with aromatic and alicyclic rings by DK17 and confirms the unique ability of the DK17 o-xylene dioxygenase to perform distinct regioselective hydroxylations. PMID:21965391

  10. Comparison of Intramolecular Forces in Dipeptides with Two Aromatic Rings: does Dispersion Dominate?

    NASA Astrophysics Data System (ADS)

    Thomas, Jessica A.

    2015-06-01

    IR/UV double resonance spectroscopy has shown that the structure of the capped dipeptide Ac-Trp-Tyr-NH2 is dominated by a hydrophobic interaction between the aromatic rings on the side chains. Using the same method, a similar molecule, Ac-Phe-Phe-NH2, had three experimentally observed conformers including one similar to that of Ac-Trp-Tyr-NH2. In this work, calculations were performed on additional dipeptides containing two aromatic rings to determine if the dispersion-dominated structure was among the lowest energy structures in all such cases. The B3LYP-DCP method developed by DiLabio and Torres was used to calculate the conformations of each dipeptide. Appending dispersion correction potentials (DCP) to B3LYP input files improves results for systems containing dispersion interactions without significantly increasing the calculation time. This method was used first on Ac-Trp-Tyr-NH2 and Ac-Phe-Phe-NH2 to confirm that it successfully identified the experimentally observed structures among the lowest energy results and was then applied to other capped dipeptides containing two aromatic rings including Ac-Phe-Tyr-NH2 and Ac-Tyr-Phe-NH2.

  11. Role of aromatic rings in the molecular recognition of aminoglycoside antibiotics: implications for drug design.

    PubMed

    Vacas, Tatiana; Corzana, Francisco; Jiménez-Osés, Gonzalo; González, Carlos; Gómez, Ana M; Bastida, Agatha; Revuelta, Julia; Asensio, Juan Luis

    2010-09-01

    Aminoglycoside antibiotics participate in a large variety of binding processes involving both RNA and proteins. The description, in recent years, of several clinically relevant aminoglycoside/receptor complexes has greatly stimulated the structural-based design of new bioactive derivatives. Unfortunately, design efforts have frequently met with limited success, reflecting our incomplete understanding of the molecular determinants for the antibiotic recognition. Intriguingly, aromatic rings of the protein/RNA receptors seem to be key actors in this process. Indeed, close inspection of the structural information available reveals that they are frequently involved in CH/pi stacking interactions with sugar/aminocyclitol rings of the antibiotic. While the interaction between neutral carbohydrates and aromatic rings has been studied in detail during past decade, little is known about these contacts when they involve densely charged glycosides. Herein we report a detailed experimental and theoretical analysis of the role played by CH/pi stacking interactions in the molecular recognition of aminoglycosides. Our study aims to determine the influence that the antibiotic polycationic character has on the stability, preferred geometry, and dynamics of these particular contacts. With this purpose, different aminoglycoside/aromatic complexes have been selected as model systems. They varied from simple bimolecular interactions to the more stable intramolecular CH/pi contacts present in designed derivatives. The obtained results highlight the key role played by electrostatic forces and the desolvation of charged groups in the molecular recognition of polycationic glycosides and have clear implications for the design of improved antibiotics.

  12. Aromatic ring-flipping in supercooled water: implications for NMR-based structural biology of proteins.

    PubMed

    Skalicky, J J; Mills, J L; Sharma, S; Szyperski, T

    2001-01-24

    We have characterized, for the first time, motional modes of a protein dissolved in supercooled water: the flipping kinetics of phenylalanyl and tyrosinyl rings of the 6 kDa protein BPTI have been investigated by NMR at temperatures between -3 and -16.5 degrees C. At T = -15 degrees C, the ring-flipping rate constants of Tyr 23, Tyr 35, and Phe 45 are smaller than 2 s(-1), i.e., flip-broadening of aromatic NMR lines is reduced beyond detection and averaging of NOEs through ring-flipping is abolished. This allows neat detection of distinct NOE sets for the individual aromatic (1)H spins. In contrast, the rings of Phe 4, Tyr 10, Tyr 21, Phe 22, and Phe 33 are flipping rapidly on the chemical shift time scale with rate constants being in the range from approximately 10(2) to 10(5) s(-1) even at T = -15 degrees C. Line width measurements in 2D [(1)H,(1)H]-NOESY showed that flipping of the Phe 4 and Phe 33 rings is, however, slowed to an extent that the onset of associated line broadening in the fast exchange limit is registered. The reduced ring-flipping rate constant of Phe 45 in supercooled water allowed very precise determination of Eyring activation enthalpy and entropy from cross relaxation suppressed 2D [(1)H,(1)H]-exchange spectroscopy. This yielded DeltaH = 14 +/- 0.5 kcal.mol(-1) and DeltaS = -4 +/- 1 cal.mol(-1).K(-1), i.e., values close to those previously derived by Wagner and Wüthrich for the temperature range from 4 to 72 degrees C (DeltaH = 16 +/- 1 kcal.mol(-1) and DeltaS = 6 +/- 2 cal.mol(-1).K(-1)). The preservation of the so far uniquely low value for DeltaS indicates that the distribution of internal motional modes associated with the ring flip of Phe 45 is hardly affected by lowering T well below 0 degrees C. Hence, if a globular protein does not cold denature, aromatic flipping rates, and thus likely also the rates of other conformational and/or chemical exchange processes occurring in supercooled water, can be expected to be well estimated from

  13. Ozonolysis of surface adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    NASA Astrophysics Data System (ADS)

    O'Neill, E. M.; Kawam, A. Z.; Van Ry, D. A.; Hinrichs, R. Z.

    2013-07-01

    Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (±0.8) × 10-7 and 2 (±1) × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ>300 nm) enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(±1) but had no effect on ozonolysis of the alkene side-chain.

  14. Distribution and ecological risk assessment of polycyclic aromatic hydrocarbons in water, suspended particulate matter and sediment from Daliao River estuary and the adjacent area, China.

    PubMed

    Zheng, Binghui; Wang, Liping; Lei, Kun; Nan, Bingxu

    2016-04-01

    Polycyclic aromatic hydrocarbons (PAHs) contamination was investigated in concurrently sampled surface water, suspended particulate matter (SPM) and sediment of Daliao River estuary and the adjacent area, China. The total concentrations of PAHs ranged from 71.12 to 4255.43 ng/L in water, from 1969.95 to 11612.21 ng/L in SPM, and from 374.84 to 11588.85 ng/g dry weight (dw) in sediment. Although the 2-3 ring PAHs were main PAH congeners in water and SPM, the 4-6 ring PAHs were also detected and their distribution was site-specific, indicating a very recent PAHs input around the area since they were hydrophobic. The PAHs pollution was identified as mixed combustion and petroleum sources. Based on species sensitivity distribution (SSD), the ecological risk in SPM from 82% stations was found to be higher obviously than that in water. The risk in water was basically ranked as medium, while the risk in SPM was ranked as high. Analysis with sediment quality guidelines (SQGs) indicated that negative eco-risk occasionally occurred in about 50% stations, while negative eco-risk frequently occurred in about 3% stations only caused by Phenanthrene(Phe) and Dibenzo(a,h)anthracene(DBA). Here freshwater acute effects data together with saltwater data were used for SSD model. And this method could quickly give the rational risk information, and achieved our objective that compared the spatial difference of risk levels among three compartments. The results confirmed that the use of freshwater acute effects data from the ECOTOX database together with saltwater effects data is acceptable for risk assessment purposes in estuary. PMID:26855211

  15. Ring expansion reactions of anti-aromatic boroles: a promising synthetic avenue to unsaturated boracycles.

    PubMed

    Barnard, Jonathan H; Yruegas, Sam; Huang, Kexuan; Martin, Caleb D

    2016-08-21

    Conjugated boron heterocycles have emerged as attractive synthetic targets due to their potential in medicinal chemistry and as electronic materials. However, the development of unsaturated boracycles has been hampered by difficulties in their preparation. Recently, a new synthetic avenue to access these species has been developed that takes advantage of the high reactivity of boroles. These five-membered anti-aromatic heterocycles can react with substrates to furnish ring expansion products via the insertion of one, two, or three atoms into the boracyclic ring. The ring expansion can occur via two pathways, the first exploits the activated diene moiety of the heterocycle in Diels-Alder chemistry with the resulting bicyclic species undergoing further rearrangements. The second reaction pathway is initiated by the coordination of the Lewis basic site of a substrate to the highly Lewis acidic boron center rendering the endocyclic B-C bond of the borole nucleophilic, inducing the formation of larger boracycles via attack at the electrophilic site of the substrate. This review summarizes the current state of this chemistry and details the mechanisms leading to the products. The methodologies described herein could very well be extended to other substrates, as well as applied to other anti-aromatic heterocycles.

  16. Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems.

    PubMed

    Okujima, Tetsuo; Mack, John; Nakamura, Jun; Kubheka, Gugu; Nyokong, Tebello; Zhu, Hua; Komobuchi, Naoki; Ono, Noboru; Yamada, Hiroko; Uno, Hidemitsu; Kobayashi, Nagao

    2016-10-01

    A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals. PMID:27558988

  17. Palladium-Catalyzed, Ring-Forming Aromatic C–H Alkylations with Unactivated Alkyl Halides

    PubMed Central

    Venning, Alexander R. O.; Bohan, Patrick T.; Alexanian, Erik J.

    2015-01-01

    A catalytic C–H alkylation using unactivated alkyl halides and a variety of arenes and heteroarenes is described. This ring-forming process is successful with a variety of unactivated primary and secondary alkyl halides, including those with β-hydrogens. In contrast to standard polar or radical cyclizations of aromatic systems, electronic activation of the substrate is not required. The mild, catalytic reaction conditions are highly functional group tolerant and facilitate access to a diverse range of synthetically and medicinally important carbocyclic and heterocyclic systems. PMID:25746442

  18. Substitution patterns in aromatic rings by increment analysis. Model development and application to natural organic matter.

    PubMed

    Perdue, E M; Hertkorn, N; Kettrup, A

    2007-02-01

    The aromatic region of two-dimensional heteronuclear 1H, 13C NMR spectra of natural organic matter and related materials (e.g., 1H and 13C chemical shifts ranging from approximately 5 to 10 and 80 to 140 ppm, respectively) is highly complex and difficult to interpret using conventional approaches. In principle, this region of the NMR spectrum should be amenable to detailed analysis, because the effects of many common substituents on the chemical shifts of aromatic carbon and hydrogen are well documented. This paper describes the development of a model for prediction of substitution patterns in aromatic rings by increment analysis (SPARIA). In the forward mode, SPARIA is used to predict the chemical shifts of 1H and 13C on aromatic moieties containing every possible combination of eight common substituents that are likely to be representative of substituents on aromatic moieties in natural organic matter. The accuracy of SPARIA in the forward mode is evaluated for 29 aromatic compounds (100 peaks) by comparison of predicted chemical shifts for 1H and 13C with experimental values and with predictions of commercially available software for prediction of NMR spectra. The most important development in this paper is the inverse mode that is built into SPARIA. Given chemical shifts for 1H and 13C (such as may be obtained from a two-dimensional, heteronuclear NMR spectrum), the inverse mode of SPARIA calculates all possible combinations of the eight selected substituents that yield chemical shifts within a specified window of chemical shift for both 1H and 13C. Both the distribution of possible substitution patterns and simple descriptive statistics of the distribution are thus obtained. The inverse mode of SPARIA has been tested on the 29 aromatic compounds (100 peaks) that were used to evaluate its forward mode, and the dependence of the inverse process on the size of the chemical shift window has been evaluated. Finally, the inverse mode of SPARIA has been applied to

  19. O-demethylation, dehydroxylation, ring-reduction and cleavage of aromatic substrates by Enterobacteriaceae under anaerobic conditions.

    PubMed

    Grbić-Galić, D

    1986-12-01

    Four fermentative facultative anaerobes, members of the genera Enterobacter and Escherichia, were tested for their ability to transform an aromatic lignin derivative, 3-methoxy-4-hydroxy-cinnamic acid (ferulic acid), under anaerobic (fermentative) conditions. The pure cultures studied were shown to O-demethylate, dehydroxylate, reduce the double bond in the side-chain, decarboxylate the aromatic ring to the stage of benzoate and to reduce the ring to an alicyclic acid. Aromatic hydrocarbons (toluene, ethylbenzene and propylbenzene), as well as phenols (phenol, o-cresol, p-cresol, 2-ethylphenol and 3-hydroxy-4-ethylphenol) were also produced. In addition, during 3 months incubation, the cleavage of the aromatic ring occurred, whereby a small fraction of the substrate was converted to straight-chain and branched (methylated, ethylated) five- to eight-carbon aliphatic acids. The results indicate that pure cultures of fermentative facultative anaerobes might be capable of degrading substituted aromatic acids to aliphatic products under strictly anaerobic (fermentative) conditions. These abilities, which have so far been found only in denitrifying pseudomonads among facultative anaerobes, might be common in Enterobacteriaceae. It is conceivable that these bacteria are important as degraders of aromatic compounds in anaerobic ecosystems.

  20. Writing with ring currents: selectively hydrogenated polycyclic aromatics as finite models of graphene and graphane.

    PubMed

    Fowler, Patrick W; Gibson, Christopher M; Bean, David E

    2014-03-01

    Alternating partial hydrogenation of the interior region of a polycyclic aromatic hydrocarbon gives a finite model system representing systems on the pathway from graphene to the graphane modification of the graphene sheet. Calculations at the DFT and coupled Hartree-Fock levels confirm that sp(2) cycles of bare carbon centres isolated by selective hydrogenation retain the essentially planar geometry and electron delocalization of the annulene that they mimic. Delocalization is diagnosed by the presence of ring currents, as detected by ipsocentric calculation and visualization of the current density induced in the π system by a perpendicular external magnetic field. These induced 'ring' currents have essentially the same sense, strength and orbital origin as in the free hydrocarbon. Subjected to the important experimental proviso of the need for atomic-scale control of hydrogenation, this finding predicts the possibility of writing single, multiple and concentric diatropic and/or paratropic ring currents on the graphene/graphane sheet. The implication is that pathways for free flow of ballistic current can be modelled in the same way.

  1. Computer-aided rational design of novel EBF analogues with an aromatic ring.

    PubMed

    Wang, Shanshan; Sun, Yufeng; Du, Shaoqing; Qin, Yaoguo; Duan, Hongxia; Yang, Xinling

    2016-06-01

    Odorant binding proteins (OBPs) are important in insect olfactory recognition. These proteins bind specifically to insect semiochemicals and induce their seeking, mating, and alarm behaviors. Molecular docking and molecular dynamics simulations were performed to provide computational insight into the interaction mode between AgamOBP7 and novel (E)-β-farnesene (EBF) analogues with an aromatic ring. The ligand-binding cavity in OBP7 was found to be mostly hydrophobic due to the presence of several nonpolar residues. The interactions between the EBF analogues and the hydrophobic residues in the binding cavity increased in strength as the distance between them decreased. The EBF analogues with an N-methyl formamide or ester linkage had higher docking scores than those with an amide linkage. Moreover, delocalized π-π and electrostatic interactions were found to contribute significantly to the binding between the ligand benzene ring and nearby protein residues. To design new compounds with higher activity, four EBF analogues D1-D4 with a benzene ring were synthesized and evaluated based on their docking scores and binding affinities. D2, which had an N-methyl formamide group linkage, exhibited stronger binding than D1, which had an amide linkage. D4 exhibited particularly strong binding due to multiple hydrophobic interactions with the protein. This study provides crucial foundations for designing novel EBF analogues based on the OBP structure. Graphical abstract The design strategy of new EBF analogues based on the OBP7 structure. PMID:27251400

  2. Computer-aided rational design of novel EBF analogues with an aromatic ring.

    PubMed

    Wang, Shanshan; Sun, Yufeng; Du, Shaoqing; Qin, Yaoguo; Duan, Hongxia; Yang, Xinling

    2016-06-01

    Odorant binding proteins (OBPs) are important in insect olfactory recognition. These proteins bind specifically to insect semiochemicals and induce their seeking, mating, and alarm behaviors. Molecular docking and molecular dynamics simulations were performed to provide computational insight into the interaction mode between AgamOBP7 and novel (E)-β-farnesene (EBF) analogues with an aromatic ring. The ligand-binding cavity in OBP7 was found to be mostly hydrophobic due to the presence of several nonpolar residues. The interactions between the EBF analogues and the hydrophobic residues in the binding cavity increased in strength as the distance between them decreased. The EBF analogues with an N-methyl formamide or ester linkage had higher docking scores than those with an amide linkage. Moreover, delocalized π-π and electrostatic interactions were found to contribute significantly to the binding between the ligand benzene ring and nearby protein residues. To design new compounds with higher activity, four EBF analogues D1-D4 with a benzene ring were synthesized and evaluated based on their docking scores and binding affinities. D2, which had an N-methyl formamide group linkage, exhibited stronger binding than D1, which had an amide linkage. D4 exhibited particularly strong binding due to multiple hydrophobic interactions with the protein. This study provides crucial foundations for designing novel EBF analogues based on the OBP structure. Graphical abstract The design strategy of new EBF analogues based on the OBP7 structure.

  3. Protonation energies of 1-5-ring polycyclic aromatic nitrogen heterocyclics: comparing experiment and theory.

    PubMed

    Wiseman, Alexander; Sims, Lacey A; Snead, Russell; Gronert, Scott; Maclagan, Robert G A R; Meot-Ner Mautner, Michael

    2015-01-01

    Polycyclic nitrogen heterocyclic compounds (PANHs) can be protonated in the gas phase in mass spectrometry, in solution in acidic and biological environments, and if present, in interstellar clouds. Intrinsic molecular effects on PANH basicities can be observed by their gas phase protonation thermochemistry. We determined the gas phase basicities/proton affinities (GBs/PAs) of prototype one-nitrogen, 3-5-ring PANH compounds of increasing sizes and polarizabilities by kinetic bracketing, using proton transfer reactions to reference bases. The experimental proton affinities increase from 1-ring (pyridine, 222.2); to 2-ring (quinoline, 227.8); to 3-5-ring compounds, 227-234 kcal mol(-1). We also calculated the GB/PA values at the M06-2X/6-311+G**//B3LYP/6-31g* level. The computed PAs agree, within the experimental uncertainty, with the experimental values anchored to the upper range of the NIST GB/PA database. Specifically, the computed PAs are smaller than the experimental values by 1.4 ± 0.9 kcal/mol for nonaromatic nitrogen reference bases and for 1-5-ring PANHs, independently of the number of rings, aromaticity, and molecular size. Therefore, a useful method to calculate proton affinities of PANH compounds can use M06-2X/6-311+G**//B3LYP/6-31g* computational PAs + 1.4 ± 0.9 kcal mol(-1). The agreement with experiment supports the NIST database within this accuracy, in the upper range up to 235 kcal mol(-1), even though there are no direct absolute experimental anchor points in this range. For astrochemical applications, the measured PAs allow calculating the energies of the (PANH)(+•) + H2 → (PANH)H(+) + H(•) reactions that may convert the radical ions to less reactive 11-electron ions. The reactions are endothermic or nearly thermoneutral for the 3-5-ring ions and would be very slow at low temperatures, allowing reactive (PANH)(+•) radical ions to persist in interstellar clouds.

  4. Compounds having aromatic rings and side-chain amide-functionality and a method for transporting monovalent anions across biological membranes using the same

    DOEpatents

    Davis, Jeffery T.; Sidorov, Vladimir; Kotch, Frank W.

    2008-04-08

    A compound containing at least two aromatic rings covalently bonded together, with each aromatic ring containing at least one oxyacetamide-based side chain, the compound being capable of forming a chloride ion channel across a lipid bilayer, and transporting chloride ion across the lipid bilayer.

  5. Pollution status of polycyclic aromatic hydrocarbons in surface sediments from the Yangtze River Estuary and its adjacent coastal zone.

    PubMed

    Wang, Chenglong; Zou, Xinqing; Gao, Jianhua; Zhao, Yifei; Yu, Wenwen; Li, Yali; Song, Qiaochu

    2016-11-01

    Polycyclic aromatic hydrocarbons (PAHs) are mainly produced by incomplete combustion and are used as indicators of anthropogenic activities on the environment. This study analyses the PAHs level in the Yangtze River Estuary (YRE), an important component of Yangtze River and a developed and populated region in China. Surface sediments were collected from 77 sites at the YRE and its adjacent coastal zone (IACZ) for a comprehensive study of PAHs. Kriging interpolation technology and Positive matrix factorization (PMF) model were applied to explore the spatial distribution and sources of PAHs. Concentrations of 16 PAHs (ΣPAHs) varied from 27.2 ng g(-1) to 621.6 ng g(-1) dry weight, with an average value of 158.2 ng g(-1). Spatially, ΣPAHs exhibited wide fluctuation and exhibited an increasing tendency from north to south. In addition, ΣPAHs exhibited a decreasing trend with increasing distance between the estuary and IACZ. The deposition flux of PAHs indicated that more than 107.8 t a(-1) PAHs was deposited in the study area annually. The results of the PMF model revealed that anthropogenic activities were the main sources of PAHs in the study area. Vehicle emissions and marine engines were the most important sources and accounted for 40.9% of the pollution. Coal combustion, petrogenic sources, and wood combustion were other sources that contributed 23.9%, 23.6%, and 11.5%, respectively. The distribution patterns of PAHs in the YRE and IACZ were influenced by many complicated factors such as sediment grain size, hydrodynamics and so on. PMID:27485799

  6. Dearomatization-Induced Cycloaddition and Aromatization-Triggered Rearrangement: Synthesis of Vertically Expanded Five-Ring Fused Benzofurans.

    PubMed

    Han, Dandan; Chen, Jinjin; He, Qiuqin; Fan, Renhua

    2016-09-16

    A dearomatization strategy has been developed for the efficient construction of vertically expanded five-ring fused benzofurans from ortho-alkynylphenols and ortho-alkynylarylaldimines. The stepwise procedure comprises a dearomatization-induced silver-catalyzed [3 + 2] cycloaddition followed by an aromatization-triggered ytterbium-catalyzed rearrangement. PMID:27598323

  7. Cytotoxic non-aromatic B-ring flavanones from Piper carniconnectivum C. DC.

    PubMed

    Freitas, Giovana C; Batista, João M; Franchi, Gilberto C; Nowill, Alexandre E; Yamaguchi, Lydia F; Vilcachagua, Janaina D; Favaro, Denize C; Furlan, Maysa; Guimarães, Elsie F; Jeffrey, Christopher S; Kato, Massuo J

    2014-01-01

    The EtOAc extract from the leaves of Piper carniconnectivum C. DC. was subjected to chromatographic separation to afford two non-aromatic B-ring flavanone compounds: 5-hydroxy-2-(1'-hydroxy-4'-oxo-cyclohex-2'-en-1'-yl)-6,7-dimethoxy-2,3-dihydro-4H-chromen-4-one (1) and 5-hydroxy-2-(1',2'-dihydroxy-4'-oxo-cyclohexyl)-6,7-dimethoxy-2,3-dihydro-4H-chromen-4-one (2). The absolute configuration of (+)-1 was unambiguously determined as 2S,1'R by electronic circular dichroism (ECD) spectroscopy and comparison to simulated spectra that were calculated using time-dependent density functional theory (TDDFT). This methodology allowed the assignment of the absolute configuration of (+)-2 also as 2S,1'R, except for the stereogenic center at C-2', which was assigned as R because of the evidence drawn from high resolution NMR experiments. The cytotoxic activity of both compounds and 3 (hydrogenated B-ring derivative of 1) was evaluated on twelve human leukemia cell lines, and the IC50 values (<10 μM) indicated the activity of 1 against seven cell lines.

  8. Biodegradation of three- and four-ring polycyclic aromatic hydrocarbons under aerobic and denitrifying conditions

    SciTech Connect

    McNally, D.L.; Mihelcic, J.R.; Lueking, D.R.

    1998-09-01

    PAHs are thought to be particularly persistent in environments where anaerobic conditions exist. This study presents evidence for the biodegradation of three- and four-ringed PAHs (anthracene, phenanthrene, and pyrene) under strict anaerobic, denitrifying conditions. Three pseudomonad strains, isolated from contrasting environments, were used in this study. All three strains were known PAH degraders and denitrifiers. Degradation proceeded to nondetectable levels in 12--80 h for anthracene, 12--44 h for phenanthrene, and 24--72 h for pyrene. The rates of anaerobic degradation were typically slower than under aerobic conditions in almost all cases, except for strain SAG-R which had similar removal rates for all three and four-ring PAHs. Denitrification activity was verified by monitoring nitrate utilization and nitrous oxide production. Although none of the pseudomonads were adapted to the denitrifying conditions, only the pseudomonad isolated from a noncontaminated site consistently exhibited an adaptation period which approximated 12 h. This study supports growing evidence that the degradation of aromatic hydrocarbons coupled to denitrification may be an important factor affecting the fate of these compounds in natural and engineered systems.

  9. Study of the Formation of the First Aromatic Rings in the Pyrolysis of Cyclopentene.

    PubMed

    Herbinet, Olivier; Rodriguez, Anne; Husson, Benoit; Battin-Leclerc, Frédérique; Wang, Zhandong; Cheng, Zhanjun; Qi, Fei

    2016-02-11

    The thermal decomposition of cyclopentene was studied in a jet-stirred reactor operated at constant pressure and temperature to provide new experimental information about the formation of the first aromatic rings from cyclic C5 species. Experiments were carried out at a residence time of 1 s, a pressure of 106.7 kPa, temperatures ranging from 773 to 1073 K and under diluted conditions (cyclopentene inlet mole fraction of 0.04). Species were quantified using three analytical methods: gas chromatography, synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), and single photon laser ionization mass spectrometry (SPI-MS). Several species could be quantified using both methods allowing comparison of experimental data obtained with the three apparatuses. Discrepancies observed in mole fraction profiles of some large aromatics suggest that the direct sampling in the gas phase (with a molecular beam or a capillary tube) provide more reliable results. The main reaction products are 1,3-cyclopentadiene and hydrogen. The formation of many unsaturated C2-C6 olefins, diolefins and alkynes was also observed but in smaller amounts. Benzene, toluene, styrene, indene, and naphthalene were detected from 923 K. SVUV-PIMS data allowed the identification of another C6H6 isomer which is 1,5-hexadien-3-yne rather than fulvene. The quantification of the cyclopentadienyl radical was obtained from SVUV-PIMS and SPI-MS data with some uncertainty induced by the possible contribution to the signal for m/z 65 of a fragment from the decomposition of a larger ion. This is the first time that a radical is quantified in a jet-stirred reactor using non-optical techniques. SPI-MS analyses allowed the detection of species likely being combination products of allyl and cyclopentadienyl radicals. A model was developed for the pyrolysis of cyclopentene. This model includes routes of formation of aromatics from the cyclopentadienyl radical. The comparison of experimental and

  10. Analysis of the magnetically induced current density of molecules consisting of annelated aromatic and antiaromatic hydrocarbon rings.

    PubMed

    Sundholm, Dage; Berger, Raphael J F; Fliegl, Heike

    2016-06-21

    Magnetically induced current susceptibilities and current pathways have been calculated for molecules consisting of two pentalene groups annelated with a benzene (1) or naphthalene (2) moiety. Current strength susceptibilities have been obtained by numerically integrating separately the diatropic and paratropic contributions to the current flow passing planes through chosen bonds of the molecules. The current density calculations provide novel and unambiguous current pathways for the unusual molecules with annelated aromatic and antiaromatic hydrocarbon moieties. The calculations show that the benzene and naphthalene moieties annelated with two pentalene units as in molecules 1 and 2, respectively, are unexpectedly antiaromatic sustaining only a local paratropic ring current around the ring, whereas a weak diatropic current flows around the C-H moiety of the benzene ring. For 1 and 2, the individual five-membered rings of the pentalenes are antiaromatic and a slightly weaker semilocal paratropic current flows around the two pentalene rings. Molecules 1 and 2 do not sustain any net global ring current. The naphthalene moiety of the molecule consisting of a naphthalene annelated with two pentalene units (3) does not sustain any strong ring current that is typical for naphthalene. Instead, half of the diatropic current passing the naphthalene moiety forms a zig-zag pattern along the C-C bonds of the naphthalene moiety that are not shared with the pentalene moieties and one third of the current continues around the whole molecule partially cancelling the very strong paratropic semilocal ring current of the pentalenes. For molecule 3, the pentalene moieties and the individual five-membered rings of the pentalenes are more antiaromatic than for 1 and 2. The calculated current patterns elucidate why the compounds with formally [4n + 2] π-electrons have unusual aromatic properties violating the Hückel π-electron count rule. The current density calculations also provide

  11. A dissected ring current model for assessing magnetic aromaticity: a general approach for both organic and inorganic rings.

    PubMed

    Foroutan-Nejad, Cina; Shahbazian, Shant; Feixas, Ferran; Rashidi-Ranjbar, Parviz; Solà, Miquel

    2011-08-01

    A model based on classical electrodynamics is used to measure the strength of ring currents of different molecular orbitals, i.e., σ- and π-orbitals, and characteristics of ring current loops, i.e., ring current radii and height of current loops above/below the ring planes, among a number of organic as well as inorganic molecules. For the π-current, the present model represents an improvement of previous approaches to determine ring current intensity. It is proven that the present model is more precise than previous models as they could not explain presence of the minimum in the plot of NICS(πzz) versus distance close to the ring plane. Variations in the charge of molecules and the types of constituent atoms of each species affect the ring current radii of both σ- and π-current loops as well as the height of π-current loops above/below the ring plane. It is suggested that variation in the distribution of the one-electron density in different systems is the main source of differences of the ring current characteristics.

  12. A dissected ring current model for assessing magnetic aromaticity: a general approach for both organic and inorganic rings.

    PubMed

    Foroutan-Nejad, Cina; Shahbazian, Shant; Feixas, Ferran; Rashidi-Ranjbar, Parviz; Solà, Miquel

    2011-08-01

    A model based on classical electrodynamics is used to measure the strength of ring currents of different molecular orbitals, i.e., σ- and π-orbitals, and characteristics of ring current loops, i.e., ring current radii and height of current loops above/below the ring planes, among a number of organic as well as inorganic molecules. For the π-current, the present model represents an improvement of previous approaches to determine ring current intensity. It is proven that the present model is more precise than previous models as they could not explain presence of the minimum in the plot of NICS(πzz) versus distance close to the ring plane. Variations in the charge of molecules and the types of constituent atoms of each species affect the ring current radii of both σ- and π-current loops as well as the height of π-current loops above/below the ring plane. It is suggested that variation in the distribution of the one-electron density in different systems is the main source of differences of the ring current characteristics. PMID:21598277

  13. Novel aromatic ring-hydroxylating dioxygenase genes from coastal marine sediments of Patagonia

    PubMed Central

    Lozada, Mariana; Riva Mercadal, Juan P; Guerrero, Leandro D; Di Marzio, Walter D; Ferrero, Marcela A; Dionisi, Hebe M

    2008-01-01

    Background Polycyclic aromatic hydrocarbons (PAHs), widespread pollutants in the marine environment, can produce adverse effects in marine organisms and can be transferred to humans through seafood. Our knowledge of PAH-degrading bacterial populations in the marine environment is still very limited, and mainly originates from studies of cultured bacteria. In this work, genes coding catabolic enzymes from PAH-biodegradation pathways were characterized in coastal sediments of Patagonia with different levels of PAH contamination. Results Genes encoding for the catalytic alpha subunit of aromatic ring-hydroxylating dioxygenases (ARHDs) were amplified from intertidal sediment samples using two different primer sets. Products were cloned and screened by restriction fragment length polymorphism analysis. Clones representing each restriction pattern were selected in each library for sequencing. A total of 500 clones were screened in 9 gene libraries, and 193 clones were sequenced. Libraries contained one to five different ARHD gene types, and this number was correlated with the number of PAHs found in the samples above the quantification limit (r = 0.834, p < 0.05). Overall, eight different ARHD gene types were detected in the sediments. In five of them, their deduced amino acid sequences formed deeply rooted branches with previously described ARHD peptide sequences, exhibiting less than 70% identity to them. They contain consensus sequences of the Rieske type [2Fe-2S] cluster binding site, suggesting that these gene fragments encode for ARHDs. On the other hand, three gene types were closely related to previously described ARHDs: archetypical nahAc-like genes, phnAc-like genes as identified in Alcaligenes faecalis AFK2, and phnA1-like genes from marine PAH-degraders from the genus Cycloclasticus. Conclusion These results show the presence of hitherto unidentified ARHD genes in this sub-Antarctic marine environment exposed to anthropogenic contamination. This information

  14. No-carrier-added (NCA) aryl [{sup 18}F]fluorides via the nucleophilic aromatic substitution of electron rich aromatic rings

    SciTech Connect

    Ding, Yu-Shin; Fowler, J.S.; Wolf, A.P.

    1991-12-31

    A method for synthesizing no-carrier-added (NCA) aryl [{sup 18}F] fluoride substituted aromatic aldehyde compositions bearing an electron donating group is described. The method includes the step of reacting aromatic nitro aldehydes having a suitably protected hydroxyl substituent on an electron rich ring. The reaction is carried out by nucleophilic aromatic substitution with a no-carrier-added (NCA) [{sup 18}F]fluoride ion. The method can be used to synthesize various no-carrier-added aryl [{sup 18}F]fluoride compositions, including 6-[{sup 18}F]fluoro-L-DOPA, 2-[{sup 18}F]fluorotyrosine, 6-[{sup 18}F]fluoronorepinephrine, and 6-[{sup 18}F]fluorodopamine. In those instances when a racemic mixture of enantiomers is produced by the present invention, such as in the synthesis of 6-[{sup 18}F]fluoronorepinephrine, a preferred method also includes resolution of the racemic mixture on a chiral HPLC column. This procedure results in a high yield of enantiomerically pure [{sup 18}F] labeled isomers, for example [-]-6-[{sup 18}F]fluoronorepinephrine and [+]-6-[{sup 18}F]fluoronorepinephrine.

  15. Non-Markovian response of ultrafast coherent electronic ring currents in chiral aromatic molecules in a condensed phase

    SciTech Connect

    Mineo, H.; Lin, S. H.; Fujimura, Y.; Xu, J.; Xu, R. X.; Yan, Y. J.

    2013-12-07

    Results of a theoretical study on non-Markov response for femtosecond laser-driven coherent ring currents in chiral aromatic molecules embedded in a condensed phase are presented. Coherent ring currents are generated by coherent excitation of a pair of quasi-degenerated π-electronic excited states. The coherent electronic dynamical behaviors are strongly influenced by interactions between the electronic system and phonon bath in a condensed phase. Here, the bath correlation time is not instantaneous but should be taken to be a finite time in ultrashort time-resolved experiments. In such a case, Markov approximation breaks down. A hierarchical master equation approach for an improved semiclassical Drude dissipation model was adopted to examine the non-Markov effects on ultrafast coherent electronic ring currents of (P)-2,2{sup ′}-biphenol in a condensed phase. Time evolution of the coherent ring current derived in the hierarchical master equation approach was calculated and compared with those in the Drude model in the Markov approximation and in the static limit. The results show how non-Markovian behaviors in quantum beat signals of ring currents depend on the Drude bath damping constant. Effects of temperatures on ultrafast coherent electronic ring currents are also clarified.

  16. Non-Markovian response of ultrafast coherent electronic ring currents in chiral aromatic molecules in a condensed phase

    NASA Astrophysics Data System (ADS)

    Mineo, H.; Lin, S. H.; Fujimura, Y.; Xu, J.; Xu, R. X.; Yan, Y. J.

    2013-12-01

    Results of a theoretical study on non-Markov response for femtosecond laser-driven coherent ring currents in chiral aromatic molecules embedded in a condensed phase are presented. Coherent ring currents are generated by coherent excitation of a pair of quasi-degenerated π-electronic excited states. The coherent electronic dynamical behaviors are strongly influenced by interactions between the electronic system and phonon bath in a condensed phase. Here, the bath correlation time is not instantaneous but should be taken to be a finite time in ultrashort time-resolved experiments. In such a case, Markov approximation breaks down. A hierarchical master equation approach for an improved semiclassical Drude dissipation model was adopted to examine the non-Markov effects on ultrafast coherent electronic ring currents of (P)-2,2'-biphenol in a condensed phase. Time evolution of the coherent ring current derived in the hierarchical master equation approach was calculated and compared with those in the Drude model in the Markov approximation and in the static limit. The results show how non-Markovian behaviors in quantum beat signals of ring currents depend on the Drude bath damping constant. Effects of temperatures on ultrafast coherent electronic ring currents are also clarified.

  17. Ozonolysis of surface-adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    NASA Astrophysics Data System (ADS)

    O'Neill, E. M.; Kawam, A. Z.; Van Ry, D. A.; Hinrichs, R. Z.

    2014-01-01

    Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion, and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near-monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (± 0.8) × 10-7 and 2 (± 1) × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ > 300 nm) enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(± 1) but had no effect on ozonolysis of the alkene side chain.

  18. A new classification system for bacterial Rieske non-heme iron aromatic ring-hydroxylating oxygenases

    PubMed Central

    Kweon, Ohgew; Kim, Seong-Jae; Baek, Songjoon; Chae, Jong-Chan; Adjei, Michael D; Baek, Dong-Heon; Kim, Young-Chang; Cerniglia, Carl E

    2008-01-01

    Background Rieske non-heme iron aromatic ring-hydroxylating oxygenases (RHOs) are multi-component enzyme systems that are remarkably diverse in bacteria isolated from diverse habitats. Since the first classification in 1990, there has been a need to devise a new classification scheme for these enzymes because many RHOs have been discovered, which do not belong to any group in the previous classification. Here, we present a scheme for classification of RHOs reflecting new sequence information and interactions between RHO enzyme components. Result We have analyzed a total of 130 RHO enzymes in which 25 well-characterized RHO enzymes were used as standards to test our hypothesis for the proposed classification system. From the sequence analysis of electron transport chain (ETC) components of the standard RHOs, we extracted classification keys that reflect not only the phylogenetic affiliation within each component but also relationship among components. Oxygenase components of standard RHOs were phylogenetically classified into 10 groups with the classification keys derived from ETC components. This phylogenetic classification scheme was converted to a new systematic classification consisting of 5 distinct types. The new classification system was statistically examined to justify its stability. Type I represents two-component RHO systems that consist of an oxygenase and an FNRC-type reductase. Type II contains other two-component RHO systems that consist of an oxygenase and an FNRN-type reductase. Type III represents a group of three-component RHO systems that consist of an oxygenase, a [2Fe-2S]-type ferredoxin and an FNRN-type reductase. Type IV represents another three-component systems that consist of oxygenase, [2Fe-2S]-type ferredoxin and GR-type reductase. Type V represents another different three-component systems that consist of an oxygenase, a [3Fe-4S]-type ferredoxin and a GR-type reductase. Conclusion The new classification system provides the following

  19. Surface chemistry of five-membered aromatic ring molecules containing two different heteroatoms on Si(111)-7 x 7.

    PubMed

    Tao, Feng; Bernasek, Steven L

    2007-04-18

    The surface chemistry of three representative aromatic molecules containing two different heteroatoms isoxazole, oxazole, and thiazole on Si(111)-7 x 7 was studied. These molecules exhibit different competition and selectivity for multiple reaction channels with this surface, determined by a combination of molecular electronic and structural factors. Isoxazole is chemically attached to Si(111)-7 x 7 through both dative-bond addition and [4 + 2]-like cycloaddition. Oxazole chemisorbs on Si(111)-7 x 7 through both dative-bond addition and [2 + 2]-like cycloaddition. The kinetically favored [2 + 2]-like cycloadduct at low temperature is thermally converted into the thermodynamically preferred [4 + 2]-like cycloadduct at a temperature higher than 300 K. Thiazole is chemically bound to this surface only through formation of a Si...N dative bond at low temperature. This dative-bonded molecule is thermally converted into a [4 + 2]-like cycloadduct. The reaction channels of the three five-membered aromatic molecules containing two different heteroatoms (isoxazole, oxazole, and thiazole) and of the aromatic molecules containing only one heteroatom (pyridine, pyrrole, furan, and thiophene) are compared and analyzed for a thorough understanding of the reaction mechanisms of various heterocyclic aromatic molecules on this surface. The intrinsic connection between surface reaction mechanism and molecular electronic structure is demonstrated. This includes the distribution of electron density on the molecular ring determined by the geometric arrangement of the heteroatoms, the electronegativity of the heteroatoms, and the electronic contribution of the heteroatoms to formation of aromatic pi conjugation, as well as the molecular polarity.

  20. Gaseous polycyclic aromatic hydrocarbon concentrations are higher in urban forests than adjacent open areas during summer but not in winter--Exploratory study.

    PubMed

    Viippola, Viljami; Rantalainen, Anna-Lea; Yli-Pelkonen, Vesa; Tervo, Peatta; Setälä, Heikki

    2016-01-01

    While the potential of plants to uptake polycyclic aromatic hydrocarbons (PAHs) is widely acknowledged, empirical evidence of the effects of this process on local atmospheric PAH concentrations and human health is tenuous. We measured gaseous PAH concentrations using passive samplers in urban tree-covered areas and adjacent open, treeless areas in a near-road environment in Finland to gain information on the ability of urban vegetation to improve air quality. The ability of urban, mostly deciduous, vegetation to affect PAHs was season dependent: during summer, concentrations were significantly higher in tree-covered areas, while in the fall, concentrations in open areas exceeded those in tree-covered areas. During winter, concentrations in tree-covered areas were either lower or did not differ from those in open areas. Results of this study imply that the commonly believed notion that trees unequivocally improve air quality does not apply to PAHs studied here.

  1. Gaseous polycyclic aromatic hydrocarbon concentrations are higher in urban forests than adjacent open areas during summer but not in winter--Exploratory study.

    PubMed

    Viippola, Viljami; Rantalainen, Anna-Lea; Yli-Pelkonen, Vesa; Tervo, Peatta; Setälä, Heikki

    2016-01-01

    While the potential of plants to uptake polycyclic aromatic hydrocarbons (PAHs) is widely acknowledged, empirical evidence of the effects of this process on local atmospheric PAH concentrations and human health is tenuous. We measured gaseous PAH concentrations using passive samplers in urban tree-covered areas and adjacent open, treeless areas in a near-road environment in Finland to gain information on the ability of urban vegetation to improve air quality. The ability of urban, mostly deciduous, vegetation to affect PAHs was season dependent: during summer, concentrations were significantly higher in tree-covered areas, while in the fall, concentrations in open areas exceeded those in tree-covered areas. During winter, concentrations in tree-covered areas were either lower or did not differ from those in open areas. Results of this study imply that the commonly believed notion that trees unequivocally improve air quality does not apply to PAHs studied here. PMID:26412199

  2. Regioselective ring opening of polycyclic aromatic hydrocarbon epoxides by polymer-supported N sub 3 sup minus anion

    SciTech Connect

    Lakshman, M.; Nadkarni, D.V.; Lehr, R.E. )

    1990-08-03

    The benzylic ring opening of some polycyclic aromatic hydrocarbon (PAH) tetrahydro epoxides and one diol epoxide has been achieved by Amberlite supported N{sub 3}{sup {minus}} ion, in a regio- and stereoselective manner. The resulting azidohydrins have been converted to the corresponding {beta}-acyloxy amines and/or amino alcohols. The {beta}-acyloxy amino compounds are suitable for incorporation into synthetic oligonucleotides, whereas the amino alcohols were synthesized in order to establish the regiochemistry of the ring-opening step. The tetrahydro models studied were the naphthalene (Np), benz(c)acridine (BcAr), benzo(a)pyrene (BaP), and benzo(e)pyrene (BeP) epoxides. In the Np and BcAr cases, the amino group is equatorial whereas in the BaP and BeP cases, it is axial. In the final stage of these ring-opening reactions, the racemic diol epoxide of benzo(a)pyrene (BaPDE) 24 was converted to the corresponding amines. In each of the cases studied, the attack by N{sub 3}{sup {minus}} ion occurred at the benzylic site. The relative stereochemistry of the azido and hydroxyl groups in every case was trans. No other regio- or stereoisomer was observed in any of these compounds in the ring-opening step.

  3. Functional characterization of diverse ring-hydroxylating oxygenases and induction of complex aromatic catabolic gene clusters in Sphingobium sp. PNB

    PubMed Central

    Khara, Pratick; Roy, Madhumita; Chakraborty, Joydeep; Ghosal, Debajyoti; Dutta, Tapan K.

    2014-01-01

    Sphingobium sp. PNB, like other sphingomonads, has multiple ring-hydroxylating oxygenase (RHO) genes. Three different fosmid clones have been sequenced to identify the putative genes responsible for the degradation of various aromatics in this bacterial strain. Comparison of the map of the catabolic genes with that of different sphingomonads revealed a similar arrangement of gene clusters that harbors seven sets of RHO terminal components and a sole set of electron transport (ET) proteins. The presence of distinctly conserved amino acid residues in ferredoxin and in silico molecular docking analyses of ferredoxin with the well characterized terminal oxygenase components indicated the structural uniqueness of the ET component in sphingomonads. The predicted substrate specificities, derived from the phylogenetic relationship of each of the RHOs, were examined based on transformation of putative substrates and their structural homologs by the recombinant strains expressing each of the oxygenases and the sole set of available ET proteins. The RHO AhdA1bA2b was functionally characterized for the first time and was found to be capable of transforming ethylbenzene, propylbenzene, cumene, p-cymene and biphenyl, in addition to a number of polycyclic aromatic hydrocarbons. Overexpression of aromatic catabolic genes in strain PNB, revealed by real-time PCR analyses, is a way forward to understand the complex regulation of degradative genes in sphingomonads. PMID:24918041

  4. Effect of aromatic ring fluorination on CHπ interactions: microwave spectrum and structure of the 1,2-difluorobenzeneacetylene dimer.

    PubMed

    Akmeemana, Anuradha G; Kang, Justin M; Dorris, Rachel E; Nelson, Rebecca D; Anderton, Ashley M; Peebles, Rebecca A; Peebles, Sean A; Seifert, Nathan A; Pate, Brooks H

    2016-09-21

    Rotational spectra for the normal isotopic species and for six additional isotopologues of the 1,2-difluorobenzeneacetylene (C6H4F2HCCH) weakly bound dimer have been assigned in the 6-18 GHz region using chirped-pulse Fourier-transform microwave spectroscopy. This is the third complex in a series of fluorinated benzeneacetylene dimers. In 1,2-difluorobenzeneHCCH, the Hπ distance (2.725(28) Å) is longer by about 0.23 Å, and the estimated binding energy (EB = 2.3(6) kJ mol(-1)) is weaker by about 1.8 kJ mol(-1), than in the previously studied fluorobenzeneHCCH complex. In addition, in 1,2-difluorobenzeneacetylene, HCCH tips ∼46(3)° away from perpendicular to the aromatic ring, with the H nearest the ring moving away from the fluorine atoms along the C2 axis of the monomer, while in the fluorobenzene and benzene complexes HCCH is perpendicular (benzeneHCCH) or nearly perpendicular (fluorobenzeneHCCH, ∼7° tilt) to the ring plane. Results from ab initio and DFT calculations will be compared to an experimental structure determined from rotational constants for the DCCD and five unique (13)C substituted isotopologues.

  5. Effect of aromatic ring fluorination on CHπ interactions: microwave spectrum and structure of the 1,2-difluorobenzeneacetylene dimer.

    PubMed

    Akmeemana, Anuradha G; Kang, Justin M; Dorris, Rachel E; Nelson, Rebecca D; Anderton, Ashley M; Peebles, Rebecca A; Peebles, Sean A; Seifert, Nathan A; Pate, Brooks H

    2016-09-21

    Rotational spectra for the normal isotopic species and for six additional isotopologues of the 1,2-difluorobenzeneacetylene (C6H4F2HCCH) weakly bound dimer have been assigned in the 6-18 GHz region using chirped-pulse Fourier-transform microwave spectroscopy. This is the third complex in a series of fluorinated benzeneacetylene dimers. In 1,2-difluorobenzeneHCCH, the Hπ distance (2.725(28) Å) is longer by about 0.23 Å, and the estimated binding energy (EB = 2.3(6) kJ mol(-1)) is weaker by about 1.8 kJ mol(-1), than in the previously studied fluorobenzeneHCCH complex. In addition, in 1,2-difluorobenzeneacetylene, HCCH tips ∼46(3)° away from perpendicular to the aromatic ring, with the H nearest the ring moving away from the fluorine atoms along the C2 axis of the monomer, while in the fluorobenzene and benzene complexes HCCH is perpendicular (benzeneHCCH) or nearly perpendicular (fluorobenzeneHCCH, ∼7° tilt) to the ring plane. Results from ab initio and DFT calculations will be compared to an experimental structure determined from rotational constants for the DCCD and five unique (13)C substituted isotopologues. PMID:27530245

  6. Identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons in a complex mixture of polycyclic aromatic hydrocarbons from coal tar.

    PubMed

    Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara; Wise, Stephen A

    2016-04-15

    A methodology for the characterization of groups of polycyclic aromatic hydrocarbons (PAHs) using a combination of normal phase liquid chromatography with ultraviolet-visible spectroscopy (NPLC/UV-vis) and gas chromatography with mass spectrometry (GC/MS) was used for the identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons, PAHs, in standard reference material (SRM) 1597a, complex mixture of PAHs from coal tar. The NPLC/UV-vis isolated the fractions based on the number of aromatic carbons and the GC/MS allowed the identification and quantification of five of the nine C26H14 PAH isomers; naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene using a retention time comparison with authentic reference standards. For the other four benzenoid isomers with no available reference standards the following two approaches were used. First, the annellation theory was used to achieve the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene, and second, the elution distribution in the GC fractions was used to support the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene and to reach the tentative identifications of dibenzo[a,ghi]perylene, naphtho[7,8,1,2,3-pqrst]pentaphene, and anthra[2,1,9,8-opqra]naphthacene. It is the first time that naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene are quantified, and the first time that benzo[qr]naphtho[3,2,1,8-defg]chrysene is potentially identified, in any sample, in any context.

  7. Recognition of Multiple Methyl Groups on Aromatic Rings by a Polyaromatic Cavity.

    PubMed

    Yamashina, Masahiro; Matsuno, Sho; Sei, Yoshihisa; Akita, Munetaka; Yoshizawa, Michito

    2016-09-26

    The methyl group is a small substituent, usually showing relatively weak or no interactions with other functional groups and metal ions. Herein, we present the recognition of the number of methyl groups on synthetic and natural aromatic compounds (i.e., benzene and xanthine derivatives, respectively) by the 1 nm-sized polyaromatic cavity of a coordination capsule in water. Detailed competitive encapsulation experiments as well as X-ray crystallographic analysis revealed that multiple guest-host CH3 -polyaromatic interactions in the confined nanospace are key driving forces for the high selectivity. PMID:27441895

  8. Heterologous expression of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase genes from a novel pyrene-degrading betaproteobacterium.

    PubMed

    Singleton, David R; Hu, Jing; Aitken, Michael D

    2012-05-01

    A betaproteobacterium within the family Rhodocyclaceae previously identified as a pyrene degrader via stable-isotope probing (SIP) of contaminated soil (designated pyrene group 1 or PG1) was cultivated as the dominant member of a mixed bacterial culture. A metagenomic library was constructed, and the largest contigs were analyzed for genes associated with polycyclic aromatic hydrocarbon (PAH) metabolism. Eight pairs of genes with similarity to the α- and β-subunits of ring-hydroxylating dioxygenases (RHDs) associated with aerobic bacterial PAH degradation were identified and linked to PG1 through PCR analyses of a simplified enrichment culture. In tandem with a ferredoxin and reductase found in close proximity to one pair of RHD genes, six of the RHDs were cloned and expressed in Escherichia coli. Each cloned RHD was tested for activity against nine PAHs ranging in size from two to five rings. Despite differences in their predicted protein sequences, each of the six RHDs was capable of transforming phenanthrene and pyrene. Three RHDs could additionally transform naphthalene and fluorene, and these genotypes were also associated with the ability of the E. coli constructs to convert indole to indigo. Only one of the six cloned RHDs was capable of transforming anthracene and benz[a]anthracene. None of the tested RHDs were capable of significantly transforming fluoranthene, chrysene, or benzo[a]pyrene.

  9. Heterologous Expression of Polycyclic Aromatic Hydrocarbon Ring-Hydroxylating Dioxygenase Genes from a Novel Pyrene-Degrading Betaproteobacterium

    PubMed Central

    Hu, Jing; Aitken, Michael D.

    2012-01-01

    A betaproteobacterium within the family Rhodocyclaceae previously identified as a pyrene degrader via stable-isotope probing (SIP) of contaminated soil (designated pyrene group 1 or PG1) was cultivated as the dominant member of a mixed bacterial culture. A metagenomic library was constructed, and the largest contigs were analyzed for genes associated with polycyclic aromatic hydrocarbon (PAH) metabolism. Eight pairs of genes with similarity to the α- and β-subunits of ring-hydroxylating dioxygenases (RHDs) associated with aerobic bacterial PAH degradation were identified and linked to PG1 through PCR analyses of a simplified enrichment culture. In tandem with a ferredoxin and reductase found in close proximity to one pair of RHD genes, six of the RHDs were cloned and expressed in Escherichia coli. Each cloned RHD was tested for activity against nine PAHs ranging in size from two to five rings. Despite differences in their predicted protein sequences, each of the six RHDs was capable of transforming phenanthrene and pyrene. Three RHDs could additionally transform naphthalene and fluorene, and these genotypes were also associated with the ability of the E. coli constructs to convert indole to indigo. Only one of the six cloned RHDs was capable of transforming anthracene and benz[a]anthracene. None of the tested RHDs were capable of significantly transforming fluoranthene, chrysene, or benzo[a]pyrene. PMID:22427500

  10. Particle on a boron disk: ring currents and disk aromaticity in B20(2-).

    PubMed

    Tai, Truong Ba; Havenith, Remco W A; Teunissen, Jos L; Dok, Ahmet R; Hallaert, Simon D; Nguyen, Minh Tho; Ceulemans, Arnout

    2013-09-16

    The B20(2-) cluster is predicted to exhibit a planar sheet-like structure with a circular circumference. Orbital plots and energy correlations demonstrate the close correspondence between the electronic structure of B20(2-) and the Bessel functions describing the waves of a quantum mechanical particle confined to a disk. The π-band of B20(2-), and its B19(-) congener, contains 12 π-electrons, forming a (1σ)(2)(1π)(4)(1δ)(4)(2σ)(2) configuration, which corresponds to a "disk aromaticity" electron count. The analogy not only applies to the π-band, but also extends to the 50 valence σ-electrons. The occupied σ-orbitals are assigned on the basis of radial and angular nodes of the scalar disk waves. The magnetic response of the cluster was examined by Nucleus Independent Chemical Shift (NICS) values and current density calculations based on the ipsocentric model. B20(2-) is found to exhibit a remarkable inner paratropic current in the σ-channel and an outer diatropic current in the π-channel. The orbital excitations responsible for the antiaromaticity in σ and the disk-aromaticity in π are identified. PMID:24011355

  11. Protonation at the aromatic ring of samarium benzophenone dianion species. Isolation and structural characterization of a samarium(III) enolate complex

    SciTech Connect

    Hou, Z.; Yoshimura, Takashi; Wakatsuki, Yasuo )

    1994-11-30

    The reduction of aromatic compounds into their dihydro derivatives by dissolving metal/alcohol systems (the Birch reduction) is a useful methodology in organic synthesis. Of particular importance is the reduction of aromatic carbonyl compounds such as aromatic acids, esters, amides, and monoaryl ketones, which usually generates in situ useful metal enolate intermediates that upon further reaction with electrophiles yield a variety of cyclohexadiene derivatives. One of the possible processes to generate these metal enolate intermediates is thought to be the monoprotonation of dianionic species at the para position of the aromatic rings. On the other hand, the reduction of diaryl ketones by alkali metals in liquid ammonia or by lanthanide metals in THF/HMPA or DME has been well known to afford the corresponding ketone dianions. The first X-ray structure of metal ketone dianion complexes, [Yb([mu]-[eta][sup 1],[eta][sup 2]-OCPh[sub 2]) (HMPA)[sub 2

  12. Reversal of Orbital Symmetry Control in Electrocyclic Ring Closures through Craig-Möbius Aromaticity.

    PubMed

    Mauksch, Michael; Tsogoeva, Svetlana B

    2016-04-01

    Experimentalists are challenged to find the organometallic thermal electrocyclizations that are computationally predicted to proceed with opposite stereoselectivity compared to their metal-free parent 4n and 4n+2 π-electron systems. While ring closure of, for example, s-cis-butadiene proceeds conrotatory, an iron alkyl complex formed by replacement of a (CH) unit by an [FeH] metal fragment results in a disrotatory electrocyclization.

  13. Reversal of Orbital Symmetry Control in Electrocyclic Ring Closures through Craig-Möbius Aromaticity.

    PubMed

    Mauksch, Michael; Tsogoeva, Svetlana B

    2016-04-01

    Experimentalists are challenged to find the organometallic thermal electrocyclizations that are computationally predicted to proceed with opposite stereoselectivity compared to their metal-free parent 4n and 4n+2 π-electron systems. While ring closure of, for example, s-cis-butadiene proceeds conrotatory, an iron alkyl complex formed by replacement of a (CH) unit by an [FeH] metal fragment results in a disrotatory electrocyclization. PMID:26817734

  14. Efficient oxidative dechlorination and aromatic ring cleavage of chlorinated phenols catalyzed by iron sulfophthalocyanine.

    PubMed

    Sorokin, A; Meunier, B; Séris, J L

    1995-05-26

    An efficient method has been developed for the catalytic oxidation of pollutants that are not easily degraded. The products of the hydrogen peroxide (H(2)O(2)) oxidation of 2,4,6,-trichlorophenol (TCP) catalyzed by the iron complex 2,9,16,23-tetrasulfophthalocyanine (FePcS) were observed to be chloromaleic, chlorofumaric, maleic, and fumaric acids from dechlorination and aromatic cycle cleavage, as well as additional products that resulted from oxidative coupling. Quantitative analysis of the TCP oxidation reaction revealed that up to two chloride ions were released per TCP molecule. This chemical system, consisting of an environmentally safe oxidant (H(2)O(2)) and an easily accessible catalyst (FePcS), can perform several key steps in the oxidative mineralization of TCP, a paradigm of recalcitrant pollutants.

  15. Identification and characterization of OSTL (RNF217) encoding a RING-IBR-RING protein adjacent to a translocation breakpoint involving ETV6 in childhood ALL

    PubMed Central

    Fontanari Krause, Luciana M.; Japp, Anna Sophia; Krause, Alexandre; Mooster, Jana; Chopra, Martin; Müschen, Markus; Bohlander, Stefan K.

    2014-01-01

    Genomic aberrations involving ETV6 on band 12p13 are amongst the most common chromosomal abnormalities in human leukemia. The translocation t(6;12)(q23;13) in a childhood B-cell acute lymphoblastic leukemia (ALL) cell line fuses ETV6 with the putative long non-coding RNA gene STL. Linking STL properties to leukemia has so far been difficult. Here, we describe a novel gene, OSTL (annotated as RNF217 in Genbank), which shares the first exon and a CpG island with STL but is transcribed in the opposite direction. Human RNF217 codes for a highly conserved RING finger protein and is mainly expressed in testis and skeletal muscle with different splice variants. RNF217 shows regulated splicing in B cell development, and is expressed in a number of human B cell leukemia cell lines, primary human chronic myeloid leukemia, acute myeloid leukemia with normal karyotype and acute T-ALL samples. Using a yeast two-hybrid screen, we identified the anti-apoptotic protein HAX1 to interact with RNF217. This interaction could be mapped to the C-terminal RING finger motif of RNF217. We propose that some of the recurring aberrations involving 6q might deregulate the expression of RNF217 and result in imbalanced apoptosis signalling via HAX1, promoting leukemia development. PMID:25298122

  16. Intermolecular sequential [4 + 2]-cycloaddition-aromatization reaction of aryl-substituted allenes with DMAD affording phenanthrene and naphthalene derivatives.

    PubMed

    Jiang, Xuefeng; Kong, Wangqing; Chen, Jie; Ma, Shengming

    2008-10-01

    An efficient entry to phenanthrene and naphthalene derivatives through intermolecular sequential [4 + 2]-cycloaddition-aromatization reactions of aryl-substituted allenes with DMAD in the absence of any catalyst was discovered. In this reaction the aromatic ring and the adjacent carbon-carbon double bond of the allene unit acted as the 1,3-diene.

  17. A Porous Aromatic Framework Constructed from Benzene Rings Has a High Adsorption Capacity for Perfluorooctane Sulfonate

    PubMed Central

    Luo, Qin; Zhao, Changwei; Liu, Guixia; Ren, Hao

    2016-01-01

    A low-cost and easily constructed porous aromatic framework (PAF-45) was successfully prepared using the Scholl reaction. PAF-45 was, for the first time, used to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Systematic experiments were performed to determine the adsorption capacity of PAF-45 for PFOS and to characterize the kinetics of the adsorption process. The adsorption of PFOS onto PAF-45 reached equilibrium in 30 min, and the adsorption capacity of PAF-45 for PFOS was excellent (5847 mg g−1 at pH 3). The amount of PFOS adsorbed by PAF-45 increased significantly as the cation (Na+, Mg2+, or Fe3+) concentration increased, which probably occurred because the cations enhanced the interactions between the negatively charged PFOS molecules and the positively charged PAF-45 surface. The cations Na+, Mg2+, and Fe3+ were found to form complexes with PFOS anions in solution. Density functional theory was used to identify the interactions between PFOS and Na+, Mg2+, and Fe3+. We expect that materials of the same type as PAF-45 could be useful adsorbents for removing organic pollutants from industrial wastewater and contaminated surface water. PMID:26843015

  18. A Porous Aromatic Framework Constructed from Benzene Rings Has a High Adsorption Capacity for Perfluorooctane Sulfonate

    NASA Astrophysics Data System (ADS)

    Luo, Qin; Zhao, Changwei; Liu, Guixia; Ren, Hao

    2016-02-01

    A low-cost and easily constructed porous aromatic framework (PAF-45) was successfully prepared using the Scholl reaction. PAF-45 was, for the first time, used to remove perfluorooctane sulfonate (PFOS) from aqueous solution. Systematic experiments were performed to determine the adsorption capacity of PAF-45 for PFOS and to characterize the kinetics of the adsorption process. The adsorption of PFOS onto PAF-45 reached equilibrium in 30 min, and the adsorption capacity of PAF-45 for PFOS was excellent (5847 mg g‑1 at pH 3). The amount of PFOS adsorbed by PAF-45 increased significantly as the cation (Na+, Mg2+, or Fe3+) concentration increased, which probably occurred because the cations enhanced the interactions between the negatively charged PFOS molecules and the positively charged PAF-45 surface. The cations Na+, Mg2+, and Fe3+ were found to form complexes with PFOS anions in solution. Density functional theory was used to identify the interactions between PFOS and Na+, Mg2+, and Fe3+. We expect that materials of the same type as PAF-45 could be useful adsorbents for removing organic pollutants from industrial wastewater and contaminated surface water.

  19. Ring flips revisited: (13)C relaxation dispersion measurements of aromatic side chain dynamics and activation barriers in basic pancreatic trypsin inhibitor.

    PubMed

    Weininger, Ulrich; Modig, Kristofer; Akke, Mikael

    2014-07-22

    Intramolecular motions of proteins are critical for biological function. Transient structural fluctuations underlie a wide range of processes, including enzyme catalysis, ligand binding to buried sites, and generic protein motions, such as 180° rotation of aromatic side chains in the protein interior, but remain poorly understood. Understanding the dynamics and molecular nature of concerted motions requires characterization of their rates and energy barriers. Here we use recently developed (13)C transverse relaxation dispersion methods to improve our current understanding of aromatic ring flips in basic pancreatic trypsin inhibitor (BPTI). We validate these methods by benchmarking ring-flip rates against the three previously characterized cases in BPTI, namely, Y23, Y35, and F45. Further, we measure conformational exchange for one additional aromatic ring, F22, which can be interpreted in terms of a flip rate of 666 s(-1) at 5 °C. Upon inclusion of our previously reported result that Y21 also flips slowly [Weininger, U., et al. (2013) J. Phys. Chem. B 117, 9241-9247], the (13)C relaxation dispersion experiments thus reveal relatively slow ring-flip rates for five of eight aromatic residues in BPTI. These results are in contrast with previous reports, which have estimated that all rings, except Y23, Y35, and F45, flip with a high rate at ambient temperature. The (13)C relaxation dispersion data result in an updated rank order of ring-flip rates in BPTI, which agrees considerably better with that estimated from a recent 1 ms molecular dynamics trajectory than do previously published NMR data. However, significant quantitative differences remain between experiment and simulation, in that the latter yields flip rates that are in many cases too fast by 1-2 orders of magnitude. By measuring flip rates across a temperature range of 5-65 °C, we determined the activation barriers of ring flips for Y23, Y35, and F45. Y23 and F45 have identical activation parameters

  20. Systematical analysis for the mixed couplings of two adjacent modified split ring resonators and the application to compact microstrip bandpass filters

    NASA Astrophysics Data System (ADS)

    Huang, Yongjun; Wen, Guangjun; Li, Jian

    2014-10-01

    In this paper we synthesize a new kind of modified split ring resonator (SRR) and characterize its mixed couplings between two adjacent such SRRs with all the possible arrangements on one side of a conventional dielectric substrate. Based on the analysis of the mixed couplings, the compact microstrip bandpass filters composed of the proposed modified SRRs are systematically analyzed. We found that two designs out of all the cases have quite well bandpass filter characteristics, e.g., low insert loss within the wide passband, sharp reductions and transmission zeros out of the passband, and harmonic suppression characteristics for a wide frequency range. Both experimental demonstrations and numerical simulations are performed to verify the designed filters and the results agree well with each other. Such kind of filter design can be flexibly integrated in the miniaturized radio frequency/microwave circuits.

  1. Photocatalytic degradation of N-heterocyclic aromatics-effects of number and position of nitrogen atoms in the ring.

    PubMed

    Kaur, Jasmeet; Pal, Bonamali

    2013-06-01

    This study demonstrates the influences of position, number of nitrogen (N) atoms and -C-N- or -N=N- linkage present in the six membered heterocyclic compounds such as pyridine, pyrazine, and pyridazine on their photocatalytic degradation by Au, Ag, and Fe(+2) deposited TiO(2) photocatalyst. The photodegradation rate of these heterocyclic compounds follow the order pyridine > pyrazine > pyridazine due to the different extent of hydroxylation and difference in position and number of N atoms in the aromatic moiety. The Au photodeposition significantly improved the TiO(2) photoactivity as compared to Ag and Fe(+2) loading. The presence of two N atoms in pyrazine and pyridazine as compared to one N atom in pyridine hamper the nucleophilc attack of OH radicals in comparison to easy hydroxylation of pyridine ring. There is 1 N atom, 4C-C, 1C-N and 1C=N bond in pyridine, 2 N atoms in the 1 and 4 positions, 2C-C, 2C-N bonds and 2C=N bonds in pyrazine, and pyridazine ring contains 2 N atoms in the 1 and 2 positions, 3C-C, 1N-N bond and 2C=N bonds. The bond strength/energy decreases gradually as: C=N- (615 KJ/mol) > -N=N- (418 KJ/mol) > -C-C- (347 KJ/mol) > -C-N- (305 KJ/mol) > -N-N- (163 KJ/mol). As pyridine has 1C-N, 1C=N, and no N-N bond, it photodegrades easily as compared to 1 N-N and 2C=N bonds of pyridazine of lowest photodecomposition rate. The improved photoactivity of Au-TiO(2) is explained on the basis of its favorable redox potential, work function, and electron-capturing capacity, etc.

  2. Initial Steps of Aromatic Ring Formation in a Laminar Premixed Fuel-Rich Cyclopentene Flame†

    SciTech Connect

    Hansen, N.; Kasper, T.; Klippenstein, S. J.; Westmoreland, P. R.; Law, M. E.; Taatjes, C. A.; Kohse-Höinghaus, K.; Wang, J.; Cool, T. A.

    2007-05-01

    A fuel-rich, nonsooting, premixed laminar cyclopentene flame (phi = 2.0) at 37.6 Torr (50 mbar) is investigated by flame-sampling photoionization molecular-beam mass spectrometry utilizing vacuum-ultraviolet synchrotron radiation. Mole fractions as a function of distance from the burner are measured for 49 intermediates with ion masses ranging from 2 (H-2) to 106 (C8H10), providing a broad database for flame modeling studies. The isomeric composition is resolved for most species, and the identification of several C4Hx, C7H6, and C7H8 isomers is discussed in detail. The presence of C5H5CCH/C5H4CCH2 and cycloheptatriene is revealed by comparisons between flame-sampled photoionization efficiency data and theoretical simulations, based on calculated ionization energies and Franck-Condon factors. This insight suggests a new potential molecular- weight growth mechanism that is characterized by C-5-C-7 ring enlargement reactions.

  3. Isolation and characterization of a Mycobacterium species capable of degrading three- and four-ring aromatic and aliphatic hydrocarbons

    SciTech Connect

    Churchill, S.A.; Harper, J.P.; Churchill, P.F.

    1999-02-01

    Mycobacterium sp. strain CH1 was isolated from polycyclic aromatic hydrocarbon (PAH)-contaminated freshwater sediments and identified by analysis of 16S rDNA sequences. Strain CH1 was capable of mineralizing three- and four-ring PAHs including phenanthrene, pyrene, and fluoranthene. In addition, strain CH1 could utilize phenanthrene or pyrene as a sole carbon and energy source. A lag phase of at least 3 days was observed during pyrene mineralization. This lag phase decreased to less than 1 day when strain CH1 was grown in the presence of phenanthrene or fluoranthene. Strain CH1 also was capable of using a wide range of alkanes as sole carbon and energy sources. No DNA hybridization was detected with the nahAc gene probe, indicating that enzymes involved in PAH metabolism are not related to the well-characterized naphthalene dioxygenase gene. DNA hybridization was not detected when the alkB gene from Pseudomonas oleovorans was used under high-stringency conditions. However, there was slight but detectable hybridization under low-stringency conditions. This suggests a distant relationship between genes involved in alkane oxidation.

  4. The relationship between repeat-dose toxicity and aromatic-ring class profile of high-boiling petroleum substances.

    PubMed

    Roth, Randy N; Simpson, Barry J; Nicolich, Mark J; Murray, F Jay; Gray, Thomas M

    2013-11-01

    A study was undertaken within the context of the U.S. EPA HPV Chemical Challenge Program to (1) characterize relationships between PAC content and repeat-dose toxicities of high-boiling petroleum substances (HBPS) and (2) develop statistical models that could be used to predict the repeat-dose toxicity of similar untested substances. The study evaluated 47 repeat-dose dermal toxicity and 157 chemical compositional studies. The four most sensitive endpoints of repeat-dose toxicity were platelet count, hemoglobin concentration, relative liver weight and thymus weight. Predictive models were developed for the dose-response relationships between the wt.% concentration of each of seven ring classes of aromatic compounds (the "ARC profile") and specific effects, with high correlations (r=0.91-0.94) between the observed and model-predicted data. The development of the mathematical models used to generate the results reported in this study is described by Nicolich et al. (2013). Model-generated dose-response curves permit the prediction of either the effect at a given dose or the dose that causes a given effect. The models generate values that are consistent with other standard measures. The models, using compositional data, can be used for predicting the repeat-dose toxicity of untested HBPS.

  5. The relationship between developmental toxicity and aromatic-ring class profile of high-boiling petroleum substances.

    PubMed

    Murray, F Jay; Roth, Randy N; Nicolich, Mark J; Gray, Thomas M; Simpson, Barry J

    2013-11-01

    In response to the US EPA HPV Challenge Program, this study was conducted to: (1) evaluate the relationship between PAC content and the developmental toxicity of high-boiling petroleum substances (HBPS) and (2) develop mathematical models to predict the developmental toxicity of similar untested substances based on their aromatic ring class (ARC) profiles. For this investigation, 68 developmental toxicity studies were reviewed. The ARC models relied on data from 21 rat dermal developmental toxicity studies conducted with similar experimental designs to ensure a consistent data set for comparison. The most sensitive general endpoints of developmental toxicity (i.e., decreased fetal survival and growth) were chosen for modeling. The ARC models demonstrated a strong correlation between the predicted vs. observed values for specific sensitive endpoints of these developmental toxicities (percent resorptions, r=0.99; live fetuses per litter, r=0.98; fetal body weight, r=0.94). Such associations provide a promising approach for predicting the developmental toxicity of untested HBPS. Efforts to corroborate the ARC models using test substances that were not used to build the ARC models produced mixed results, and further development and refinement of the ARC models is recommended before they can be reliably applied to all HBPS.

  6. Low-pressure effective fluorescence lifetimes and photo-physical rate constants of one- and two-ring aromatics

    NASA Astrophysics Data System (ADS)

    Benzler, Thorsten; Faust, Stephan; Dreier, Thomas; Schulz, Christof

    2015-12-01

    One- and two-ring aromatics such as toluene and naphthalene are frequently used molecular tracer species in laser-induced fluorescence (LIF) imaging diagnostics. Quantifying LIF signal intensities requires knowledge of the photo-physical processes that determine the fluorescence quantum yield. Collision-induced and intramolecular energy transfer processes in the excited electronic state closely interact under practical conditions. They can be separated through experiments at variable low pressures. Effective fluorescence lifetimes of gaseous toluene, 1,2,4-trimethylbenzene, anisole, naphthalene, and 1-methylnaphthalene diluted in CO2 were measured after picosecond laser excitation at 266 nm and time-resolved detection of fluorescence intensities. Measurements in an optically accessible externally heated cell between 296 and 475 K and 0.010-1 bar showed that effective fluorescence lifetimes generally decrease with temperature, while the influence of the bath-gas pressure depends on the respective target species and temperature. The results provide non-radiative and fluorescence rate constants and experimentally validate the effect of photo-induced cooling.

  7. Isolation and Characterization of a Mycobacterium Species Capable of Degrading Three- and Four-Ring Aromatic and Aliphatic Hydrocarbons

    PubMed Central

    Churchill, Sharon A.; Harper, Jennifer P.; Churchill, Perry F.

    1999-01-01

    Mycobacterium sp. strain CH1 was isolated from polycyclic aromatic hydrocarbon (PAH)-contaminated freshwater sediments and identified by analysis of 16S rDNA sequences. Strain CH1 was capable of mineralizing three- and four-ring PAHs including phenanthrene, pyrene, and fluoranthene. In addition, strain CH1 could utilize phenanthrene or pyrene as a sole carbon and energy source. A lag phase of at least 3 days was observed during pyrene mineralization. This lag phase decreased to less than 1 day when strain CH1 was grown in the presence of phenanthrene or fluoranthene. Strain CH1 also was capable of using a wide range of alkanes as sole carbon and energy sources. No DNA hybridization was detected with the nahAc gene probe, indicating that enzymes involved in PAH metabolism are not related to the well-characterized naphthalene dioxygenase gene. DNA hybridization was not detected when the alkB gene from Pseudomonas oleovorans was used under high-stringency conditions. However, there was slight but detectable hybridization under low-stringency conditions. This suggests a distant relationship between genes involved in alkane oxidation. PMID:9925581

  8. Bacterial polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenases in the sediments from the Pearl River estuary, China.

    PubMed

    Wu, Peng; Wang, You-Shao; Sun, Fu-Lin; Wu, Mei-Lin; Peng, Ya-lan

    2014-01-01

    Bacterial community compositions were characterized using denaturing gradient gel electrophoresis analysis of bacterial 16S rRNA gene in the sediments of the Pearl River estuary. Sequencing analyses of the excised bands indicated that Gram-negative bacteria, especially Gammaproteobacteria, were dominant in the Pearl River estuary. The diversity of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase (PAH-RHD) gene in this estuary was then assessed by clone library analysis. The phylogenetic analyses showed that all PAH-RHD gene sequences of Gram-negative bacteria (PAH-RHD[GN]) were closely related to the nagAc gene described for Ralstonia sp. U2 or nahAc gene for Pseudomonas sp. 9816-4, while the PAH-RHD gene sequences of Gram-positive bacteria (PAH-RHD[GP]) at sampling site A1 showed high sequence similarity to the nidA gene from Mycobacterium species. Meanwhile, molecular diversity of the two functional genes was higher at the upstream of this region, while lower at the downstream. Redundancy analysis indicated that environmental factors, such as NH₄--N, ∑PAHs, pH, SiO₃--Si, and water depth, affected the distribution of the PAH-RHD[GN] gene in the Pearl River estuary.

  9. Copper Causes Regiospecific Formation of C4 F8 -Containing Six-Membered Rings and their Defluorination/Aromatization to C4 F4 -Containing Rings in Triphenylene/1,4-C4 F8 I2 Reactions.

    PubMed

    Rippy, Kerry C; Bukovsky, Eric V; Clikeman, Tyler T; Chen, Yu-Sheng; Hou, Gao-Lei; Wang, Xue-Bin; Popov, Alexey A; Boltalina, Olga V; Strauss, Steven H

    2016-01-18

    The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4 F8 I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4 F8 -containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive-defluorination/aromatization (RD/A) to form C4 F4 -containing aromatic rings. Without Cu, the reactions of TRPH and 1,4-C4 F8 I2 were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cu-promoted 1) regiospecific perfluoroannulation, 2) preparative C-F activation, and 3) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and (1) H/(19) F NMR. PMID:26581454

  10. Structure-plant phytotoxic activity relationship of 7,7'-epoxylignanes, (+)- and (-)-verrucosin: simplification on the aromatic ring substituents.

    PubMed

    Yamauchi, Satoshi; Nakayama, Kumiko; Nishiwaki, Hisashi; Shuto, Yoshihiro

    2014-10-15

    The synthesized 7-aryl derivatives of (7R,7'S,8S,8'S)-(+)-verrucosin were applied to growth inhibitory activity test against ryegrass at 1mM. 7-(3-Ethoxy-4-hydroxyphenyl) derivative 12 and 7-(2-hydroxyphenyl) derivative 4 showed comparable activity to those of (+)-verrucosin against the root (-95%) and the shoot (-60%), respectively. The growth inhibitory activity test against lettuce using synthesized 7-aryl derivatives of (7S,7'R,8R,8'R)-(-)-verrucosin at 1mM showed that the activities of 7-(3-hydroxyphenyl) derivative 20 and 7-(3-ethoxy-4-hydroxyphenyl) derivative 28 are similar to that of (-)-verrucosin against the root (-95%). Against the shoot, 7-(3-hydroxyphenyl) derivative 20 showed higher activity (-80%) than that of (-)-verrucosin (-60%). As the next step, (7S,7'R,8R,8'R)-7-(3-hydroxyphenyl)-7'-aryl-(-)-verrucosin derivatives, in which the most effective 3-hydroxyphenyl group is employed as 7-aromatic ring, were synthesized for the assay against lettuce. In this experiment, 7'-(2-hydroxyphenyl) derivative 37 and 7'-(3-hydroxyphenyl) derivative 38 showed similar activity to that of derivative 20. The effect of 7- and 7'-aryl structures of 7,7'-epoxylignanes on the plant growth inhibitory activity was clarified. The 7- and 7'-aryl structures were simplified to show comparable activity to or higher activity than that of (-)-verrucosin. The plant growth inhibitory activity of a nutmeg component, (+)-fragransin C3b, was estimated as -80% inhibition at 1mM against ryegrass roots. PMID:25248684

  11. Non-aromatic A-ring replacement in the triaryl bis-sulfone CB2 receptor inhibitors.

    PubMed

    Gilbert, Eric J; Zhou, Guowei; Wong, Michael K C; Tong, Ling; Shankar, Bandarpalle B; Huang, Chunli; Kelly, Joseph; Lavey, Brian J; McCombie, Stuart W; Chen, Lei; Rizvi, Razia; Dong, Youhao; Shu, Youheng; Kozlowski, Joseph A; Shih, Neng-Yang; Hipkin, R William; Gonsiorek, Waldemar; Malikzay, Asra; Lunn, Charles A; Favreau, Len; Lundell, Daniel J

    2010-01-15

    The triaryl bis-sulfone 1 was modified by converting the aryl A-ring to a piperidine ring. The piperidine ring was further elaborated to a spirocyclopropyl piperidine moiety. The effect on CB2 binding potency, rat calcium channel affinity, and CYP 2C9 inhibition is described.

  12. Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons.

    PubMed

    Liu, Junzhi; Narita, Akimitsu; Osella, Silvio; Zhang, Wen; Schollmeyer, Dieter; Beljonne, David; Feng, Xinliang; Müllen, Klaus

    2016-03-01

    Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be rationalized by density functional theory (DFT) calculations. The theoretical results suggest that the formation of the bistetracene analogue with five-membered rings is kinetically controlled while an "expected" product with six-membered rings is thermodynamically more favored. These experimental and theoretical results provide further insights into the still controversial mechanism of the Scholl reaction as well as open up an unprecedented entry to extend the variety of PAHs by programing otherwise unpredictable rearrangements during the Scholl reaction. PMID:26859522

  13. Recoupled long-range C-H dipolar dephasing in solid-state NMR, and its use for spectral selection of fused aromatic rings

    NASA Astrophysics Data System (ADS)

    Mao, J.-D.; Schmidt-Rohr, K.

    2003-05-01

    This work introduces a simple new solid-state 13C NMR method for distinguishing various types of aromatic residues, e.g. those of lignin from fused rings of charcoal. It is based on long-range dipolar dephasing, which is achieved by recoupling of long-range C-H dipolar interactions, using two 1H 180° pulses per rotation period. This speeds up dephasing of unprotonated carbon signals approximately threefold compared to standard dipolar dephasing without recoupling and thus provides much more efficient differential dephasing. It also reduces the effects of spinning-speed dependent effective proton-proton dipolar couplings on the heteronuclear dephasing. Signals of unprotonated carbons with two or more protons at a two-bond distance dephase to <3% within less than 0.9 ms, significantly faster than those of aromatic sites separated from the nearest proton by three or more bonds. Differential dephasing among different unprotonated carbons is demonstrated in a substituted anthraquinone and 3-methoxy benzamide. The data yield a calibration curve for converting the dephasing rates into estimated distances from the carbon to the nearest protons. This can be used for peak assignment in heavily substituted or fused aromatic molecules. Compared to lignin, slow dephasing is observed for the aromatic carbons in wood charcoal, and even slower for inorganic carbonate. Direct 13C polarization is used on these structurally complex samples to prevent loss of the signals of interest, which by design originate from carbons that are distant from protons and therefore crosspolarize poorly. In natural organic matter such as humic acids, this combination of recoupled dipolar dephasing and direct polarization at 7-kHz MAS enables selective observation of signals from fused rings that are characteristic of charcoal.

  14. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    SciTech Connect

    Wang, Sujing; Li, Jing

    2015-04-15

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

  15. The Broken Ring: Reduced Aromaticity in Lys-Trp Cations and High pH Tautomer Correlates with Lower Quantum Yield and Shorter Lifetimes

    PubMed Central

    2015-01-01

    Several nonradiative processes compete with tryptophan fluorescence emission. The difficulty in spectral interpretation lies in associating specific molecular environmental features with these processes and thereby utilizing the fluorescence spectral data to identify the local environment of tryptophan. Here, spectroscopic and molecular modeling study of Lys-Trp dipeptide charged species shows that backbone-ring interactions are undistinguished. Instead, quantum mechanical ground state isosurfaces reveal variations in indole π electron distribution and density that parallel charge (as a function of pK1, pK2, and pKR) on the backbone and residues. A pattern of aromaticity-associated quantum yield and fluorescence lifetime changes emerges. Where quantum yield is high, isosurfaces have a charge distribution similar to the highest occupied molecular orbital (HOMO) of indole, which is the dominant fluorescent ground state of the 1La transition dipole moment. Where quantum yield is low, isosurface charge distribution over the ring is uneven, diminished, and even found off ring. At pH 13, the indole amine is deprotonated, and Lys-Trp quantum yield is extremely low due to tautomer structure that concentrates charge on the indole amine; the isosurface charge distribution bears scant resemblance to the indole HOMO. Such greatly diminished fluorescence has been observed for proteins where the indole nitrogen is hydrogen bonded, lending credence to the association of aromaticity changes with diminished quantum yield in proteins as well. Thus tryptophan ground state isosurfaces are an indicator of indole aromaticity, signaling the partition of excitation energy between radiative and nonradiative processes. PMID:24882092

  16. One-pot hydrogen peroxide and hydrohalic acid induced ring closure and selective aromatic halogenation to give new ring-fused benzimidazoles.

    PubMed

    Gurry, Michael; Sweeney, Martin; McArdle, Patrick; Aldabbagh, Fawaz

    2015-06-01

    A new series of selectively dichlorinated and dibrominated five- to eight-membered-ring [1,2-a]-fused benzimidazoles and [1,4]oxazino[4,3-a]benzimidazoles are synthesized in mostly high yields of >80% using the reaction of hydrogen peroxide and hydrohalic acid with commercially available o-cyclic amine substituted anilines. Domestic bleach with HCl can also be used for a one-pot ring closure and chlorination.

  17. Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8).

    PubMed

    Xu, Chang; Cheng, Longjiu; Yang, Jinlong

    2014-09-28

    It is well known that double-ring boron clusters have got the special double aromaticity with delocalized π orbitals in two directions (tangential and radial), which are potential ligands centered by a transition metal. In this article, the transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8) are theoretically investigated by density functional theory calculations. These endohedral compounds have also got double aromaticity in both tangential and radial directions. Interestingly, the tangential delocalized π orbitals of boron ligands following the Huckle's (4n + 2) rule do not interact with the central metal, while the radial π orbitals of boron ligands are bonded with the central mental to form spd-π endohedral bonding. The spd-π endohedral bonding follows the 18e-principle in Ni@B14 and Fe@B16. However, due to the flat shape of the compounds, 14e (Cr@B14) and 16e (Ni@B12) can also be electronically very stable where the energy levels of the spd-π orbitals delocalized in z-direction rise up. This intriguing bonding model makes sense in further study of the boron chemistry.

  18. Effects of Lewis acid catalysts on the hydrogenation and cracking of two-ring aromatic and hydroaromatic structures related to coal

    SciTech Connect

    Salim, Sadie S.; Bell, Alexis T.

    1982-08-01

    Little is known about the hydrogenation of fused aromatic nuclei during the liquefaction of coal under the influence of Lewis acid catalysts. For this paper, this study was conducted to establish the effects of catalyst acidity on the activity and selectivity of Lewis acid catalysts, the sources of hydrogen involved in hydrogenation and cracking, and the relations between reactant structure and reactivity. Two-ring aromatic and hydroaromatic compounds were used to simulate some of the structural units present in coal. The catalysts examined were ZnCl2 and AlCl3. ZnCl2 is less active than AlCl3 for both hydrogenation and cracking but it does not promote the formation of tars via Scholl condensation: Methyl or hydroxyl substitution of the reactants greatly enhances their reactivity towards hydrogenation and cracking. The source of hydrogen consumed during hydrogenation depends on the choice of catalyst. In the presence of AlCl3, Scholl condensation of aromatic nuclei serves as the principal source of hydrogen. Molecular hydrogen is used exclusively, though, when hydrogenation is catalysed by ZnCl2. The formation of reaction products and the trends in reactant reactivity can be interpreted on the basis of carbonium ion mechanisms. Finally, the results of this study provide a basis for assessing the extent of hydrogenation occurring during the liquefaction of coal using ZnCl2 or AlCl3.

  19. Distributions and sources of petroleum, aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in surface sediments from Bohai Bay and its adjacent river, China.

    PubMed

    Wang, Min; Wang, Chuanyuan; Hu, Xiaoke; Zhang, Haijiang; He, Shijie; Lv, Shuangyan

    2015-01-15

    Surface sediment samples from Bohai Bay and its adjacent river, China, were analyzed for aliphatic hydrocarbon, PAHs and biomarkers in order to determine the distribution, composition and source of organic matter in a coastal environment. Results suggested that the input of organic matter from anthropogenic activities has a more significant influence on its distribution than that from natural processes. Petroleum contamination, mainly from offshore oil exploration and discharge of pollutants from rivers, was the main source of n-alkanes. PAHs were mostly of pyrogenic origin; while some sites in Yellow River Estuary were derived mainly from the petrogenic sources. The toxic assessment suggested that the PAHs in surface sediments will not cause immediately adverse biological effects in sediments from Bohai Bay and its adjacent river, China. PMID:25499964

  20. Distributions and sources of petroleum, aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in surface sediments from Bohai Bay and its adjacent river, China.

    PubMed

    Wang, Min; Wang, Chuanyuan; Hu, Xiaoke; Zhang, Haijiang; He, Shijie; Lv, Shuangyan

    2015-01-15

    Surface sediment samples from Bohai Bay and its adjacent river, China, were analyzed for aliphatic hydrocarbon, PAHs and biomarkers in order to determine the distribution, composition and source of organic matter in a coastal environment. Results suggested that the input of organic matter from anthropogenic activities has a more significant influence on its distribution than that from natural processes. Petroleum contamination, mainly from offshore oil exploration and discharge of pollutants from rivers, was the main source of n-alkanes. PAHs were mostly of pyrogenic origin; while some sites in Yellow River Estuary were derived mainly from the petrogenic sources. The toxic assessment suggested that the PAHs in surface sediments will not cause immediately adverse biological effects in sediments from Bohai Bay and its adjacent river, China.

  1. Rotational jumps of the tyrosine side chain in crystalline enkephalin. /sup 2/H NMR line shapes for aromatic ring motion in solids

    SciTech Connect

    Rice, D.N.; Wittebort, R.J.; Griffin, R.G.; Meirovitch, E.; Stimson, E.R.; Meinwald, Y.C.; Freed, J.H.; Scheraga, H.A.

    1981-12-30

    Deuterium NMR spectra of polycrystalline (tyrosine-3,5-/sup 2/H/sub 2/)(Leu/sup 5/)enkephalin show that the aromatic tyrosyl ring of this pentapeptide is executing 180/sup 0/ flips about the C/sup ..beta../-C/sup ..gamma../ axis in the solid state. Specifically, the axially symmetric powder pattern observed at low temperature collapses to an axially asymmetric pattern with eta approx. = 0.6 at high temperature. Computer simulation of the NMR line shapes, which account for spectral distortions induced by the quadrupole echo technique, indicate that at room temperature the flipping rate is approximately 5 x 10/sup 4/ s/sup -1/ and that it increases to about 10/sup 6/ s/sup -1/ at 101 /sup 0/C.

  2. Catalytic trimerization of aromatic nitriles and triaryl-s-triazine ring cross-linked high temperature resistant polymers and copolymers made thereby

    NASA Technical Reports Server (NTRS)

    Hsu, L. C. (Inventor)

    1979-01-01

    Triazine compounds and cross-linked polymer compositions are made by heating aromatic nitriles to a temperature in the range of from about 100 C to about 700 C, and preferably in the range of from about 200 C to about 350 C, in the presence of a catalyst or mixture of catalysts selected from one or more of the following groups: (1) organic sulfonic and sulfinic acids, (2) organic phosphonic and phosphinic acids, and (3)metallic acetylacetonates, at a pressure in the range of from about atmospheric pressure to about 10,000 psi and preferably in the range of from about 200 psi to about 750 psi. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers are made which are trimerized with or without a filler by the aforementioned catalytic trimerization process into triaryl-s-triazine ring containing or cross-linked polymeric or copolymeric products useful in applications requiring high thermal-oxidative stability and high performance structural properties at elevated temperatures.

  3. The development of statistical models to determine the relationship between aromatic-ring class profile and repeat-dose and developmental toxicities of high-boiling petroleum substances.

    PubMed

    Nicolich, Mark J; Simpson, Barry J; Murray, F Jay; Roth, Randy N; Gray, Thomas M

    2013-11-01

    The repeat-dose and developmental toxicities of certain petroleum refinery streams are related to their polycyclic aromatic compound (PAC) content (Feuston et al., 1994). Building on this foundation, and working within the context of the US EPA High Production Volume (HPV) Chemical Challenge Program, we: (1) characterized relationships between PAC content and repeat-dose and developmental toxicities of high boiling petroleum substances (HBPS), and (2) developed statistical models that can be used to predict critical effects of similar untested substances. Data from 39 dermal toxicity studies of HBPS were used to develop statistical models to predict the dose-response relationships between the weight percent concentration of each of their 1-7 aromatic ring classes and 4 repeat-dose and 3 developmental endpoints (absolute thymus weight, hemoglobin count, platelet count, liver to body weight, live fetus count, fetal weight, and percent resorptions). The correlations between the observed and model-predicted values are >0.90. The predictive ability of the models was tested via a series of evaluation or corroboration methods. As is shown in the paper, using only compositional data of untested HBPS, the models can be used to predict the effect at a given dose or the dose that causes an effect of a stipulated magnitude.

  4. Asymmetric Hydrogenation of Azaindoles: Chemo- and Enantioselective Reduction of Fused Aromatic Ring Systems Consisting of Two Heteroarenes.

    PubMed

    Makida, Yusuke; Saita, Masahiro; Kuramoto, Takahiro; Ishizuka, Kentaro; Kuwano, Ryoichi

    2016-09-19

    High enantioselectivity was achieved for the hydrogenation of azaindoles by using the chiral catalyst, which was prepared from [Ru(η(3) -methallyl)2 (cod)] and a trans-chelating bis(phosphine) ligand (PhTRAP). The dearomative reaction exclusively occurred on the five-membered ring, thus giving the corresponding azaindolines with up to 97:3 enantiomer ratio. PMID:27561154

  5. Aromatic Ring Currents Illustrated--NMR Spectra of Tin(IV) Porphyrin Complexes. An Advanced Undergraduate Experiment.

    ERIC Educational Resources Information Center

    Arnold, Dennis P.

    1988-01-01

    Attempts to show that in the closed loops of cyclic structures the protons situated in conic regions above and below the ring will be shielded. Uses the diamagnetic and air stable octahedral tin(IV) complexes of porphyrins for study. Notes complexes crystallize easily and offer spectacular purple colors. (MVL)

  6. Effect of aromatic ring fluorination on CH···π interactions: rotational spectrum and structure of the fluorobenzene···acetylene weakly bound dimer.

    PubMed

    Ulrich, Nathan W; Songer, Tabitha S; Peebles, Rebecca A; Peebles, Sean A; Seifert, Nathan A; Pérez, Cristóbal; Pate, Brooks H

    2013-11-01

    The rotational spectra for the normal isotopic species and for six (13)C singly substituted isotopologues (in natural abundance) of the fluorobenzene···acetylene (C6H5F···HCCH) weakly bound dimer have been measured in the 6.5-18.5 GHz region using chirped-pulse Fourier-transform microwave spectroscopy. The HCCH molecule interacts with the fluorobenzene via a CH···π contact and is determined to lie almost over the center of, and approximately perpendicular to, the aromatic ring, with an H···π distance (perpendicular distance from the H atom to the ring plane) of around 2.492(47) Å; a slight tilt of HCCH towards the para carbon atom of the fluorobenzene is evident. Binding energies of this complex and related benzene and fluorobenzene dimers obtained from the pseudodiatomic approximation are compared and indicate that fluorobenzene···acetylene lies among the more weakly bound of the complexes exhibiting some type of CH···π interaction.

  7. Substrate-dependent aromatic ring fission of catechol and 2-aminophenol with O2 catalyzed by a nonheme iron complex of a tripodal N4 ligand.

    PubMed

    Lakshman, Triloke Ranjan; Chatterjee, Sayanti; Chakraborty, Biswarup; Paine, Tapan Kanti

    2016-06-01

    The catalytic reactivity of an iron(ii) complex [(TPA)Fe(II)(CH3CN)2](2+) (1) (TPA = tris(2-pyridylmethyl)amine) towards oxygenative aromatic C-C bond cleavage of catechol and 2-aminophenol is presented. Complex 1 exhibits catalytic and regioselective C-C bond cleavage of 3,5-di-tert-butylcatechol (H2DBC) to form intradiol products, whereas it catalyzes extradiol-type C-C bond cleavage of 2-amino-4,6-di-tert-butylphenol (H2AP). The catalytic reactions are found to be pH-dependent and the complex exhibits maximum turnovers at pH 5 in acetonitrile-phthalate buffer. An iron(iii)-catecholate complex [(TPA)Fe(III)(DBC)](+) (2) is formed in the ring cleavage of catechol. In the extradiol-type cleavage of H2AP, an iron(iii)-2-iminobenzosemiquinonate complex [(TPA)Fe(III)(ISQ)](2+) (3) (ISQ = 4,6-di-tert-butyl-2-iminobenzosemiquinonate radical anion) is observed in the reaction pathway. This work shows the importance of the nature of 'redox non-innocent' substrates in governing the mode of ring fission reactivity.

  8. Coprophagy by wild ring-tailed lemurs (Lemur catta) in human-disturbed locations adjacent to the Beza Mahafaly Special Reserve, Madagascar.

    PubMed

    Fish, Krista D; Sauther, Michelle L; Loudon, James E; Cuozzo, Frank P

    2007-06-01

    Coprophagy occurs in a number of animal species, including nonhuman primates. During the 2003-2004 dry seasons at the Beza Mahafaly Special Reserve, Madagascar, we observed wild ring-tailed lemurs (Lemur catta) consuming dried fecal matter from three different species. Ring-tailed lemurs consumed human feces on 12 occasions, cattle feces twice, and feral dog feces once. Coprophagy in this population may be a behavioral adaptation that provides animals access to energy and nutrients and may be an important nutritional source for older, and/or dentally impaired individuals during the dry season. PMID:17253614

  9. Coprophagy by wild ring-tailed lemurs (Lemur catta) in human-disturbed locations adjacent to the Beza Mahafaly Special Reserve, Madagascar.

    PubMed

    Fish, Krista D; Sauther, Michelle L; Loudon, James E; Cuozzo, Frank P

    2007-06-01

    Coprophagy occurs in a number of animal species, including nonhuman primates. During the 2003-2004 dry seasons at the Beza Mahafaly Special Reserve, Madagascar, we observed wild ring-tailed lemurs (Lemur catta) consuming dried fecal matter from three different species. Ring-tailed lemurs consumed human feces on 12 occasions, cattle feces twice, and feral dog feces once. Coprophagy in this population may be a behavioral adaptation that provides animals access to energy and nutrients and may be an important nutritional source for older, and/or dentally impaired individuals during the dry season.

  10. Mechanism of alkoxy groups substitution by Grignard reagents on aromatic rings and experimental verification of theoretical predictions of anomalous reactions.

    PubMed

    Jiménez-Osés, Gonzalo; Brockway, Anthony J; Shaw, Jared T; Houk, K N

    2013-05-01

    The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone, and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated. PMID:23601086

  11. Mechanism of Alkoxy Groups Substitution by Grignard Reagents on Aromatic Rings and Experimental Verification of Theoretical Predictions of Anomalous Reactions

    PubMed Central

    Jiménez-Osés, Gonzalo; Brockway, Anthony J.; Shaw, Jared T.; Houk, K. N.

    2013-01-01

    The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated. PMID:23601086

  12. Desorption of polycyclic aromatic hydrocarbons from soot surface: five- and six-ring (C22, C24) PAHs.

    PubMed

    Bedjanian, Yuri; Nguyen, Mai Lan; Guilloteau, Angélique

    2010-03-18

    The kinetics of thermal desorption of five soot-bound nonvolatile (C(22), C(24)) polycyclic aromatic hydrocarbons (benzo(ghi)perylene (BghiP), indeno(1,2,3-cd)pyrene (IdP), anthanthrene (Antha), dibenz(ah)anthracene (DBahA), dibenzo(ae)pyrene (DBaeP)) identified in laboratory-generated kerosene soot were studied over the temperature range 335-370 K in a low pressure flow reactor. The PAH desorption rate constants were measured using off-line HPLC monitoring of their concentrations in soot samples as a function of desorption time. The following Arrhenius expressions were determined for the desorption rate constants of the soot-bound PAHs studied: k(des) = 8.4 x 10(15) exp[-(129.7 +/- 4.4)/RT], 1.0 x 10(16) exp[-(130.6 +/- 6.1)/RT], 1.1 x 10(16) exp[-(131.6 +/- 3.2)/RT], 1.0 x 10(16) exp[-(128.0 +/- 3.9)/RT], and 1.4 x 10(16) exp[-(134.2 +/- 10.7)/RT] (k(des) are in s(-1) and activation energies in kJ mol(-1)) for BghiP, IdP, Antha, DBahA, and DBaeP, respectively. Analysis of the present and previous experimental data showed that PAH-soot binding energies linearly correlate with the number of PAH carbon atoms. The present data and those from previous studies are discussed in the frame of the existing theoretical gas-to-particle partitioning model. PMID:20170139

  13. Cardiac toxicity of 5-ring polycyclic aromatic hydrocarbons is differentially dependent on the aryl hydrocarbon receptor 2 isoform during zebrafish development

    SciTech Connect

    Incardona, John P. Linbo, Tiffany L.; Scholz, Nathaniel L.

    2011-12-15

    Petroleum-derived compounds, including polycyclic aromatic hydrocarbons (PAHs), commonly occur as complex mixtures in the environment. Recent studies using the zebrafish experimental model have shown that PAHs are toxic to the embryonic cardiovascular system, and that the severity and nature of this developmental cardiotoxicity varies by individual PAH. In the present study we characterize the toxicity of the relatively higher molecular weight 5-ring PAHs benzo[a]pyrene (BaP), benzo[e]pyrene (BeP), and benzo[k]fluoranthene (BkF). While all three compounds target the cardiovascular system, the underlying role of the ligand-activated aryl hydrocarbon receptor (AHR2) and the tissue-specific induction of the cytochrome p450 metabolic pathway (CYP1A) were distinct for each. BaP exposure (40 {mu}M) produced AHR2-dependent bradycardia, pericardial edema, and myocardial CYP1A immunofluorescence. By contrast, BkF exposure (4-40 {mu}M) caused more severe pericardial edema, looping defects, and erythrocyte regurgitation through the atrioventricular valve that were AHR2-independent (i.e., absent myocardial or endocardial CYP1A induction). Lastly, exposure to BeP (40 {mu}M) yielded a low level of CYP1A+ signal in the vascular endothelium of the head and trunk, without evident toxic effects on cardiac function or morphogenesis. Combined with earlier work on 3- and 4-ring PAHs, our findings provide a more complete picture of how individual PAHs may drive the cardiotoxicity of mixtures in which they predominate. This will improve toxic injury assessments and risk assessments for wild fish populations that spawn in habitats altered by overlapping petroleum-related human impacts such as oil spills, urban stormwater runoff, or sediments contaminated by legacy industrial activities. -- Highlights: Black-Right-Pointing-Pointer PAH compounds with 5 rings in different arrangements caused differential tissue-specific patterns of CYP1A induction in zebrafish embryos. Black

  14. Comparison of ab initio and DFT electronic structure methods for peptides containing an aromatic ring: effect of dispersion and BSSE.

    PubMed

    Shields, Ashley E; van Mourik, Tanja

    2007-12-20

    We establish that routine B3LYP and MP2 methods give qualitatively wrong conformations for flexible organic systems containing pi systems and that recently developed methods can overcome the known inadequacies of these methods. This is illustrated for a molecule (a conformer of the Tyr-Gly dipeptide) for which B3LYP/6-31+G(d) and MP2/6-31+G(d) geometry optimizations yield strikingly different structures [Mol. Phys. 2006, 104, 559-570]: MP2 predicts a folded "closed-book" conformer with the glycine residue located above the tyrosine ring, whereas B3LYP predicts a more open conformation. By employing different levels of theory, including the local electron correlation methods LMP2 (local MP2) and LCCSD(T0) (local coupled cluster with single, double, and noniterative local triple excitations) and large basis sets (aug-cc-pVnZ, n=D, T, Q), it is shown that the folded MP2 minimum is an artifact caused by large intramolecular BSSE (basis set superposition error) effects in the MP2/6-31+G(d) calculations. The B3LYP functional gives the correct minimum, but the potential energy apparently rises too steeply when the glycine and tyrosine residues approach each other, presumably due to missing dispersion effects in the B3LYP calculations. The PWB6K and M05-2X functionals, designed to give good results for weak interactions, remedy this to some extent. The reduced BSSE in the LMP2 calculations leads to faster convergence with increasing basis set quality, and accurate results can be obtained with smaller basis sets as compared to canonical MP2. We propose LMP2 as a suitable method to study interactions with pi-electron clouds.

  15. Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

    PubMed

    Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

    2016-06-01

    We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique. PMID:27152774

  16. A metal-bridged tricyclic aromatic system: synthesis of osmium polycyclic aromatic complexes.

    PubMed

    Zhu, Congqing; Zhu, Qin; Fan, Jinglan; Zhu, Jun; He, Xumin; Cao, Xiao-Yu; Xia, Haiping

    2014-06-10

    Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla-aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal-bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal-bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five-membered rings. These metalla-aromatics are formed by reaction between osmapentalyne and arene nucleophiles. Experimental results and theoretical calculations reveal that the three five-membered rings around the osmium center are aromatic. In addition, the broad absorption bands in the UV/Vis absorption spectra of these novel aromatic systems cover almost the entire visible region. This straightforward synthetic strategy may be extended to the synthesis of other metal-bridged polycyclic aromatics. PMID:24782397

  17. Polynuclear aromatic hydrocarbons for fullerene synthesis in flames

    DOEpatents

    Alford, J. Michael; Diener, Michael D.

    2006-12-19

    This invention provides improved methods for combustion synthesis of carbon nanomaterials, including fullerenes, employing multiple-ring aromatic hydrocarbon fuels selected for high carbon conversion to extractable fullerenes. The multiple-ring aromatic hydrocarbon fuels include those that contain polynuclear aromatic hydrocarbons. More specifically, multiple-ring aromatic hydrocarbon fuels contain a substantial amount of indene, methylnapthalenes or mixtures thereof. Coal tar and petroleum distillate fractions provide low cost hydrocarbon fuels containing polynuclear aromatic hydrocarbons, including without limitation, indene, methylnapthalenes or mixtures thereof.

  18. Near-infrared continuum and 3.3 micrometer(s) polycyclic aromatic hydrocarbon imaging of the starburst ring in the type 1 Seyfert galaxy NGC 7469

    NASA Technical Reports Server (NTRS)

    Mazzarella, J. M.; Voit, G. M.; Soifer, B. T.; Matthews, K.; Graham, J. R.; Armus, L.; Shupe, D.

    1994-01-01

    High resolution near-infrared images of the type 1 Seyfert galaxy NGC 7469 have been obtained to probe its dusty nuclear environment. Direct J, H, and K images are relatively featureless, but residual images created by subtracting a smooth model based on best-fitting elliptical isophotes reveal a tight inner spiral whose high surface-brightness portions correspond to a previously detected 3 sec (1 kpc) diameter ring of radio continuum emission. The inner infrared spiral arms extended approximately equal to 4 sec NW and SE from the nucleus, and the NW arm joins up with large-scale spiral structure visible in the R band. The residual images also show a bar-like structure aligned with the brightest infrared/radio hotspots at PA approximately equal to 50 deg. Three infrared hotspots are detected which align remarkably well with 6 cm radio continuum sources. The near-infrared ring and the hotspots are visible in the residual images, and in a high-resolution direct K-band image restored to an effective resolution of 0.65 sec (FWHM) using the Richardson-Lucy algorithm. The infrared hotspots have luminosities of nuL(sub nu) (2.2 micrometer(s)) approximately equal to 10(exp 8) solar luminosity (M(sub k) approximately equal to -16 mag), suggesting they are either giant H II regions or individual supernovae. The two brightest regions may be associated with enhanced star formation triggered by orbit crowding of gas where spiral arms emerge from an inner bar. Narrowband (delta lambda/lambda approximately 1.5%) imaging in the 3.28 micrometer(s) dust emission feature and surrounding continuum confirms the 3 sec diameter 3.28 micrometer(s) emission region detected previously using multiaperture photometry. The extended polycyclic aromatic hydrocarbon (PAH) emission is slightly elongated and aligned with published 1O III1 line emission and 12.5 micrometer(s) continuum emission, apparently tracing the starburst. The presence of approximately equal to 25% of the total 3.28 micrometer

  19. Developmental toxicity of 4-ring polycyclic aromatic hydrocarbons in zebrafish is differentially dependent on AH receptor isoforms and hepatic cytochrome P4501A metabolism

    SciTech Connect

    Incardona, John P. . E-mail: john.incardona@noaa.gov; Day, Heather L.; Collier, Tracy K.; Scholz, Nathaniel L.

    2006-12-15

    Polycyclic aromatic hydrocarbons (PAHs) derived from fossil fuels are ubiquitous contaminants and occur in aquatic habitats as highly variable and complex mixtures of compounds containing 2 to 6 rings. For aquatic species, PAHs are generally accepted as acting through either of two modes of action: (1) 'dioxin-like' toxicity mediated by activation of the aryl hydrocarbon receptor (AHR), which controls a battery of genes involved in PAH metabolism, such as cytochrome P4501A (CYP1A) and (2) 'nonpolar narcosis', in which tissue uptake is dependent solely on hydrophobicity and toxicity is mediated through non-specific partitioning into lipid bilayers. As part of a systematic analysis of mechanisms of PAH developmental toxicity in zebrafish, we show here that three tetracyclic PAHs (pyrene, chrysene, and benz[a]anthracene) activate the AHR pathway tissue-specifically to induce distinct patterns of CYP1A expression. Using morpholino knockdown of ahr1a, ahr2, and cyp1a, we show that distinct embryolarval syndromes induced by exposure to two of these compounds are differentially dependent on tissue-specific activation of AHR isoforms or metabolism by CYP1A. Exposure of embryos with and without circulation (silent heart morphants) resulted in dramatically different patterns of CYP1A induction, with circulation required to deliver some compounds to internal tissues. Therefore, biological effects of PAHs cannot be predicted simply by quantitative measures of AHR activity or a compound's hydrophobicity. These results indicate that current models of PAH toxicity in fish are greatly oversimplified and that individual PAHs are pharmacologically active compounds with distinct and specific cellular targets.

  20. [Comparative study of aromatic ring meta-cleavage enzymes in Pseudomonas strains with plasmid and chromosomal genetic control of the catabolism of biphenyl and m-toluate].

    PubMed

    Selifonov, S A; Starozoĭtov, I I

    1990-12-01

    It was shown that two different enzymes of aromatic ring oxidative meta-cleavage (2,3-dihydroxybiphenyl-1,2-dioxygenase), DBO and catechol-2,3-dioxygenase, C230) function in Pseudomonas strains with a plasmid and chromosomal genetic control of biphenyl and toluate catabolism. A comparative analysis of DBO's and C230's expressed by the pBS241 biphenyl degradative plasmid in P. putida BS893, pBS311 in P. putida U83, chromosomal genes in P. putida BF and C230 from P. putida PaW160 (pWWO) was carried out. It was found that the DBO's of all strains under study are highly specialized enzymes in respect of 2,3-dihydroxybiphenyl cleavage and are also able to cleave 3-methyl-catechol and catechol (but not 4-methylcatechol) at low rates. In contrast with DBO's, in Pseudomonas strains the substrate specificities of all C230's are variable. The C230's expressed by the D-plasmids pBS241 and pBC311 have a moderate affinity for catechol, 3-methyl- and 4-methylcatechol, but are unable to cleave 2,3-dihydroxybiphenyl. The C230 which is encoded by the chromosomal structure gene from P. putida BF is very similar to C230 which codes for the TOL-plasmid pWWO. These plasmid differ from C230's expressed by biphenyl D-plasmids due to their capability to cleave 2,3-dihydroxybiphenyl in addition to catechol cleavage. All DBO's and C230's under study possess a number of properties that are typical for the enzymes having an oxidative meta-cleaving effect. The different roles of these enzymes in biphenyl and toluate catabolism in Pseudomonas strains are discussed.

  1. Aromaticity Competition in Differentially Fused Borepin-Containing Polycyclic Aromatics.

    PubMed

    Messersmith, Reid E; Siegler, Maxime A; Tovar, John D

    2016-07-01

    This report describes the synthesis and characterization of a series of borepin-based polycyclic aromatics bearing two different arene fusions. The borepin synthesis features streamlined Ti-mediated alkyne reduction, leading to Z-olefins, followed by direct lithiation and borepin formation. These molecules allow for an assessment of aromatic competition between the fused rings and the central borepin core. Crystallographic, magnetic, and computational studies yielded insights about the aromaticity of novel, differentially fused [b,f]borepins and allowed for comparison to literature compounds. Multiple borepin motifs were also incorporated into polycyclic aromatics with five or six rings in the main backbone, and their properties were also evaluated.

  2. Insights into Hydrocarbon Chain and Aromatic Ring Formation in the Interstellar Medium: Computational Study of the Isomers of C4H3+ C6H3+ and C6H5+ and Their Formation Pathways

    NASA Astrophysics Data System (ADS)

    Peverati, Roberto; Bera, Partha P.; Lee, Timothy J.; Head-Gordon, Martin

    2016-10-01

    Small hydrocarbons such as acetylene is present in circumstellar envelopes of carbon-rich stars, but the processes that yield larger molecules, and eventually polycyclic aromatic hydrocarbons (PAHs), remain poorly understood. To gain additional insight into the early steps of such processes, electronic structure calculations were performed on the potential energy surfaces of {{{C}}}4{{{{H}}}3}+, {{{C}}}6{{{{H}}}3}+ and {{{C}}}6{{{{H}}}5}+. The results establish reactive pathways from acetylene and its ion to formation of the first aromatic ring. We characterize the stable isomers, their spectroscopic properties, and many of the transition structures that represent barriers to isomerization. The pathways to stabilized {{{C}}}4{{{{H}}}3}+ and {{{C}}}6{{{{H}}}3}+ are most likely to arise from unimolecular decomposition of hot {{{C}}}4{{{{H}}}4}+ and {{{C}}}6{{{{H}}}4}+ by H atom elimination. By contrast, we found an ion-molecule pathway to {{{C}}}6{{{{H}}}5}+ to be very stable to fragmentation and elimination reactions even without collisional stabilization. This aromatic species is a good nucleation center for the growth of larger PAHs in interstellar conditions.

  3. Effects of Fluorine Substitution on the Microsolvation of Aromatic Azines: The Microwave Spectrum of 3-Fluoropyridine-Water.

    PubMed

    Calabrese, Camilla; Gou, Qian; Spada, Lorenzo; Maris, Assimo; Caminati, Walther; Melandri, Sonia

    2016-07-14

    The rotational spectra of the parent species and of four water isotopologues (-DOH, -HOD, -DOD, and -H(18)OH) of the adduct 3-fluoropyridine-water have been investigated using pulsed supersonic-jet Fourier-transform microwave spectroscopy. From the rotational constants, the structure of the adduct was deduced where the water is linked to the aromatic ring through an intermolecular O-H···N hydrogen bond with a bond distance of 1.9961(5) Å and an O-H···N angle of 156.8(1)°. The shape of the complex is such that the water oxygen is in the plane of the aromatic ring, on the opposite side of fluorine, and forming a C-H···N weak hydrogen bond with the adjacent aromatic hydrogen.

  4. Effects of Fluorine Substitution on the Microsolvation of Aromatic Azines: The Microwave Spectrum of 3-Fluoropyridine-Water.

    PubMed

    Calabrese, Camilla; Gou, Qian; Spada, Lorenzo; Maris, Assimo; Caminati, Walther; Melandri, Sonia

    2016-07-14

    The rotational spectra of the parent species and of four water isotopologues (-DOH, -HOD, -DOD, and -H(18)OH) of the adduct 3-fluoropyridine-water have been investigated using pulsed supersonic-jet Fourier-transform microwave spectroscopy. From the rotational constants, the structure of the adduct was deduced where the water is linked to the aromatic ring through an intermolecular O-H···N hydrogen bond with a bond distance of 1.9961(5) Å and an O-H···N angle of 156.8(1)°. The shape of the complex is such that the water oxygen is in the plane of the aromatic ring, on the opposite side of fluorine, and forming a C-H···N weak hydrogen bond with the adjacent aromatic hydrogen. PMID:26959997

  5. Möbius Aromatic Core-Modified Heterocyclic [20] Macrocycles (4.1.1) with a Protruding N-Methyl Pyrrole Ring.

    PubMed

    Mallick, Abhijit; Rath, Harapriya

    2016-04-01

    Herein, we report the first synthesis of an unorthodox tripyrrane moiety from the regioselective β-benzoylation of pyrrole and the acid-catalyzed condensation of the desired precursors. A [3+1] Mac Donald type condensation strategy for this tripyrrane has led to the exclusive isolation of two hitherto-unknown aromatic [20] heterocyclic macrocycles (4.1.1). PMID:26812474

  6. Concentric ring flywheel without expansion separators

    DOEpatents

    Kuklo, T.C.

    1999-08-24

    A concentric ring flywheel wherein the adjacent rings are configured to eliminate the need for differential expansion separators between the adjacent rings. This is accomplished by forming a circumferential step on an outer surface of an inner concentric ring and forming a matching circumferential step on the inner surface of an adjacent outer concentric ring. During operation the circumferential steps allow the rings to differentially expand due to the difference in the radius of the rings without the formation of gaps therebetween, thereby eliminating the need for expansion separators to take up the gaps formed by differential expansion. 3 figs.

  7. Concentric ring flywheel without expansion separators

    DOEpatents

    Kuklo, Thomas C.

    1999-01-01

    A concentric ring flywheel wherein the adjacent rings are configured to eliminate the need for differential expansion separators between the adjacent rings. This is accomplished by forming a circumferential step on an outer surface of an inner concentric ring and forming a matching circumferential step on the inner surface of an adjacent outer concentric ring. During operation the circumferential steps allow the rings to differentially expand due to the difference in the radius of the rings without the formation of gaps therebetween, thereby eliminating the need for expansion separators to take up the gaps formed by differential expansion.

  8. Magnetic criteria of aromaticity.

    PubMed

    Gershoni-Poranne, Renana; Stanger, Amnon

    2015-09-21

    This review describes the current state of magnetic criteria of aromaticity. The introduction contains the fundamentals of ring currents in aromatic and antiaromatic systems, followed by a brief description of experimental and computational tools: NMR, diamagnetic susceptibility exaltation, current density analyses (CDA) and nucleus independent chemical shifts (NICS). This is followed by more comprehensive chapters: NMR - focusing on the work of R. Mitchell - NICS and CDA - describing the progress and development of the methods to their current state and presenting some examples of representative work. PMID:26035305

  9. Magnetic criteria of aromaticity.

    PubMed

    Gershoni-Poranne, Renana; Stanger, Amnon

    2015-09-21

    This review describes the current state of magnetic criteria of aromaticity. The introduction contains the fundamentals of ring currents in aromatic and antiaromatic systems, followed by a brief description of experimental and computational tools: NMR, diamagnetic susceptibility exaltation, current density analyses (CDA) and nucleus independent chemical shifts (NICS). This is followed by more comprehensive chapters: NMR - focusing on the work of R. Mitchell - NICS and CDA - describing the progress and development of the methods to their current state and presenting some examples of representative work.

  10. Synthesis of tetra- and octa-aurated heteroaryl complexes towards probing aromatic indoliums

    PubMed Central

    Yuan, Jun; Sun, Tingting; He, Xin; An, Ke; Zhu, Jun; Zhao, Liang

    2016-01-01

    Polymetalated aromatic compounds are particularly challenging synthetic goals because of the limited thermodynamic stability of polyanionic species arising from strong electrostatic repulsion between adjacent carbanionic sites. Here we describe a facile synthesis of two polyaurated complexes including a tetra-aurated indole and an octa-aurated benzodipyrrole. The imido trinuclear gold(I) moiety exhibits nucleophilicity and undergoes an intramolecular attack on a gold(I)-activated ethynyl to generate polyanionic heteroaryl species. Their computed magnetic properties reveal the aromatic character in the five-membered ring. The incorporation of the aurated substituents at the nitrogen atom can convert non-aromaticity in the parent indolium into aromaticity in the aurated one because of hyperconjugation. Thus, the concept of hyperconjugative aromaticity is extended to heterocycles with transition metal substituents. More importantly, further analysis indicates that the aurated substituents can perform better than traditional main-group substituents. This work highlights the difference in aromaticity between polymetalated aryls and their organic prototypes. PMID:27186982

  11. Aromatic Gain in a Supramolecular Polymer.

    PubMed

    Saez Talens, Victorio; Englebienne, Pablo; Trinh, Thuat T; Noteborn, Willem E M; Voets, Ilja K; Kieltyka, Roxanne E

    2015-09-01

    The synergy of aromatic gain and hydrogen bonding in a supramolecular polymer is explored. Partially aromatic bis(squaramide) bolaamphiphiles were designed to self-assemble through a combination of hydrophobic, hydrogen-bonding, and aromatic effects into stiff, high-aspect-ratio fibers. UV and IR spectroscopy show electron delocalization and geometric changes within the squaramide ring indicative of strong hydrogen bonding and aromatic gain of the monomer units. The aromatic contribution to the interaction energy was further supported computationally by nucleus-independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) indices, demonstrating greater aromatic character upon polymerization: at least 30% in a pentamer. The aromatic gain-hydrogen bonding synergy results in a significant increase in thermodynamic stability and a striking difference in aggregate morphology of the bis(squaramide) bolamphiphile compared to isosteres that cannot engage in this effect. PMID:26179942

  12. The aromatic ene reaction

    PubMed Central

    Niu, Dawen; Hoye, Thomas R.

    2014-01-01

    The ene reaction is a pericyclic process in which an alkene having an allylic hydrogen atom (the ene donor) reacts with a second unsaturated species (the enophile) to form a new product with a transposed π-bond. The aromatic ene reaction, in which the alkene component is embedded in an aromatic ring, has only been reported in a few (four) instances and has proceeded in low yield (≤6%). Here we show efficient aromatic ene reactions in which a thermally generated aryne engages a pendant m-alkylarene substituent to produce a dearomatized isotoluene, itself another versatile but rare reactive intermediate. Our experiments were guided by computational studies that revealed structural features conducive to the aromatic ene process. We proceeded to identify a cascade comprising three reactions: (i) hexadehydro-Diels-Alder (for aryne generation), (ii) intramolecular aromatic ene, and (iii) bimolecular Alder ene. The power of this cascade is evident from the structural complexity of the final products, the considerable scope, and the overall efficiency of these multi-stage, reagent- and byproduct-free, single-pot transformations. PMID:24345944

  13. A Gene Expression Study of the Activities of Aromatic Ring-Cleavage Dioxygenases in Mycobacterium gilvum PYR-GCK to Changes in Salinity and pH during Pyrene Degradation

    PubMed Central

    Badejo, Abimbola Comfort; Badejo, Adegoke Olugboyega; Shin, Kyung Hoon; Chai, Young Gyu

    2013-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are toxic pollutants found in the environment which can be removed through the use of physical and biological agents. The rate of PAH biodegradation is affected by environmental conditions of pH, salinity and temperature. Adaptation of the pyrene degrading bacteria, Mycobacterium gilvum PYR-GCK, to fluctuating environmental conditions during pyrene biodegrading activity was studied using the quantitative real time – Polymerase Chain Reaction (qRT-PCR) technique. Four aromatic ring-cleavage dioxygenase genes: phdF, phdI, pcaG and pcaH; critical to pyrene biodegradation, were studied in pH states of 5.5, 6.5, 7.5 and NaCl concentrations 0 M, 0.17 M, 0.5 M, 0.6 M, 1 M. First, we conducted a residual pyrene study using gas chromatography and flame ionization technologies. Central to a gene expression study is the use of a valid endogenous reference gene, making its determination our next approach, using the geNorm/NormFinder algorithms. Armed with a valid control gene, rpoB, we applied it to a gene expression study, using the comparative critical threshold (2ΔΔCT) quantification method. The pyrene degrading activity of the strain was strongly functional in all the NaCl concentration states, with the least activity found at 1M (∼70% degraded after 48 hours of cultivation). The transcripts quantification of three genes backed this observation with high expression levels. The gene expression levels also revealed pH 6.5 as optimal for pyrene degradation and weak degradation activity at pH of 5.5, corroborating the residual pyrene analysis. The expression of these genes as proteins has already been studied in our laboratory using proteomics techniques and this validates our current study. PMID:23469141

  14. In situ determination of the depuration of three- and four-ringed polycyclic aromatic hydrocarbons co-adsorbed onto mangrove leaf surfaces.

    PubMed

    Sun, Haifeng; Shi, Jing; Guo, Shuai; Zhang, Yong; Duan, Lusha

    2016-01-01

    A dual-wavelength fiber-optic fluorimetry for the in situ simultaneous determinations of fluorene (Flu), phenanthrene (Phe) and pyrene (Pyr) adsorbed onto the leaf surfaces of living Avicennia marina (Am) seedling were developed and used to study the depuration kinetics of the three PAHs, adsorbed individually or mixed together, onto living Am leaf surfaces. Limits of detection for the in situ measurements of adsorbed Flu, Phe and Pyr were 4.62, 2.75 and 1.38 ng spot(-1), respectively. The depuration kinetics of the three selected polycyclic aromatic hydrocarbons (PAHs) are divided into rapid and slow phases; both phases followed the same first-order kinetics with relative clearance rates of Flu > Phe > Pyr during the rapid phase, and a clearance rate order of Pyr > Flu > Phe during the slow phase. For the three PAHs co-adsorbed on living Am leaf surfaces, a significant synergistic effect was detected during the rapid phase clearance; conversely, an antagonistic effect was observed during the slow phase. However, the synergistic effect dominated during both phases of the depuration process, and the co-adsorption of PAHs promoted the clearance of all three compounds from the mangrove leaf surfaces. These findings demonstrate a novel analytical method for in situ characterization of multiple PAHs adsorbed onto the plant surfaces.

  15. Molecular and functional analysis of the TOL plasmid pWWO from Pseudomonas putida and cloning of genes for the entire regulated aromatic ring meta cleavage pathway.

    PubMed Central

    Franklin, F C; Bagdasarian, M; Bagdasarian, M M; Timmis, K N

    1981-01-01

    The genetic organization of the Pseudomonas putida plasmid pWWO-161, which encodes enzymes for the degradation of toluene and related aromatic hydrocarbons, has been investigated by transposition mutagenesis and gene cloning. Catabolic genes were localized to two clusters, one for upper pathway (hydrocarbon leads to carboxylic acid) enzymes and the other for lower pathway (carboxylic acid leads to tricarboxylic acid cycle) enzymes, that are separated by a 14-kilobase DNA segment. The physical organization of the catabolic genes thus reflects their functional organization into two regulatory blocks. The pWWO-161 DNA fragments Sst I fragment C and fragment D were cloned in a broad host range vector to produce plasmid pKT530. This hybrid encodes toluate oxygenase and all meta cleavage pathway enzymes, and it enables P. putida mt-2 and Escherichia coli K-12 cells to grow on m-toluate as sole carbon source. The pKT530 plasmid also carries xylS (a gene whose product has been postulated to regulate expression of the lower pathway genes) and the control sequences of the pathway that interact with this product, because catechol 2,3-oxygenase synthesis is specifically induced by m-toluate in both P. putida and E. coli. Evidence is presented that suggests the promoter operator of the meta pathway gene functions less effectively with the RNA polymerase or xylS product of E. coli than with the enzyme or product of P. putida. PMID:6950388

  16. Introduction of aromatic ring-containing substituents in cyclic nucleotides is associated with inhibition of toxin uptake by the hepatocyte transporters OATP 1B1 and 1B3.

    PubMed

    Herfindal, Lars; Krakstad, Camilla; Myhren, Lene; Hagland, Hanne; Kopperud, Reidun; Teigen, Knut; Schwede, Frank; Kleppe, Rune; Døskeland, Stein Ove

    2014-01-01

    Analogs of the cyclic nucleotides cAMP and cGMP have been extensively used to mimic or modulate cellular events mediated by protein kinase A (PKA), Exchange protein directly activated by cAMP (Epac), or protein kinase G (PKG). We report here that some of the most commonly used cyclic nucleotide analogs inhibit transmembrane transport mediated by the liver specific organic anion transporter peptides OATP1B1 and OATP1B3, unrelated to actions on Epac, PKA or PKG. Several cAMP analogs, particularly with 8-pCPT-substitution, inhibited nodularin (Nod) induced primary rat hepatocyte apoptosis. Inhibition was not mediated by PKA or Epac, since increased endogenous cAMP, and some strong PKA- or Epac-activating analogs failed to protect cells against Nod induced apoptosis. The cAMP analogs inhibiting Nod induced hepatocyte apoptosis also reduced accumulation of radiolabeled Nod or cholic acid in primary rat hepatocytes. They also inhibited Nod induced apoptosis in HEK293 cells with enforced expression of OATP1B1 or 1B3, responsible for Nod transport into cells. Similar results were found with adenosine analogs, disconnecting the inhibitory effect of certain cAMP analogs from PKA or Epac. The most potent inhibitors were 8-pCPT-6-Phe-cAMP and 8-pCPT-2'-O-Me-cAMP, whereas analogs like 6-MB-cAMP or 8-Br-cAMP did not inhibit Nod uptake. This suggests that the addition of aromatic ring-containing substituents like the chloro-phenyl-thio group to the purines of cyclic nucleotides increases their ability to inhibit the OATP-mediated transport. Taken together, our data show that aromatic ring substituents can add unwanted effects to cyclic nucleotides, and that such nucleotide analogs must be used with care, particularly when working with cells expressing OATP1B1/1B3, like hepatocytes, or intact animals where hepatic metabolism can be an issue, as well as certain cancer cells. On the other hand, cAMP analogs with substituents like bromo, monobutyryl were non-inhibitory, and could be

  17. Introduction of aromatic ring-containing substituents in cyclic nucleotides is associated with inhibition of toxin uptake by the hepatocyte transporters OATP 1B1 and 1B3.

    PubMed

    Herfindal, Lars; Krakstad, Camilla; Myhren, Lene; Hagland, Hanne; Kopperud, Reidun; Teigen, Knut; Schwede, Frank; Kleppe, Rune; Døskeland, Stein Ove

    2014-01-01

    Analogs of the cyclic nucleotides cAMP and cGMP have been extensively used to mimic or modulate cellular events mediated by protein kinase A (PKA), Exchange protein directly activated by cAMP (Epac), or protein kinase G (PKG). We report here that some of the most commonly used cyclic nucleotide analogs inhibit transmembrane transport mediated by the liver specific organic anion transporter peptides OATP1B1 and OATP1B3, unrelated to actions on Epac, PKA or PKG. Several cAMP analogs, particularly with 8-pCPT-substitution, inhibited nodularin (Nod) induced primary rat hepatocyte apoptosis. Inhibition was not mediated by PKA or Epac, since increased endogenous cAMP, and some strong PKA- or Epac-activating analogs failed to protect cells against Nod induced apoptosis. The cAMP analogs inhibiting Nod induced hepatocyte apoptosis also reduced accumulation of radiolabeled Nod or cholic acid in primary rat hepatocytes. They also inhibited Nod induced apoptosis in HEK293 cells with enforced expression of OATP1B1 or 1B3, responsible for Nod transport into cells. Similar results were found with adenosine analogs, disconnecting the inhibitory effect of certain cAMP analogs from PKA or Epac. The most potent inhibitors were 8-pCPT-6-Phe-cAMP and 8-pCPT-2'-O-Me-cAMP, whereas analogs like 6-MB-cAMP or 8-Br-cAMP did not inhibit Nod uptake. This suggests that the addition of aromatic ring-containing substituents like the chloro-phenyl-thio group to the purines of cyclic nucleotides increases their ability to inhibit the OATP-mediated transport. Taken together, our data show that aromatic ring substituents can add unwanted effects to cyclic nucleotides, and that such nucleotide analogs must be used with care, particularly when working with cells expressing OATP1B1/1B3, like hepatocytes, or intact animals where hepatic metabolism can be an issue, as well as certain cancer cells. On the other hand, cAMP analogs with substituents like bromo, monobutyryl were non-inhibitory, and could be

  18. Aromatic aldehyde-catalyzed gas-phase decarboxylation of amino acid anion via imine intermediate: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Xiang, Zhang

    2013-10-01

    It is generally appreciated that carbonyl compound can promote the decarboxylation of the amino acid. In this paper, we have performed the experimental and theoretical investigation into the gas-phase decarboxylation of the amino acid anion catalyzed by the aromatic aldehyde via the imine intermediate on the basis of the tandem mass spectrometry (MS/MS) technique and density functional theory (DFT) calculation. The results show that the aromatic aldehyde can achieve a remarkable catalytic effect. Moreover, the catalytic mechanism varies according to the type of amino acid: (i) The decarboxylation of α-amino acid anion is determined by the direct dissociation of the Csbnd C bond adjacent to the carboxylate, for the resulting carbanion can be well stabilized by the conjugation between α-carbon, Cdbnd N bond and benzene ring. (ii) The decarboxylation of non-α-amino acid anion proceeds via a SN2-like transition state, in which the dissociation of the Csbnd C bond adjacent to the carboxylate and attacking of the resulting carbanion to the Cdbnd N bond or benzene ring take place at the same time. Specifically, for β-alanine, the resulting carbanion preferentially attacks the benzene ring leading to the benzene anion, because attacking the Cdbnd N bond in the decarboxylation can produce the unstable three or four-membered ring anion. For the other non-α-amino acid anion, the Cdbnd N bond preferentially participates in the decarboxylation, which leads to the pediocratic nitrogen anion.

  19. Metabolic activation of N-hydroxy arylamines, N-hydroxy heterocyclic amines and ring-hydroxymethyl polycyclic aromatic hydrocarbons by human sulfotransferases

    SciTech Connect

    Chou, H.C.

    1993-01-01

    Arylamines and polycyclic aromatic hydrocarbons (PAHs) are two major classes of chemical carcinogens. N-Hydroxylation of arylamines is regarded to be a necessary process for their mutagenicity and carcinogenicity, while alkyl-hydroxylation is the major metabolic pathway for alkyl-substituted PAHs. Evidence has been presented that sulfation of several N-hydroxy arylamines and hydroxymethyl PAHs is an important pathway leading to the formation of ultimate carcinogens in experiment animals. Sulfation of these chemicals forms putative sulfuric acid ester intermediates that can rearrange to electrophilic nitrenium or carbenium ions capable of forming covalent adducts with important cellular macromolecules. In order to study the metabolic activation by sulfotransferase(s) in various human tissue preparations an in vitro enzymatic assay was established. A metabolic phenotyping method was also developed for thermostable phenolsulfotransferase (TS-PST) in platelet homogenates (correlated with TS-PST activity in other tissues) based on a simple colorimetric assay using 2-naphthol as substrate. By using a PAPS-regenerating system to supply the activated sulfate and calf thymus DNA to trap the reactive metabolites, we found that N-hydroxy derivatives of the carcinogens, 4-aminobiphenyl (4-ABP), 4,4[prime]-methylene-bis(2-chloroaniline) (MOCA), 2-acetylaminofluorene (2-AAF), 2-aminofluorene (2-AF), 2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine (PhIP), and 2-amino-6-methyldipyrido [1,2-1:3[prime],2[prime]-d]imidazole (Glu-P-1) were metabolically activated by human TS-PST. On the other hand, three methyl-hydroxylated derivatives (7-OH, 12-OH, and 7,12-diOH) of 7, 12-dimethylbenz[a]anthracene (DMBA) were metabolically activated by human steroid sulfotransferase. Human sulfotransferase(s)-mediated activation of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) or 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) was not observed.

  20. Structural characterization of 2,6-dichloro-p-hydroquinone 1,2-dioxygenase (PcpA) from Sphingobium chlorophenolicum, a new type of aromatic ring-cleavage enzyme

    PubMed Central

    Hayes, Robert P.; Green, Abigail R.; Nissen, Mark S.; Lewis, Kevin M.; Xun, Luying; Kang, ChulHee

    2014-01-01

    Summary PcpA (2,6-dichloro-p-hydroquinone 1,2-dioxygenase) from Sphingobium chlorophenolicum, a non-haem Fe(II) dioxygenase capable of cleaving the aromatic ring of p-hydroquinone and its substituted variants, is a member of the recently discovered p-hydroquinone 1,2-dioxygenases. Here we report the 2.6 Å structure of PcpA, which consists of four βαβββ motifs, a hallmark of the vicinal oxygen chelate superfamily. The secondary co-ordination sphere of the Fe(II) centre forms an extensive hydrogen-bonding network with three solvent exposed residues, linking the catalytic Fe(II) to solvent. A tight hydrophobic pocket provides p-hydroquinones access to the Fe(II) centre. The p-hydroxyl group is essential for the substrate-binding, thus phenols and catechols, lacking a p-hydroxyl group, do not bind to PcpA. Site-directed mutagenesis and kinetic analysis confirm the critical catalytic role played by the highly conserved His10, Thr13, His226 and Arg259. Based on these results, we propose a general reaction mechanism for p-hydroquinone 1,2-dioxygenases. PMID:23489289

  1. Soil type-dependent responses to phenanthrene as revealed by determining the diversity and abundance of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase genes by using a novel PCR detection system.

    PubMed

    Ding, Guo-Chun; Heuer, Holger; Zühlke, Sebastian; Spiteller, Michael; Pronk, Geertje Johanna; Heister, Katja; Kögel-Knabner, Ingrid; Smalla, Kornelia

    2010-07-01

    A novel PCR primer system that targets a wide range of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase (PAH-RHD(alpha)) genes of both Gram-positive and Gram-negative bacteria was developed and used to study their abundance and diversity in two different soils in response to phenanthrene spiking. The specificities and target ranges of the primers predicted in silico were confirmed experimentally by cloning and sequencing of PAH-RHD(alpha) gene amplicons from soil DNA. Cloning and sequencing showed the dominance of phnAc genes in the contaminated Luvisol. In contrast, high diversity of PAH-RHD(alpha) genes of Gram-positive and Gram-negative bacteria was observed in the phenanthrene-spiked Cambisol. Quantitative real-time PCR based on the same primers revealed that 63 days after phenanthrene spiking, PAH-RHD(alpha) genes were 1 order of magnitude more abundant in the Luvisol than in the Cambisol, while they were not detected in both control soils. In conclusion, sequence analysis of the amplicons obtained confirmed the specificity of the novel primer system and revealed a soil type-dependent response of PAH-RHD(alpha) gene-carrying soil bacteria to phenanthrene spiking.

  2. Reinforcement core facilitates O-ring installation

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Reinforcement core holds O-ring in place within a structure while adjacent parts are being assembled. The core in the O-ring adds circumferential rigidity to the O-ring material. This inner core does not appreciably affect the sectional elasticity or gland-sealing characteristics of the O-ring.

  3. Presence and potential significance of aromatic-ketone groups in aquatic humic substances

    USGS Publications Warehouse

    Leenheer, J.A.; Wilson, M.A.; Malcolm, R.L.

    1987-01-01

    Aquatic humic- and fulvic-acid standards of the International Humic Substances Society were characterized, with emphasis on carbonyl-group nature and content, by carbon-13 nuclear-magnetic-resonance spectroscopy, proton nuclear-magnetic-resonance spectroscopy, and infrared spectroscopy. After comparing spectral results of underivatized humic and fulvic acids with spectral results of chemically modified derivatives, that allow improved observation of the carbonyl group, the data clearly indicated that aromatic ketone groups comprised the majority of the carbonyl-group content. About one ketone group per monocyclic aromatic ring was determined for both humic and fulvic acids. Aromatic-ketone groups were hypothesized to form by photolytic rearrangements and oxidation of phenolic ester and hydrocarbon precursors; these groups have potential significance regarding haloform formation in water, reactivity resulting from active hydrogen of the methyl and methylene adjacent to the ketone groups, and formation of hemiketal and lactol structures. Aromatic-ketone groups also may be the point of attachment between aliphatic and aromatic moieties of aquatic humic-substance structure. ?? 1987.

  4. "Carbo-aromaticity" and novel carbo-aromatic compounds.

    PubMed

    Cocq, Kévin; Lepetit, Christine; Maraval, Valérie; Chauvin, Remi

    2015-09-21

    While the concept of aromaticity is being more and more precisely delineated, the category of "aromatic compounds" is being more and more expanded. This is illustrated by an introductory highlight of the various types of "aromaticity" previously invoked, and by a focus on the recently proposed "aromatic character" of the "two-membered rings" of the acetylene and butatriene molecules. This serves as a general foundation for the definition of "carbo-aromaticity", the relevance of which is surveyed through recent results in the synthetic, physical, and theoretical chemistry of carbo-mers and in particular macrocyclic-polycyclic representatives constituting a natural family of "novel aromatic compounds". With respect to their parent molecules, carbo-mers are constitutionally defined as "carbon-enriched", and can also be functionally regarded as "π-electron-enriched". This is exemplified by recent experimental and theoretical results on functional, aromatic, rigid, σ,π-macrocyclic carbo-benzene archetypes of various substitution patterns, with emphasis on the quadrupolar pattern. For the purpose of comparison, several types of non-aromatic references of carbo-benzenes are then considered, i.e. freely rotating σ,π-acyclic carbo-n-butadienes and flexible σ-cyclic, π-acyclic carbo-cyclohexadienes, and to "pro-aromatic" congeners, i.e. rigid σ,π-macrocyclic carbo-quinoids. It is shown that functional carbo-mers are entering the field of "molecular materials" for properties such as linear or nonlinear optical properties (e.g. dichromism and two-photon absorption) and single molecule conductivity. Since total or partial carbo-mers of aromatic carbon-allotropes of infinite size such as graphene (graphynes and graphdiynes) and graphite ("graphitynes") have long been addressed at the theoretical or conceptual level, recent predictive advances on the electrical, optical and mechanical properties of such carbo-materials are surveyed. Very preliminary experimental results

  5. "Carbo-aromaticity" and novel carbo-aromatic compounds.

    PubMed

    Cocq, Kévin; Lepetit, Christine; Maraval, Valérie; Chauvin, Remi

    2015-09-21

    While the concept of aromaticity is being more and more precisely delineated, the category of "aromatic compounds" is being more and more expanded. This is illustrated by an introductory highlight of the various types of "aromaticity" previously invoked, and by a focus on the recently proposed "aromatic character" of the "two-membered rings" of the acetylene and butatriene molecules. This serves as a general foundation for the definition of "carbo-aromaticity", the relevance of which is surveyed through recent results in the synthetic, physical, and theoretical chemistry of carbo-mers and in particular macrocyclic-polycyclic representatives constituting a natural family of "novel aromatic compounds". With respect to their parent molecules, carbo-mers are constitutionally defined as "carbon-enriched", and can also be functionally regarded as "π-electron-enriched". This is exemplified by recent experimental and theoretical results on functional, aromatic, rigid, σ,π-macrocyclic carbo-benzene archetypes of various substitution patterns, with emphasis on the quadrupolar pattern. For the purpose of comparison, several types of non-aromatic references of carbo-benzenes are then considered, i.e. freely rotating σ,π-acyclic carbo-n-butadienes and flexible σ-cyclic, π-acyclic carbo-cyclohexadienes, and to "pro-aromatic" congeners, i.e. rigid σ,π-macrocyclic carbo-quinoids. It is shown that functional carbo-mers are entering the field of "molecular materials" for properties such as linear or nonlinear optical properties (e.g. dichromism and two-photon absorption) and single molecule conductivity. Since total or partial carbo-mers of aromatic carbon-allotropes of infinite size such as graphene (graphynes and graphdiynes) and graphite ("graphitynes") have long been addressed at the theoretical or conceptual level, recent predictive advances on the electrical, optical and mechanical properties of such carbo-materials are surveyed. Very preliminary experimental results

  6. Influence of methoxy- and nitro-substitutions in the aromatic ring on proton donation ability in hydrogen bond and on the amino group parameters of free and H-bonded molecules of 2-aminopyrimidine

    NASA Astrophysics Data System (ADS)

    Borisenko, V. E.; Krekov, S. A.; Fomenko, M. Yu.; Koll, A.; Lipkovski, P.

    2008-06-01

    Amino- and imino- forms of pyrimidine are widely presented as part of antibiotics, corrective medications for heart failures and metabolic stimulators. Hydrogen bonding is one of the fundamental interactions between biologically active molecules. This type of interactions provides flexibility, speed and variety of the biochemical processes. Proton donation properties of aminopyrimidines significantly depend on the position, number and kind of the substituent in its aromatic ring. In present work we studied the influence of the methoxy- and nitro-substitutions in the phenyl radical of pyridine and pyrimidine cycles on the proton donation ability of the amino group in hydrogen bonds as well as on its geometrical, force, electro-optical and thermodynamical characteristics in free and H-bonded (1:1 and 1:2, with various proton acceptors) molecules of primary aromatic amines. Acetonitrile, dioxane, tetrahydrofourane, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide (whose proton accepting properties vary within a wide range) were used as proton acceptors in our research. In the region of the amino group stretching and deformation vibrations the IR spectra of free and H-bonded (1:1) molecules of 2-amino-4,6-dimethoxy- and 2-amino-5-nitropyrimidine were studied in complexes with proton acceptors in CCl 4 within the temperature range 288-328 K. The spectra of 1:2 complexes were studied in undiluted aprotic solvents. The following spectral characteristics of absorption bands in amino group stretching vibrations were determined: M(0) (zero spectral moment, integrated intensity B); M(1) (first spectral moment, band "centre of gravity"); effective half width, related to the second central moment (Δ ν1/2) eff = 2( M(2)) 1/2, frequencies of the deformation vibrations δ(HNH) of free and H-bonded molecules. It was shown that changes of the absorption band spectral characteristics of the amino group stretching and deformation vibrations in the analyzed

  7. Adjacent segment disease.

    PubMed

    Virk, Sohrab S; Niedermeier, Steven; Yu, Elizabeth; Khan, Safdar N

    2014-08-01

    EDUCATIONAL OBJECTIVES As a result of reading this article, physicians should be able to: 1. Understand the forces that predispose adjacent cervical segments to degeneration. 2. Understand the challenges of radiographic evaluation in the diagnosis of cervical and lumbar adjacent segment disease. 3. Describe the changes in biomechanical forces applied to adjacent segments of lumbar vertebrae with fusion. 4. Know the risk factors for adjacent segment disease in spinal fusion. Adjacent segment disease (ASD) is a broad term encompassing many complications of spinal fusion, including listhesis, instability, herniated nucleus pulposus, stenosis, hypertrophic facet arthritis, scoliosis, and vertebral compression fracture. The area of the cervical spine where most fusions occur (C3-C7) is adjacent to a highly mobile upper cervical region, and this contributes to the biomechanical stress put on the adjacent cervical segments postfusion. Studies have shown that after fusion surgery, there is increased load on adjacent segments. Definitive treatment of ASD is a topic of continuing research, but in general, treatment choices are dictated by patient age and degree of debilitation. Investigators have also studied the risk factors associated with spinal fusion that may predispose certain patients to ASD postfusion, and these data are invaluable for properly counseling patients considering spinal fusion surgery. Biomechanical studies have confirmed the added stress on adjacent segments in the cervical and lumbar spine. The diagnosis of cervical ASD is complicated given the imprecise correlation of radiographic and clinical findings. Although radiological and clinical diagnoses do not always correlate, radiographs and clinical examination dictate how a patient with prolonged pain is treated. Options for both cervical and lumbar spine ASD include fusion and/or decompression. Current studies are encouraging regarding the adoption of arthroplasty in spinal surgery, but more long

  8. Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

    DOEpatents

    Baker, E.G.; Elliott, D.C.

    1993-01-19

    The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compounds as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

  9. Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

    DOEpatents

    Baker, Eddie G.; Elliott, Douglas C.

    1993-01-01

    The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compouns as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

  10. Elucidating the role of aromatic interactions in rotational barriers involving aromatic systems.

    PubMed

    Lima, Carlos F R A C; Gomes, Lígia R; Low, John N; Silva, Artur M S; Santos, Luís M N B F

    2012-11-16

    The measurement of aryl-naphthyl rotational barriers, ΔG(⧧), in various solvents for two substituted 1,8-diarylnaphthalenes by dynamic (1)H NMR showed that ΔG(‡) trends in aromatic systems can be fully rationalized only when considering the different types of aromatic interactions that can be established in the ground and transition states, namely, intramolecular interactions involving the aromatic rings and specific solvation interactions. PMID:23106141

  11. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: Unified Method for Predicting Aerosol Composition and Formation.

    PubMed

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Kacarab, Mary; Cocker, David R

    2016-06-21

    Innovative secondary organic aerosol (SOA) composition analysis methods normalizing aerosol yield and chemical composition on an aromatic ring basis are developed and utilized to explore aerosol formation from oxidation of aromatic hydrocarbons. SOA yield and chemical composition are revisited using 15 years of University of California, Riverside/CE-CERT environmental chamber data on 17 aromatic hydrocarbons with HC:NO ranging from 11.1 to 171 ppbC:ppb. SOA yield is redefined in this work by normalizing the molecular weight of all aromatic precursors to the molecular weight of the aromatic ring [Formula: see text], where i is the aromatic hydrocarbon precursor. The yield normalization process demonstrates that the amount of aromatic rings present is a more significant driver of aerosol formation than the vapor pressure of the precursor aromatic. Yield normalization also provided a basis to evaluate isomer impacts on SOA formation. Further, SOA elemental composition is explored relative to the aromatic ring rather than on a classical mole basis. Generally, four oxygens per aromatic ring are observed in SOA, regardless of the alkyl substitutes attached to the ring. Besides the observed SOA oxygen to ring ratio (O/R ∼ 4), a hydrogen to ring ratio (H/R) of 6 + 2n is observed, where n is the number of nonaromatic carbons. Normalization of yield and composition to the aromatic ring clearly demonstrates the greater significance of aromatic ring carbons compared with alkyl carbon substituents in determining SOA formation and composition. PMID:27177154

  12. Multicenter bond index analysis of influence of metal cations on the aromaticity of aromatic amino acids: Phenylalanine and tyrosine

    NASA Astrophysics Data System (ADS)

    Pakiari, A. H.; Farrokhnia, M.; Azami, S. M.

    2008-05-01

    In order to provide insight into the influence of metal cations on the aromaticity of amino acids, evaluation of six-center delocalization indices is accomplished in the context of quantum theory of atoms in molecules (QTAIM). Aromaticity of two amino acids, phenylalanine and tyrosine, is investigated as typical amino acids containing aromatic ring in their isolated state and complexed by some metal cations. The results showed that the metal cations affect the most important three connectivities differently. Also, it is shown that the existence of metal cations can increase two-center delocalization in certain parts of the aromatic rings.

  13. Planetary rings

    SciTech Connect

    Greenberg, R.; Brahic, A.

    1984-01-01

    Among the topics discussed are the development history of planetary ring research, the view of planetary rings in astronomy and cosmology over the period 1600-1900, the characteristics of the ring systems of Saturn and Uranus, the ethereal rings of Jupiter and Saturn, dust-magnetosphere interactions, the effects of radiation forces on dust particles, the collisional interactions and physical nature of ring particles, transport effects due to particle erosion mechanisms, and collision-induced transport processes in planetary rings. Also discussed are planetary ring waves, ring particle dynamics in resonances, the dynamics of narrow rings, the origin and evolution of planetary rings, the solar nebula and planetary disk, future studies of the planetary rings by space probes, ground-based observatories and earth-orbiting satellites, and unsolved problems in planetary ring dynamics.

  14. Nature of the attractive interaction between proton acceptors and organic ring systems.

    PubMed

    Arras, Emmanuel; Seitsonen, Ari Paavo; Klappenberger, Florian; Barth, Johannes V

    2012-12-14

    Systematic ab initio calculations are combined with a deconvolution of electrostatic contributions to analyze the interplay between potential hydrogen bond acceptors and organic rings with C(sp(2))-H groups (benzene, pyridine and cyclopentadiene). A distinct anisotropic interaction between the ring systems and the electron lone pairs of cyanide, water and other acceptor species is revealed that favors the in-plane orientation of the proton acceptor group. In the attractive regime this interaction carries a pronounced electrostatic signature. By decomposing the electrostatic contribution into parts attributed to different subunits of the ring systems we demonstrate that a major proportion of the interaction energy gain is originating from the non-adjacent moieties, that are not in close contact with. This behavior holds equally for homocyclic, heterocyclic and non-aromatic rings but contrasts that of the ethyne molecule, taken as reference for a weak hydrogen bond donor clearly exhibiting the expected localized character. The ring interaction requires the presence of π-electron clouds and typically results in an interaction energy gain of 40 to 80 meV. Our findings suggest the proton acceptor-ring interaction as a new category of intermolecular non-covalent interactions.

  15. Aromatic graphene

    NASA Astrophysics Data System (ADS)

    Das, D. K.; Sahoo, S.

    2016-04-01

    In recent years graphene attracts the scientific and engineering communities due to its outstanding electronic, thermal, mechanical and optical properties and many potential applications. Recently, Popov et al. [1] have studied the properties of graphene and proved that it is aromatic but without fragrance. In this paper, we present a theory to prepare graphene with fragrance. This can be used as scented pencils, perfumes, room and car fresheners, cosmetics and many other useful household substances.

  16. Dehalogenation of aromatics by nucleophilic aromatic substitution.

    PubMed

    Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J

    2014-09-16

    Nucleophilic aromatic substitution has been implicated as a mechanism for both the biotic and abiotic hydrodehalogenation of aromatics. Two mechanisms for the aqueous dehalogenation of aromatics involving nucleophilic aromatic substitution with hydride as a nucleophile are investigated using a validated density functional and continuum solvation protocol. For chlorinated and brominated aromatics, nucleophilic addition ortho to carbon-halogen bonds via an anionic intermediate is predicted to be the preferred mechanism in the majority of cases, while concerted substitution is predicted to be preferred for most fluorinated aromatics. Nucleophilic aromatic substitution reactions with the hydroxide and hydrosulfide anions as nucleophiles are also investigated and compared.

  17. Fluorescent aromatic sensors and their methods of use

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor); Tyson, Daniel S. (Inventor); Ilan, Ulvi F. (Inventor)

    2012-01-01

    Aromatic molecules that can be used as sensors are described. The aromatic sensors include a polycyclic aromatic hydrocarbon core with a five-membered imide rings fused to the core and at least two pendant aryl groups. The aromatic sensor molecules can detect target analytes or molecular strain as a result of changes in their fluorescence, in many cases with on-off behavior. Aromatic molecules that fluoresce at various frequencies can be prepared by altering the structure of the aromatic core or the substituents attached to it. The aromatic molecules can be used as sensors for various applications such as, for example, the detection of dangerous chemicals, biomedical diagnosis, and the detection of damage or strain in composite materials. Methods of preparing aromatic sensor molecules are also described.

  18. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    PubMed

    Yang, Yang

    2010-12-23

    Si-E bondings in hexacoordinate silicon phthalocyanine were analyzed using bond order (BO), energy partition, atoms in molecules (AIM), electron localization function (ELF), and localized orbital locator (LOL). Bond models were proposed to explain differences between hexacoordinate and tetracoordinate Si-E bondings. Aromaticity of silicon phthalocyanine was investigated using nucleus-independent chemical shift (NICS), harmonic oscillator model of aromaticity (HOMA), conceptual density functional theory (DFT), ring critical point (RCP) descriptors, and delocalization index (DI). Structure, energy, bonding, and aromaticity of tetracoordinate silicon phthalocyanine were studied and compared with hexacoordinate one. PMID:21105726

  19. Ring laser gyroscope anode

    SciTech Connect

    Ljung, B.H.

    1981-03-17

    An anode for a ring laser gyroscope which provides improved current stability in the glow discharge path is disclosed. The anode of this invention permits operation at lower currents thereby allowing a reduction of heat dissipation in the ring laser gyroscope. The anode of one embodiment of this invention is characterized by a thumbtack appearance with a spherical end where the normal sharp end of the thumbtack would be located. The stem of the anode extends from the outside of the gyroscope structure to the interior of the structure such that the spherical end is substantially adjacent to the laser beam.

  20. Assessing Uncertainty of Interspecies Correlation Estimation Models for Aromatic Compounds

    EPA Science Inventory

    We developed Interspecies Correlation Estimation (ICE) models for aromatic compounds containing 1 to 4 benzene rings to assess uncertainty in toxicity extrapolation in two data compilation approaches. ICE models are mathematical relationships between surrogate and predicted test ...

  1. Evaluation of antibacterial activity of synthetic aliphatic and aromatic monoacylglycerols.

    PubMed

    Batovska, Daniela; Todorova, Iva; Parushev, Stoyan; Tsvetkova, Iva; Najdenski, Hristo; Ubukata, Makoto

    2008-01-01

    The antibacterial activity of synthetic aliphatic and aromatic monoacylglycerols (MAGs) was studied against two human pathogens: Staphylococcus aureus and Escherichia coli. The active compounds inhibited selectively S. aureus. The most active compounds amongst them were those with medium size aliphatic chain and aromatic MAGs with electron withdrawing substituents at the aryl ring. The introduction of one or two-carbon spacer between the aryl ring and the carboxylic function did not influence antibacterial effectiveness. PMID:19004249

  2. Mechanisms for polycyclic aromatic hydrocarbon degradation by ligninolytic fungi

    SciTech Connect

    Hammel, K.E.

    1995-06-01

    Ligninolytic fungi accomplish the partial degradation of numerous aromatic organopollutants. Their ability to degrade polycyclic aromatic hydrocarbons (PAHs) is particularly interesting because eukaryotes were previously considered to be unable to cleave fused-ring aromatics. Recent results indicate that extracellular peroxidases of these fungi are responsible for the initial oxidation of PAHs. Fungal lignin peroxidases oxidize certain PAHs directly, whereas fungal manganese peroxidases co-oxidize them indirectly during enzyme-mediated lipid peroxidation. 14 refs., 3 figs., 1 tab.

  3. Epoxy Coenzyme A Thioester Pathways for Degradation of Aromatic Compounds

    PubMed Central

    Gescher, Johannes

    2012-01-01

    Aromatic compounds (biogenic and anthropogenic) are abundant in the biosphere. Some of them are well-known environmental pollutants. Although the aromatic nucleus is relatively recalcitrant, microorganisms have developed various catabolic routes that enable complete biodegradation of aromatic compounds. The adopted degradation pathways depend on the availability of oxygen. Under oxic conditions, microorganisms utilize oxygen as a cosubstrate to activate and cleave the aromatic ring. In contrast, under anoxic conditions, the aromatic compounds are transformed to coenzyme A (CoA) thioesters followed by energy-consuming reduction of the ring. Eventually, the dearomatized ring is opened via a hydrolytic mechanism. Recently, novel catabolic pathways for the aerobic degradation of aromatic compounds were elucidated that differ significantly from the established catabolic routes. The new pathways were investigated in detail for the aerobic bacterial degradation of benzoate and phenylacetate. In both cases, the pathway is initiated by transforming the substrate to a CoA thioester and all the intermediates are bound by CoA. The subsequent reactions involve epoxidation of the aromatic ring followed by hydrolytic ring cleavage. Here we discuss the novel pathways, with a particular focus on their unique features and occurrence as well as ecological significance. PMID:22582071

  4. Epoxy Coenzyme A Thioester pathways for degradation of aromatic compounds.

    PubMed

    Ismail, Wael; Gescher, Johannes

    2012-08-01

    Aromatic compounds (biogenic and anthropogenic) are abundant in the biosphere. Some of them are well-known environmental pollutants. Although the aromatic nucleus is relatively recalcitrant, microorganisms have developed various catabolic routes that enable complete biodegradation of aromatic compounds. The adopted degradation pathways depend on the availability of oxygen. Under oxic conditions, microorganisms utilize oxygen as a cosubstrate to activate and cleave the aromatic ring. In contrast, under anoxic conditions, the aromatic compounds are transformed to coenzyme A (CoA) thioesters followed by energy-consuming reduction of the ring. Eventually, the dearomatized ring is opened via a hydrolytic mechanism. Recently, novel catabolic pathways for the aerobic degradation of aromatic compounds were elucidated that differ significantly from the established catabolic routes. The new pathways were investigated in detail for the aerobic bacterial degradation of benzoate and phenylacetate. In both cases, the pathway is initiated by transforming the substrate to a CoA thioester and all the intermediates are bound by CoA. The subsequent reactions involve epoxidation of the aromatic ring followed by hydrolytic ring cleavage. Here we discuss the novel pathways, with a particular focus on their unique features and occurrence as well as ecological significance.

  5. Saturn's Rings

    NASA Astrophysics Data System (ADS)

    Cuzzi, J. N.

    2014-12-01

    The rings are changing before our eyes; structure varies on all timescales and unexpected things have been discovered. Many questions have been answered, but some answers remain elusive (see Cuzzi et al 2010 for a review). Here we highlight the major ring science progress over the mission to date, and describe new observations planned for Cassini's final three years. Ring Composition and particle sizes: The rings are nearly all water ice with no other ices - so why are they reddish? The C Ring and Cassini Division are "dirtier" than the more massive B and A Rings, as shown by near-IR and, recently, microwave observations. Particle sizes, from stellar and radio occultations, vary from place to place. Ring structure, micro and macro: numerous spiral density waves and ubiquitous "self-gravity wakes" reveal processes which fostered planet formation in the solar system and elsewhere. However, big puzzles remain regarding the main ring divisions, the C Ring plateau structures, and the B Ring irregular structure. Moonlets, inside and out, seen and unseen: Two gaps contain sizeable moonlets, but more gaps seem to contain none; even smaller embedded "propeller" objects wander, systematically or randomly, through the A ring. Rubble pile ringmoons just outside the rings may escaped from the rings, and the recently discovered "Peggy" may be trying this as we watch. Impact bombardment of the rings: Comet fragments set the rings to rippling on century-timescales, and boulders crash through hourly; meanwhile, the constant hail of infalling Kuiper belt material has a lower mass flux than previously thought. Origin and Age of the Rings: The ring mass and bombardment play key roles. The ring mass is well known everywhere but in the B Ring (where most of it is). New models suggest how tidal breakup of evolving moons may have formed massive ancient rings, of which the current ring is just a shadow. During its last three years, the Cassini tour profile will allow entirely new

  6. Planetary rings

    NASA Technical Reports Server (NTRS)

    Cook, A. F.

    1980-01-01

    Observations of the Rings of Saturn from the Pioneer spacecraft, discovery of the Ring of Jupiter, ground based polarimetry of the Rings of Saturn and some theoretical studies may be combined to markedly advance our understanding of the Rings of Jupiter, Saturn and Uranus. In particular, narrow rings can be self-gravitatingly stable inside Roche's limit and outside another closer limit. They can be created from a satellite which evolves across its Roche limit either by inward tidal drift or by growth of the planet by accretion. These considerations suggest that Neptune may well be surrounded by one or more narrow rings like those of Uranus.

  7. Reaction of disubstituted aromatic compounds with styrene

    SciTech Connect

    Grushin, A.I.; Grigor'ev, V.V.; Prokof'ev, K.V.; Kozlova, N.M.

    1988-03-20

    Hydrocarbons of the 1,1-diphenylethane type were obtained by the reaction of styrene with various disubstituted derivatives of benzene in the presence of titanium tetrachloride. It was found that the yield of the desired compound depends on the strength of the electron-donating substituents and on steric factors in the aromatic ring.

  8. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: SOA Yield and Chemical Composition

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Qi, Li; Kacarab, Mary; Cocker, David

    2016-04-01

    Aromatic hydrocarbons account for 20%-30% of urban atmospheric VOCs and are major contributors to anthropogenic secondary organic aerosol (SOA). However, prediction of SOA from aromatic hydrocarbons as a function of structure, NOx concentration, and OH radical levels remains elusive. Innovative SOA yield and chemical composition evaluation approaches are developed here to investigate SOA formation from aromatic hydrocarbons. SOA yield is redefined in this work by adjusting the molecular weight of all aromatic precursors to the molecular weight of benzene (Yield'= Yieldi×(MWi/MWBenzene); i: aromatic hydrocarbon precursor). Further, SOA elemental ratio is calculated on an aromatic ring basis rather than the classic mole basis. Unified and unique characteristics in SOA formed from aromatic hydrocarbons with different alkyl groups (varying in carbon number and location on aromatic ring) are explored by revisiting fifteen years of UC Riverside/CE-CERT environmental chamber data on 129 experiments from 17 aromatic precursors at urban region relevant low NOx conditions (HC:NO 11.1-171 ppbC:ppb). Traditionally, SOA mass yield of benzene is much greater than that of other aromatic species. However, when adjusting for molecular weight, a similar yield is found across the 17 different aromatic precursors. More importantly, four oxygens per aromatic ring are observed in the resulting SOA regardless of the alkyl substitutes attached to the ring, which majorly affect H/C ratio in SOA. Therefore, resulting SOA bulk composition from aromatic hydrocarbons can be predicted as C6+nH6+2nO4 (n: alkyl substitute carbon number). Further, the dominating role of the aromatic ring carbons is confirmed by studying the chemical composition of SOA formed from the photooxidation of an aromatic hydrocarbon with a 13C isotopically labeled alkyl carbon. Overall, this study unveils the similarity in SOA formation from aromatic hydrocarbons enhancing the understanding of SOA formation from

  9. The fundamental chemical equation of aromaticity.

    PubMed

    Chauvin, Remi; Lepetit, Christine

    2013-03-21

    In the search for the chemical measure of molecular aromaticity, namely the energetic gain of a cyclic delocalized structure for just being cyclic, the numerous definitions of generic aromatic stabilisation energies proposed hitherto stand as approximates of the conceptual limit devised within the framework of spectral graph theory, i.e. the topological resonance energy (TRE). After a 36 year challenge, the TRE acyclic reference of any π-cyclic molecule, originally merely defined by an abstract matching polynomial, is now given a real chemical structure: the Möbius-twisted head-to-tail metathesis cyclo-dimer of the parent ring. The original treatment at the Hückel molecular orbital level of theory can now be extended to DFT or ab initio levels. The corresponding ring opening-closing-twisting chemical transformation provides the observable basis for the measure of aromaticity under either vertical or adiabatic conditions.

  10. Inhibitory effects of polycyclic aromatic hydrocarbons (PAHs) on photosynthetic performance are not related to their aromaticity.

    PubMed

    Jajoo, Anjana; Mekala, Nageswara Rao; Tomar, Rupal Singh; Grieco, Michele; Tikkanen, Mikko; Aro, Eva-Mari

    2014-08-01

    Polycyclic aromatic hydrocarbons (PAHs) are very toxic and highly persistent environmental pollutants which accumulate in soil and affect growth of the plants adversely. This study aims to investigate inhibitory effects of 3 major PAH particularly on photosynthetic processes in Arabidopsis thaliana grown in soil treated with PAH. The 3 PAH chosen differ from each other in aromaticity (number of rings) comprising their structure (2 rings: naphthalene, 3 rings: anthracene and 4 rings: pyrene). Several growth parameters and Chlorophyll a fluorescence was monitored in PAH treated plants. BN-PAGe analysis was done in order to get information about change in the protein conformation. PAH treatment led to increased value of Fo which collaborated with increase in the amount of free LHC as seen through BN-Page analysis. Thus PAH were found to inhibit PS II photochemistry and caused distinct change in pigment composition. However the results led us to infer that 3-ring anthracence is more inhibitory as compared to 2-ring naphthalene and 4-ring pyrene. This indicates that aromaticity of PAH is unrelated to their response on photosynthetic processes.

  11. Concentric ring flywheel with hooked ring carbon fiber separator/torque coupler

    DOEpatents

    Kuklo, Thomas C.

    1999-01-01

    A concentric ring flywheel with expandable separators, which function as torque couplers, between the rings to take up the gap formed between adjacent rings due to differential expansion between different radius rings during rotation of the flywheel. The expandable separators or torque couplers include a hook-like section at an upper end which is positioned over an inner ring and a shelf-like or flange section at a lower end onto which the next adjacent outer ring is positioned. As the concentric rings are rotated the gap formed by the differential expansion there between is partially taken up by the expandable separators or torque couplers to maintain torque and centering attachment of the concentric rings.

  12. Concentric ring flywheel with hooked ring carbon fiber separator/torque coupler

    DOEpatents

    Kuklo, T.C.

    1999-07-20

    A concentric ring flywheel with expandable separators, which function as torque couplers, between the rings to take up the gap formed between adjacent rings due to differential expansion between different radius rings during rotation of the flywheel. The expandable separators or torque couplers include a hook-like section at an upper end which is positioned over an inner ring and a shelf-like or flange section at a lower end onto which the next adjacent outer ring is positioned. As the concentric rings are rotated the gap formed by the differential expansion there between is partially taken up by the expandable separators or torque couplers to maintain torque and centering attachment of the concentric rings. 2 figs.

  13. Neptune's rings

    NASA Technical Reports Server (NTRS)

    1999-01-01

    This 591-second exposure of the rings of Neptune were taken with the clear filter by the Voyager 2 wide-angle camera. The two main rings are clearly visible and appear complete over the region imaged. Also visible in this image is the inner faint ring and the faint band which extends smoothly from the ring roughly halfway between the two bright rings. Both of these newly discovered rings are broad and much fainter than the two narrow rings. The bright glare is due to over-exposure of the crescent on Neptune. Numerous bright stars are evident in the background. Both bright rings have material throughout their entire orbit, and are therefore continuous. The Voyager Mission is conducted by JPL for NASA's Office of Space Science and Applications.

  14. Vascular ring

    MedlinePlus

    ... with aberrant subclavian and left ligamentum ateriosus; Congenital heart defect - vascular ring; Birth defect heart - vascular ring ... accounts for less than 1% of all congenital heart problems. The condition occurs as often in males ...

  15. Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

    SciTech Connect

    Castaldi, M.J.; Marinov, N.M.; Melius, C.F.

    1996-02-01

    Experimental and detailed chemical kinetic modeling has been performed to investigate aromatic and polyaromatic hydrocarbon formation pathways in a rich, sooting, ethylene-oxygen-argon premixed flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.5 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer (GC/MS) technique. Measurements were made in the flame and post-flame zone for a number of low molecular weight species, aliphatics, aromatics and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-aromatic fused rings. The modeling results show the key reaction sequences leading to aromatic and polycyclic aromatic hydrocarbon growth involve the combination of resonantly stabilized radicals. In particular, propargyl and 1-methylallenyl combination reactions lead to benzene and methyl substituted benzene formation, while polycyclic aromatics are formed from cyclopentadienyl radicals and fused rings that have a shared C{sub 5} side structure. Naphthalene production through the reaction step of cyclopentadienyl self-combination and phenanthrene formation from indenyl and cyclopentadienyl combination were shown to be important in the flame modeling study. The removal of phenyl by O{sub 2} leading to cyclopentadienyl formation is expected to play a pivotal role in the PAH or soot precursor growth process under fuel-rich oxidation conditions.

  16. Nucleophilic fluorination of aromatic compounds

    DOEpatents

    Satyamurthy, Nagichettiar; Barrio, Jorge R

    2014-03-18

    Iodylbenzene derivatives substituted with electron donating as well as electron withdrawing groups on the aromatic ring are used as precursors in aromatic nucleophilic substitution reactions. The iodyl group (IO.sub.2) is regiospecifically substituted by nucleophilic fluoride to provide the corresponding fluoroaryl derivatives. No-carrier-added [F-18]fluoride ion derived from anhydrous [F-18](F/Kryptofix, [F-18]CsF or a quaternary ammonium fluoride (e.g., Me.sub.4NF, Et.sub.4NF, n-Bu.sub.4NF, (PhCH.sub.2).sub.4NF) exclusively substitutes the iodyl moiety in these derivatives and provides high specific activity F-18 labeled fluoroaryl analogs. Iodyl derivatives of a benzothiazole analog and 6-iodyl-L-dopa derivatives have been synthesized as precursors and have been used in the preparation of no-carrier-added [F-18]fluorobenzothiazole as well as 6-[F-18]fluoro-L-dopa.

  17. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

    SciTech Connect

    Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.

    2015-08-18

    A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

  18. (Hetero)aromatics from dienynes, enediynes and enyne-allenes.

    PubMed

    Raviola, Carlotta; Protti, Stefano; Ravelli, Davide; Fagnoni, Maurizio

    2016-08-01

    The construction of aromatic rings has become a key objective for organic chemists. While several strategies have been developed for the functionalization of pre-formed aromatic rings, the direct construction of an aromatic core starting from polyunsaturated systems is yet a less explored field. The potential of such reactions in the formation of aromatics increased at a regular pace in the last few years. Nowadays, there are reliable and well-established procedures to prepare polyenic derivatives, such as dienynes, enediynes, enyne-allenes and hetero-analogues. This has stimulated their use in the development of innovative cycloaromatizations. Different examples have recently emerged, suggesting large potential of this strategy in the preparation of (hetero)aromatics. Accordingly, this review highlights the recent advancements in this field and describes the different conditions exploited to trigger the process, including thermal and photochemical activation, as well as the use of transition metal catalysis and the addition of electrophiles/nucleophiles or radical species.

  19. Five-membered heterocycles. Part III. Aromaticity of 1,3-imidazole in 5+ n hetero-bicyclic molecules

    NASA Astrophysics Data System (ADS)

    Mrozek, Agnieszka; Karolak-Wojciechowska, Janina; Kieć-Kononowicz, Katarzyna

    2003-08-01

    The aromaticity (in the form of HOMA index) of 1,3-imidazole ring and its bicyclic derivatives was studied on the basis of statistical data from Cambridge Structural Database and X-ray investigations performed by authors. As a starting point, aromaticity of the 1,3-imidazoles with exocyclic X substituent at C2 (XN, O or S) was calculated. Subsequently, the HOMA index was calculated for various 5+ n bicyclic skeletons with N, O, and S as endocyclic heteroatoms in the second ring. For the isolated 1,3-imidazole ring, aromaticity depends on exocyclic substituent at C2 and decreases in sequence N, S, O. For bicyclic derivatives it was found that both rings are aromatic and coplanar in very few molecules (17% of investigated ones), and positive charge—located on endocyclic heteroatom—increases the aromaticity. For remaining compounds, presence of sp 3 carbons excludes possibility of aromatic ring existence.

  20. Aromatic and polycyclic aromatic hydrocarbon formation in a laminar premixed n-butane flame

    SciTech Connect

    Marinov, N.M.; Pitz, W.J.; Westbrook, C.K.; Vincitore, A.M.; Castaldi, M.J.; Senkan, S.M.; Melius, C.F.

    1998-07-01

    Experimental and detailed chemical kinetic modeling work has been performed to investigate aromatic and polycyclic aromatic hydrocarbon (PAH) formation pathways in a premixed, rich, sooting, n-butane-oxygen-argon burner stabilized flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.6 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer technique. Measurements were made in the main reaction and post-reaction zones for a number of low molecular weight species, aliphatics, aromatics, and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-fused aromatic rings. Reaction flux and sensitivity analysis were used to help identify the important reaction sequences leading to aromatic and PAH growth and destruction in the n-butane flame. Reaction flux analysis showed the propargyl recombination reaction was the dominant pathway to benzene formation. The consumption of propargyl by H atoms was shown to limit propargyl, benzene, and naphthalene formation in flames as exhibited by the large negative sensitivity coefficients. Naphthalene and phenanthrene production was shown to be plausibly formed through reactions involving resonantly stabilized cyclopentadienyl and indenyl radicals. Many of the low molecular weight aliphatics, combustion by-products, aromatics, branched aromatics, and PAHs were fairly well simulated by the model. Additional work is required to understand the formation mechanisms of phenyl acetylene, pyrene, and fluoranthene in the n-butane flame. 73 refs.

  1. The making of ring currents.

    PubMed

    Monaco, Guglielmo; Zanasi, Riccardo

    2016-04-28

    Benzene, planar cyclooctatetraene, and borazine have been taken into account as archetypal aromatic, anti-aromatic, and non-aromatic systems. Then, the making of the π-electron diatropic ring current of benzene, huge paratropic ring current of planar cyclooctatetraene, and weak diatropic ring current of borazine, has been monitored by means of DFT calculations of current density maps and bond current strengths along a concerted, highly symmetric reaction pathway for the trimerization and tetramerization of acetylene to benzene and planar cyclooctatetraene and the trimerization of the simplest iminoborane (BH2N) to borazine. Besides, a simple model is presented that permits to infer the presence of a ring current only on account of the sum of homotropic local vortices. The model works satisfactorily for borazine and surely as well for benzene with a substantial difference. On the one hand, for borazine, the evolution of the current density along the formation reaction can be recast summing three virtually unchanged diatropic current loops with respect to parent iminoborane molecules. On the other hand, the benzene ring current is an emerging property that can be re-elaborated as the sum of three diatropic current loops of increased diatropicity with respect to parent acetylene molecules, i.e., the radius of the maximum current increases form 0.76 to 0.97 Å and the current strength increases from 3.6 to 6.7 nA T(-1). In these terms, the difference between the aromatic benzene and non-aromatic borazine can be understood as the attitude of the acetylene molecules to form always wider and stronger current loops as they get closer, a behavior not shared by the iminoborane molecules. For planar cyclooctatetraene, the paratropic circulation arising from the HOMO-LUMO transition makes the model inapplicable, since the initial hypothesis of homotropic circulations over the reaction coordinate is violated. In a sense, the fact that the model works only for a bit of the

  2. Polycyclic aromatic hydrocarbons (PAHs) in bottom sediments of the Kara Sea shelf, Gulf of Ob and Yenisei Bay.

    PubMed

    Dahle, Salve; Savinov, Vladimir M; Matishov, Gennadij G; Evenset, Anita; Naes, Kristoffer

    2003-05-01

    PAH concentration and distribution has been examined in surface sediments samples from the Kara Sea, Russia. The study includes 13 samples from the South-eastern Kara Sea shelf, one sample from the south-western part of the sea, 4 samples from the Baydaratskaya Bay, 5 samples from the Gulf of Ob and 4 samples from the Yenisei Bay, collected in August-September 1993-1994. Cluster analysis and principal component analysis (PCA) were used to identify common patterns and possible sources of PAHs. The total PAH concentration (sum of two- to six-ring aromatic hydrocarbons) in the Kara Sea sediments was generally lower than in the Barents Sea sediments and comparable to the levels in the Pechora and White seas. Two- and three-ring aromatic hydrocarbons predominated in Kara Sea sediments, which indicate a relatively stronger petrogenic origin than that in the adjacent seas. The highest total PAH concentrations within the Kara Sea were found in sediments from the Yenisei Bay and in the South-western part of the Kara Sea in the Eastern Novaya Zemlya Trough. The PAHs of the Yenisei Bay sediments were dominated by perylene and PAHs of petrogenic origin, but had also a strong indication of PAHs of pyrogenic origin. The dominating PAH group in the South-western part of the Kara Sea were four- to six-ring aromatic hydrocarbons, indicating pyrogenic origin. Perylene levels were high in all the Kara Sea samples, and highest levels were found in areas of strong terrigenous influence. The most probable source is decaying peat products being transported to the Kara Sea by both large and small rivers. PMID:12699918

  3. Infrared spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. 4. The tetracyclic PAH isomers chrysene and 1,2-benzanthracene.

    PubMed

    Hudgins, D M; Allamandola, L J

    1997-05-01

    The mid-infrared spectra of the polycyclic aromatic hydrocarbon (PAH) cations of the tetracyclic isomers chrysene (C18H12+) and 1,2-benzanthracene (C18H12+) are presented. As with previous PAH cations studied to date, the CC stretching and CH in-plane bending mode absorptions are about an order of magnitude stronger than the aromatic CH out-of-plane bending absorptions and nearly 2 orders of magnitude more intense than the corresponding bands in the neutral molecule. The CH bands arising from the out-of-plane bends in the cation are slightly weaker than the corresponding bands in the neutral species. The strongest cation bands of these species fall between 1300 and 1330 cm-1, close to the peak of the most intense interstellar emission feature in HII regions and reflection nebulae. A strong PAH cation band at slightly higher frequency than 1300 cm-1 may be associated with an asymmetric CC stretching vibration involving rings adjacent to the kink in the chain of aromatic rings. PMID:11541094

  4. Planetary Rings

    NASA Technical Reports Server (NTRS)

    Cuzzi, Jeffrey N.

    1994-01-01

    Just over two decades ago, Jim Pollack made a critical contribution to our understanding of planetary ring particle properties, and resolved a major apparent paradox between radar reflection and radio emission observations. At the time, particle properties were about all there were to study about planetary rings, and the fundamental questions were, why is Saturn the only planet with rings, how big are the particles, and what are they made of? Since then, we have received an avalanche of observations of planetary ring systems, both from spacecraft and from Earth. Meanwhile, we have seen steady progress in our understanding of the myriad ways in which gravity, fluid and statistical mechanics, and electromagnetism can combine to shape the distribution of the submicron-to-several-meter size particles which comprise ring systems into the complex webs of structure that we now know them to display. Insights gained from studies of these giant dynamical analogs have carried over into improved understanding of the formation of the planets themselves from particle disks, a subject very close to Jim's heart. The now-complete reconnaissance of the gas giant planets by spacecraft has revealed that ring systems are invariably found in association with families of regular satellites, and there is ark emerging perspective that they are not only physically but causally linked. There is also mounting evidence that many features or aspects of all planetary ring systems, if not the ring systems themselves, are considerably younger than the solar system

  5. Properties of the indole ring in metal complexes. A comparison with the phenol ring.

    PubMed

    Shimazaki, Yuichi; Yajima, Tatsuo; Yamauchi, Osamu

    2015-07-01

    Tryptophan (Trp), an essential amino acid, has an indole ring with a high electron density and is frequently seen at the proximal position of the metal site in metalloproteins. For example, the indole ring of Trp has been reported to interact weakly with Cu(I) in a Cu chaperone CusF. Another aromatic amino acid, tyrosine (Tyr), has a phenol ring, which is an important metal binding site in various metalloproteins. Although the structures of the aromatic rings are different, they both have a weakly acidic moiety and perform some similar roles in biological systems, such as radical formation and electron transfer. In this review, we focus on these and other properties of the indole and phenol rings in metal-containing systems.

  6. Jupiter's ring

    NASA Technical Reports Server (NTRS)

    1979-01-01

    First evidence of a ring around the planet Jupiter is seen in this photograph taken by Voyager 1 on March 4, 1979. The multiple exposure of the extremely thin faint ring appears as a broad light band crossing the center of the picture. The edge of the ring is 1,212,000 km from the spacecraft and 57,000 km from the visible cloud deck of Jupiter. The background stars look like broken hair pins because of spacecraft motion during the 11 minute 12 second exposure. The wavy motion of the star trails is due to the ultra-slow natural oscillation of the spacecraft (with a period of 78 seconds). The black dots are geometric calibration points in the camera. The ring thickness is estimated to be 30 km or less. The photograph was part of a sequence planned to search for such rings in Jupiter's equatorial plane. The ring has been invisible from Earth because of its thinness and its transparency when viewed at any angle except straight on. JPL manages and controls the Voyager Project for NASA's Office of Space Science.

  7. Effect of intercalated aromatic sulfonates on uptake of aromatic compounds from aqueous solutions by modified Mg-Al layered double hydroxide

    SciTech Connect

    Kameda, Tomohito; Yamazaki, Takashi; Yoshioka, Toshiaki

    2010-06-15

    In this study, we utilized Mg-Al layered double hydroxide (Mg-Al LDH) modified by intercalation with three aromatic sulfonates-2,7-naphthalene disulfonate (2,7-NDS{sup 2-}), benzenesulfonate (BS{sup -}), and benzenedisulfonate (BDS{sup 2-})-for the uptake of two aromatics-1,3-dinitrobenzene (DNB) and anisole (AS)-from aqueous solution and determined the effect of the aromatic sulfonates on the uptake of these aromatics. We found that the electron-rich aromatic ring of the intercalated aromatic sulfonates such as 2,7-NDS{sup 2-} undergoes strong {pi}-{pi} stacking interactions with the electron-poorer benzene ring of DNB in aqueous solution, and these interactions result in a higher uptake of DNB by the modified Mg-Al LDHs. In contrast, the electron-poor aromatic ring of the aromatic sulfonates such as BDS{sup 2-} undergoes weak {pi}-{pi} stacking interactions with the electron-poorer benzene ring of DNB, and these interactions result in a lower uptake of DNB by the modified Mg-Al LDHs.

  8. Distribution and mass inventory of polycyclic aromatic hydrocarbons in the sediments of the south Bohai Sea, China.

    PubMed

    Qin, Yanwen; Zheng, Binghui; Lei, Kun; Lin, Tian; Hu, Limin; Guo, Zhigang

    2011-02-01

    Recent occurrence, distribution and mass inventories of 16 priority polycyclic aromatic hydrocarbons (PAHs) proposed by USEPA in the south Bohai Sea (BS) were studied based on the analytical data of 71 surface sediment samples. The concentrations of 16 PAHs varied from 37 to 537 ngg⁻¹ (dry weight). A clear difference was observed between the coastal Bohai Bay (CBB) and its adjacent BS (ABS) in the distribution and compositions of PAHs. The petrogenic source of phenanthrene in CBB was attributable to the industrial wastewater, fugitive fuel leakages from ships and offshore oil production. Four to six ring PAHs were predominantly from the coal and wood combustions in the whole area. The estimated PAH input to the south BS (43,000 km², 56% of BS in area) was 36.6 ton yr⁻¹, indicating that the study area was one of the important reservoirs of PAHs in world.

  9. Pioneering Metal-Free Oxidative Coupling Strategy of Aromatic Compounds Using Hypervalent Iodine Reagents.

    PubMed

    Kita, Yasuyuki; Dohi, Toshifumi

    2015-10-01

    We started our hypervalent iodine research about 30 years ago in the mid-1980s. We soon successfully developed the single-electron-transfer oxidation ability of a hypervalent iodine reagent, specifically, phenyliodine(III) bis(trifluoroacetate) (PIFA), toward aromatic rings of phenyl ethers for forming aromatic cation radicals. This was one of the exciting and unexpected events in our research studies so far, and the discovery was reported in 1991. It also led to the next challenge, developing the metal-free oxidative couplings for C-H functionalizations and direct couplings between the C-H bonds of valuable aromatic compounds in organic synthesis. In order to realize the effective oxidative coupling, pioneering new aromatic ring activations was essential and several useful methodologies have been found for oxidizable arenes. The achievements regarding this objective obtained in our continuous research are herein summarized with classification of the aromatic ring activation strategies.

  10. Plant uptake, translocation, and return of polycyclic aromatic hydrocarbons via fine root branch orders in a subtropical forest ecosystem.

    PubMed

    Chen, Zheng-Xia; Ni, Hong-Gang; Jing, Xin; Chang, Wen-Jing; Sun, Jian-Lin; Zeng, Hui

    2015-07-01

    Fine roots of woody plants are a heterogeneous system differing markedly in structure and function. Nevertheless, knowledge about the plant uptake of organic pollutants via fine roots is scarce to date. In the present study, plant uptake, translocation, and return of polycyclic aromatic hydrocarbons (PAHs) via fine roots in a subtropical forest ecosystem were investigated. Levels of Σ15PAHs in different fine root branch orders of Michelia macclurei, Cryptocarya concinna, Cryptocarya chinensis, and Canthium dicoccums varied from 5072±1419 ng g(-1) to 6080±1656 ng g(-1), 4037±410 ng g(-1) to 6101±972 ng g(-1), 3308±1191 ng g(-1) to 4283±237 ng g(-1), and 3737±800 ng g(-1) to 4895±1216 ng g(-1), respectively. Overall, concentrations of low-molecular-weight PAHs with 2-3 aromatic rings were higher than high-molecular-weight PAHs with 4-6 aromatic rings in all fine root branch orders. There were obvious translocations of PAHs between adjacent branch orders and a net accumulation of PAHs may occur in the fourth- and fifth-order roots. The storage of PAHs in the fine root system showed an obvious increasing trend along the branch orders ascending for all tree species. The return flux of PAHs via fine roots mortality showed an obvious decreasing trend with the branch orders ascending across the four tree species. Lower order roots contributed greatly to the total PAHs return flux. Our results indicated that fine roots turnover is an effective pathway for perennial tree species to remove environmental toxicants absorbed into them.

  11. Plant uptake, translocation, and return of polycyclic aromatic hydrocarbons via fine root branch orders in a subtropical forest ecosystem.

    PubMed

    Chen, Zheng-Xia; Ni, Hong-Gang; Jing, Xin; Chang, Wen-Jing; Sun, Jian-Lin; Zeng, Hui

    2015-07-01

    Fine roots of woody plants are a heterogeneous system differing markedly in structure and function. Nevertheless, knowledge about the plant uptake of organic pollutants via fine roots is scarce to date. In the present study, plant uptake, translocation, and return of polycyclic aromatic hydrocarbons (PAHs) via fine roots in a subtropical forest ecosystem were investigated. Levels of Σ15PAHs in different fine root branch orders of Michelia macclurei, Cryptocarya concinna, Cryptocarya chinensis, and Canthium dicoccums varied from 5072±1419 ng g(-1) to 6080±1656 ng g(-1), 4037±410 ng g(-1) to 6101±972 ng g(-1), 3308±1191 ng g(-1) to 4283±237 ng g(-1), and 3737±800 ng g(-1) to 4895±1216 ng g(-1), respectively. Overall, concentrations of low-molecular-weight PAHs with 2-3 aromatic rings were higher than high-molecular-weight PAHs with 4-6 aromatic rings in all fine root branch orders. There were obvious translocations of PAHs between adjacent branch orders and a net accumulation of PAHs may occur in the fourth- and fifth-order roots. The storage of PAHs in the fine root system showed an obvious increasing trend along the branch orders ascending for all tree species. The return flux of PAHs via fine roots mortality showed an obvious decreasing trend with the branch orders ascending across the four tree species. Lower order roots contributed greatly to the total PAHs return flux. Our results indicated that fine roots turnover is an effective pathway for perennial tree species to remove environmental toxicants absorbed into them. PMID:25863163

  12. Ghostly Ring

    NASA Technical Reports Server (NTRS)

    2008-01-01

    [figure removed for brevity, see original site] Click on image for poster version

    This image shows a ghostly ring extending seven light-years across around the corpse of a massive star. The collapsed star, called a magnetar, is located at the exact center of this image. NASA's Spitzer Space Telescope imaged the mysterious ring around magnetar SGR 1900+14 in infrared light. The magnetar itself is not visible in this image, as it has not been detected at infrared wavelengths (it has been seen in X-ray light).

    Magnetars are formed when a massive giant star ends its life in a supernova explosion, leaving behind a super dense neutron star with an incredibly strong magnetic field. The ring seen by Spitzer could not have formed during the original explosion, as any material as close to the star as the ring would have been disrupted by the supernova shock wave. Scientists suspect that the ring my actually be the edges of a bubble that was hollowed out by an explosive burst from the magnetar in 1998. The very bright region near the center of the image is a cluster of young stars, which may be illuminating the inner edge of the bubble, making it look like a ring in projection.

    This composite image was taken using all three of Spitzer's science instruments. The blue color represents 8-micron infrared light taken by the infrared array camera, green is 16-micron light from the infrared spectograph, and red is 24-micron radiation from the multiband imaging photometer.

  13. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds.

    PubMed

    Odachowski, Marcin; Bonet, Amadeu; Essafi, Stephanie; Conti-Ramsden, Philip; Harvey, Jeremy N; Leonori, Daniele; Aggarwal, Varinder K

    2016-08-01

    The stereospecific cross-coupling of secondary boronic esters with sp(2) electrophiles (Suzuki-Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel-Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C-C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp(2))-C(sp(3)) and an adjacent C-B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations. PMID:27384259

  14. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds

    PubMed Central

    2016-01-01

    The stereospecific cross-coupling of secondary boronic esters with sp2 electrophiles (Suzuki–Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel–Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C–C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp2)–C(sp3) and an adjacent C–B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations. PMID:27384259

  15. Birds and polycyclic aromatic hydrocarbons

    USGS Publications Warehouse

    Albers, P.H.

    2006-01-01

    Polycyclic aromatic hydrocarbons (PAH) are present throughout the global environment and are produced naturally and by activities of humans. Effects of PAH on birds have been determined by studies employing egg injection, egg immersion, egg shell application, single and multiple oral doses, subcutaneous injection, and chemical analysis of field-collected eggs and tissue. The four-to six-ring aromatic compounds are the most toxic to embryos, young birds, and adult birds. For embryos, effects include death, developmental abnormalities, and a variety of cellular and biochemical responses. For adult and young birds, effects include reduced egg production and hatching, increased clutch or brood abandonment, reduced growth, increased organweights, and a variety of biochemical responses. Trophic level accumulation is unlikely. Environmental exposure to PAH in areas of high human population or habitats affected by recent petroleum spills might be sufficient to adversely affect reproduction. Evidence of long-term effects of elevated concentrations of environmental PAH on bird populations is very limited and the mechanisms of effect are unclear.

  16. Tunable Control of Polyproline Helix (PPII) Structure via Aromatic Electronic Effects: An Electronic Switch of Polyproline Helix

    PubMed Central

    2015-01-01

    Aromatic rings exhibit defined interactions via the unique aromatic π face. Aromatic amino acids interact favorably with proline residues via both the hydrophobic effect and aromatic–proline interactions, C−H/π interactions between the aromatic π face and proline ring C–H bonds. The canonical aromatic amino acids Trp, Tyr, and Phe strongly disfavor a polyproline helix (PPII) when they are present in proline-rich sequences because of the large populations of cis amide bonds induced by favorable aromatic–proline interactions (aromatic–cis-proline and proline–cis-proline–aromatic interactions). We demonstrate the ability to tune polyproline helix conformation and cis–trans isomerism in proline-rich sequences using aromatic electronic effects. Electron-rich aromatic residues strongly disfavor polyproline helix and exhibit large populations of cis amide bonds, while electron-poor aromatic residues exhibit small populations of cis amide bonds and favor polyproline helix. 4-Aminophenylalanine is a pH-dependent electronic switch of polyproline helix, with cis amide bonds favored as the electron-donating amine, but trans amide bonds and polyproline helix preferred as the electron-withdrawing ammonium. Peptides with block proline–aromatic PPXPPXPPXPP sequences exhibited electronically switchable pH-dependent structures. Electron-poor aromatic amino acids provide special capabilities to integrate aromatic residues into polyproline helices and to serve as the basis of aromatic electronic switches to change structure. PMID:25075447

  17. Origin and distribution of polycyclic aromatic hydrocarbons in surficial sediments from the savannah river.

    PubMed

    Sanders, M; Sivertsen, S; Scott, G

    2002-11-01

    Surface sediments collected from the Savannah River, located in the southeastern state of Georgia, USA, in June-July 1994 were analyzed for individual polycyclic aromatic hydrocarbons (PAHs). Three subdivisions of the river were identified for the study: upstream from, adjacent to, and downstream from the city of Savannah. There was high spatial variability in the total PAH (SigmaPAH) concentrations that ranged from 29 to 5,375 ng/g with an average concentration of 1,216 +/- 1,161 (SD). Of the three subdivisions, the highest SigmaPAH concentrations were in the middle segment, which was adjacent to urban and industrial areas. To elucidate sources, molecular indices based on indices among phenanthrene versus anthracene and fluoranthene versus pyrene were used to determine pyrogenic and petrogenic sources, respectively. These indices have been used by other authors to differentiate sources. In most cases, PAHs in sediments nearest the city of Savannah were of high temperature and pyrogenic origin. These pyrogenic PAHs were highly associated with toxicity to benthic organisms. The two-ringed naphthalene and substituted naphthalenes, which are petroleum-related PAHs, were significantly higher in the lower section of the river relative to the subdivisions. This river segment receives inputs primarily from shipping and boating traffic. Perylene, which is indicative of nonanthropogenic terrestrial inputs of carbon, had the highest concentration among the individual PAHs measured. High perylene concentrations were found at stations located upstream and adjacent to forested terrain and where salinity level was low. To discriminate pattern differences and similarities of individual PAHs among samples, principal component analysis (PCA) was performed on the more hydrophobic and persistent nonalkylated PAHs. These differences and similarities were used to infer perylene origin. PCA was performed on 14 nonalkylated PAHs that was normalized to the sum of nonalkylated PAHs, using

  18. Annulation of aromatic imines via directed C-H bond activation.

    PubMed

    Thalji, Reema K; Ahrendt, Kateri A; Bergman, Robert G; Ellman, Jonathan A

    2005-08-19

    A directed C-H bond activation approach to the synthesis of indans, tetralins, dihydrofurans, dihydroindoles, and other polycyclic aromatic compounds is presented. Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using (PPh3)3RhCl (Wilkinson's catalyst). The cyclization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with good regioselectivity. Different ring sizes and substitution patterns can be accessed through the coupling of monosubstituted, 1,1- or 1,2-disubstituted, and trisubstituted alkenes bearing both electron-rich and electron-deficient functionality.

  19. Enzyme catalytic nitration of aromatic compounds.

    PubMed

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun

    2015-06-01

    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration. PMID:26002502

  20. Enzyme catalytic nitration of aromatic compounds.

    PubMed

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun

    2015-06-01

    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration.

  1. New adjacent Bis-tetrahydrofuran Annonaceous acetogenins from Annona muricata.

    PubMed

    Chang, Fang-Rong; Liaw, Chih-Chuang; Lin, Chih-Yuan; Chou, Chi-Jung; Chiu, Hui-Fen; Wu, Yang-Chang

    2003-03-01

    Bioactivity-guided fractionation led to the isolation of two new Annonaceous acetogenins, annocatacin A ( 1). and annocatacin B ( 2). from the seeds and the leaves, respectively, of Annona muricata. Compounds 1 and 2 are the first examples where the adjacent bis-tetrahydrofuran ring system is located at C-15. The new structures were elucidated and characterized by spectral and chemical methods. Both Annonaceous acetogenins 1 and 2 showed significant in vitro cytotoxicity toward the human hepatoma cell lines, Hep G2 and 2,2,15, and were compared with the known adjacent bis-tetrahydrofuran acetogenins, neoannonin ( 3). desacetyluvaricin ( 4). bullatacin ( 5). asimicin ( 6). annoglaucin ( 7). squamocin ( 8). and rollimusin ( 9).

  2. [Inhibition of aromatics on ammonia-oxidizing activity of sediment].

    PubMed

    Dong, Chun-hong; Hu, Hong-ying; Wei, Dong-bin; Huang, Xia; Qian, Yi

    2004-03-01

    The inhibition of 24 aromatics on ammonia-oxidizing activity of nitrifying bacteria in sediment was measured. The effects of the kind, number and position of substituted groups on ammonia-oxidizing activity of nitrifying bacteria were discussed. The inhibition of mono-substituted benzenes on ammonia-oxidizing activity of nitrifying bacteria were in order of -OH > -NO2 > -NH2 > -Cl > -CH3 > -H. The position of substituted groups of di-substituted benzenes also affected the inhibition, and the inhibitions of dimethylbenzenes(xylene) were in order of meta-> ortho-> para-. The increase in number of substituted group on benzene-ring enhanced the inhibition of aromatics studied in this study on nitrifying bacteria. There was a linear relationship between inhibition (IC50, mumol.L-1) of aromatics on ammonia-oxidizing activity and total electronegativity (sigma E) of aromatics: lgIC50 = 14.72 - 0.91 sigma E.

  3. Six-Membered Aromatic Polyazides: Synthesis and Application.

    PubMed

    Chapyshev, Sergei V

    2015-10-21

    Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C₃N₄ carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring.

  4. Ringing wormholes

    SciTech Connect

    Konoplya, R.A.; Molina, C.

    2005-06-15

    We investigate the response of traversable wormholes to external perturbations through finding their characteristic frequencies and time-domain profiles. The considered solution describes traversable wormholes between the branes in the two brane Randall-Sundrum model and was previously found within Einstein gravity with a conformally coupled scalar field. The evolution of perturbations of a wormhole is similar to that of a black hole and represents damped oscillations (ringing) at intermediately late times, which are suppressed by power-law tails (proportional to t{sup -2} for monopole perturbations) at asymptotically late times.

  5. Nucleophilic Aromatic Substitution.

    ERIC Educational Resources Information Center

    Avila, Walter B.; And Others

    1990-01-01

    Described is a microscale organic chemistry experiment which demonstrates one feasible route in preparing ortho-substituted benzoic acids and provides an example of nucleophilic aromatic substitution chemistry. Experimental procedures and instructor notes for this activity are provided. (CW)

  6. Synthetic fuel aromaticity and staged combustion

    SciTech Connect

    Longanbach, J. R.; Chan, L. K.; Levy, A.

    1982-11-15

    Samples of middle and heavy SRC-II distillates were distilled into 50 C boiling point range fractions. These were characterized by measurements of their molecular weight, elemental analysis and basic nitrogen content and calculation of average molecular structures. The structures typically consisted of 1 to 3 aromatic rings fused to alicyclic rings with short, 1 to 3 carbon aliphatic side chains. The lower boiling fractions contained significant amounts (1 atom/molecule) of oxygen while the heavier fractions contained so few heteroatoms that they were essentially hydrocarbons. Laboratory scale oxidative-pyrolysis experiments were carried out at pyrolysis temperatures of 500 to 1100 C and oxygen concentrations from 0 to 100 percent of stoichiometry. Analysis of liquid products, collected in condensers cooled with liquid nitrogen showed that aromatization is a major reaction in the absence of oxygen. The oxygen-containing materials (phenolics) seem to be more resistant to thermal pyrolysis than unsubstituted aromatics. Nitrogen converts from basic to nonbasic forms at about 500 C. The nonbasic nitrogen is more stable and survives up to 700 C after which it is slowly removed. A recently constructed 50,000 Btu/hr staged combustor was used to study the chemistry of the nitrogen and aromatics. SRC II combustion was studied under fuel-rich, first-stage conditions at air/fuel ratios from 0.6 to 1.0 times stoichiometric. The chemistry of the fuel during combustion calls for further investigation in order to examine the mechanism by which HCN is evolved as a common intermediate for the formation of the nitrogen-containing gaseous combustion products. 25 references, 45 figures, 25 tables.

  7. Trimerization of aromatic nitriles

    NASA Technical Reports Server (NTRS)

    Hsu, L. C. (Inventor)

    1977-01-01

    Triazine compounds and cross-linked polymer compositions were made by heating aromatic nitriles to a temperature in the range of about 100 C to about 700 C, in the presence of a catalyst or mixture of catalysts. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers were made which were trimerized with or without a filler by the aforementioned catalytic trimerization process.

  8. Nonlinearity of cationic aromatic amine sorption to aluminosilicates and soils: role of intermolecular cation-π interactions.

    PubMed

    Vasudevan, Dharni; Arey, Teresa A; Dickstein, Daniel R; Newman, Mark H; Zhang, Tina Y; Kinnear, Heather M; Bader, Mohammad M

    2013-12-17

    Through the study of substituted anilines and benzylamines, we demonstrated that cooperative cation-π, π-π, and van der Waals interactions can increase aromatic cationic amine sorption to Na/Ca-montmorillonite well beyond the extent expected by cation exchange alone. Cationic amines exhibiting cooperative interactions displayed nonlinear S-shaped isotherms and increased affinity for the sorbent at low surface coverage; parallel cation exchange and cooperative interactions were noted above a sorption threshold of 0.3-2.3% of exchange sites occupied. Our experiments revealed the predominance of intermolecular cation-π interactions, which occurred between the π system of a compound retained on the surface via cation exchange and the cationic amine group of an adjacent molecule. Compounds with greater amine charge/area and electron-donating substituents that allowed for greater electron density at the center of the aromatic ring showed a greater potential for cation-π interactions on montmorillonite surfaces. However, benzylamine sorption to nine soils, at charge loadings comparable to the experiments with montmorillonite, revealed no significant cooperative interactions. It appears that cation-π interactions may be likely in soils with exceptionally high cation exchange capacities (>0.7 mol charge/kg) and low organic matter contents, abundant in montmorillonite and other expanding clay minerals.

  9. Aromatic Polyimide Foam

    NASA Technical Reports Server (NTRS)

    Weiser, Erik S. (Inventor); St.Clair, Terry L. (Inventor); Echigo, Yoshiaki (Inventor); Kaneshiro, Hisayasu (Inventor)

    2000-01-01

    A mechanically undensified aromatic polyimide foam is made from an aromatic polyimide precursor solid residuum and has the following combination of properties: a density according to ASTM D-3574A of about 0.5 pounds/cu.ft to about 20 pounds/cu.ft; a compression strength according to ASTM D-3574C of about 1.5 psi to about 1500 psi; and a limiting oxygen index according to ASTM D-2863 of about 35% oxygen to about 75% oxygen at atmospheric pressure. The aromatic polyimide foam has no appreciable solid inorganic contaminants which are residues of inorganic blowing agents. The aromatic polyimide which constitutes the aromatic polyimide foam has a glass transition temperature (Tg) by differential scanning calorimetry of about 235 C to about 400 C; and a thermal stability of 0 to about 1% weight loss at 204 C as determined by thermogravinietric analysis (TGA). The aromatic polyimide foam has utility as foam insulation and as structural foam, for example, for aeronautical, aerospace and maritime applications.

  10. [32]π Fused Core-Modified Heptaphyrin with Möbius Aromaticity.

    PubMed

    Ghosh, Arindam; Chaudhary, Arvind; Srinivasan, A; Suresh, Cherumuttathu H; Chandrashekar, Tavarekere K

    2016-03-14

    A new fused core-modified 32π heptaphyrin with Möbius aromatic character is reported. The (1)H NMR data indicated a weak Möbius aromaticity at 298 K; however, at 213-183 K, the molecule predominates [4n]π Möbius conformation with strong diatropic ring current, which was further confirmed by X-ray analysis. The protonation experiment led to preservation of the Möbius aromaticity at 298 K. Nevertheless, the experimental results were further supported by theoretical studies. Overall, this study represents the first example of Möbius aromatic fused core-modified expanded porphyrin. PMID:26781367

  11. Chemical applications of neural networks: aromaticity of pyrimidine derivatives.

    PubMed

    Alonso, Mercedes; Miranda, Carlos; Martín, Nazario; Herradón, Bernardo

    2011-12-14

    Neural networks are computational tools able to apprehend non-linear relationships between different parameters, having the capacity to order a large amount of input data and transform them into a graphical pattern of output data. We have previously reported their use for the quantification of the aromaticity through the Euclidean distance between neurons. In this article, we apply the method to a variety of pyrimidine derivatives with electron-donor and electron-withdrawing groups as substituents, with capacity to produce push-pull compounds. We have calculated the aromaticity of benzene (as a reference molecule), parent pyrimidine and other 11 pyrimidine derivatives having amino, dimethylamino and tricyanovinyl substitution. The neural network has been generated using ASE, Λ, NICS(zz)(1) and HOMA as aromaticity descriptors, since our previous work showed that the combination of these indices provided the best performance of the network. On studying the influence of the substituent on the aromaticity of the molecule, we have found that, opposite to benzene derivatives, all the substituents decrease the aromaticity of the ring. The interplay between aromaticity, planarity and push-pull properties of all the substituted pyrimidines has also been addressed. An interesting feature of the neural network to quantify aromaticity is that the importance of the reference reaction used to evaluate energy stabilization and magnetic susceptibility exaltation is minimized.

  12. Anaerobic metabolism of aromatic compounds by phototrophic bacteria: Progress report

    SciTech Connect

    Harwood, C.S.; Gibson, J.

    1986-12-19

    Vast quantities of aromatic compounds in the form of lignin, lignin derivatives, and aromatic pollutants are continually being introduced into the biosphere and much of this material accumulates in anaerobic environments. This project seeks to elucidate anaerobic routes of benzoate and 4-hydroxybenzoate metabolism by the photorophic bacterium, Rhodopseudomonas palustris. Recent evidence suggests that diverse aromatics must first be metabolized to form one or the other of these compounds prior to cleavage of the aromatic ring and so these pathways probably play general role as major degradative routes. R. palustris is particularly well suited for these studies because its ability to separate carbon metabolism from energy generating mechanisms frees it from the thermodynamic constraints that restrict the anaerobic metabolism of aromatics by pure cultures of fermentative bacteria. Studies include identification of the number and specificity of enzymes involved in benzoate and 4-hydroxybenzoate metabolism, identification of cofactors and electron carriers involved in each pathway, and a determination of the precise nature of the products formed. Mutants that are blocked in aromatic metabolism have been isolated. These mutants will be used, together with physiological approaches, to identify compounds (inducers and repressors) that regulate the expression of genes for aromatic degradation. 8 refs., 2 figs., 1 tab.

  13. Polycyclic aromatic hydrocarbons profile of kitchen dusts.

    PubMed

    Iwegbue, Chukwujindu M A

    2011-03-01

    Concentrations and profiles of polycyclic aromatic hydrocarbons (PAHs) were determined in thirty dust samples collected from kitchens that use wood cook system (WCS), kerosene stove cook system (KSCS) and butane gas cook system (BGCS). The total PAHs concentrations ranged from 52 to 497, 39 to 96 and 37 to 155 μg kg(-1) for WCS, KSCS and BGCS respectively. The results indicate predominance of lower molecular weight (2-3 rings) over higher molecular weight PAHs and users of wood cook system are more exposed to higher levels of PAHs than the users of either kerosene cook system or butane gas cook system.

  14. Metabolism of aromatic compounds by Caulobacter crescentus

    SciTech Connect

    Chatterjee, D.K.; Bourquin, A.W.

    1987-05-01

    Cultures of Caulobacter crescentus were found to grow on a variety of aromatic compounds. Degradation of benzoate, p-hydroxybenzoate, and phenol was found to occur via ..beta..-ketoadipate. The induction of degradative enzymes such as benzoate 1,2-dioxygenase, the ring cleavage enzyme catechol 1,2-dioxygenase, and cis,cis-muconate lactonizing enzyme appeared similar to the control mechanism present in Pseudomonas spp. Both benzoate 1,2-dioxygenase and catechol 1,2-dioxygenase had stringent specificities, as revealed by their action toward substituted benzoates and substituted catechols, respectively.

  15. Structural basis of enzymatic benzene ring reduction.

    PubMed

    Weinert, Tobias; Huwiler, Simona G; Kung, Johannes W; Weidenweber, Sina; Hellwig, Petra; Stärk, Hans-Joachim; Biskup, Till; Weber, Stefan; Cotelesage, Julien J H; George, Graham N; Ermler, Ulrich; Boll, Matthias

    2015-08-01

    In chemical synthesis, the widely used Birch reduction of aromatic compounds to cyclic dienes requires alkali metals in ammonia as extremely low-potential electron donors. An analogous reaction is catalyzed by benzoyl-coenzyme A reductases (BCRs) that have a key role in the globally important bacterial degradation of aromatic compounds at anoxic sites. Because of the lack of structural information, the catalytic mechanism of enzymatic benzene ring reduction remained obscure. Here, we present the structural characterization of a dearomatizing BCR containing an unprecedented tungsten cofactor that transfers electrons to the benzene ring in an aprotic cavity. Substrate binding induces proton transfer from the bulk solvent to the active site by expelling a Zn(2+) that is crucial for active site encapsulation. Our results shed light on the structural basis of an electron transfer process at the negative redox potential limit in biology. They open the door for biological or biomimetic alternatives to a basic chemical synthetic tool.

  16. Overview of Polycyclic Aromatic Compounds (PAC)

    PubMed Central

    Achten, Christine; Andersson, Jan T.

    2015-01-01

    The chemical group of polycyclic aromatic compounds (PAC), including the better-known subgroup of polycyclic aromatic hydrocarbons (PAH) and the heterocyclic aromatic compounds (NSO-PAC, heterocycles), comprise several thousand individual compounds. It is hard to find a comprehensive overview in the literature of these PACs that includes a substantial amount of relevant properties. Here an attempt is made to summarize the most studied but also some less well-known PACs. In addition to basic data such as recommended names, abbreviations, CAS numbers, molecular formulas, chemical structures, and exact mono-isotopic molecular weights, physico-chemical properties taken from the literature like boiling points, vapor pressures, water solubilities, Henry's Law constants, n-octanol-water partition coefficients (log KOW), and pKa are summarized. Selected toxicological data are listed indicating carcinogenic and mutagenic activity or effects on different organisms. PAC nomenclature is a complex topic, so suggestions for practical use are made. Regarding available data, estimated (instead of measured) values should be used with caution because considerable deviations from experimentally determined values can occur. For an enhanced understanding of the behavior of single PACs in comparison with each other, some of the properties mentioned above are plotted vs. the number of rings or the degree of alkylation. Also, some physico-chemical data are correlated with different functional groups as substituents of the PAHs. This article reveals that rather little is known about the less common PACs, e.g., higher molecular weight compounds, alkylated or otherwise substituted aromatics, for instance, keto-, oxo-, amino-, nitro-, cyano-PAHs, or some heterocyclic aromatic compounds, including their derivatives. It mirrors the limited state of knowledge about the variety of PACs that do not belong to the 16 EPA PAHs. PMID:26823644

  17. Aromatic amines and cancer.

    PubMed

    Vineis, P; Pirastu, R

    1997-05-01

    Epidemiological evidence on the relation between aromatic amines and cancer risk is reviewed. In particular, cancer risk in humans resulting from exposure to aromatic amines from occupational sources and tobacco smoking is assessed with reference to ecologic, cohort, and case-control studies. Seven arylamines have been classified by the International Agency for Research on Cancer: benzidine-based dyes and MOCA (4,4'-methylene bis 2-choloroaniline) were considered 'probably' carcinogenic, Group 2A, because of a high level of evidence in experimental animals; two occupational chemicals (2-naphthylamine and benzidine), one drug (Chlornaphazine), and two manufacturing processes (manufacture of auramine and magenta) were included in Group 1 on the basis of 'sufficient' evidence of carcinogenicity in humans. Occupational exposures to aromatic amines explain up to 25 percent of bladder cancers in some areas of Western countries; these estimates might be higher in limited areas of developing countries. Aromatic amines contaminate the ambient air as a component of environmental tobacco smoke. There is increasing evidence that the excess of bladder cancer in smokers is attributable to aromatic amines rather than to other contaminants of tobacco smoke such as polycyclic aromatic hydrocarbons (PAH). A modulating role in the risk of bladder cancer associated with exposure to aromatic amines is played by metabolic polymorphisms, such as the N-acetyltransferase genotype, raising important social and ethical issues. The consistent observation of a difference between men and women in bladder cancer risk, after allowing for known risk factors, suggests consideration of gender-related biological determinants for future investigation.

  18. The oxidation degradation of aromatic compounds

    NASA Technical Reports Server (NTRS)

    Brezinsky, Kenneth; Glassman, Irvin

    1987-01-01

    A series of experiments were conducted which focused on understanding the role that the O atom addition to aromatic rings plays in the oxidation of benzene and toluene. Flow reactor studies of the oxidation of toluene gave an indication of the amount of O atoms available during an oxidation and the degree to which the O atom adds to the ring. Flow reactor studies of the oxidation of toluene and benzene to which NO2 was added, have shown that NO2 appears to suppress the formation of O atoms and consequently reduce the amount of phenols and cresols formed by O atom addition. A high temperature pyrolysis study of phenol has confirmed that the major decomposition products are carbon monoxide and cyclopentadiene. A preliminary value for the overall decomposition rate constant was also obtained.

  19. Basin-ring spacing on the Moon, Mercury, and Mars

    USGS Publications Warehouse

    Pike, R.J.; Spudis, P.D.

    1987-01-01

    Radial spacing between concentric rings of impact basins that lack central peaks is statistically similar and nonrandom on the Moon, Mercury, and Mars, both inside and outside the main ring. One spacing interval, (2.0 ?? 0.3)0.5D, or an integer multiple of it, dominates most basin rings. Three analytical approaches yield similar results from 296 remapped or newly mapped rings of 67 multi-ringed basins: least-squares of rank-grouped rings, least-squares of rank and ring diameter for each basin, and averaged ratios of adjacent rings. Analysis of 106 rings of 53 two-ring basins by the first and third methods yields an integer multiple (2 ??) of 2.00.5D. There are two exceptions: (1) Rings adjacent to the main ring of multi-ring basins are consistently spaced at a slightly, but significantly, larger interval, (2.1 ?? 0.3)0.5D; (2) The 88 rings of 44 protobasins (large peak-plus-inner-ring craters) are spaced at an entirely different interval (3.3 ?? 0.6)0.5D. The statistically constant and target-invariant spacing of so many rings suggests that this characteristic may constrain formational models of impact basins on the terrestrial planets. The key elements of such a constraint include: (1) ring positions may not have been located by the same process(es) that formed ring topography; (2) ring location and emplacement of ring topography need not be coeval; (3) ring location, but not necessarily the mode of ring emplacement, reflects one process that operated at the time of impact; and (4) the process yields similarly-disposed topographic features that are spatially discrete at 20.5D intervals, or some multiple, rather than continuous. These four elements suggest that some type of wave mechanism dominates the location, but not necessarily the formation, of basin rings. The waves may be standing, rather than travelling. The ring topography itself may be emplaced at impact by this and/or other mechanisms and may reflect additional, including post-impact, influences. ?? 1987

  20. Distribution and sources of the polycyclic aromatic hydrocarbons in the sediments of the Pearl River estuary, China.

    PubMed

    Zhang, Jian-Dong; Wang, You-Shao; Cheng, Hao; Jiang, Zhao-Yu; Sun, Cui-Ci; Wu, Mei-Lin

    2015-10-01

    The Pearl River delta, one of the most prosperous economically region in China, has experienced significant contaminant inputs. However, the dynamics of pollutants in the Pearl River estuary and the adjacent coastal areas are still unclear at present. In the paper, distribution and sources of polycyclic aromatic hydrocarbons (PAHs) were investigated in the surface sediments of the Pearl River estuary. The total PAHs concentrations ranged from 126.08 to 3828.58 ng/g with a mean value of 563.52 ng/g, whereas the highest PAHs were observed in Guangzhou channel. Among the U.S. Environmental Protection Agency's 16 priority PAHs, PAHs with 3-4 rings exhibited relative higher levels. A positive relationship was found between PAHs and total organic carbon. The source analysis further showed that the major sources of PAHs in the Pearl River estuary were originated from the pyrolytic inputs, reflecting a mixed energy structure such as wood, coal and petroleum combustion. In summary, although PAHs in Lingding Bay and the adjacent coastal areas of the Pearl River estuary exhibited a relatively low pollution level, the relatively high pollution level of PAHs in Guangzhou channel will be attended.

  1. Disordered organic electronic materials based on non-benzenoid 1,6-methano[10]annulene rings

    SciTech Connect

    Tovar, John D; Streifel, Benjamin C; Peart, Patricia A

    2014-10-07

    Conjugated polymers and small molecules including the nonplanar aromatic 1,6-methano[10]annulene ring structure along with aromatic subunits, such as diketopyrrolopyrrole, and 2,1,3-benzothiadiazole, substituted with alkyl chains in a "Tail In," "Tail Out," or "No Tail" regiochemistry are disclosed.

  2. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    SciTech Connect

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul

    2004-03-31

    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  3. Oxidative aromatic coupling of meso-arylamino-porphyrins.

    PubMed

    Nowak-Król, Agnieszka; Gryko, Daniel T

    2013-11-15

    Strategic placement of the bis-arylamino group at the meso-position of porphyrins allowed fusion of these two moieties via aromatic dehydrogenation. By placing two di(naphthalene-2-yl)amine or bis(3,5-dimethoxyphenyl)amine groups at positions 5 and 15 of the porphyrin, the oxidative aromatic coupling was directed toward closing one six-membered ring. The extension of the porphyrin chromophore leads to significant change in linear optical properties, such as a bathochromic shift of absorption and broadening of the Q-band. PMID:24168727

  4. The Phylogenetic Signature Underlying ATP Synthase c-Ring Compliance.

    PubMed

    Pandini, Alessandro; Kleinjung, Jens; Taylor, Willie R; Junge, Wolfgang; Khan, Shahid

    2015-09-01

    The proton-driven ATP synthase (FOF1) is comprised of two rotary, stepping motors (FO and F1) coupled by an elastic power transmission. The elastic compliance resides in the rotor module that includes the membrane-embedded FO c-ring. Proton transport by FO is firmly coupled to the rotation of the c-ring relative to other FO subunits (ab2). It drives ATP synthesis. We used a computational method to investigate the contribution of the c-ring to the total elastic compliance. We performed principal component analysis of conformational ensembles built using distance constraints from the bovine mitochondrial c-ring x-ray structure. Angular rotary twist, the dominant ring motion, was estimated to show that the c-ring accounted in part for the measured compliance. Ring rotation was entrained to rotation of the external helix within each hairpin-shaped c-subunit in the ring. Ensembles of monomer and dimers extracted from complete c-rings showed that the coupling between collective ring and the individual subunit motions was independent of the size of the c-ring, which varies between organisms. Molecular determinants were identified by covariance analysis of residue coevolution and structural-alphabet-based local dynamics correlations. The residue coevolution gave a readout of subunit architecture. The dynamic couplings revealed that the hinge for both ring and subunit helix rotations was constructed from the proton-binding site and the adjacent glycine motif (IB-GGGG) in the midmembrane plane. IB-GGGG motifs were linked by long-range couplings across the ring, while intrasubunit couplings connected the motif to the conserved cytoplasmic loop and adjacent segments. The correlation with principal collective motions shows that the couplings underlie both ring rotary and bending motions. Noncontact couplings between IB-GGGG motifs matched the coevolution signal as well as contact couplings. The residue coevolution reflects the physiological importance of the dynamics that may

  5. Aromatic site description of soot particles

    SciTech Connect

    Celnik, Matthew; Raj, Abhijeet; West, Richard; Patterson, Robert; Kraft, Markus

    2008-10-15

    A new, advanced soot particle model is developed that describes soot particles by their aromatic structure, including functional site descriptions and a detailed surface chemistry mechanism. A methodology is presented for the description of polyaromatic hydrocarbon (PAH) structures by their functional sites. The model is based on statistics that describe aromatic structural information in the form of easily computed correlations, which were generated using a kinetic Monte Carlo algorithm to study the growth of single PAH molecules. A comprehensive surface reaction mechanism is presented to describe the growth and desorption of aromatic rings on PAHs. The model is capable of simulating whole particle ensembles which allows bulk properties such as soot volume fraction and number density to be found, as well as joint particle size and surface area distributions. The model is compared to the literature-standard soot model [J. Appel, H. Bockhorn, M. Frenklach, Combust. Flame 121 (2000) 122-136] in a plug-flow reactor and is shown to predict well the experimental results of soot mass, average particle size, and particle size distributions at different flow times. Finally, the carbon/hydrogen ratio and the distribution of average PAH sizes in the ensemble, as predicted by the model, are discussed. (author)

  6. Relaxed specificity in aromatic prenyltransferases.

    PubMed

    Koehl, Patrice

    2005-07-01

    Prenylation represent a critical step in the biosynthesis of many natural products, A new study reveals how aromatic prenyltransferase enzymes tolerate diverse aromatic polyketides while still controlling the length of prenyl side chains.

  7. Ab initio theoretical study of non-covalent adsorption of aromatic molecules on boron nitride nanotubes.

    PubMed

    Zhao, Yu; Wu, Xiaojun; Yang, Jinlong; Zeng, Xiao Cheng

    2011-06-28

    We have studied non-covalent functionalization of boron nitride nanotubes (BNNTs) with benzene molecule and with seven other different heterocyclic aromatic rings (furan, thiophene, pyrrole, pyridine, pyrazine, pyrimidine, and pyridazine, respectively). A hybrid density functional theory (DFT) method with the inclusion of dispersion correction is employed. The structural and electronic properties of the functionalized BNNTs are obtained. The DFT calculation shows that upon adsorption to the BNNT, the center of aromatic rings tend to locate on top of the nitrogen site. The trend of adsorption energy for the aromatic rings on the BNNTs shows marked dependence on different intermolecular interactions, including the dispersion interaction (area of the delocalized π bond), the dipole-dipole interaction (polarization), and the electrostatic repulsion (lone pair electrons). The DFT calculation also shows that non-covalent functionalization of BNNTs with aromatic rings can give rise to new impurity states within the band gap of pristine BNNTs, suggesting possible carrier doping of BNNTs via selective adsorption of aromatic rings. PMID:21603684

  8. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids

    PubMed Central

    Rodrigues, Ana S.M.C.; Almeida, Hugo F. D.; Freire, Mara G.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Santos, Luís M. N. B. F.

    2016-01-01

    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs’ thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso-alkyl group leads to an increase of the temperature of the glass transition, Tg. The iso-pyrrolidinium (5 atoms ring cation core) and iso-piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso-alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n-alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso-alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress. PMID:27682333

  9. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids

    PubMed Central

    Rodrigues, Ana S.M.C.; Almeida, Hugo F. D.; Freire, Mara G.; Lopes-da-Silva, José A.; Coutinho, João A. P.; Santos, Luís M. N. B. F.

    2016-01-01

    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs’ thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso-alkyl group leads to an increase of the temperature of the glass transition, Tg. The iso-pyrrolidinium (5 atoms ring cation core) and iso-piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso-alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n-alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso-alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

  10. Asymmetric dipolar ring

    DOEpatents

    Prosandeev, Sergey A.; Ponomareva, Inna V.; Kornev, Igor A.; Bellaiche, Laurent M.

    2010-11-16

    A device having a dipolar ring surrounding an interior region that is disposed asymmetrically on the ring. The dipolar ring generates a toroidal moment switchable between at least two stable states by a homogeneous field applied to the dipolar ring in the plane of the ring. The ring may be made of ferroelectric or magnetic material. In the former case, the homogeneous field is an electric field and in the latter case, the homogeneous field is a magnetic field.

  11. Mechanical seal having a double-tier mating ring

    DOEpatents

    Khonsari, Michael M.; Somanchi, Anoop K.

    2005-09-13

    An apparatus and method to enhance the overall performance of mechanical seals in one of the following ways: by reducing seal face wear, by reducing the contact surface temperature, or by increasing the life span of mechanical seals. The apparatus is a mechanical seal (e.g., single mechanical seals, double mechanical seals, tandem mechanical seals, bellows, pusher mechanical seals, and all types of rotating and reciprocating machines) comprising a rotating ring and a double-tier mating ring. In a preferred embodiment, the double-tier mating ring comprises a first and a second stationary ring that together form an agitation-inducing, guided flow channel to allow for the removal of heat generated at the seal face of the mating ring by channeling a coolant entering the mating ring to a position adjacent to and in close proximity with the interior surface area of the seal face of the mating ring.

  12. Polybenzimidazole via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G. (Inventor)

    1994-01-01

    Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

  13. Proximity effect: insight into the fundamental forces governing chemical reactivity of aromatic systems.

    PubMed

    Vidhani, Dinesh V; Krafft, Marie E

    2015-03-26

    The analysis of different layers of proximity effect in ortho-substituted aromatic compounds, using a DFT-level study, is reported. Polar and steric components of the proximity effect have been partitioned by applying multivariate regression analysis to an unusual six-electron heteroelectrocyclic reaction of the ortho-substituted nitrosostyrenes. The two pathways, 1,5- and 1,6-cyclizations, emanating from these substrates result into zwitterionic five-membered and neutral six-membered rings, respectively. The substituents at position 1, which are adjacent to the polar nitroso group, influenced the barrier primarily through electronic effect. Furthermore, a mechanistic shift from the 1,5 to 1,6 pathway, for certain substrates, is explained by the electronic repulsion. In contrast to position 1, the substituents on position 4 stereoelectronically interacted with a bulkier alkene moiety. Furthermore, unlike position 1, the position-4-substituted substrates are predicted to give only 1,5 products. A comparison of the two ortho positions with position 2, which is meta to the nitroso and para to the alkene, revealed an intriguing relationship between various electronic factors.

  14. Phenylalanyl-Glycyl-Phenylalanine Tripeptide: A Model System for Aromatic-Aromatic Side Chain Interactions in Proteins

    SciTech Connect

    Valdes, Haydee; Pluhackova, Kristyna; Hobza, Pavel

    2009-09-08

    The performance of a wide range of quantum chemical calculations for the ab initio study of realistic model systems of aromatic-aromatic side chain interactions in proteins (in particular those π-π interactions occurring between adjacent residues along the protein sequence) is here assessed on the phenylalanyl-glycyl-phenylalanine (FGF) tripeptide. Energies and geometries obtained at different levels of theory are compared with CCSD(T)/CBS benchmark energies and RI-MP2/cc-pVTZ benchmark geometries, respectively. Consequently, a protocol of calculation alternative to the very expensive CCSD(T)/CBS is proposed. In addition to this, the preferred orientation of the Phe aromatic side chains is discussed and compared with previous results on the topic.

  15. Proton nuclear magnetic resonance characterization of the aromatic residues in the variant-3 neurotoxin from Centruroides sculpturatus Ewing

    SciTech Connect

    Krishna, N.R.; Nettesheim, D.G.; Klevit, R.E.; Drobny, G.; Watt, D.D.; Bugg, C.E. )

    1989-02-21

    The amino acid sequence for the variant-3 (CsE-v3) toxin from the venom of the scorpion Centruroides sculpturatus Ewing contains eight aromatic residues. By use of 2D NMR spectroscopic methods, the resonances from the individual protons (NH, C{sup alpha}H, C{sup beta}H{prime}, H{double prime}, and the ring) for each of the individual aromatic residues have been completely assigned. The spatial arrangement of the aromatic ring systems with respect to each other has been qualitatively analyzed by 2D-NOESY techniques. The results show that Trp-47, Tyr-4, and Tyr-42 are in close spatial proximity to each other. The NOESY contacts and the ring current induced shifts in the resonances of the individual protons of Tyr-4 and Trp-47 suggest that the aromatic ring planes of these residues are in an orthogonal arrangement. A comparison with the published crystal structure suggests that there is a minor rearrangement of the aromatic rings in the solution phase. No 2D-NOESY contacts involving Phe-44 and Tyr-14 to any other aromatic ring protons have been observed. The pH dependence of the aromatic ring proton chemical shifts has also been studied. These results suggest that the Tyr-58 phenolic group is experiencing a hydrogen-bonding interaction with a positively charged group, while Tyr-4, -14, -38, and -40 are experiencing through-space interactions with proximal negatively charged groups. These studies define the microenvironment of the aromatic residues in the variant-3 neurotoxin in aqueous solution.

  16. Saturn's Ring Images/Dynamics by Cassini

    NASA Astrophysics Data System (ADS)

    Burns, J. A.; Tiscareno, M. S.

    2005-12-01

    Since its orbit insertion in mid-2004, the Cassini spacecraft has been able to view Saturn's magnificent rings at various phase and elevation angles, with resolutions ranging from ~200 m on orbit insertion, through a km or two during typical closest approaches, up to many tens of km at distant apoapses. Significant changes have occurred in isolated regions of the rings between the Voyager encounters a quarter century ago and the continuing observations over the last eighteen months. This talk will focus on observations and understandings of the past year. As time permits, we will discuss bending and density wave structures (emphasizing the changes in those caused by the switching orbits of Janus and Epimetheus); features that are temporally variable over short times (F ring, Encke ringlets, ring edges) and longer (D and G rings); odd patterns (short streaks, "straw", "knots" and "turbulence"); and interactions with adjacent satellites, especially those embedded in the Encke and Keeler gaps. Since the spacecraft will spend most of Fall 2005 near the ring plane, we anticipate few discoveries during this period; this should allow us time to do a better job at interpreting those data currently in hand. As J. C. Maxwell wrote in 1857, we are "still grinding at Saturn's rings."

  17. Aromatic Structure in Simulates Titan Aerosol

    NASA Technical Reports Server (NTRS)

    Trainer, Melissa G.; Loeffler, M. J.; Anderson, C. M.; Hudson, R. L.; Samuelson, R. E.; Moore, M. A.

    2011-01-01

    Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are

  18. Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter.

    PubMed

    Sagan, C; Khare, B N; Thompson, W R; McDonald, G D; Wing, M R; Bada, J L; Vo-Dinh, T; Arakawa, E T

    1993-09-01

    Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state 13C NMR spectroscopy suggests approximately equal to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of approximately equal to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.

  19. Metabolic Pathways for Degradation of Aromatic Hydrocarbons by Bacteria.

    PubMed

    Ladino-Orjuela, Guillermo; Gomes, Eleni; da Silva, Roberto; Salt, Christopher; Parsons, John R

    2016-01-01

    The aim of this review was to build an updated collection of information focused on the mechanisms and elements involved in metabolic pathways of aromatic hydrocarbons by bacteria. Enzymes as an expression of the genetic load and the type of electron acceptor available, as an environmental factor, were highlighted. In general, the review showed that both aerobic routes and anaerobic routes for the degradation of aromatic hydrocarbons are divided into two pathways. The first, named the upper pathways, entails the route from the original compound to central intermediate compounds still containing the aromatic ring but with the benzene nucleus chemically destabilized. The second, named the lower pathway, begins with ring de-aromatization and subsequent cleavage, resulting in metabolites that can be used by bacteria in the production of biomass. Under anaerobic conditions the five mechanisms of activation of the benzene ring described show the diversity of chemical reactions that can take place. Obtaining carbon and energy from an aromatic hydrocarbon molecule is a process that exhibits the high complexity level of the metabolic apparatus of anaerobic microorganisms. The ability of these bacteria to express enzymes that catalyze reactions, known only in non-biological conditions, using final electron acceptors with a low redox potential, is a most interesting topic. The discovery of phylogenetic and functional characteristics of cultivable and noncultivable hydrocarbon degrading bacteria has been made possible by improvements in molecular research techniques such as SIP (stable isotope probing) tracing the incorporation of (13)C, (15)N and (18)O into nucleic acids and proteins. Since many metabolic pathways in which enzyme and metabolite participants are still unknown, much new research is required. Therefore, it will surely allow enhancing the known and future applications in practice.

  20. Integrated reforming/aromatization process

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1990-06-26

    This patent describes an integrated process for increasing the gasoline yield from a catalytic reforming process. It comprises: charging a naphtha boiling range feedstream to a catalytic reforming reaction zone under reforming conversion conditions; withdrawing a reactor effluent stream from the reforming reaction zone; separating the reactor effluent stream into a hydrogen-rich gas stream and an unstabilized reformate stream; further separating the unstabilized reformate in a fractionator into an overhead stream containing C{sub 4} - components and a bottom stream containing C{sub 6} + components; charging the fractionator overhead stream to a catalytic aromatization zone under aromatization conversion conditions; withdrawing an aromatization zone effluent stream from the aromatization zone; cooling the aromatization zone effluent stream; separating the cooled aromatization zone effluent steam into a C{sub 4} - stream and a C{sub 5} + stream; and refluxing the C{sub 5} + aromatic gasoline stream to the fractionation zone.

  1. Stirling engine piston ring

    DOEpatents

    Howarth, Roy B.

    1983-01-01

    A piston ring design for a Stirling engine wherein the contact pressure between the piston and the cylinder is maintained at a uniform level, independent of engine conditions through a balancing of the pressure exerted upon the ring's surface and thereby allowing the contact pressure on the ring to be predetermined through the use of a preloaded expander ring.

  2. Efficient Route to Deuterated Aromatics by the Deamination of Anilines.

    PubMed

    Burglova, Kristyna; Okorochenkov, Sergei; Hlavac, Jan

    2016-07-15

    One-step replacement of NH2 groups in ring-substituted anilines by deuterium is reported. Approaches comprising both solid-phase and solution-phase syntheses can be used on a large variety of substrates. The method uses diazotization in a mixture of water and either dichloromethane or chloroform, which serve as a source of hydrogen. This protocol can be used as a general method for fast and easy incorporation of deuterium into an aromatic system using deuterated chloroform.

  3. Efficient Route to Deuterated Aromatics by the Deamination of Anilines.

    PubMed

    Burglova, Kristyna; Okorochenkov, Sergei; Hlavac, Jan

    2016-07-15

    One-step replacement of NH2 groups in ring-substituted anilines by deuterium is reported. Approaches comprising both solid-phase and solution-phase syntheses can be used on a large variety of substrates. The method uses diazotization in a mixture of water and either dichloromethane or chloroform, which serve as a source of hydrogen. This protocol can be used as a general method for fast and easy incorporation of deuterium into an aromatic system using deuterated chloroform. PMID:27378277

  4. Actin Rings of Power.

    PubMed

    Schwayer, Cornelia; Sikora, Mateusz; Slováková, Jana; Kardos, Roland; Heisenberg, Carl-Philipp

    2016-06-20

    Circular or ring-like actin structures play important roles in various developmental and physiological processes. Commonly, these rings are composed of actin filaments and myosin motors (actomyosin) that, upon activation, trigger ring constriction. Actomyosin ring constriction, in turn, has been implicated in key cellular processes ranging from cytokinesis to wound closure. Non-constricting actin ring-like structures also form at cell-cell contacts, where they exert a stabilizing function. Here, we review recent studies on the formation and function of actin ring-like structures in various morphogenetic processes, shedding light on how those different rings have been adapted to fulfill their specific roles. PMID:27326928

  5. The rings of Saturn

    NASA Technical Reports Server (NTRS)

    Pollack, J. B.

    1978-01-01

    Consideration is given to the development of theories concerning the rings of Saturn. Particular attention is given to ring structure, noting its thinness, the separations between rings, and observed variations in brightness. Data gathered via infrared, radio and radar techniques are described in terms of ring particle composition and size. Hypotheses about ring origin and evolution are outlined, including the tidal disruption model, calculations of Saturn's gravitational contraction history, grazing, and meteoroid bombardment. Prospects for future observations of Saturn's rings are reviewed, such as the variation in their radar reflectivity as a function of the tilt of the ring plane.

  6. New Dust Belts of Uranus: One Ring, Two Ring, Red Ring, Blue Ring

    SciTech Connect

    de Pater, I; Hammel, H B; Gibbard, S G; Showalter, M R

    2006-02-02

    We compare near-infrared observations of the recently discovered outer rings of Uranus with HST results. We find that the inner ring, R/2003 U 2, is red, whereas the outer ring, R/2003 U 1, is very blue. Blue is an unusual color for rings; Saturn's enigmatic E ring is the only other known example. By analogy to the E ring, R/2003 U 1 is probably produced via impacts into the embedded moon Mab, which apparently orbits at a location where non-gravitational perturbations favor the survival and spreading of sub-micron sized dust. R/2003 U 2 more closely resembles Saturn's G ring.

  7. Solid-supported acids as mild and versatile reagents for the deprotection of aromatic ethers.

    PubMed

    Ploypradith, Poonsakdi; Cheryklin, Pannarin; Niyomtham, Nattisa; Bertoni, Daniel R; Ruchirawat, Somsak

    2007-07-01

    p-Toluene sulfonic acid (p-TsOH) immobilized either on polystyrene (PS) or silica (Si) was found to be effective in cleaving aromatic ethers containing isopropyl, tert-butyl, allyl, and benzyl groups, as well as mono-, di-, and trimethoxylated benzyl groups, in moderate to excellent yields (54-95%). These protecting groups could be selectively deprotected when they were simultaneously present on the same or different aromatic rings in a substrate.

  8. New insights into aromatic pathways of carbachlorins and carbaporphyrins based on calculations of magnetically induced current densities.

    PubMed

    Benkyi, Isaac; Fliegl, Heike; Valiev, Rashid R; Sundholm, Dage

    2016-04-28

    Magnetically induced current densities have been calculated and analyzed for a number of synthesized carbachlorins and carbaporphyrins using density functional theory and the gauge including magnetically induced current (GIMIC) method. Aromatic properties have been determined by using accurate numerical integration of the current flow yielding reliable current strengths and pathways that are related to the degree of aromaticity and the aromatic character of the studied molecules. All investigated compounds are found to be aromatic. However, the obtained aromatic pathways differ from those previously deduced from spectroscopic data and magnetic shielding calculations. For all studied compounds, the ring current divides into an outer and an inner branch at each pyrrolic subring, showing that all π-electrons of the pyrrolic rings take part in the delocalization pathway. The calculations do not support the common notion that the main share of the current takes the inner route at the pyrrolic rings without an inner hydrogen and follows an 18π aromatic pathway. The aromatic pathways of the investigated carbaporphyrins and carbachlorins are very similar, since the current strength via the Cβ[double bond, length as m-dash]Cβ' bond of the cyclopentadienyl ring of the carbaporphyrins is almost as weak as the current density passing the corresponding saturated Cβ-Cβ' bond of the carbachlorins.

  9. New insights into aromatic pathways of carbachlorins and carbaporphyrins based on calculations of magnetically induced current densities.

    PubMed

    Benkyi, Isaac; Fliegl, Heike; Valiev, Rashid R; Sundholm, Dage

    2016-04-28

    Magnetically induced current densities have been calculated and analyzed for a number of synthesized carbachlorins and carbaporphyrins using density functional theory and the gauge including magnetically induced current (GIMIC) method. Aromatic properties have been determined by using accurate numerical integration of the current flow yielding reliable current strengths and pathways that are related to the degree of aromaticity and the aromatic character of the studied molecules. All investigated compounds are found to be aromatic. However, the obtained aromatic pathways differ from those previously deduced from spectroscopic data and magnetic shielding calculations. For all studied compounds, the ring current divides into an outer and an inner branch at each pyrrolic subring, showing that all π-electrons of the pyrrolic rings take part in the delocalization pathway. The calculations do not support the common notion that the main share of the current takes the inner route at the pyrrolic rings without an inner hydrogen and follows an 18π aromatic pathway. The aromatic pathways of the investigated carbaporphyrins and carbachlorins are very similar, since the current strength via the Cβ[double bond, length as m-dash]Cβ' bond of the cyclopentadienyl ring of the carbaporphyrins is almost as weak as the current density passing the corresponding saturated Cβ-Cβ' bond of the carbachlorins. PMID:26974190

  10. Irradiation of ethylene/styrene copolymers: evidence of sensitization of the aromatic moiety as counterpart of the radiation protection effect.

    PubMed

    Ferry, M; Bessy, E; Harris, H; Lutz, P J; Ramillon, J-M; Ngono-Ravache, Y; Balanzat, E

    2012-02-16

    Molecules containing aromatics systems are more stable in the presence of ionizing radiations than alkanes. In the same way, introducing aromatic rings into aliphatic compounds increases their stability. The protective effect is nonlocal and likely results from the transfer of energy and species from the aliphatic moiety to the aromatic one. For years, it was commonly assumed that the aromatic moiety, which is very radiation resistant, accommodates the extra energy remaining unaffected. The use of Fourier transform infrared spectroscopy, online with high energy ion beam irradiation of ethylene/styrene random copolymers, allows us to bring experimental evidence that the benzene rings are sensitized by transfer reactions and consequently that this effect is more important in polymers with low benzene ring molar content. PMID:22236059

  11. Graphene Layer Growth: Collision of Migrating Five-MemberRings

    SciTech Connect

    Whitesides, Russell; Kollias, Alexander C.; Domin, Dominik; Lester Jr., William A.; Frenklach, Michael

    2005-12-02

    A reaction pathway is explored in which two cyclopenta groups combine on the zigzag edge of a graphene layer. The process is initiated by H addition to a five-membered ring, followed by opening of that ring and the formation of a six-membered ring adjacent to another five-membered ring. The elementary steps of the migration pathway are analyzed using density functional theory to examine the region of the potential energy surface associated with the pathway. The calculations are performed on a substrate modeled by the zigzag edge of tetracene. Based on the obtained energetics, the dynamics of the system are analyzed by solving the energy transfer master equations. The results indicate energetic and reaction-rate similarity between the cyclopenta combination and migration reactions. Also examined in the present study are desorption rates of migrating cyclopenta rings which are found to be comparable to cyclopenta ring migration.

  12. Polycyclic aromatic hydrocarbons profiles of spent drilling fluids deposited at Emu-Uno, Delta State, Nigeria.

    PubMed

    Iwegbue, Chukwujindu M A

    2011-10-01

    The concentrations and profiles of polycyclic aromatic hydrocarbons were determined in spent drilling fluid deposited at Emu-Uno, Delta State of Nigeria. The total concentrations of polycyclic aromatic hydrocarbons in the spent drilling fluid deposits ranged between 40 and 770 μg kg(-1). The PAHs profile were predominantly 2- and 3-rings with acenaphthalene, phenanthrene, fluorene being the predominant PAHs. The prevalence of 2- and 3-rings PAHs in the spent drilling fluid deposits indicate contamination of the drilling fluids with crude oil during drilling. Incorporation of spent drilling fluids into the soil has serious implication for soil, surface water and groundwater quality.

  13. Polycyclic aromatic hydrocarbons profiles of spent drilling fluids deposited at Emu-Uno, Delta State, Nigeria.

    PubMed

    Iwegbue, Chukwujindu M A

    2011-10-01

    The concentrations and profiles of polycyclic aromatic hydrocarbons were determined in spent drilling fluid deposited at Emu-Uno, Delta State of Nigeria. The total concentrations of polycyclic aromatic hydrocarbons in the spent drilling fluid deposits ranged between 40 and 770 μg kg(-1). The PAHs profile were predominantly 2- and 3-rings with acenaphthalene, phenanthrene, fluorene being the predominant PAHs. The prevalence of 2- and 3-rings PAHs in the spent drilling fluid deposits indicate contamination of the drilling fluids with crude oil during drilling. Incorporation of spent drilling fluids into the soil has serious implication for soil, surface water and groundwater quality. PMID:21809098

  14. Evidence of Accretion in Saturn's F Ring (Invited)

    NASA Astrophysics Data System (ADS)

    Agnor, C. B.; Buerle, K.; Murray, C. D.; Evans, M. W.; Cooper, N. J.; Williams, G. W.

    2010-12-01

    Lying slightly outside the classical Roche radius and being strongly perturbed by the adjacent moons Prometheus and Pandora, Saturn's F ring represents a unique astrophysical laboratory for examining the processes of mass accretion and moonlet formation. Recent images from the Cassini spacecraft reveal optically thick clumps, capable of casting shadows, and associated structures in regions of the F ring following close passage by Prometheus. Here we examine the accretion environment of the F ring and Prometheus' role in moonlet formation and evolution. Using the observed structures adjacent to these clumps and dynamical arguments we estimate the masses of these clumps and find them comparable to that of ~10-20-km contiguous moonlets. Further, we show that Prometheus' perturbations on the F ring create regions of enhanced density and low relative velocity that may accelerate the accretion of clumps and moonlets.

  15. A Description of Vibrational Modes in Hexaphyrins: Understanding the Aromaticity Reversal in the Lowest Triplet State.

    PubMed

    Sung, Young Mo; Oh, Juwon; Naoda, Koji; Lee, Taegon; Kim, Woojae; Lim, Manho; Osuka, Atsuhiro; Kim, Dongho

    2016-09-19

    Aromaticity reversal in the lowest triplet state, or Baird's rule, has been postulated for the past few decades. Despite numerous theoretical works on aromaticity reversal, experimental study is still at a rudimentary stage. Herein, we investigate the aromaticity reversal in the lowest excited triplet state using a comparable set of [26]- and [28]hexaphyrins by femtosecond time-resolved infrared (IR) spectroscopy. Compared to the relatively simple IR spectra of [26]bis(rhodium) hexaphyrin (R26H), those of [28]bis(rhodium) hexaphyrin (R28H) show complex IR spectra the region for the stretching modes of conjugated rings. Whereas time-resolved IR spectra of R26H in the excited triplet state are dominated by excited state IR absorption peaks, while those of R28H largely show ground state IR bleaching peaks, reflecting the aromaticity reversal in the lowest triplet state. These contrasting IR spectral features serve as new experimental aromaticity indices for Baird's rule. PMID:27510963

  16. Optimizing Thomson's jumping ring

    NASA Astrophysics Data System (ADS)

    Tjossem, Paul J. H.; Brost, Elizabeth C.

    2011-04-01

    The height to which rings will jump in a Thomson jumping ring apparatus is the central question posed by this popular lecture demonstration. We develop a simple time-averaged inductive-phase-lag model for the dependence of the jump height on the ring material, its mass, and temperature and apply it to measurements of the jump height for a set of rings made by slicing copper and aluminum alloy pipe into varying lengths. The data confirm a peak jump height that grows, narrows, and shifts to smaller optimal mass when the rings are cooled to 77 K. The model explains the ratio of the cooled/warm jump heights for a given ring, the reduction in optimal mass as the ring is cooled, and the shape of the mass resonance. The ring that jumps the highest is found to have a characteristic resistance equal to the inductive reactance of the set of rings.

  17. Two- and three-dimensional rings in drugs.

    PubMed

    Aldeghi, Matteo; Malhotra, Shipra; Selwood, David L; Chan, Ah Wing Edith

    2014-04-01

    Using small, flat aromatic rings as components of fragments or molecules is a common practice in fragment-based drug discovery and lead optimization. With an increasing focus on the exploration of novel biological and chemical space, and their improved synthetic accessibility, 3D fragments are attracting increasing interest. This study presents a detailed analysis of 3D and 2D ring fragments in marketed drugs. Several measures of properties were used, such as the type of ring assemblies and molecular shapes. The study also took into account the relationship between protein classes targeted by each ring fragment, providing target-specific information. The analysis shows the high structural and shape diversity of 3D ring systems and their importance in bioactive compounds. Major differences in 2D and 3D fragments are apparent in ligands that bind to the major drug targets such as GPCRs, ion channels, and enzymes. PMID:24472495

  18. Two- and three-dimensional rings in drugs.

    PubMed

    Aldeghi, Matteo; Malhotra, Shipra; Selwood, David L; Chan, Ah Wing Edith

    2014-04-01

    Using small, flat aromatic rings as components of fragments or molecules is a common practice in fragment-based drug discovery and lead optimization. With an increasing focus on the exploration of novel biological and chemical space, and their improved synthetic accessibility, 3D fragments are attracting increasing interest. This study presents a detailed analysis of 3D and 2D ring fragments in marketed drugs. Several measures of properties were used, such as the type of ring assemblies and molecular shapes. The study also took into account the relationship between protein classes targeted by each ring fragment, providing target-specific information. The analysis shows the high structural and shape diversity of 3D ring systems and their importance in bioactive compounds. Major differences in 2D and 3D fragments are apparent in ligands that bind to the major drug targets such as GPCRs, ion channels, and enzymes.

  19. Ring opening of methylcyclohexane over platinum-loaded zeolites.

    PubMed

    Calemma, Vincenzo; Carati, Angela; Flego, Cristina; Giardino, Roberto; Gagliardi, Federica; Millini, Roberto; Bellussi, Giuseppe

    2008-01-01

    The activity of different platinum-loaded zeolites (Mordenite, ZSM-12, ZSM-5, ZSM-23) was investigated in the hydroconversion of methylcyclohexane (MCH), in the context of upgrading highly aromatic distillates for fuel blending. In all cases, conversion of MCH proceeds according to a pathway where the primary products are a mixture of dimethylcyclopentanes and ethylcyclopentane formed by isomerization and ring contraction of MCH. The primary products undergo consecutive ring-opening reactions with formation of n- and isoheptanes. The latter further react to form lower-molecular-weight n- and isoalkanes. The selectivity and distribution of products deriving from ring-contraction and ring-opening reactions are strongly affected by the pore size and topology of the zeolites. ZSM-5 exhibits a strong reactant shape-selectivity effect on ring-opening products. The evaluated zeolites show the following order of activity in the conversion of methylcyclohexane: Mordenite>ZSM-12>ZSM-5>ZSM-23. PMID:18702154

  20. Two- and Three-dimensional Rings in Drugs

    PubMed Central

    Aldeghi, Matteo; Malhotra, Shipra; Selwood, David L; Chan, Ah Wing Edith

    2014-01-01

    Using small, flat aromatic rings as components of fragments or molecules is a common practice in fragment-based drug discovery and lead optimization. With an increasing focus on the exploration of novel biological and chemical space, and their improved synthetic accessibility, 3D fragments are attracting increasing interest. This study presents a detailed analysis of 3D and 2D ring fragments in marketed drugs. Several measures of properties were used, such as the type of ring assemblies and molecular shapes. The study also took into account the relationship between protein classes targeted by each ring fragment, providing target-specific information. The analysis shows the high structural and shape diversity of 3D ring systems and their importance in bioactive compounds. Major differences in 2D and 3D fragments are apparent in ligands that bind to the major drug targets such as GPCRs, ion channels, and enzymes. PMID:24472495

  1. Polyimidazoles via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor)

    1991-01-01

    Polyimidazoles (Pl) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethylacetamide, sulfolane, N-methylpyrroldinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperature under nitrogen. The di(hydroxyphenyl)imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl)imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxyphenyl)imidazole monomer. This synthetic route has provided high molecular weight Pl of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

  2. Polyimidazoles via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor)

    1992-01-01

    Polyimidazoles (PI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethyl acetamide, sulfolane, N-methylpyrrolidinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl) imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxphenyl) imidazole monomer. This synthetic route has provided high molecular weight PI of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

  3. Mechanistic Investigation into the Decarboxylation of Aromatic Carboxylic Acids

    SciTech Connect

    Britt, P F; Buchanan, III, A C; Eskay, T P; Mungall, W S

    1999-08-22

    It has been proposed that carboxylic acids and carboxylates are major contributors to cross-linking reactions in low-rank coals and inhibit its thermochemical processing. Therefore, the thermolysis of aromatic carboxylic acids was investigated to determine the mechanisms of decarboxylation at temperatures relevant to coal processing, and to determine if decarboxylation leads to cross-linking (i.e., formation of more refractory products). From the thcrmolysis of simple and polymeric coal model compounds containing aromatic carboxylic acids at 250-425 °C, decarboxylation was found to occur primarily by an acid promoted ionic pathway. Carboxylate salts were found to enhance the decarboxylation rate, which is consistent with the proposed cationic mechanism. Thermolysis of the acid in an aromatic solvent, such as naphthalene, produced a small amount of arylated products (~5 mol%)), which constitute a low-temperature cross-link. These arylated products were formed by the rapid decomposition of aromatic anhydrides, which are in equilibrium with the acid. These anhydrides decompose by a free radical induced decomposition pathway to form atyl radicals that can add to aromatic rings to form cross-links or abstract hydrogen. Large amounts of CO were formed in the thennolysis of the anhydrides which is consistent with the induced decomposition pathway. CO was also formed in the thermolysis of the carboxylic acids in aromatic solvents which is consistent with the formation and decomposition of the anhydride. The formation of anhydride linkages and cross-links was found to be very sensitive to the reactions conditions. Hydrogen donor solvents, such as tetralin, and water were found to decrease the formation of arylated products. Silar reaction pathways were also found in the thermolysis of a polymeric model that contained aromatic carboxylic acids. In this case, anhydride formation and decomposition produced an insoluble polymer, while the O-methylated polymer and the non

  4. Exploring aromatic chemical space with NEAT: novel and electronically equivalent aromatic template.

    PubMed

    Tu, Meihua; Rai, Brajesh K; Mathiowetz, Alan M; Didiuk, Mary; Pfefferkorn, Jeffrey A; Guzman-Perez, Angel; Benbow, John; Guimarães, Cristiano R W; Mente, Scot; Hayward, Matthew M; Liras, Spiros

    2012-05-25

    In this paper, we describe a lead transformation tool, NEAT (Novel and Electronically equivalent Aromatic Template), which can help identify novel aromatic rings that are estimated to have similar electrostatic potentials, dipoles, and hydrogen bonding capabilities to a query template; hence, they may offer similar bioactivity profiles. In this work, we built a comprehensive heteroaryl database, and precalculated high-level quantum mechanical (QM) properties, including electrostatic potential charges, hydrogen bonding ability, dipole moments, chemical reactivity, and othe properties. NEAT bioisosteric similarities are based on the electrostatic potential surface calculated by Brood, using the precalculated QM ESP charges and other QM properties. Compared with existing commercial lead transformation software, (1) NEAT is the only one that covers the comprehensive heteroaryl chemical space, and (2) NEAT offers a better characterization of novel aryl cores by using high-evel QM properties that are relevant to molecular interactions. NEAT provides unique value to medicinal chemists quickly exploring the largely uncharted aromatic chemical space, and one successful example of its application is discussed herein.

  5. Contorted polycyclic aromatics.

    PubMed

    Ball, Melissa; Zhong, Yu; Wu, Ying; Schenck, Christine; Ng, Fay; Steigerwald, Michael; Xiao, Shengxiong; Nuckolls, Colin

    2015-02-17

    CONSPECTUS: This Account describes a body of research in the design, synthesis, and assembly of molecular materials made from strained polycyclic aromatic molecules. The strain in the molecular subunits severely distorts the aromatic molecules away from planarity. We coined the term "contorted aromatics" to describe this class of molecules. Using these molecules, we demonstrate that the curved pi-surfaces are useful as subunits to make self-assembled electronic materials. We have created and continue to study two broad classes of these "contorted aromatics": discs and ribbons. The figure that accompanies this conspectus displays the three-dimensional surfaces of a selection of these "contorted aromatics". The disc-shaped contorted molecules have well-defined conformations that create concave pi-surfaces. When these disc-shaped molecules are substituted with hydrocarbon side chains, they self-assemble into columnar superstructures. Depending on the hydrocarbon substitution, they form either liquid crystalline films or macroscopic cables. In both cases, the columnar structures are photoconductive and form p-type, hole- transporting materials in field effect transistor devices. This columnar motif is robust, allowing us to form monolayers of these columns attached to the surface of dielectrics such as silicon oxide. We use ultrathin point contacts made from individual single-walled carbon nanotubes that are separated by a few nanometers to probe the electronic properties of short stacks of a few contorted discs. We find that these materials have high mobility and can sense electron-deficient aromatic molecules. The concave surfaces of these disc-shaped contorted molecules form ideal receptors for the molecular recognition and assembly with spherical molecules such as fullerenes. These interfaces resemble ball-and-socket joints, where the fullerene nests itself in the concave surface of the contorted disc. The tightness of the binding between the two partners can be

  6. Contorted polycyclic aromatics.

    PubMed

    Ball, Melissa; Zhong, Yu; Wu, Ying; Schenck, Christine; Ng, Fay; Steigerwald, Michael; Xiao, Shengxiong; Nuckolls, Colin

    2015-02-17

    CONSPECTUS: This Account describes a body of research in the design, synthesis, and assembly of molecular materials made from strained polycyclic aromatic molecules. The strain in the molecular subunits severely distorts the aromatic molecules away from planarity. We coined the term "contorted aromatics" to describe this class of molecules. Using these molecules, we demonstrate that the curved pi-surfaces are useful as subunits to make self-assembled electronic materials. We have created and continue to study two broad classes of these "contorted aromatics": discs and ribbons. The figure that accompanies this conspectus displays the three-dimensional surfaces of a selection of these "contorted aromatics". The disc-shaped contorted molecules have well-defined conformations that create concave pi-surfaces. When these disc-shaped molecules are substituted with hydrocarbon side chains, they self-assemble into columnar superstructures. Depending on the hydrocarbon substitution, they form either liquid crystalline films or macroscopic cables. In both cases, the columnar structures are photoconductive and form p-type, hole- transporting materials in field effect transistor devices. This columnar motif is robust, allowing us to form monolayers of these columns attached to the surface of dielectrics such as silicon oxide. We use ultrathin point contacts made from individual single-walled carbon nanotubes that are separated by a few nanometers to probe the electronic properties of short stacks of a few contorted discs. We find that these materials have high mobility and can sense electron-deficient aromatic molecules. The concave surfaces of these disc-shaped contorted molecules form ideal receptors for the molecular recognition and assembly with spherical molecules such as fullerenes. These interfaces resemble ball-and-socket joints, where the fullerene nests itself in the concave surface of the contorted disc. The tightness of the binding between the two partners can be

  7. Aromatic molecules as spintronic devices

    SciTech Connect

    Ojeda, J. H.; Orellana, P. A.; Laroze, D.

    2014-03-14

    In this paper, we study the spin-dependent electron transport through aromatic molecular chains attached to two semi-infinite leads. We model this system taking into account different geometrical configurations which are all characterized by a tight binding Hamiltonian. Based on the Green's function approach with a Landauer formalism, we find spin-dependent transport in short aromatic molecules by applying external magnetic fields. Additionally, we find that the magnetoresistance of aromatic molecules can reach different values, which are dependent on the variations in the applied magnetic field, length of the molecules, and the interactions between the contacts and the aromatic molecule.

  8. Atomic-phase interference devices based on ring-shaped Bose-Einstein condensates: Two-ring case

    NASA Astrophysics Data System (ADS)

    Anderson, B. P.; Dholakia, K.; Wright, E. M.

    2003-03-01

    We theoretically investigate the ground-state properties and quantum dynamics of a pair of adjacent ring-shaped Bose-Einstein condensates that are coupled via tunneling. This device, which is the analog of a symmetric superconducting quantum interference device, is the simplest version of what we term an atomic-phase interference device (APHID). The two-ring APHID is shown to be sensitive to rotation.

  9. The biodegradation vs. biotransformation of fluorosubstituted aromatics.

    PubMed

    Kiel, Martina; Engesser, Karl-Heinrich

    2015-09-01

    Fluoroaromatics are widely and--in recent years--increasingly used as agrochemicals, starting materials for chemical syntheses and especially pharmaceuticals. This originates from the special properties the carbon-fluorine bond is imposing on organic molecules. Hence, fluoro-substituted compounds more and more are considered to be important potential environmental contaminants. On the other hand, the microbial potentials for their transformation and mineralization have received less attention in comparison to other haloaromatics. Due to the high electronegativity of the fluorine atom, its small size, and the extraordinary strength of the C-F bond, enzymes and mechanisms known to facilitate the degradation of chloro- or bromoarenes are not necessarily equally active with fluoroaromatics. Here, we review the literature on the microbial degradation of ring and side-chain fluorinated aromatic compounds under aerobic and anaerobic conditions, with particular emphasis being placed on the mechanisms of defluorination reactions.

  10. Paleozoic oil in Uzbekistan and adjacent territories

    SciTech Connect

    Ryzhkov, O.A.; Khaimov, R.N.; Vitchinkin, M.M.; Zuev, Yu.N.

    1983-01-01

    Direct evidence of the presence of oil in the region is characteristically widespread within a broad stratigraphic span as well as territorially. This Paleozoic oil is of the naphthene aromatic type, in contrast with the Mesozoic and Tertiary oils of Uzbekistan, suggesting a justifiable hypothesis of an independent Paleozoic cycle of oleogenesis involving accumulation of hydrocarbons.

  11. Vascular ring (image)

    MedlinePlus

    Vascular ring is a term used to describe a number of abnormal formations of the aorta, the large artery ... the pulmonary artery. The abnormal vessel(s) forms a ring, which encircles and may press down on the ...

  12. New dust belts of Uranus: one ring, two ring, red ring, blue ring.

    PubMed

    de Pater, Imke; Hammel, Heidi B; Gibbard, Seran G; Showalter, Mark R

    2006-04-01

    We compared near-infrared observations of the recently discovered outer rings of Uranus with Hubble Space Telescope results. We find that the inner ring, R/2003 U 2, is red, whereas the outer ring, R/2003 U 1, is very blue. Blue is an unusual color for rings; Saturn's enigmatic E ring is the only other known example. By analogy to the E ring, R/2003 U 1 is probably produced by impacts into the embedded moon Mab, which apparently orbits at a location where nongravitational perturbations favor the survival and spreading of submicron-sized dust. R/2003 U 2 more closely resembles Saturn's G ring, which is red, a typical color for dusty rings. PMID:16601188

  13. New dust belts of Uranus: one ring, two ring, red ring, blue ring.

    PubMed

    de Pater, Imke; Hammel, Heidi B; Gibbard, Seran G; Showalter, Mark R

    2006-04-01

    We compared near-infrared observations of the recently discovered outer rings of Uranus with Hubble Space Telescope results. We find that the inner ring, R/2003 U 2, is red, whereas the outer ring, R/2003 U 1, is very blue. Blue is an unusual color for rings; Saturn's enigmatic E ring is the only other known example. By analogy to the E ring, R/2003 U 1 is probably produced by impacts into the embedded moon Mab, which apparently orbits at a location where nongravitational perturbations favor the survival and spreading of submicron-sized dust. R/2003 U 2 more closely resembles Saturn's G ring, which is red, a typical color for dusty rings.

  14. The AHA Moment: Assessment of the Redox Stability of Ionic Liquids Based on Aromatic Heterocyclic Anions (AHAs) for Nuclear Separations and Electric Energy Storage.

    PubMed

    Shkrob, Ilya A; Marin, Timothy W

    2015-11-19

    Because of their extended conjugated bond network, aromatic compounds generally have higher redox stability than less saturated compounds. We conjectured that ionic liquids (ILs) consisting of aromatic heterocyclic anions (AHAs) may exhibit improved radiation and electrochemical stability. Such properties are important in applications of these ILs as diluents in radionuclide separations and electrolytes in the electric energy storage devices. In this study, we systematically examine the redox chemistry of the AHAs. Three classes of these anions have been studied: (i) simple 5-atom ring AHAs, such as the pyrazolide and triazolides, (ii) AHAs containing an adjacent benzene ring, and (iii) AHAs containing electron-withdrawing groups that were introduced to reduce their basicity and interaction with metal ions. It is shown that fragmentation in the reduced and oxidized states of these AHAs does not generally occur, and the two main products, respectively, are the H atom adduct and the imidyl radical. The latter species occurs either as an N σ-radical or as an N π-radical, depending on the length of the N-N bond, and the state that is stabilized in the solid matrix is frequently different from that having the lowest energy in the gas phase. In some instances, the formation of the sandwich π-stack dimer radical anions has been observed. For trifluoromethylated anions, H adduct formation did not occur; instead, there was facile loss of fluoride from their fluorinated groups. The latter can be problematic in nuclear separations, but beneficial in batteries. Overall, our study suggests that AHA-based ILs are viable candidates for use as radiation-exposed diluents and electrolytes.

  15. Saturn's F-Ring

    NASA Technical Reports Server (NTRS)

    2000-01-01

    This narrow-angle camera image of Saturn's F Ring was taken through the Clear filter while at a distance of 6.9 million km from Saturn on 8 November 1980. The brightness variations of this tightly-constrained ring shown here indicate that the ring is less uniform in makeup than the larger rings. JPL managed the Voyager Project for NASA's Office of Space Science

  16. The Jumping Ring Experiment

    ERIC Educational Resources Information Center

    Baylie, M.; Ford, P. J.; Mathlin, G. P.; Palmer, C.

    2009-01-01

    The jumping ring experiment has become central to liquid nitrogen shows given as part of the outreach and open day activities carried out within the University of Bath. The basic principles of the experiment are described as well as the effect of changing the geometry of the rings and their metallurgical state. In general, aluminium rings are…

  17. Rings Around Uranus

    ERIC Educational Resources Information Center

    Maran, Stephen P.

    1977-01-01

    Events leading up to the discovery of the rings of Uranus are described. The methods used and the logic behind the methods are explained. Data collected to prove the existence of the rings are outlined and theories concerning the presence of planetary rings are presented. (AJ)

  18. On the time-course of adjacent and non-adjacent transposed-letter priming

    PubMed Central

    Ktori, Maria; Kingma, Brechtsje; Hannagan, Thomas; Holcomb, Phillip J.; Grainger, Jonathan

    2014-01-01

    We compared effects of adjacent (e.g., atricle-ARTICLE) and non-adjacent (e.g., actirle-ARTICLE) transposed-letter (TL) primes in an ERP study using the sandwich priming technique. TL priming was measured relative to the standard double-substitution condition. We found significantly stronger priming effects for adjacent transpositions than non-adjacent transpositions (with 2 intervening letters) in behavioral responses (lexical decision latencies), and the adjacent priming effects emerged earlier in the ERP signal, at around 200 ms post-target onset. Non-adjacent priming effects emerged about 50 ms later and were short-lived, being significant only in the 250-300 ms time-window. Adjacent transpositions on the other hand continued to produce priming in the N400 time-window (300-500 ms post-target onset). This qualitatively different pattern of priming effects for adjacent and non-adjacent transpositions is discussed in the light of different accounts of letter transposition effects, and the utility of drawing a distinction between positional flexibility and positional noise. PMID:25364497

  19. Electronic Structure Principles and Aromaticity

    ERIC Educational Resources Information Center

    Chattaraj, P. K.; Sarkar, U.; Roy, D. R.

    2007-01-01

    The relationship between aromaticity and stability in molecules on the basis of quantities such as hardness and electrophilicity is explored. The findings reveal that aromatic molecules are less energetic, harder, less polarizable, and less electrophilic as compared to antiaromatic molecules, as expected from the electronic structure principles.

  20. Anaerobic degradation of homocyclic aromatic compounds via arylcarboxyl-coenzyme A esters: organisms, strategies and key enzymes.

    PubMed

    Boll, Matthias; Löffler, Claudia; Morris, Brandon E L; Kung, Johannes W

    2014-03-01

    Next to carbohydrates, aromatic compounds are the second most abundant class of natural organic molecules in living organic matter but also make up a significant proportion of fossil carbon sources. Only microorganisms are capable of fully mineralizing aromatic compounds. While aerobic microbes use well-studied oxygenases for the activation and cleavage of aromatic rings, anaerobic bacteria follow completely different strategies to initiate catabolism. The key enzymes related to aromatic compound degradation in anaerobic bacteria are comprised of metal- and/or flavin-containing cofactors, of which many use unprecedented radical mechanisms for C-H bond cleavage or dearomatization. Over the past decade, the increasing number of completed genomes has helped to reveal a large variety of anaerobic degradation pathways in Proteobacteria, Gram-positive microbes and in one archaeon. This review aims to update our understanding of the occurrence of aromatic degradation capabilities in anaerobic microorganisms and serves to highlight characteristic enzymatic reactions involved in (i) the anoxic oxidation of alkyl side chains attached to aromatic rings, (ii) the carboxylation of aromatic rings and (iii) the reductive dearomatization of central arylcarboxyl-coenzyme A intermediates. Depending on the redox potential of the electron acceptors used and the metabolic efficiency of the cell, different strategies may be employed for identical overall reactions.

  1. Saturn's largest ring.

    PubMed

    Verbiscer, Anne J; Skrutskie, Michael F; Hamilton, Douglas P

    2009-10-22

    Most planetary rings in the Solar System lie within a few radii of their host body, because at these distances gravitational accelerations inhibit satellite formation. The best known exceptions are Jupiter's gossamer rings and Saturn's E ring, broad sheets of dust that extend outward until they fade from view at five to ten planetary radii. Source satellites continuously supply the dust, which is subsequently lost in collisions or by radial transport. Here we report that Saturn has an enormous ring associated with its outer moon Phoebe, extending from at least 128R(S) to 207R(S) (Saturn's radius R(S) is 60,330 km). The ring's vertical thickness of 40R(S) matches the range of vertical motion of Phoebe along its orbit. Dynamical considerations argue that these ring particles span the Saturnian system from the main rings to the edges of interplanetary space. The ring's normal optical depth of approximately 2 x 10(-8) is comparable to that of Jupiter's faintest gossamer ring, although its particle number density is several hundred times smaller. Repeated impacts on Phoebe, from both interplanetary and circumplanetary particle populations, probably keep the ring populated with material. Ring particles smaller than centimetres in size slowly migrate inward and many of them ultimately strike the dark leading face of Iapetus.

  2. SC correction coils and magnets for the HERA proton ring

    NASA Astrophysics Data System (ADS)

    Daum, C.; Geerinck, J.; Moeller, H.; Heller, R.; Schmueser, P.; Bracke, P.

    1986-05-01

    The design, manufacture and performance of correction elements of the HERA proton ring is described. The quadrupole and sextupole correction coils are mounted on the cold beam pipe inside the main dipole magnets. Superferric dipole magnets for orbit correction are located adjacent to the main quadrupole magnets in a common cryostat which also contains the beam monitor.

  3. Interspecies metabolism of heterocyclic aromatic amines

    SciTech Connect

    Turesky, R.J.; Welti, D.H.; Fay, L.B.

    1996-12-31

    2-Amino-3,8-dimethylimadazo[4,5-f]quinoxaline (MeIQx) and other heterocyclic aromatic amines (HAAs) are rodent carcinogens and potential human carcinogens formed in cooked meats and fish. Metabolic activation of MeIQx to a genotoxin occurs through cytochrome P450 mediated N-oxidation to form N-hydroxy-MeIQx which may undergo further activation by esterification to product species which bind to DNA. Pathways of MeIQx metabolism have been elucidated in rodents and nonhuman primates to develop strategies of human biomonitoring. In addition to N-oxidation, predominant routes of detoxification include direct conjugation at the exoyclic amino group with sulfate or glucuronic acid and cytochrome P450 mediated ring oxidation. Analysis of urine from five human subjects exposed to MeIQx reveals that phase II conjugation reactions to the exocyclic amine group are prominent detoxifaction pathways while heterocyclic ring oxidation is a minor pathway. Notably, the N{sup 2-} glucuronide conjugate of N-hydroxy-MeIQx is an important metabolite in human urine. Several other metabolites have been detected in human urine which have not been previously identified in rats or nonhuman primates. Similarities and differences exist in the metabolic processing of MeIQx by humans and other species and may be a critical determinant in assessing the human health risk of HAAs.

  4. Nature of the water/aromatic parallel alignment interactions.

    PubMed

    Mitoraj, Mariusz P; Janjić, Goran V; Medaković, Vesna B; Veljković, Dušan Ž; Michalak, Artur; Zarić, Snežana D; Milčić, Miloš K

    2015-01-30

    The water/aromatic parallel alignment interactions are interactions where the water molecule or one of its O-H bonds is parallel to the aromatic ring plane. The calculated energies of the interactions are significant, up to ΔE(CCSD)(T)(limit) = -2.45 kcal mol(-1) at large horizontal displacement, out of benzene ring and CH bond region. These interactions are stronger than CH···O water/benzene interactions, but weaker than OH···π interactions. To investigate the nature of water/aromatic parallel alignment interactions, energy decomposition methods, symmetry-adapted perturbation theory, and extended transition state-natural orbitals for chemical valence (NOCV), were used. The calculations have shown that, for the complexes at large horizontal displacements, major contribution to interaction energy comes from electrostatic interactions between monomers, and for the complexes at small horizontal displacements, dispersion interactions are dominant binding force. The NOCV-based analysis has shown that in structures with strong interaction energies charge transfer of the type π → σ*(O-H) between the monomers also exists.

  5. PERSONAL EXPOSURE TO FINE PARTICLE POLYCYCLIC AROMATIC HYDROCARBONS: OUTDOOR SOURCE TRACERS

    EPA Science Inventory


    The most carcinogenic and toxic polycyclic aromatic hydrocarbons (PAH) are the 4-5 ring PAH found preferentially adsorbed to the fine particles (<2.54u in urban ambient air and personal air. Personal exposure to the carcinogenic particle bound PAH is also highly correlated ...

  6. What are preferred water-aromatic interactions in proteins and crystal structures of small molecules?

    PubMed

    Janjić, Goran V; Malkov, Saša N; Zivković, Miodrag V; Zarić, Snežana D

    2014-11-21

    The distribution of water molecules around aromatic rings in the protein structures and crystal structures of small molecules shows quite a small number of the strongest OH-π interactions, a larger number of parallel interactions, and the largest number of the weakest CH-O interactions.

  7. Dust and Planetary Rings

    NASA Astrophysics Data System (ADS)

    Siddiqui, Muddassir

    ABSTRACT Space is not empty it has comic radiations (CMBR), dust etc. Cosmic dust is that type of dust which is composed of particles in space which vary from few molecules to 0.1micro metres in size. This type of dust is made up of heavier atoms born in the heart of stars and supernova. Mainly it contains dust grains and when these dust grains starts compacting then it turns to dense clouds, planetary ring dust and circumstellar dust. Dust grains are mainly silicate particles. Dust plays a major role in our solar system, for example in zodiacal light, Saturn's B ring spokes, planetary rings at Jovian planets and comets. Observations and measurements of cosmic dust in different regions of universe provide an important insight into the Universe's recycling processes. Astronomers consider dust in its most recycled state. Cosmic dust have radiative properties by which they can be detected. Cosmic dusts are classified as intergalactic dusts, interstellar dusts and planetary rings. A planetary ring is a ring of cosmic dust and other small particles orbiting around a planet in flat disc shape. All of the Jovian planets in our solar system have rings. But the most notable one is the Saturn's ring which is the brightest one. In March 2008 a report suggested that the Saturn's moon Rhea may have its own tenuous ring system. The ring swirling around Saturn consists of chunks of ice and dust. Most rings were thought to be unstable and to dissipate over course of tens or hundreds of millions of years but it now appears that Saturn's rings might be older than that. The dust particles in the ring collide with each other and are subjected to forces other than gravity of its own planet. Such collisions and extra forces tend to spread out the rings. Pluto is not known to have any ring system but some Astronomers believe that New Horizons probe might find a ring system when it visits in 2015.It is also predicted that Phobos, a moon of Mars will break up and form into a planetary ring

  8. MINARETS WILDERNESS AND ADJACENT AREAS, CALIFORNIA.

    USGS Publications Warehouse

    Huber, N. King; Thurber, Horace K.

    1984-01-01

    A mineral survey of the Minarets Wilderness and adjacent areas in the central Sierra Nevada, California was conducted. The results of the survey indicate that the study area has a substantiated resource potential for small deposits of copper, silver, zinc, lead, and iron, and a probable mineral-resource potential for molybdenum. No energy-resource potential was identified in the study.

  9. 46 CFR 148.445 - Adjacent spaces.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE OF BULK SOLID MATERIALS... transporting a material that Table 148.10 of this part associates with a reference to this section, the following requirements must be met: (a) Each space adjacent to a cargo hold must be ventilated by...

  10. 46 CFR 148.445 - Adjacent spaces.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE OF BULK SOLID MATERIALS... transporting a material that Table 148.10 of this part associates with a reference to this section, the following requirements must be met: (a) Each space adjacent to a cargo hold must be ventilated by...

  11. 46 CFR 148.445 - Adjacent spaces.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE OF BULK SOLID MATERIALS... transporting a material that Table 148.10 of this part associates with a reference to this section, the following requirements must be met: (a) Each space adjacent to a cargo hold must be ventilated by...

  12. 46 CFR 148.445 - Adjacent spaces.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE OF BULK SOLID MATERIALS... transporting a material that Table 148.10 of this part associates with a reference to this section, the following requirements must be met: (a) Each space adjacent to a cargo hold must be ventilated by...

  13. Pyrene degradation by a Mycobacterium sp. : Identification of ring oxidation and ring fission products

    SciTech Connect

    Heitkamp, M.A.; Freeman, J.P.; Miller, D.W.; Cerniglia, C.E. )

    1988-10-01

    The degradation of pyrene, a polycyclic aromatic hydrocarbon containing four aromatic rings, by pure cultures of a Mycobacterium sp. was studied. Over 60% of ({sup 14}C)pyrene was mineralized to CO{sub 2} after 96 h of incubation at 24{degree}C. High-pressure liquid chromatography analyses showed the presence of one major and at least six other metabolites that accounted for 95% of the total organic-extractable {sup 14}C-labeled residues. Analyses by UV, infrared, mass, and nuclear magnetic resonance spectrometry and gas chromatography identified both pyrene cis- and trans-4,5-dihydrodiols and pyrenol as initial microbial ring-oxidation products of pyrene. The major metabolite, 4-phenanthroic acid, and 4-hydroxyperinaphthenone and cinnamic and phthalic acids were identified as ring fission products. {sup 18}O{sub 2} studies showed that the formation of cis- and trans-4,5-dihydrodiols were catalyzed by dioxygenase and monooxygenase enzymes, respectively. This is the first report of the chemical pathway for the microbial catabolism of pyrene.

  14. Solid Phase Synthesis of Helically Folded Aromatic Oligoamides.

    PubMed

    Dawson, S J; Hu, X; Claerhout, S; Huc, I

    2016-01-01

    Aromatic amide foldamers constitute a growing class of oligomers that adopt remarkably stable folded conformations. The folded structures possess largely predictable shapes and open the way toward the design of synthetic mimics of proteins. Important examples of aromatic amide foldamers include oligomers of 7- or 8-amino-2-quinoline carboxylic acid that have been shown to exist predominantly as well-defined helices, including when they are combined with α-amino acids to which they may impose their folding behavior. To rapidly iterate their synthesis, solid phase synthesis (SPS) protocols have been developed and optimized for overcoming synthetic difficulties inherent to these backbones such as low nucleophilicity of amine groups on electron poor aromatic rings and a strong propensity of even short sequences to fold on the solid phase during synthesis. For example, acid chloride activation and the use of microwaves are required to bring coupling at aromatic amines to completion. Here, we report detailed SPS protocols for the rapid production of: (1) oligomers of 8-amino-2-quinolinecarboxylic acid; (2) oligomers containing 7-amino-8-fluoro-2-quinolinecarboxylic acid; and (3) heteromeric oligomers of 8-amino-2-quinolinecarboxylic acid and α-amino acids. SPS brings the advantage to quickly produce sequences having varied main chain or side chain components without having to purify multiple intermediates as in solution phase synthesis. With these protocols, an octamer could easily be synthesized and purified within one to two weeks from Fmoc protected amino acid monomer precursors. PMID:27586338

  15. Quantification of Aromaticity Based on Interaction Coordinates: A New Proposal.

    PubMed

    Pandey, Sarvesh Kumar; Manogaran, Dhivya; Manogaran, Sadasivam; Schaefer, Henry F

    2016-05-12

    Attempts to establish degrees of aromaticity in molecules are legion. In the present study, we begin with a fictitious fragment arising from only those atoms contributing to the aromatic ring and having a force field projected from the original system. For example, in benzene, we adopt a fictitious C6 fragment with a force field projected from the full benzene force field. When one bond or angle is stretched and kept fixed, followed by a partial optimization for all other internal coordinates, structures change from their respective equilibria. These changes are the responses of all other internal coordinates for constraining the bond or angle by unit displacements and relaxing the forces on all other internal coordinates. The "interaction coordinate" derived from the redundant internal coordinate compliance constants measures how a bond (its electron density) responds for constrained optimization when another bond or angle is stretched by a specified unit (its electron density is perturbed by a finite amount). The sum of interaction coordinates (responses) of all bonded neighbors for all internal coordinates of the fictitious fragment is a measure of the strength of the σ and π electron interactions leading to aromatic stability. This sum, based on interaction coordinates, appears to be successful as an aromaticity index for a range of chemical systems. Since the concept involves analyzing a fragment rather than the whole molecule, this idea is more general and is likely to lead to new insights.

  16. Synthesis of aromatic secondary diamines

    NASA Technical Reports Server (NTRS)

    Wolfe, J. F.; Greenwood, T. D.; Kahley, R. A.

    1979-01-01

    A series of N-methyl substituted aromatic polyamides derived from the secondary aromatic diamines, 4,4'-bis(methylamino)diphenylmethane, 3,3'-bis(methylamino) diphenylmethane, 4,4'-bis(methylamino)benzophenone or 3,3'-bis(methylamino)benzophenone and isophthaloyl dichloride, terphthaloyl dichloride or 3,3'diphenylmethane dicarboxylic acid dichloride was prepared by high temperature solution polymerization in s-tetrachloroethane. Compared to analogous unsubstituted and partially N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures, reduced crystallinity, improved thermal stability and good solubility in chlorinated solvents.

  17. Revisiting Aromaticity and Chemical Bonding of Fluorinated Benzene Derivatives

    PubMed Central

    Torres-Vega, Juan J; Vásquez-Espinal, Alejandro; Ruiz, Lina; Fernández-Herrera, María A; Alvarez-Thon, Luis; Merino, Gabriel; Tiznado, William

    2015-01-01

    The electron delocalization of benzene (C6H6) and hexafluorobenzene (C6F6) was analyzed in terms of the induced magnetic field, nucleus-independent chemical shift (NICS), and ring current strength (RCS). The computed out-of-plane component of the induced magnetic field at a distance (r) greater than or equal to 1.0 Å above the ring center correlates well (R2>0.99) with the RCS value. According to these criteria, fluorination has two effects on the C6 skeleton; concomitantly, the resonant effects diminish the π electron delocalization and the inductive effects decrease the charge density at the ring center and therefore reduce the magnitude of the paratropic current generated in this region. The equilibrium between both effects decreases aromaticity in the fluorinated benzene derivatives. These results can be extrapolated to determine the aromaticity of any derivative within the series of fluorinated benzene derivatives (C6H(6−n)Fn, where n=1–5). PMID:26246992

  18. On multiple Einstein rings

    NASA Astrophysics Data System (ADS)

    Werner, M. C.; An, J.; Evans, N. W.

    2008-12-01

    A number of recent surveys for gravitational lenses have found examples of double Einstein rings. Here, we analytically investigate the occurrence of multiple Einstein rings. We prove, under very general assumptions, that at the most one Einstein ring can arise from a mass distribution in a single plane lensing a single background source. Two or more Einstein rings can therefore only occur in multiplane lensing. Surprisingly, we show that it is possible for a single source to produce more than one Einstein ring. If two point masses, or two isothermal spheres, in different planes are aligned with observer and source on the optical axis, we show that there are up to three Einstein rings. We also discuss the image morphologies for these two models if axisymmetry is broken, and give the first instances of magnification invariants in the case of two-lens planes.

  19. The Phylogenetic Signature Underlying ATP Synthase c-Ring Compliance

    SciTech Connect

    Pandini, Alessandro; Kleinjung, Jens; Taylor, Willie R.; Junge, Wolfgang; Khan, Shahid

    2015-09-01

    The proton-driven ATP synthase (FOF1) is comprised of two rotary, stepping motors (FO and F1) coupled by an elastic power transmission. The elastic compliance resides in the rotor module that includes the membrane-embedded FO c-ring. Proton transport by FO is firmly coupled to the rotation of the c-ring relative to other FO subunits (ab2). It drives ATP synthesis. We used a computational method to investigate the contribution of the c-ring to the total elastic compliance. We performed principal component analysis of conformational ensembles built using distance constraints from the bovine mitochondrial c-ring x-ray structure. Angular rotary twist, the dominant ring motion, was estimated to show that the c-ring accounted in part for the measured compliance. Ring rotation was entrained to rotation of the external helix within each hairpin-shaped c-subunit in the ring. Ensembles of monomer and dimers extracted from complete c-rings showed that the coupling between collective ring and the individual subunit motions was independent of the size of the c-ring, which varies between organisms. Molecular determinants were identified by covariance analysis of residue coevolution and structural-alphabet-based local dynamics correlations. The residue coevolution gave a readout of subunit architecture. The dynamic couplings revealed that the hinge for both ring and subunit helix rotations was constructed from the proton-binding site and the adjacent glycine motif (IB-GGGG) in the midmembrane plane. IB-GGGG motifs were linked by long-range couplings across the ring, while intrasubunit couplings connected the motif to the conserved cytoplasmic loop and adjacent segments. The correlation with principal collective motions shows that the couplings underlie both ring rotary and bending motions. Noncontact couplings between IB-GGGG motifs matched the coevolution signal as well as contact couplings

  20. Radioactive gold ring dermatitis

    SciTech Connect

    Miller, R.A.; Aldrich, J.E. )

    1990-08-01

    A superficial squamous cell carcinoma developed in a woman who wore a radioactive gold ring for more than 30 years. Only part of the ring was radioactive. Radiation dose measurements indicated that the dose to basal skin layer was 2.4 Gy (240 rad) per week. If it is assumed that the woman continually wore her wedding ring for 37 years since purchase, she would have received a maximum dose of approximately 4600 Gy.

  1. Phylogenetic comparison of two polycyclic aromatic hydrogen-degrading mycobacteria

    SciTech Connect

    Govindaswami, M.; Loper, J.C.; Feldhake, D.J.

    1995-09-01

    Two mycobacterial strains previously isolated from fossil-fuel-contaminated environments and shown to degrade four- and/or five-ring polycyclic aromatic hydrocarbons were further characterized. The two strains, PYR-I and RJGII-135, had similar growth characteristics, colony morphologies, and scotochromogenic pigmentations. DNA amplification fringerprints obtained with total genomic DNA indicated some strain similarities but with several distinctly different bands. Moreover, phylogenetic analysis based upon essentially full-length 16S rRNA gene sequences separates the two strains as distinct species within the fast-growing group of mycobacteria. Although both strains are thermosensitive, strain PYR-I has the bulged U between positions 184 and 193 characteristic of thermotolerant mycobacteria. Both strains are of potential use for reintroduction into and bioremediation of polycyclic aromatic hydrocarbon-contaminated soils. 26 refs., 4 figs., 1 tab.

  2. Temperatures of Saturn's rings.

    NASA Technical Reports Server (NTRS)

    Murphy, R. E.

    1973-01-01

    The 20-micron brightness temperatures of the rings were determined using the 224-cm telescope of the Mauna Kea Observatory, and the standard University of Hawaii radiometer with a 17- to 25-micron filter. The observations were made on the nights of Aug. 20 and 21, and Sept. 26 and 27, 1972. The brightness temperatures of the A, B, and C rings are, respectively, 89 plus or minus 3 K, 94 plus or minus 2 K, and 89 plus or minus 4 K. A possible explanation of the relatively high temperature of the C ring is that Saturn has radiation belts and the inner ring is heated by particle bombardment.

  3. [Determination of aromatics in light petroleum products by comprehensive two-dimensional gas chromatography].

    PubMed

    Li, Yanyan

    2006-07-01

    In recent years, comprehensive two-dimensional gas chromatography (GC x GC) have been used widely, and the applications of this technique to many fields have already been reported. In the standard method of oil analysis, the concentrations of aromatics and naphthalene hydrocarbons in light petroleum products must be detected by more than two methods. Mono-aromatics, di-aromatics etc. in light petroleum products were detected only by comprehensive two-dimensional gas chromatography. After the proper selection of column system and optimization of chromatographic conditions, the method can achieve the group separations of paraffins, olefins, naphthenes, aromatics with 1 to 2 rings and some target components in light petroleum products with good reproducibility and good precision. The recoveries of standard compounds were 89.5% - 106.1%, and the relative standard deviations of repeatedly detecting the components were all lower than 5.8%. It took only 30 min to finish a determination.

  4. Infrared Signature of the Cation-π Interaction between Calcite and Aromatic Hydrocarbons.

    PubMed

    Wang, Haitao; Grant, Daniel J; Burns, Peter C; Na, Chongzheng

    2015-06-01

    The cation-π interaction is proposed as an important mechanism for the adsorption of aromatic hydrocarbons having non-zero quadrupole moments by mineral surfaces. Direct evidence supporting such a mechanism is, however, limited. Using the model mineral calcite, we probe the cation-π interaction with adsorbed benzene, toluene, and ethylbenzene (BTE) molecules using attenuated total reflectance Fourier transform infrared spectroscopy. We show that the presence of calcite increases the energy required to excite the synchronized bending of aromatic C-H bonds of BTE molecules. The unique conformation of this vibrational mode indicates that the planar aromatic rings of BTE molecules are constrained in a tilted face-down position by the cation-π interaction, as further confirmed by density functional theory calculations. Our results suggest that the shift of the excitation energy of the aromatic C-H bending may be used as an infrared signature for the cation-π interaction occurring on mineral surfaces.

  5. Polyimidazoles Via Aromatic Nucleophilic Displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul M.

    1990-01-01

    Experiments show variety of polyimidazoles prepared by aromatic nucleophilic displacement, from reactions of bisphenol imidazoles with activated difluoro compounds. Polyimidazoles have good mechanical properties making them suitable for use as films, moldings, and adhesives.

  6. Polybenzimidazoles via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1995-01-01

    Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl) benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl) benzimidazoles are synthesizedby reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

  7. Three-dimensional aromatic networks.

    PubMed

    Toyota, Shinji; Iwanaga, Tetsuo

    2014-01-01

    Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

  8. Polybenzimidazoles Via Aromatic Nucleophilic Displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergerrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1997-01-01

    Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

  9. On the fused-to-single ring transition in 10π structures. Insights from naphthalene to [10]annulene series

    NASA Astrophysics Data System (ADS)

    Muñoz-Castro, Alvaro

    2016-04-01

    The fused-to-single-ring transition is studied through a 10πe series given the series from naphthalene to [10]annulene. Our results suggest that change occurs at certain structure instead of a gradual transition. In the transition point, given by bicyclo[7.1.0]decapentaene, similar magnetic behavior in comparison to the single ring counterpart is found. The systems can be considered to behave as a whole single aromatic structure where the fused counterparts can be treated as a modification in the aromatic path of a single ring aromatic motif, which can viewed as a useful approach to evaluate the formation of defects or larger-rings in graphene motifs.

  10. Hydrophilic properties of aromatics.

    PubMed

    Bonadeo, I; Lodi, V; Ghidini, D

    1980-10-01

    Synopsis The study of the behaviour of perfume ingredients in emulsions involves several technological problems. Recently, the scientific and practical validity of the parameter known as 'hydrophilic value' K(d) (according to Bonadeo) was recognised; it relates to the behaviour of fatty materials in emulsions. The purpose of this research was to verify the reliability of the above parameter as applied to perfume ingredients. From the experimental results it is possible to establish a mathematical relationship between K(d) and the 'required emulsification value' (HLB(r)) of the aromatics used in perfuming cosmetics and toiletries. From the K(d) value it is possible to calculate the critical limit of the water phase (CLWP) concerning the single ingredients of a perfume compound. These parameters are particularly important in predicting the optimal behaviour of perfumes in the chemical-physical balance of emulsions, with which are connected the principal parameters of the chemical and olfactive stability. Thus, in practice, it has been demonstrated that the perfumed substances behave as, and can be considered as, other fatty bodies forming the fatty phase of emulsions.

  11. Bioassay of polycyclic aromatic hydrocarbons

    SciTech Connect

    Van Kirk, E.A.

    1980-08-01

    A positive relationship was found between the photodynamic activity of 24 polycyclic aromatic hydrocarbons versus published results on the mutagenicity, carcinogenicity, and initiation of unscheduled DNA synthesis. Metabolic activation of benzo(a)pyrene resulted in detection of increased mutagenesis in Paramecium tetraurelia as found also in the Ames Salmonella assay. The utility of P. tetraurelia as a biological detector of hazardous polycyclic aromatic hydrocarbons is discussed.

  12. Multiple Functions of Aromatic-Carbohydrate Interactions in a Processive Cellulase Examined with Molecular Simulation*

    PubMed Central

    Payne, Christina M.; Bomble, Yannick J.; Taylor, Courtney B.; McCabe, Clare; Himmel, Michael E.; Crowley, Michael F.; Beckham, Gregg T.

    2011-01-01

    Proteins employ aromatic residues for carbohydrate binding in a wide range of biological functions. Glycoside hydrolases, which are ubiquitous in nature, typically exhibit tunnels, clefts, or pockets lined with aromatic residues for processing carbohydrates. Mutation of these aromatic residues often results in significant activity differences on insoluble and soluble substrates. However, the thermodynamic basis and molecular level role of these aromatic residues remain unknown. Here, we calculate the relative ligand binding free energy by mutating tryptophans in the Trichoderma reesei family 6 cellulase (Cel6A) to alanine. Removal of aromatic residues near the catalytic site has little impact on the ligand binding free energy, suggesting that aromatic residues immediately upstream of the active site are not directly involved in binding, but play a role in the glucopyranose ring distortion necessary for catalysis. Removal of aromatic residues at the entrance and exit of the Cel6A tunnel, however, dramatically impacts the binding affinity, suggesting that these residues play a role in chain acquisition and product stabilization, respectively. The roles suggested from differences in binding affinity are confirmed by molecular dynamics and normal mode analysis. Surprisingly, our results illustrate that aromatic-carbohydrate interactions vary dramatically depending on the position in the enzyme tunnel. As aromatic-carbohydrate interactions are present in all carbohydrate-active enzymes, these results have implications for understanding protein structure-function relationships in carbohydrate metabolism and recognition, carbon turnover in nature, and protein engineering strategies for biomass utilization. Generally, these results suggest that nature employs aromatic-carbohydrate interactions with a wide range of binding affinities for diverse functions. PMID:21965672

  13. Aromatic-aromatic interaction of amitriptyline: implication of overdosed drug detoxification.

    PubMed

    Lee, Dong-Won; Flint, Jason; Morey, Timothy; Dennis, Donn; Partch, Richard; Baney, Ronald

    2005-02-01

    The objectives of this work are to explore the pi-pi complexation of amitriptyline with pi electron-deficient aromatic rings and demonstrate the feasibility of pi-pi complexation for overdosed drug detoxification. Water-soluble oligochitosan was chemically modified with dinitrobenzenesulfonyl groups to induce selective binding toward amitriptyline through pi-pi complexation. NMR studies showed that benzenesulfonyl and dinitrobenzenesulfonyl protons were upfield shifted by the addition of amitriptyline, indicating the formation of pi-pi complexes. The pi-pi complexation of amitriptyline is driven primarily by a desolvation driving force, whereas the magnitude of interaction is dictated by the complementrary electrostatic interaction. Isolated rat heart tests revealed that dinitrobenzenesulfonyl oligochitosan prevented the amitriptyline-induced cardiotoxicity and was itself not cardiotoxic. PMID:15614810

  14. Adjacent Segment Pathology after Lumbar Spinal Fusion.

    PubMed

    Lee, Jae Chul; Choi, Sung-Woo

    2015-10-01

    One of the major clinical issues encountered after lumbar spinal fusion is the development of adjacent segment pathology (ASP) caused by increased mechanical stress at adjacent segments, and resulting in various radiographic changes and clinical symptoms. This condition may require surgical intervention. The incidence of ASP varies with both the definition and methodology adopted in individual studies; various risk factors for this condition have been identified, although a significant controversy still exists regarding their significance. Motion-preserving devices have been developed, and some studies have shown their efficacy of preventing ASP. Surgeons should be aware of the risk factors of ASP when planning a surgery, and accordingly counsel their patients preoperatively. PMID:26435804

  15. Adjacent Segment Pathology after Lumbar Spinal Fusion

    PubMed Central

    Lee, Jae Chul

    2015-01-01

    One of the major clinical issues encountered after lumbar spinal fusion is the development of adjacent segment pathology (ASP) caused by increased mechanical stress at adjacent segments, and resulting in various radiographic changes and clinical symptoms. This condition may require surgical intervention. The incidence of ASP varies with both the definition and methodology adopted in individual studies; various risk factors for this condition have been identified, although a significant controversy still exists regarding their significance. Motion-preserving devices have been developed, and some studies have shown their efficacy of preventing ASP. Surgeons should be aware of the risk factors of ASP when planning a surgery, and accordingly counsel their patients preoperatively. PMID:26435804

  16. The Dependence of Carbohydrate-Aromatic Interaction Strengths on the Structure of the Carbohydrate.

    PubMed

    Hsu, Che-Hsiung; Park, Sangho; Mortenson, David E; Foley, B Lachele; Wang, Xiaocong; Woods, Robert J; Case, David A; Powers, Evan T; Wong, Chi-Huey; Dyson, H Jane; Kelly, Jeffery W

    2016-06-22

    Interactions between proteins and carbohydrates are ubiquitous in biology. Therefore, understanding the factors that determine their affinity and selectivity are correspondingly important. Herein, we have determined the relative strengths of intramolecular interactions between a series of monosaccharides and an aromatic ring close to the glycosylation site in an N-glycoprotein host. We employed the enhanced aromatic sequon, a structural motif found in the reverse turns of some N-glycoproteins, to facilitate face-to-face monosaccharide-aromatic interactions. A protein host was used because the dependence of the folding energetics on the identity of the monosaccharide can be accurately measured to assess the strength of the carbohydrate-aromatic interaction. Our data demonstrate that the carbohydrate-aromatic interaction strengths are moderately affected by changes in the stereochemistry and identity of the substituents on the pyranose rings of the sugars. Galactose seems to make the weakest and allose the strongest sugar-aromatic interactions, with glucose, N-acetylglucosamine (GlcNAc) and mannose in between. The NMR solution structures of several of the monosaccharide-containing N-glycoproteins were solved to further understand the origins of the similarities and differences between the monosaccharide-aromatic interaction energies. Peracetylation of the monosaccharides substantially increases the strength of the sugar-aromatic interaction in the context of our N-glycoprotein host. Finally, we discuss our results in light of recent literature regarding the contribution of electrostatics to CH-π interactions and speculate on what our observations imply about the absolute conservation of GlcNAc as the monosaccharide through which N-linked glycans are attached to glycoproteins in eukaryotes. PMID:27249581

  17. Polybenzoxazole via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1993-01-01

    Polybenzoxazoles (PBO) are heterocyclic macromolecules which were first synthesized in a two-step process by the initial formation of aromatic diacid chlorides with bis(o-aminophenol)s through solution condensation of aromatic diacid chlorides with bis(o-aminophenol)s followed by thermal cyclodehydration. Since then several methods were utilized in their synthesis. The most common synthetic method for PBO involves a polycondensation of bis(o-aminophenol)s with aromatic diacid diphenyl esters. Another preparative route involves the solution polycondensation of the hydrochloride salts of bis(o-amino phenol)s with aromatic diacids in polyphosphoric acid. Another synthetic method involves the initial formation of poly(o-hydroxy amide)s from silylated bis(o-aminophenol)s with aromatic diacid chlorides followed by thermal cyclodehydration to PBO. A recent preparative route involves the reaction of aromatic bisphenols with bis(fluorophenyl) benzoxazoles by the displacement reaction to form PBO. The novelty of the present invention is that high molecular weight PBO of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

  18. Ring Around a Galaxy

    NASA Technical Reports Server (NTRS)

    1999-01-01

    Space Telescope Science Institute astronomers are giving the public chances to decide where to aim NASA's Hubble Space Telescope. Guided by 8,000 Internet voters, Hubble has already been used to take a close-up, multi-color picture of the most popular object from a list of candidates, the extraordinary 'polar-ring' galaxy NGC 4650A. Located about 130 million light-years away, NGC 4650A is one of only 100 known polar-ring galaxies. Their unusual disk-ring structure is not yet understood fully. One possibility is that polar rings are the remnants of colossal collisions between two galaxies sometime in the distant past, probably at least 1 billion years ago. What is left of one galaxy has become the rotating inner disk of old red stars in the center. Meanwhile, another smaller galaxy which ventured too close was probably severely damaged or destroyed. The bright bluish clumps, which are especially prominent in the outer parts of the ring, are regions containing luminous young stars, examples of stellar rebirth from the remnants of an ancient galactic disaster. The polar ring appears to be highly distorted. No regular spiral pattern stands out in the main part of the ring, and the presence of young stars below the main ring on one side and above on the other shows that the ring is warped and does not lie in one plane. Determining the typical ages of the stars in the polar ring is an initial goal of our Polar Ring Science Team that can provide a clue to the evolution of this unusual galaxy. The HST exposures were acquired by the Hubble Heritage Team, consisting of Keith Noll, Howard Bond, Carol Christian, Jayanne English, Lisa Frattare, Forrest Hamilton, Anne Kinney and Zolt Levay, and guest collaborators Jay Gallagher (University of Wisconsin-Madison), Lynn Matthews (National Radio Astronomy Observatory-Charlottesville), and Linda Sparke (University of Wisconsin-Madison).

  19. Adjacent Segment Pathology after Anterior Cervical Fusion.

    PubMed

    Chung, Jae Yoon; Park, Jong-Beom; Seo, Hyoung-Yeon; Kim, Sung Kyu

    2016-06-01

    Anterior cervical fusion has become a standard of care for numerous pathologic conditions of the cervical spine. However, subsequent development of clinically significant disc disease at levels adjacent to fused discs is a serious long-term complication of this procedure. As more patients live longer after surgery, it is foreseeable that adjacent segment pathology (ASP) will develop in increasing numbers of patients. Also, ASP has been studied more intensively with the recent popularity of motion preservation technologies like total disc arthroplasty. The true nature and scope of ASP remains poorly understood. The etiology of ASP is most likely multifactorial. Various factors including altered biomechanical stresses, surgical disruption of soft tissue and the natural history of cervical disc disease contribute to the development of ASP. General factors associated with disc degeneration including gender, age, smoking and sports may play a role in the development of ASP. Postoperative sagittal alignment and type of surgery are also considered potential causes of ASP. Therefore, a spine surgeon must be particularly careful to avoid unnecessary disruption of the musculoligamentous structures, reduced risk of direct injury to the disc during dissection and maintain a safe margin between the plate edge and adjacent vertebrae during anterior cervical fusion.

  20. Adjacent Segment Pathology after Anterior Cervical Fusion

    PubMed Central

    Chung, Jae Yoon; Park, Jong-Beom; Seo, Hyoung-Yeon

    2016-01-01

    Anterior cervical fusion has become a standard of care for numerous pathologic conditions of the cervical spine. However, subsequent development of clinically significant disc disease at levels adjacent to fused discs is a serious long-term complication of this procedure. As more patients live longer after surgery, it is foreseeable that adjacent segment pathology (ASP) will develop in increasing numbers of patients. Also, ASP has been studied more intensively with the recent popularity of motion preservation technologies like total disc arthroplasty. The true nature and scope of ASP remains poorly understood. The etiology of ASP is most likely multifactorial. Various factors including altered biomechanical stresses, surgical disruption of soft tissue and the natural history of cervical disc disease contribute to the development of ASP. General factors associated with disc degeneration including gender, age, smoking and sports may play a role in the development of ASP. Postoperative sagittal alignment and type of surgery are also considered potential causes of ASP. Therefore, a spine surgeon must be particularly careful to avoid unnecessary disruption of the musculoligamentous structures, reduced risk of direct injury to the disc during dissection and maintain a safe margin between the plate edge and adjacent vertebrae during anterior cervical fusion. PMID:27340541

  1. Iron piston having selectively hardened ring groove

    SciTech Connect

    Brann, D.E.; Lindsay, J.E.

    1987-02-17

    This patent describes a long-lasting cast iron piston body for an internal combustion engine, the piston body comprising a generally cylindrical sidewall and having an annular groove in the wall encircling the body for receiving a piston ring. The groove is defined by opposed faces that intersect the wall, the piston body being composed predominantly of gray iron characterized by an as-cast pearlitic microstructure, the groove face comprising an integrally cast, selectively hardened iron band adjacent the piston sidewall and encircling the piston body. The band is characterized by a martensitic microstructure substantially harder than the pearlitic microstructure and is effective to reduce wear resulting from a piston ring seated within the groove.

  2. The Phylogenetic Signature Underlying ATP Synthase c-Ring Compliance

    DOE PAGES

    Pandini, Alessandro; Kleinjung, Jens; Taylor, Willie R.; Junge, Wolfgang; Khan, Shahid

    2015-09-01

    The proton-driven ATP synthase (FOF1) is comprised of two rotary, stepping motors (FO and F1) coupled by an elastic power transmission. The elastic compliance resides in the rotor module that includes the membrane-embedded FO c-ring. Proton transport by FO is firmly coupled to the rotation of the c-ring relative to other FO subunits (ab2). It drives ATP synthesis. We used a computational method to investigate the contribution of the c-ring to the total elastic compliance. We performed principal component analysis of conformational ensembles built using distance constraints from the bovine mitochondrial c-ring x-ray structure. Angular rotary twist, the dominant ringmore » motion, was estimated to show that the c-ring accounted in part for the measured compliance. Ring rotation was entrained to rotation of the external helix within each hairpin-shaped c-subunit in the ring. Ensembles of monomer and dimers extracted from complete c-rings showed that the coupling between collective ring and the individual subunit motions was independent of the size of the c-ring, which varies between organisms. Molecular determinants were identified by covariance analysis of residue coevolution and structural-alphabet-based local dynamics correlations. The residue coevolution gave a readout of subunit architecture. The dynamic couplings revealed that the hinge for both ring and subunit helix rotations was constructed from the proton-binding site and the adjacent glycine motif (IB-GGGG) in the midmembrane plane. IB-GGGG motifs were linked by long-range couplings across the ring, while intrasubunit couplings connected the motif to the conserved cytoplasmic loop and adjacent segments. The correlation with principal collective motions shows that the couplings underlie both ring rotary and bending motions. Noncontact couplings between IB-GGGG motifs matched the coevolution signal as well as contact couplings. The residue coevolution reflects the physiological importance of the dynamics

  3. [GC x GC measurements of atmospheric aromatic compounds near a busy high-speed road in Beijing].

    PubMed

    Mao, Ting; Xu, Xiao-bin; Wang, Ying

    2009-10-15

    Comprehensive two-dimensional gas chromatography (GC x GC) is a powerful instrumental tool often used to analyze complex mixtures. An optimized GC x GC method had been applied to the quantitative analysis of aromatic compounds in air samples collected near a busy high-speed road in Beijing during the 2007 National Holidays. In the resulting GC x GC chromatograms, aromatic species were resolved from other compound classes and were grouped in a manner that facilitated identification and integration, showing more information of aromatic compounds compared to traditional one-dimensional GC. Totally more than 30 aromatic species were identified and quantified. The average concentrations of monocyclic aromatic compounds ranged from 0.75 x 10(-9) to 24.64 x 10(-9) C, with toluene having the highest concentration, followed by m, p-xylene and ethylbenzene. The average concentrations of the measured polycyclic aromatic compounds ranged from 0.03 x 10(-9) to 2.28 x 10(-9) C, with naphthalene having the highest concentration, followed by 2-methyl-naphthalene and 4-methyl-1, 1'-biphenyl. The four-ring and higher polycyclic aromatic compounds were not detectable in the gaseous samples. The levels of aromatic compounds were significantly influenced by meteorological parameters. Benzene and toluene were poorly correlated with higher aromatic compounds though the latter compounds were highly correlated among each other, suggesting that both were significantly influenced by sources other than vehicle exhaust and gasoline evaporation.

  4. Smoke Ring Physics

    ERIC Educational Resources Information Center

    Huggins, Elisha

    2011-01-01

    The behavior of smoke rings, tornados, and quantized vortex rings in superfluid helium has many features in common. These features can be described by the same mathematics we use when introducing Ampere's law in an introductory physics course. We discuss these common features. (Contains 7 figures.)

  5. Lower esophageal ring (Schatzki)

    MedlinePlus

    ... narrowed area to stretch the ring. Sometimes, a balloon is placed in the area and inflated, to help widen the ring. Outlook (Prognosis) Swallowing problems may return. You may need repeat treatment. When to Contact a Medical Professional Call your health care provider if you ...

  6. EBT ring physics

    SciTech Connect

    Uckan, N.A.

    1980-04-01

    This workshop attempted to evaluate the status of the current experimental and theoretical understanding of hot electron ring properties. The dominant physical processes that influence ring formation, scaling, and their optimal behavior are also studied. Separate abstracts were prepared for each of the 27 included papers. (MOW)

  7. Contactless Magnetic Slip Ring

    NASA Technical Reports Server (NTRS)

    Kumagai, Hiroyuki (Inventor); Deardon, Joe D. (Inventor)

    1997-01-01

    A contactless magnetic slip ring is disclosed having a primary coil and a secondary coil. The primary and secondary coils are preferably magnetically coupled together, in a highly reliable efficient manner, by a magnetic layered core. One of the secondary and primary coils is rotatable and the contactless magnetic slip ring provides a substantially constant output.

  8. Smoke Ring Physics

    NASA Astrophysics Data System (ADS)

    Huggins, Elisha

    2011-11-01

    The behavior of smoke rings, tornados, and quantized vortex rings in superfluid helium has many features in common. These features can be described by the same mathematics we use when introducing Ampère's law in an introductory physics course. We discuss these common features.

  9. Jupiter's Gossamer Rings Explained.

    NASA Astrophysics Data System (ADS)

    Hamilton, D. P.

    2003-05-01

    Over the past several years, Galileo measurements and groundbased imaging have drastically improved our knowledge of Jupiter's faint ring system. We now recognize that the ring consists of four components: a main ring 7000km wide, whose inner edge blossoms into a vertically-extended halo, and a pair of more tenuous Gossamer rings, one associated with each of the small moons Thebe and Amalthea. When viewed edge on, the Gossamer rings appear as diaphanous disks whose thicknesses agree with the vertical excursions of the inclined satellites from the equatorial plane. In addition, the brightness of each Gossamer ring drops off sharply outside the satellite orbits. These correlations allowed Burns etal (1999, Science, 284, 1146) to argue convincingly that the satellites act as sources of the dusty ring material. In addition, since most material is seen inside the orbits of the source satellites, an inwardly-acting dissipative force such as Poynting-Robertson drag is implicated. The most serious problem with this simple and elegant picture is that it is unable to explain the existence of a faint swath of material that extends half a jovian radius outward from Thebe. A key constraint is that this material has the same thickness as the rest of the Thebe ring. In this work, we identify the mechanism responsible for the outward extension: it is a shadow resonance, first investigated by Horanyi and Burns (1991, JGR, 96, 19283). When a dust grain enters Jupiter's shadow, photoelectric processes shut down and the grain's electric charge becomes more negative. The electromagnetic forces associated with the varying charge cause periodic oscillations in the orbital eccentricity and semimajor axis as the orbital pericenter precesses. This results in a ring which spreads both inward and outward of its source satellite while preserving its vertical thickness - just as is observed for the Thebe ring. Predictions of the model are: i) gaps of micron-sized material interior to Thebe and

  10. Jupiter's Rings: Sharpest View

    NASA Technical Reports Server (NTRS)

    2007-01-01

    The New Horizons spacecraft took the best images of Jupiter's charcoal-black rings as it approached and then looked back at Jupiter. The top image was taken on approach, showing three well-defined lanes of gravel- to boulder-sized material composing the bulk of the rings, as well as lesser amounts of material between the rings. New Horizons snapped the lower image after it had passed Jupiter on February 28, 2007, and looked back in a direction toward the sun. The image is sharply focused, though it appears fuzzy due to the cloud of dust-sized particles enveloping the rings. The dust is brightly illuminated in the same way the dust on a dirty windshield lights up when you drive toward a 'low' sun. The narrow rings are confined in their orbits by small 'shepherding' moons.

  11. Polycyclic Aromatic Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Salama, Farid

    2010-01-01

    Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of the carbonaceous materials. PAHs are the best-known candidates to account for the IR emission bands. They are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge is to reproduce in the laboratory the physical conditions that exist in the emission and absorption interstellar zones. The harsh physical conditions of the ISM -low temperature, collisionless, strong UV radiation fields- are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions and radicals are formed from the neutral precursors in an isolated environment at low temperature and probed with high-sensitivity cavity ringdown spectroscopy in the NUV-NIR range. Carbon nanoparticles are also formed during the short residence time of the precursors in the plasma and are characterized with time-offlight mass spectrometry. These experiments provide unique information on the spectra of large carbonaceous molecules and ions in the gas phase that can now be directly compared to interstellar and circumstellar observations (IR emission bands, DIBs, extinction curve). These findings also hold great potential for understanding the formation process of interstellar carbonaceous grains. We will review recent progress in the experimental and theoretical studies of PAHs, compare the laboratory data with astronomical observations and discuss the global implications.

  12. STEEL TRUSS TENSION RING SUPPORTING DOME ROOF. TENSION RING COVERED ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    STEEL TRUSS TENSION RING SUPPORTING DOME ROOF. TENSION RING COVERED BY ARCHITECTURAL FINISH. TENSION RING ROLLER SUPPORT AT COLUMN OBSCURED BY COLUMN COVERINGS. - Houston Astrodome, 8400 Kirby Drive, Houston, Harris County, TX

  13. Gas and Particulate Sampling of Airborne Polycyclic Aromatic Compounds

    SciTech Connect

    Lane, D.A.; Gundel, L.A.

    1995-10-01

    The denuder surfaces of the gas and particle (GAP) sampler (developed at the Atmospheric Environment Service of Environment Canada) have been modified by coating with XAD-4 resin, using techniques developed at Lawrence Berkeley National Laboratory (LBNL) for the lower capacity integrated organic vapor/particle sampler (IOVPS). The resulting high capacity integrated organic gas and particle sampler (IOGAPS) has been operated in ambient air at 16.7 L min{sup -1} for a 24-hour period in Berkeley, California, USA. Simultaneous measurements were made at the same collection rate with a conventional sampler that used a filter followed by two sorbent beds. Gas and particle partition measurements were determined for 13 polycyclic aromatic hydrocarbons (PAH) ranging from 2-ring to 6-ring species. The IOGAPS indicated a higher particle fraction of these compounds than did the conventional sampler, suggesting that the conventional sampler suffered from 'blow-off' losses from the particles collected on the filter.

  14. The Enceladus Ring

    NASA Technical Reports Server (NTRS)

    2006-01-01

    [figure removed for brevity, see original site] The Enceladus Ring (labeled)

    This excellent view of the faint E ring -- a ring feature now known to be created by Enceladus -- also shows two of Saturn's small moons that orbit within the ring, among a field of stars in the background.

    The E ring extends from three to eight Saturn radii -- about 180,000 kilometers (118,000 miles) to 482,000 kilometers (300,000 miles). Its full extent is not visible in this view.

    Calypso (22 kilometers, or 14 miles across) and Helene (32 kilometers, or 20 miles across) orbit within the E ring's expanse. Helene skirts the outer parts of the E ring, but here it is projected in front of a region deeper within the ring.

    Calypso and Helene are trojan satellites, or moons that orbit 60 degrees in front or behind a larger moon. Calypso is a Tethys trojan and Helene is a trojan of Dione.

    An interesting feature of note in this image is the double-banded appearance of the E-ring, which is created because the ring is somewhat fainter in the ringplane than it is 500-1,000 kilometers (300-600 miles) above and below the ringplane. This appearance implies that the particles in this part of the ring have nonzero inclinations (a similar affect is seen in Jupiter's gossamer ring). An object with a nonzero inclination does not orbit exactly at Saturn's ringplane. Instead, its orbit takes it above and below the ringplane. Scientists are not entirely sure why the particles should have such inclinations, but they are fairly certain that the reason involves Enceladus.

    One possible explanation is that all the E ring particles come from the plume of icy material that is shooting due south out of the moon's pole. This means all of the particles are created with a certain velocity out of the ringplane, and then they orbit above and below that plane.

    Another possible explanation is that Enceladus produces particles with a range of speeds, but the moon gravitationally

  15. Actions of a versatile fluorene-degrading bacterial isolate on polycyclic aromatic compounds.

    PubMed Central

    Grifoll, M; Selifonov, S A; Gatlin, C V; Chapman, P J

    1995-01-01

    Pseudomonas cepacia F297 grew with fluorene as a sole source of carbon and energy; its growth yield corresponded to an assimilation of about 40% of fluorene carbon. The accumulation of a ring meta-cleavage product during growth and the identification of 1-indanone in growth media and washed-cell suspensions suggest that strain F297 metabolizes fluorene by mechanisms analogous to those of naphthalene degradation. In addition to fluorene, strain F297 utilized for growth a wide variety of polycyclic aromatic compounds (PACs), including naphthalene, 2,3-dimethylnaphthalene, phenanthrene, anthracene, and dibenzothiophene. Fluorene-induced cells of the strain also transformed 2,6-dimethylnaphthalene, biphenyl, dibenzofuran, acenaphthene, and acenaphthylene. The identification of products formed from those substrates (by gas chromatography-mass spectrometry) in washed-cell suspensions indicates that P. cepacia F297 carries out the following reactions: (i) aromatic ring oxidation and cleavage, apparently using the pyruvate released for growth, (ii) methyl group oxidations, (iii) methylenic oxidations, and (iv) S oxidations of aromatic sulfur heterocycles. Strain F297 grew with a creosote-PAC mixture, producing an almost complete removal of all aromatic compounds containing 2 to 3 rings in 14 days, as demonstrated by gas chromatography analysis of the remaining PACs recovered from cultures. The identification of key chemicals confirmed that not only are certain compounds depleted but also the anticipated reaction products are found. PMID:7487007

  16. Bacterial degradation of monocyclic aromatic amines

    PubMed Central

    Arora, Pankaj K.

    2015-01-01

    Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic, and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic amines has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines. PMID:26347719

  17. Earth: A Ringed Planet?

    NASA Astrophysics Data System (ADS)

    Hancock, L. O.; Povenmire, H.

    2010-12-01

    Among the most beautiful findings of the Space Age have been the discoveries of planetary rings. Not only Saturn but also Jupiter, Uranus and Neptune have rings; Saturn’s ring system has structures newly discovered; even Saturn's moon Rhea itself has a ring. All these are apparently supplied by material from the planetary moons (Rhea's ring by Rhea itself). The question naturally arises, why should the Earth not have a ring, and on the other hand, if it does, why has it not been observed? No rings have yet been observed in the inner solar system, but after all, rings in the inner solar system might simply tend to be fainter and more transient than those of the outer solar system: the inner solar system is more affected by the solar wind, and the Sun’s perturbing gravitational influence is greater. J.A. O’Keefe first suggested (1980) that Earth might have a ring system of its own. An Earth ring could account for some climate events. O’Keefe remarked that formation or thickening of a ring system in Earth’s equatorial plane could drive glaciation by deepening the chill of the winter hemisphere. (It is very well established that volcanic dust is an effective agent for the extinction of sunlight; this factor can be overwhelmingly apparent in eclipse observations.) O’Keefe died in 2000 and the speculation was not pursued, but the idea of an Earth ring has a prima facie reasonableness that calls for its renewed consideration. The program of this note is to hypothesize that, as O’Keefe proposed: (a) an Earth ring system exists; (b) it affects Earth's weather and climate; (c) the tektite strewn fields comprise filaments of the ring fallen to Earth's surface on various occasions of disturbance by comets or asteroids. On this basis, and drawing on the world's weather records, together with the Twentieth Century Reanalysis by NCEP/CIRES covering the period 1870-2010 and the geology of the tektite strewn fields, we herein propose the hypothesized Earth ring

  18. Design of aromatic-containing cell-penetrating peptide mimics with structurally modified π electronics.

    PubMed

    deRonde, Brittany M; Birke, Alexander; Tew, Gregory N

    2015-02-01

    Cell-penetrating peptides (CPPs) and their synthetic mimics (CPPMs) represent a class of molecules that facilitate the intracellular delivery of various cargo. Previous studies indicated that the presence of aromatic functionalities improved CPPM activity. Given that aromatic functionalities play prominent roles in membrane biology and participate in various π interactions, we explored whether these interactions could be optimized for improved CPPM activity. CPPMs were synthesized by ring-opening metathesis polymerization by using monomers that contained aromatic rings substituted with electron-donating and electron-withdrawing groups and covered an electrostatic potential range from -29.69 to +15.57 kcal mol(-1) . These groups altered the quadrupole moments of the aromatic systems and were used to test if such structural modifications changed CPPM activity. CPPMs were added to dye-loaded vesicles and the release of carboxyfluorescein was monitored as a function of polymer concentration. Changes in the effective polymer concentration to release 50% of the dye (effective concentration, EC50 ) were monitored. Results from this assay showed that the strength of the electron-donating and electron-withdrawing groups incorporated in the CPPMs did not alter polymer EC50 values or activity. This suggests that other design parameters may have a stronger impact on CPPM activity. In addition, these results indicate that a wide range of aromatic groups can be incorporated without negatively impacting polymer activity.

  19. Evaluation of the aromaticity of non-planar and bowl-shaped molecules by NICS criterion.

    PubMed

    Reisi-Vanani, Adel; Rezaei, Ali Asghar

    2015-09-01

    Nucleus independent chemical shift (NICS) criterion was used to gauge the amount of aromaticity in a lot of publications in two last decades. Non-planar molecules with many polygons in different sheets that make angle together have not been studied by this criterion. Perhaps, one ascribes this deficiency to NICS index, but we think it is concern to depauperation in evaluation methods. Therefore, in this work, we try to evaluate aromaticity of two fullerene substructures bowl-shaped molecules, namely corannulene and sumanene as typical non-planar molecules by using of the NICSzz-scan method. The gauge-independent atomic orbital (GIAO) NMR calculations were done at B3LYP/6-311+G(d) level of theory. Energetic criterion as another tool for evaluation of the aromaticity of compounds was used and discussed. Results shows that pentagon and hexagon rings in corannulene have antiaromatic and aromatic character, respectively and in sumanene, pentagon and outer hexagon rings have antiaromatic and aromatic character, respectively. However, the picture obtained based on the NICS computations did not provide any insight towards the real nature of current density in the corannulene and sumanene. PMID:26188797

  20. Spiral and Rotor Patterns Produced by Fairy Ring Fungi.

    PubMed

    Karst, Nathaniel; Dralle, David; Thompson, Sally

    2016-01-01

    A broad class of soil fungi form the annular patterns known as 'fairy rings' and provide one of the only means to observe spatio-temporal dynamics of otherwise cryptic fungal growth processes in natural environments. We present observations of novel spiral and rotor patterns produced by fairy ring fungi and explain these behaviors mathematically by first showing that a well known model of fairy ring fungal growth and the Gray-Scott reaction-diffusion model are mathematically equivalent. We then use bifurcation analysis and numerical simulations to identify the conditions under which spiral waves and rotors can arise. We demonstrate that the region of dimensionless parameter space supporting these more complex dynamics is adjacent to that which produces the more familiar fairy rings, and identify experimental manipulations to test the transitions between these spatial modes. These same manipulations could also feasibly induce fungal colonies to transition from rotor/spiral formation to a set of richer, as yet unobserved, spatial patterns.

  1. Hot piston ring tests

    NASA Astrophysics Data System (ADS)

    Allen, David J.; Tomazic, William A.

    1987-12-01

    As part of the DOE/NASA Automotive Stirling Engine Project, tests were made at NASA Lewis Research Center to determine whether appendix gap losses could be reduced and Stirling engine performance increased by installing an additional piston ring near the top of each piston dome. An MTI-designed upgraded Mod I Automotive Stirling Engine was used. Unlike the conventional rings at the bottom of the piston, these hot rings operated in a high temperature environment (700 C). They were made of a high temperature alloy (Stellite 6B) and a high temperature solid lubricant coating (NASA Lewis-developed PS-200) was applied to the cylinder walls. Engine tests were run at 5, 10, and 15 MPa operating pressure over a range of operating speeds. Tests were run both with hot rings and without to provide a baseline for comparison. Minimum data to assess the potential of both the hot rings and high temperature low friction coating was obtained. Results indicated a slight increase in power and efficiency, an increase over and above the friction loss introduced by the hot rings. Seal leakage measurements showed a significant reduction. Wear on both rings and coating was low.

  2. Dynamics of narrow rings

    NASA Technical Reports Server (NTRS)

    Dermott, S. F.

    1984-01-01

    The ring models described here were developed to account for the dynamical problems posed by the narrow rings of Uranus. Some of these rings are now known to be eccentric, inclined, nonuniform in width, optically thick, and narrow, with very sharp edges. The eccentric rings have common pericenters and large, positive eccentricity gradients. The theory of shepherding satellites successfully accounts for most of these features and can also account for some features of the narrow Saturnian rings, in particular, waves, kinks, and periodic variations in brightness. Outstanding problems include the putative relation between eccentricity and inclination displayed by eight of the nine Uranian rings, and the magnitudes of the tidal torques acting on the shepherding satellites. The horseshoe-orbit model, although viable, probably has more application to the narrow rings from which the Saturnian coorbital satellites formed. The angular momentum flow rate due to particle collisions is a minimum at the Lagrangian equilibrium points L(4) and L(5), and one can expect accretion to be rapid at these points.

  3. Hot piston ring tests

    NASA Technical Reports Server (NTRS)

    Allen, David J.; Tomazic, William A.

    1987-01-01

    As part of the DOE/NASA Automotive Stirling Engine Project, tests were made at NASA Lewis Research Center to determine whether appendix gap losses could be reduced and Stirling engine performance increased by installing an additional piston ring near the top of each piston dome. An MTI-designed upgraded Mod I Automotive Stirling Engine was used. Unlike the conventional rings at the bottom of the piston, these hot rings operated in a high temperature environment (700 C). They were made of a high temperature alloy (Stellite 6B) and a high temperature solid lubricant coating (NASA Lewis-developed PS-200) was applied to the cylinder walls. Engine tests were run at 5, 10, and 15 MPa operating pressure over a range of operating speeds. Tests were run both with hot rings and without to provide a baseline for comparison. Minimum data to assess the potential of both the hot rings and high temperature low friction coating was obtained. Results indicated a slight increase in power and efficiency, an increase over and above the friction loss introduced by the hot rings. Seal leakage measurements showed a significant reduction. Wear on both rings and coating was low.

  4. Aromatization and etherification process integration

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1989-08-08

    This patent describes a continuous process for the production of aromatics-rich high octane gasoline and ether-rich high octane gasoline. It comprises the steps of: contacting a C/sub 4/+ hydrocarbon feedstream containing iso-olefins and excess methanol based on the iso-olefins with an acid etherification catalyst under etherification conditions in an etherification zone whereby an effluent stream is produced comprising methyl tertiary alkyl ethers, unreacted methanol and hydrocarbons; distilling the effluent stream whereby a distillate bottom stream is produced comprising high octane ether-rich C/sub 5/+ gasoline and a distillate overhead stream comprising unreacted methanol and C/sub 5/- hydrocarbons; passing the distillate overhead stream and an aromatization hydrocarbon feedstream comprising an ethene rich gas feedstream and C/sub 3/ hydrocarbons to an olefins and paraffins fixed, fluid or moving bed aromatization zone under aromatization conditions in contact with medium pore size shape selective metallosilicate catalyst having the structure of ZSM-5 whereby a high octane aromatics-rich C/sub 5/+ gasoline is procluded and hydrogen-rich fuel gas.

  5. Tunable recognition of the steroid α-face by adjacent π-electron density

    PubMed Central

    Friščić, T.; Lancaster, R. W.; Fábián, L.; Karamertzanis, P. G.

    2010-01-01

    We report a previously unknown recognition motif between the α-face of the steroid hydrocarbon backbone and π-electron-rich aromatic substrates. Our study is based on a systematic and comparative analysis of the solid-state complexation of four steroids with 24 aromatic molecules. By using the solid state as a medium for complexation, we circumvent solubility and solvent competition problems that are inherent to the liquid phase. Characterization is performed using powder and single crystal X-ray diffraction, infrared solid-state spectroscopy and is complemented by a comprehensive cocrystal structure prediction methodology that surpasses earlier computational approaches in terms of realism and complexity. Our combined experimental and theoretical approach reveals that the α⋯π stacking is of electrostatic origin and is highly dependent on the steroid backbone’s unsaturated and conjugated character. We demonstrate that the α⋯π stacking interaction can drive the assembly of molecules, in particular progesterone, into solid-state complexes without the need for additional strong interactions. It results in a marked difference in the solid-state complexation propensities of different steroids with aromatic molecules, suggesting a strong dependence of the steroid-binding affinity and even physicochemical properties on the steroid’s A-ring structure. Hence, the hydrocarbon part of the steroid is a potentially important variable in structure-activity relationships for establishing the binding and signaling properties of steroids, and in the manufacture of pharmaceutical cocrystals. PMID:20624985

  6. Tunable recognition of the steroid alpha-face by adjacent pi-electron density.

    PubMed

    Friscić, T; Lancaster, R W; Fábián, L; Karamertzanis, P G

    2010-07-27

    We report a previously unknown recognition motif between the alpha-face of the steroid hydrocarbon backbone and pi-electron-rich aromatic substrates. Our study is based on a systematic and comparative analysis of the solid-state complexation of four steroids with 24 aromatic molecules. By using the solid state as a medium for complexation, we circumvent solubility and solvent competition problems that are inherent to the liquid phase. Characterization is performed using powder and single crystal X-ray diffraction, infrared solid-state spectroscopy and is complemented by a comprehensive cocrystal structure prediction methodology that surpasses earlier computational approaches in terms of realism and complexity. Our combined experimental and theoretical approach reveals that the alpha...pi stacking is of electrostatic origin and is highly dependent on the steroid backbone's unsaturated and conjugated character. We demonstrate that the alpha...pi stacking interaction can drive the assembly of molecules, in particular progesterone, into solid-state complexes without the need for additional strong interactions. It results in a marked difference in the solid-state complexation propensities of different steroids with aromatic molecules, suggesting a strong dependence of the steroid-binding affinity and even physicochemical properties on the steroid's A-ring structure. Hence, the hydrocarbon part of the steroid is a potentially important variable in structure-activity relationships for establishing the binding and signaling properties of steroids, and in the manufacture of pharmaceutical cocrystals.

  7. Dynamics of the Uranian Rings

    NASA Technical Reports Server (NTRS)

    Dermott, S. F.

    1984-01-01

    Some of the problems of the shepherding satellite model of Goldreich ant tremaine are discussed. The following topics are studied: (1) optical depths of the all the observed narrow rings; (2) satellite and ring separation timescales; (3) ring edge sharpness; (4) shock formation in narrow rings; (5) the existence of small satellites near the Uranian rings; and (6) the apse and node alignments of the eccentric and inclined rings.

  8. Theodolite Ring Lights

    NASA Technical Reports Server (NTRS)

    Clark, David

    2006-01-01

    Theodolite ring lights have been invented to ease a difficulty encountered in the well-established optical-metrology practice of using highly reflective spherical tooling balls as position references. A theodolite ring light produces a more easily visible reflection and eliminates the need for an autocollimating device. A theodolite ring light is a very bright light source that is well centered on the optical axis of the instrument. It can be fabricated, easily and inexpensively, for use on a theodolite or telescope of any diameter.

  9. Alternative parallel ring protocols

    NASA Technical Reports Server (NTRS)

    Mukkamala, R.; Foudriat, E. C.; Maly, Kurt J.; Kale, V.

    1990-01-01

    Communication protocols are know to influence the utilization and performance of communication network. The effect of two token ring protocols on a gigabit network with multiple ring structure is investigated. In the first protocol, a mode sends at most one message on receiving a token. In the second protocol, a mode sends all the waiting messages when a token is received. The behavior of these protocols is shown to be highly dependent on the number of rings as well as the load in the network.

  10. Computer Simulations Reveal Multiple Functions for Aromatic Residues in Cellulase Enzymes (Fact Sheet)

    SciTech Connect

    Not Available

    2012-07-01

    NREL researchers use high-performance computing to demonstrate fundamental roles of aromatic residues in cellulase enzyme tunnels. National Renewable Energy Laboratory (NREL) computer simulations of a key industrial enzyme, the Trichoderma reesei Family 6 cellulase (Cel6A), predict that aromatic residues near the enzyme's active site and at the entrance and exit tunnel perform different functions in substrate binding and catalysis, depending on their location in the enzyme. These results suggest that nature employs aromatic-carbohydrate interactions with a wide variety of binding affinities for diverse functions. Outcomes also suggest that protein engineering strategies in which mutations are made around the binding sites may require tailoring specific to the enzyme family. Cellulase enzymes ubiquitously exhibit tunnels or clefts lined with aromatic residues for processing carbohydrate polymers to monomers, but the molecular-level role of these aromatic residues remains unknown. In silico mutation of the aromatic residues near the catalytic site of Cel6A has little impact on the binding affinity, but simulation suggests that these residues play a major role in the glucopyranose ring distortion necessary for cleaving glycosidic bonds to produce fermentable sugars. Removal of aromatic residues at the entrance and exit of the cellulase tunnel, however, dramatically impacts the binding affinity. This suggests that these residues play a role in acquiring cellulose chains from the cellulose crystal and stabilizing the reaction product, respectively. These results illustrate that the role of aromatic-carbohydrate interactions varies dramatically depending on the position in the enzyme tunnel. As aromatic-carbohydrate interactions are present in all carbohydrate-active enzymes, the results have implications for understanding protein structure-function relationships in carbohydrate metabolism and recognition, carbon turnover in nature, and protein engineering strategies for

  11. Degradation of aromatic hydrocarbons by Sphingomonas paucimobilis strain EPA505.

    PubMed

    Story, S P; Kline, E L; Hughes, T A; Riley, M B; Hayasaka, S S

    2004-08-01

    To determine the substrate range capability of Sphingomonas paucimobilis strain EPA505, a number of aromatic compounds were tested as potential growth substrates. Strain EPA505 grew on phenanthrene, naphthalene, fluoranthene, toluene, benzoic acid, 2,3- and 3,4-dihydroxybenzoic acids, 1-chloro-2,4-dinitrobenzene, anthracene, 2-hydroxy-3-naphthoic acid and 1-hydroxy- 2-naphthoic acid, salicylic acid, and catechol. Strain EPA505 was unable to grow on coumarine 3-carboxylic acid, naphthalene dicarboxylic acid, acenaphthene, chrysene, pyrene, benzo[b]fluoranthene, and fluorene. Catabolic products were not detected or identified when the bacterium was incubated with coumarine 3-carboxylic acid, naphthalene dicarboxylic acid, acenaphthene, chrysene, or benzo[b]fluoranthene. Dihydroxypyrene, the ortho ring fission product of pyrene, and 10-hydroxy-1- phenanthroic acid were detected when the bacterium was incubated with pyrene. The open rings of benzo[b]fluoranthene, hydroxyacephenanthroic acid, hydroxyacephenanthrene, and phenanthrene anhydride, catabolites of benzo[b]fluoranthene degradation, were detected with Tn5 mutants of EPA505. With strain EPA505, both 9-fluorenone and an open ring fission product accumulated during incubation with fluorene. Other catabolites beyond the open ring of fluorene were detected, specifically dihydroxyfluorene, hydroxy-9-fluorenone, dihydroxy-9-fluorenone, hydroxyindane, and a putative glutathione-conjugated benzylanhydride. Benzylanhydride appeared to be a final end product of fluorene degradation by strain EPA505.

  12. Detection of chlorinated aromatic compounds

    DOEpatents

    Ekechukwu, Amy A.

    1996-01-01

    A method for making a composition for measuring the concentration of chloated aromatic compounds in aqueous fluids, and an optical probe for use with the method. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis.

  13. Detection of chlorinated aromatic compounds

    DOEpatents

    Ekechukwu, A.A.

    1996-02-06

    A method for making a composition for measuring the concentration of chlorinated aromatic compounds in aqueous fluids, and an optical probe for use with the method are disclosed. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis. 5 figs.

  14. Efficient Route to Highly Water-Soluble Aromatic Cyclic Hydroxamic Acid Ligands

    SciTech Connect

    Seitz, Michael; Raymond, Kenneth N.

    2008-02-06

    2-Hydroxyisoquinolin-1-one (1,2-HOIQO) is a new member of the important class of aromatic cyclic hydroxamic acid ligands which are widely used in metal sequestering applications and metal chelating therapy. The first general approach for the introduction of substituents at the aromatic ring of the chelating moiety is presented. As a useful derivative, the highly water-soluble sulfonic acid has been synthesized by an efficient route that allows general access to 1,2-HOQIO 3-carboxlic acid amides, which are the most relevant for applications.

  15. Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework.

    PubMed

    Vermeulen, Nicolaas A; Karagiaridi, Olga; Sarjeant, Amy A; Stern, Charlotte L; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2013-10-01

    The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide. PMID:24047342

  16. Atmospheric chemistry of gas-phase polycyclic aromatic hydrocarbons: formation of atmospheric mutagens.

    PubMed Central

    Atkinson, R; Arey, J

    1994-01-01

    The atmospheric chemistry of the 2- to 4-ring polycyclic aromatic hydrocarbons (PAH), which exist mainly in the gas phase in the atmosphere, is discussed. The dominant loss process for the gas-phase PAH is by reaction with the hydroxyl radical, resulting in calculated lifetimes in the atmosphere of generally less than one day. The hydroxyl (OH) radical-initiated reactions and nitrate (NO3) radical-initiated reactions often lead to the formation of mutagenic nitro-PAH and other nitropolycyclic aromatic compounds, including nitrodibenzopyranones. These atmospheric reactions have a significant effect on ambient mutagenic activity, indicating that health risk assessments of combustion emissions should include atmospheric transformation products. PMID:7821285

  17. Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework.

    PubMed

    Vermeulen, Nicolaas A; Karagiaridi, Olga; Sarjeant, Amy A; Stern, Charlotte L; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2013-10-01

    The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide.

  18. Structural and functional characterization of solute binding proteins for aromatic compounds derived from lignin: p-coumaric acid and related aromatic acids

    PubMed Central

    Tan, Kemin; Chang, Changsoo; Cuff, Marianne; Osipiuk, Jerzy; Landorf, Elizabeth; Mack, Jamey C.; Zerbs, Sarah; Joachimiak, Andrzej; Collart, Frank R.

    2013-01-01

    Lignin comprises 15.25% of plant biomass and represents a major environmental carbon source for utilization by soil microorganisms. Access to this energy resource requires the action of fungal and bacterial enzymes to break down the lignin polymer into a complex assortment of aromatic compounds that can be transported into the cells. To improve our understanding of the utilization of lignin by microorganisms, we characterized the molecular properties of solute binding proteins of ATP.binding cassette transporter proteins that interact with these compounds. A combination of functional screens and structural studies characterized the binding specificity of the solute binding proteins for aromatic compounds derived from lignin such as p-coumarate, 3-phenylpropionic acid and compounds with more complex ring substitutions. A ligand screen based on thermal stabilization identified several binding protein clusters that exhibit preferences based on the size or number of aromatic ring substituents. Multiple X-ray crystal structures of protein-ligand complexes for these clusters identified the molecular basis of the binding specificity for the lignin-derived aromatic compounds. The screens and structural data provide new functional assignments for these solute.binding proteins which can be used to infer their transport specificity. This knowledge of the functional roles and molecular binding specificity of these proteins will support the identification of the specific enzymes and regulatory proteins of peripheral pathways that funnel these compounds to central metabolic pathways and will improve the predictive power of sequence-based functional annotation methods for this family of proteins. PMID:23606130

  19. Structural and functional characterization of solute binding proteins for aromatic compounds derived from lignin: p-coumaric acid and related aromatic acids.

    PubMed

    Tan, Kemin; Chang, Changsoo; Cuff, Marianne; Osipiuk, Jerzy; Landorf, Elizabeth; Mack, Jamey C; Zerbs, Sarah; Joachimiak, Andrzej; Collart, Frank R

    2013-10-01

    Lignin comprises 15-25% of plant biomass and represents a major environmental carbon source for utilization by soil microorganisms. Access to this energy resource requires the action of fungal and bacterial enzymes to break down the lignin polymer into a complex assortment of aromatic compounds that can be transported into the cells. To improve our understanding of the utilization of lignin by microorganisms, we characterized the molecular properties of solute binding proteins of ATP-binding cassette transporter proteins that interact with these compounds. A combination of functional screens and structural studies characterized the binding specificity of the solute binding proteins for aromatic compounds derived from lignin such as p-coumarate, 3-phenylpropionic acid and compounds with more complex ring substitutions. A ligand screen based on thermal stabilization identified several binding protein clusters that exhibit preferences based on the size or number of aromatic ring substituents. Multiple X-ray crystal structures of protein-ligand complexes for these clusters identified the molecular basis of the binding specificity for the lignin-derived aromatic compounds. The screens and structural data provide new functional assignments for these solute-binding proteins which can be used to infer their transport specificity. This knowledge of the functional roles and molecular binding specificity of these proteins will support the identification of the specific enzymes and regulatory proteins of peripheral pathways that funnel these compounds to central metabolic pathways and will improve the predictive power of sequence-based functional annotation methods for this family of proteins.

  20. Storage Ring EDM Experiments

    NASA Astrophysics Data System (ADS)

    Semertzidis, Yannis K.

    2016-04-01

    Dedicated storage ring electric dipole moment (EDM) methods show great promise advancing the sensitivity level by a couple orders of magnitude over currently planned hadronic EDM experiments. We describe the present status and recent updates of the field.

  1. Highlights in planetary rings

    NASA Astrophysics Data System (ADS)

    Porco, Carolyn C.

    1995-07-01

    There is a rich phenomenology within the planetary rings surrounding the giant planets, most of it discovered by the Voyagers during their historic tours of t he outer solar system in the 1980s. In the last decade, there have been two detailed IUGG reviews of planetary rings. Cuzzi [1983] covered the time period from 1979-1983 which included the Pioneer 11 encounter with Saturn (1979), the Voyager 1 and 2 encounters with Jupiter (1979) and with Saturn (1980 and 1981). Nicholson and Dones [1991] reviewed the developments in the field between 1984 and 1991, a period of time which included the Voyager 2 Uranus (1986) and Neptune (1989) encounters. (References t o additional reviews of planetary rings and related fields can be found in Nicholson and Dones [1991].) Rather than being comprehensive in nature, this review will concentrate on only those areas of ring research in which particularly promising developments have occurred in the last half decade.

  2. Heating Saturn's Clumpy Rings

    NASA Astrophysics Data System (ADS)

    Turner, Neal J.; Morishima, Ryuji; Spilker, Linda J.

    2015-11-01

    We model Cassini CIRS data using a Monte Carlo radiative transfer -- thermal balance technique first developed for protostellar disks, with the goals of:1. Exploring whether the A- and B-ring temperatures' variation with viewing angle is consistent with the wake structures suggested by the observed azimuthal asymmetry in optical depth, by analytic arguments, and by numerical N-body modeling.2. Better constraining the shape, size, spacing and optical depths of substructure in the A-ring, using the unexpectedly high temperatures observed at equinox. If the wake features have high enough contrast, Saturn-shine may penetrate the gaps between the wakes and heat thering particles both top and bottom.3. Determining how much of the heating of the A- and B-rings' unlit sides is due to radiative transport and how much is due to particle motions, especially vertical motions. This will help in constraining the rings' surface densities and masses.

  3. Saturn's dynamic D ring

    USGS Publications Warehouse

    Hedman, M.M.; Burns, J.A.; Showalter, M.R.; Porco, C.C.; Nicholson, P.D.; Bosh, A.S.; Tiscareno, M.S.; Brown, R.H.; Buratti, B.J.; Baines, K.H.; Clark, R.

    2007-01-01

    The Cassini spacecraft has provided the first clear images of the D ring since the Voyager missions. These observations show that the structure of the D ring has undergone significant changes over the last 25 years. The brightest of the three ringlets seen in the Voyager images (named D72), has transformed from a narrow, <40-km wide ringlet to a much broader and more diffuse 250-km wide feature. In addition, its center of light has shifted inwards by over 200 km relative to other features in the D ring. Cassini also finds that the locations of other narrow features in the D ring and the structure of the diffuse material in the D ring differ from those measured by Voyager. Furthermore, Cassini has detected additional ringlets and structures in the D ring that were not observed by Voyager. These include a sheet of material just interior to the inner edge of the C ring that is only observable at phase angles below about 60??. New photometric and spectroscopic data from the ISS (Imaging Science Subsystem) and VIMS (Visual and Infrared Mapping Spectrometer) instruments onboard Cassini show the D ring contains a variety of different particle populations with typical particle sizes ranging from 1 to 100 microns. High-resolution images reveal fine-scale structures in the D ring that appear to be variable in time and/or longitude. Particularly interesting is a remarkably regular, periodic structure with a wavelength of ??? 30 ?? km extending between orbital radii of 73,200 and 74,000 km. A similar structure was previously observed in 1995 during the occultation of the star GSC5249-01240, at which time it had a wavelength of ??? 60 ?? km. We interpret this structure as a periodic vertical corrugation in the D ring produced by differential nodal regression of an initially inclined ring. We speculate that this structure may have formed in response to an impact with a comet or meteoroid in early 1984. ?? 2006 Elsevier Inc. All rights reserved.

  4. Ultrasonic Newton's rings

    SciTech Connect

    Hsu, D.K. ); Dayal, V. )

    1992-03-09

    Interference fringes due to bondline thickness variation were observed in ultrasonic scans of the reflected echo amplitude from the bondline of adhesively joined aluminum skins. To demonstrate that full-field interference patterns are observable in point-by-point ultrasonic scans, an optical setup for Newton's rings was scanned ultrasonically in a water immersion tank. The ultrasonic scan showed distinct Newton's rings whose radii were in excellent agreement with the prediction.

  5. Volatile profiles of aromatic and non-aromatic rice

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rice is enjoyed by many people as a staple food because of its flavor and texture. Some scented varieties command a premium in the marketplace because of their distinctive aroma and flavor. The compound most commonly associated with the popcorn or nutty scent of aromatic rice is 2-acetyl-1-pyrroline...

  6. Nardo Ring, Italy

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Nardo Ring is a striking visual feature from space, and astronauts have photographed it several times. The Ring is a race car test track; it is 12.5 kilometers long and steeply banked to reduce the amount of active steering needed by drivers. The Nardo Ring lies in a remote area on the heel of Italy's 'boot,' 50 kilometers east of the naval port of Taranto. The Ring encompasses a number of active (green) and fallow (brown to dark brown) agricultural fields. In this zone of intensive agriculture, farmers gain access to their fields through the Ring via a series of underpasses. Winding features within the southern section of the Ring appear to be smaller, unused race tracks.

    The image covers an area of 18.8 x 16.4 km, was acquired on August 17. 2007, and is located at 49.3 degrees north latitude, 17.8 degrees east longitude.

    The U.S. science team is located at NASA's Jet Propulsion Laboratory, Pasadena, Calif. The Terra mission is part of NASA's Science Mission Directorate.

  7. Biodegradation of aliphatic and aromatic polycarbonates.

    PubMed

    Artham, Trishul; Doble, Mukesh

    2008-01-01

    Polycarbonate is one of the most widely used engineering plastics because of its superior physical, chemical, and mechanical properties. Understanding the biodegradation of this polymer is of great importance to answer the increasing problems in waste management of this polymer. Aliphatic polycarbonates are known to biodegrade either through the action of pure enzymes or by bacterial whole cells. Very little information is available that deals with the biodegradation of aromatic polycarbonates. Biodegradation is governed by different factors that include polymer characteristics, type of organism, and nature of pretreatment. The polymer characteristics such as its mobility, tacticity, crystallinity, molecular weight, the type of functional groups and substituents present in its structure, and plasticizers or additives added to the polymer all play an important role in its degradation. The carbonate bond in aliphatic polycarbonates is facile and hence this polymer is easily biodegradable. On the other hand, bisphenol A polycarbonate contains benzene rings and quaternary carbon atoms which form bulky and stiff chains that enhance rigidity. Even though this polycarbonate is amorphous in nature because of considerable free volume, it is non-biodegradable since the carbonate bond is inaccessible to enzymes because of the presence of bulky phenyl groups on either side. In order to facilitate the biodegradation of polymers few pretreatment techniques which include photo-oxidation, gamma-irradiation, or use of chemicals have been tested. Addition of biosurfactants to improve the interaction between the polymer and the microorganisms, and blending with natural or synthetic polymers that degrade easily, can also enhance the biodegradation.

  8. Collisional simulations of particles in a narrow planetary ring

    NASA Technical Reports Server (NTRS)

    Kolvoord, Robert A.; Burns, Joseph A.

    1992-01-01

    A model is used to investigate how particle-particle collisions might modify some consequences of satellite perturbations relevant to short-term features of narrow planetary rings. A Monte Carlo-like simulation ring-model particle velocity alteration allows the simulation of collisions while individual particles are tracked. Periodic features visible in Voyager images are reproduced in a 2D numerical model which incorporates the collisional simulation as well as the perturbations of adjacent satellites. Collisions are noted to wash out periodic features within one collisional relaxation time.

  9. THE PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    The U.S. Environmental Protection Agency (EPA) continues to be interested in developing methods for the detection of polycyclic aromatic hydrocarbons (PAHS) in the environment. Polycyclic aromatic hydrocarbons (PAHS) are common contaminants in our environment. Being major product...

  10. Propellers in Saturn's rings

    NASA Astrophysics Data System (ADS)

    Sremcevic, M.; Stewart, G. R.; Albers, N.; Esposito, L. W.

    2014-04-01

    Theoretical studies and simulations have demonstrated the effects caused by objects embedded in planetary rings [5, 8]. Even if the objects are too small to be directly observed, each creates a much larger gravitational imprint on the surrounding ring material. These strongly depend on the mass of the object and range from "S" like propeller-shaped structures for about 100m-sized icy bodies to the opening of circumferential gaps as in the case of the embedded moons Pan and Daphnis and their corresponding Encke and Keeler Gaps. Since the beginning of the Cassini mission many of these smaller objects (~ 100m in size) have been identified in Saturn's A ring through their propeller signature in the images [10, 7, 9, 11]. Furthermore, recent Cassini observations indicate the possible existence of objects embedded even in Saturn's B and C ring [6, 2]. In this paper we present our new results about by now classical A ring propellers and more enigmatic B ring population. Due to the presence of self-gravity wakes the analysis of propeller brightness in ISS images always bears some ambiguity [7, 9] and consequently the exact morphology of propellers is not a settled issue. In 2008 we obtained a fortunate Cassini Ultraviolet Imaging Spectrograph (UVIS) occultation of the largest A ring propeller Bleriot. Utilizing Cassini ISS images we obtain Bleriot orbit and demonstrate that UVIS Persei Rev42 occultation did cut across Bleriot about 100km downstream from the center. The occultation itself shows a prominent partial gap and higher density outer flanking wakes, while their orientation is consistent with a downstream cut. While in the UVIS occultation the partial gap is more prominent than the flanking wakes, the features mostly seen in Bleriot images are actually flanking wakes. One of the most interesting aspects of the A ring propellers are their wanderings, or longitudinal deviations from a pure circular orbit [11]. We numerically investigated the possibility of simple moon

  11. Fluorinated Aromatic Amino Acids Distinguish Cation-π Interactions from Membrane Insertion.

    PubMed

    He, Tao; Gershenson, Anne; Eyles, Stephen J; Lee, Yan-Jiun; Liu, Wenshe R; Wang, Jiangyun; Gao, Jianmin; Roberts, Mary F

    2015-07-31

    Cation-π interactions, where protein aromatic residues supply π systems while a positive-charged portion of phospholipid head groups are the cations, have been suggested as important binding modes for peripheral membrane proteins. However, aromatic amino acids can also insert into membranes and hydrophobically interact with lipid tails. Heretofore there has been no facile way to differentiate these two types of interactions. We show that specific incorporation of fluorinated amino acids into proteins can experimentally distinguish cation-π interactions from membrane insertion of the aromatic side chains. Fluorinated aromatic amino acids destabilize the cation-π interactions by altering electrostatics of the aromatic ring, whereas their increased hydrophobicity enhances membrane insertion. Incorporation of pentafluorophenylalanine or difluorotyrosine into a Staphylococcus aureus phosphatidylinositol-specific phospholipase C variant engineered to contain a specific PC-binding site demonstrates the effectiveness of this methodology. Applying this methodology to the plethora of tyrosine residues in Bacillus thuringiensis phosphatidylinositol-specific phospholipase C definitively identifies those involved in cation-π interactions with phosphatidylcholine. This powerful method can easily be used to determine the roles of aromatic residues in other peripheral membrane proteins and in integral membrane proteins. PMID:26092728

  12. Synthesis, structure, and fullerene-complexing property of azacalix[6]aromatics.

    PubMed

    Fa, Shi-Xin; Wang, Li-Xia; Wang, De-Xian; Zhao, Liang; Wang, Mei-Xiang

    2014-04-18

    Synthesis, structure, and fullerene-binding property of azacalix[6]aromatics were systematically studied. By means of [3 + 3] and [2 + 2 + 2] fragment coupling protocols, a number of azacalix[6]aromatics containing different combinations of benzene, pyridine, and pyrimidine rings and various substituents on the bridging nitrogen atoms were synthesized conveniently in moderate to good yields. The resulting macrocycles adopt in the solid state symmetric and heavily distorted 1,3,5-alternate conformations depending on the aromatic building units, whereas, in solution, they exist as a mixture of conformers that undergo rapid interchanges relative to the NMR time scale. All macrocycles were able to form 1:1 complexes with C60 and C70 in toluene with the association constants up to 7.28 × 10(4) M(-1). In the crystalline state, azacalix[6]aromatics form complexes with C60 and C70 with 2:1, 1:1, and 1:2 stoichiometric ratios between host and guest. Azacalix[6]aromatics interact with fullerene by forming mainly the sandwich structure in which C60 or C70 is sandwiched by two macrocycles. X-ray molecular structures revealed that multiple π-π and CH-π interactions between concave azacalix[6]aromatics and convex fullerenes C60 and C70 contribute a joint driving force to the formation of host-guest complexes.

  13. Determination of polycyclic aromatic hydrocarbons in indoor and outdoor air with chromatographic methods.

    PubMed

    Zhu, Li-Zhong; Shen, Xueyou; Liu, Yong-Jian

    2003-05-01

    Polycyclic aromatic hydrocarbons in indoor and outdoor air of four typical homes in Hangzhou, China were determined with a highly automated chromatographic method. The results indicated that the concentrations of the 15 polycyclic aromatic hydrocarbons in the indoor air were between 1.907 microg/m3 and 14.29 microg/m3, which were much higher than those in the corresponding outdoor air. Because of the popular use of mothball in wardrobes, naphthalene had the highest concentration in all the 15 polycyclic aromatic hydrocarbons, which was up to 13.17 microg/m3 and contributed 68% to the total polycyclic aromatic hydrocarbons in the room. In kitchen, because of the representative cooking method, there had much of three- and four-ring polycyclic aromatic hydrocarbons. The indoor smoking not only led to high concentration of polycyclic aromatic hydrocarbons in the indoor air, but also contributed almost all the benzo(a)pyrene. Naphthalene, acenaphthene and pyrene were considered being generated by the indoor sources in all the four homes.

  14. Environmental diagnostic analysis of ground water bacteria and their involvement in utilization of aromatic compounds

    SciTech Connect

    Wear, J.E. Jr.

    1993-05-01

    The objective of this study was to examine the hypothesis that select functional groups of bacteria from pristine sites have an innate ability to degrade synthetic aromatics that often contaminate groundwater environments,due to exposure to naturally occurring recalcitrant aromatics in their environment. This study demonstrates that subsurface microbial communities are capable of utilizing lignin and humic acid breakdown products. Utilizers of these compounds were found to be present in most all the wells tested. Even the deepest aquifer tested had utilizers present for all six of the aromatics tested. Highest counts for the aromatics tested were observed with the naturally occurring breakdown products of either lignin or humic acid. Carboxylic acids were found to be an important sole carbon source for groundwater bacteria possibly explained by the fact that they are produced by the oxidative cleavage of aromatic ring structures. The carbohydrate sole carbon sources that demonstrated the greatest densities were ones commonly associated with humics. This study indicates that utilization of naturally occurring aromatic compounds in the subsurface is an important nutritional source for groundwater bacteria. In addition, it suggests that adaptation to naturally occurring recalcitrant substrates is the origin of degradative pathways for xenobiotic compounds with analogous structure. This work has important implications for in situ bioremediation as a method of environmental cleanup.

  15. Characterization of nitrogen-rich biomaterial-derived biochars and their sorption for aromatic compounds.

    PubMed

    Zhang, Meng; Shu, Liang; Shen, Xiaofang; Guo, Xiaoying; Tao, Shu; Xing, Baoshan; Wang, Xilong

    2014-12-01

    Biochars from nitrogen-rich biomaterials (i.e., α-amylase, chitin and zein) were produced at different temperatures (i.e. 170, 250, 350 and 450 °C) and characterized, and their sorption for phenanthrene, naphthalene and 1-naphthol was investigated. The organic carbon content normalized-sorption coefficient (Koc) of the tested compounds by biochars increased with increasing charring temperature, attributed to the reduction of O-containing polar moieties especially the O-alkyl components, and the newly created aromatic carbon domains. The N-heterocyclic ring structure formed during charring process may enhance π-π interactions between aromatics and the aromatic components in the resulting biochars. However, π-π interactions did not dominate sorption of aromatics by N-rich biochars. Sorption of the tested compounds by N-rich biochars was predominantly controlled by the hydrophobic interactions between these chemicals and the aromatic components in biochars. Both N- and O-containing polar moieties at the biochar surfaces negatively affected their sorption for aromatics.

  16. Fluorinated Aromatic Amino Acids Distinguish Cation-π Interactions from Membrane Insertion*

    PubMed Central

    He, Tao; Gershenson, Anne; Eyles, Stephen J.; Lee, Yan-Jiun; Liu, Wenshe R.; Wang, Jiangyun; Gao, Jianmin; Roberts, Mary F.

    2015-01-01

    Cation-π interactions, where protein aromatic residues supply π systems while a positive-charged portion of phospholipid head groups are the cations, have been suggested as important binding modes for peripheral membrane proteins. However, aromatic amino acids can also insert into membranes and hydrophobically interact with lipid tails. Heretofore there has been no facile way to differentiate these two types of interactions. We show that specific incorporation of fluorinated amino acids into proteins can experimentally distinguish cation-π interactions from membrane insertion of the aromatic side chains. Fluorinated aromatic amino acids destabilize the cation-π interactions by altering electrostatics of the aromatic ring, whereas their increased hydrophobicity enhances membrane insertion. Incorporation of pentafluorophenylalanine or difluorotyrosine into a Staphylococcus aureus phosphatidylinositol-specific phospholipase C variant engineered to contain a specific PC-binding site demonstrates the effectiveness of this methodology. Applying this methodology to the plethora of tyrosine residues in Bacillus thuringiensis phosphatidylinositol-specific phospholipase C definitively identifies those involved in cation-π interactions with phosphatidylcholine. This powerful method can easily be used to determine the roles of aromatic residues in other peripheral membrane proteins and in integral membrane proteins. PMID:26092728

  17. Exchange coupling between laterally adjacent nanomagnets

    NASA Astrophysics Data System (ADS)

    Dey, H.; Csaba, G.; Bernstein, G. H.; Porod, W.

    2016-09-01

    We experimentally demonstrate exchange-coupling between laterally adjacent nanomagnets. Our results show that two neighboring nanomagnets that are each antiferromagnetically exchange-coupled to a common ferromagnetic bottom layer can be brought into strong ferromagnetic interaction. Simulations show that interlayer exchange coupling effectively promotes ferromagnetic alignment between the two nanomagnets, as opposed to antiferromagnetic alignment due to dipole-coupling. In order to experimentally demonstrate the proposed scheme, we fabricated arrays of pairs of elongated, single-domain nanomagnets. Magnetic force microscopy measurements show that most of the pairs are ferromagnetically ordered. The results are in agreement with micromagnetic simulations. The presented scheme can achieve coupling strengths that are significantly stronger than dipole coupling, potentially enabling far-reaching applications in Nanomagnet Logic, spin-wave devices and three-dimensional storage and computing.

  18. Boundary Layers of Air Adjacent to Cylinders

    PubMed Central

    Nobel, Park S.

    1974-01-01

    Using existing heat transfer data, a relatively simple expression was developed for estimating the effective thickness of the boundary layer of air surrounding cylinders. For wind velocities from 10 to 1000 cm/second, the calculated boundary-layer thickness agreed with that determined for water vapor diffusion from a moistened cylindrical surface 2 cm in diameter. It correctly predicted the resistance for water vapor movement across the boundary layers adjacent to the (cylindrical) inflorescence stems of Xanthorrhoea australis R. Br. and Scirpus validus Vahl and the leaves of Allium cepa L. The boundary-layer thickness decreased as the turbulence intensity increased. For a turbulence intensity representative of field conditions (0.5) and for νwindd between 200 and 30,000 cm2/second (where νwind is the mean wind velocity and d is the cylinder diameter), the effective boundary-layer thickness in centimeters was equal to [Formula: see text]. PMID:16658855

  19. 33 CFR 80.1395 - Puget Sound and adjacent waters.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 33 Navigation and Navigable Waters 1 2012-07-01 2012-07-01 false Puget Sound and adjacent waters... INTERNATIONAL NAVIGATION RULES COLREGS DEMARCATION LINES Thirteenth District § 80.1395 Puget Sound and adjacent waters. The 72 COLREGS shall apply on all waters of Puget Sound and adjacent waters, including Lake...

  20. 33 CFR 80.1395 - Puget Sound and adjacent waters.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 33 Navigation and Navigable Waters 1 2013-07-01 2013-07-01 false Puget Sound and adjacent waters... INTERNATIONAL NAVIGATION RULES COLREGS DEMARCATION LINES Thirteenth District § 80.1395 Puget Sound and adjacent waters. The 72 COLREGS shall apply on all waters of Puget Sound and adjacent waters, including Lake...

  1. 33 CFR 80.1395 - Puget Sound and adjacent waters.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 33 Navigation and Navigable Waters 1 2014-07-01 2014-07-01 false Puget Sound and adjacent waters... INTERNATIONAL NAVIGATION RULES COLREGS DEMARCATION LINES Thirteenth District § 80.1395 Puget Sound and adjacent waters. The 72 COLREGS shall apply on all waters of Puget Sound and adjacent waters, including Lake...

  2. 33 CFR 80.1395 - Puget Sound and adjacent waters.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false Puget Sound and adjacent waters... INTERNATIONAL NAVIGATION RULES COLREGS DEMARCATION LINES Thirteenth District § 80.1395 Puget Sound and adjacent waters. The 72 COLREGS shall apply on all waters of Puget Sound and adjacent waters, including Lake...

  3. 33 CFR 80.1395 - Puget Sound and adjacent waters.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 33 Navigation and Navigable Waters 1 2011-07-01 2011-07-01 false Puget Sound and adjacent waters... INTERNATIONAL NAVIGATION RULES COLREGS DEMARCATION LINES Thirteenth District § 80.1395 Puget Sound and adjacent waters. The 72 COLREGS shall apply on all waters of Puget Sound and adjacent waters, including Lake...

  4. Polybenzimidazoles Via Aromatic Nucleophilic Displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul M.; Smith, Joseph G.

    1994-01-01

    Soluble polybenzimidazoles (PBI's) synthesized by nucleophilic displacement reaction of di(hydroxyphenyl)-benzimidazole monomers with activated aromatic difluoride compounds in presence of anhydrous potassium carbonate. These polymers exhibit good thermal, thermo-oxidative, and chemical stability, and high mechanical properties. Using benzimidazole monomers, more economical, and new PBI's processed more easily than commercial PBI, without loss of desirable physical properties.

  5. Retaining-Ring Installation Tool

    NASA Technical Reports Server (NTRS)

    Christian, S.

    1983-01-01

    New tool eliminates damage to ring through improper tool use. Tool installs spiral-wound retaining rings quickly, reliably, and safely. Tool inserts rings in splined or irregularly shaped bores, bores at bottom of deep ring and slides it along bore until it nests in groove. Pistons are moved by variety of linkages.

  6. The Aromaticity of Pericyclic Reaction Transition States

    ERIC Educational Resources Information Center

    Rzepa, Henry S.

    2007-01-01

    An approach is presented that starts from two fundamental concepts in organic chemistry, chirality and aromaticity, and combines them into a simple rule for stating selection rules for pericyclic reactions in terms of achiral Huckel-aromatic and chiral Mobius-aromatic transition states. This is illustrated using an example that leads to apparent…

  7. Asymmetrical/symmetrical D-π-A/D-π-D thiazole-containing aromatic heterocyclic fluorescent compounds having the same triphenylamino chromophores.

    PubMed

    Tao, Tao; Ma, Bin-Bin; Peng, Yu-Xin; Wang, Xiao-Xu; Huang, Wei; You, Xiao-Zeng

    2013-09-01

    A family of linear asymmetrical D-π-A and symmetrical D-π-D types of thiazole-based aromatic heterocyclic fluorescent compounds bearing various electron-donating and electron-withdrawing tails (bromo, triphenylamino, pyridyl, thienyl and benzoic acid) have been designed and prepared successfully. Synthetic, structural, thermal, spectral and computational comparisons have been carried out for related compounds because of their adjustable electronic properties. It is interesting to mention that compound 2 can be prepared from 5-bromothiazole by one-pot Suzuki-Miyaura coupling and subsequent C-H activation reactions via a 5-TPA-substituted thiazole intermediate 1. X-ray single-crystal structures of six compounds indicate that they all crystallize in the triclinic P1 space group and the thiazole core exhibits different dihedral angles with its adjacent benzene ring of the triphenylamino group (3.6(3)-40.8(3)°). The photophysical and electrochemical results demonstrate that compound 7 exhibits high electrochemical activity with a green fluorescence emission. Meanwhile, compounds 1, 2, and 6 show high luminescence quantum yields, and compound 8 exhibits excellent thermal stability (T(d(10)) = 503 °C).

  8. Single kernel method for detection of 2-acetyl-1-pyrroline in aromatic rice germplasm using SPME-GC/MS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    INTRODUCTION Aromatic rice or fragrant rice, (Oryza sativa L.), has a strong popcorn-like aroma due to the presence of a five-membered N-heterocyclic ring compound known as 2-acetyl-1-pyrroline (2-AP). To date, existing methods for detecting this compound in rice require the use of several kernels. ...

  9. Thermodynamic black di-rings

    SciTech Connect

    Iguchi, Hideo; Mishima, Takashi

    2010-10-15

    Previously the five dimensional S{sup 1}-rotating black rings have been superposed in a concentric way by some solitonic methods, and regular systems of two S{sup 1}-rotating black rings were constructed by the authors and then Evslin and Krishnan (we called these solutions 'black di-rings'). In this place we show some characteristics of the solutions of five dimensional black di-rings, especially in thermodynamic equilibrium. After the summary of the di-ring expressions and their physical quantities, first we comment on the equivalence of the two different solution sets of the black di-rings. Then the existence of thermodynamic black di-rings is shown, in which both isothermality and isorotation between the inner black ring and the outer black ring are realized. We also give detailed analysis of peculiar properties of the thermodynamic black di-ring including discussion about a certain kind of thermodynamic stability (instability) of the system.

  10. Speciation of atmospheric polycyclic aromatic hydrocarbons (PAHs) present during fog time collected submicron particles.

    PubMed

    Singh, Dharmendra Kumar; Sharma, Swati; Habib, Gazala; Gupta, Tarun

    2015-08-01

    Airborne submicron particles (PM1) were collected using PM1 sampler during the fog-dominated days (December 2013-January 2014). PM1 values varied between 58.12 μg/m(3) and 198.75 μg/m(3), and average mass concentration was 162.33 ± 38.25 μg/m(3) while total average concentration of particle-associated polycyclic aromatic hydrocarbon (PAHs) determined was 616.31 ± 30.31 ng/m(3). This is a signal for an alarming high pollution level at this site situated in the Indo-Gangetic Plain (IGP). PAHs were extracted from filters using toluene and acetonitrile. Quantitative measurements of polycyclic aromatic hydrocarbons (PAHs) were carried out using the high performance liquid chromatography (HPLC) technique. The extracts were analyzed for 16 target polycyclic aromatic hydrocarbons (PAHs) including carcinogenic compound benzo(a)pyrene (19.86 ± 38.98 ng/m(3)). Fluoranthene, benzo(a)anthracene, anthracene, and fluorene were the predominant compounds found in the samples collected during foggy days. Based on number of rings, four-ring PAH compounds had maximum contribution (43%) in this fog time collected submicron particles followed by three-ring (21%), five-ring (20%), six-ring (13%), and two-ring (3%), respectively. In winter and foggy days, wood and coal combustion and biomass burning also significantly contribute to the PAH levels. However, diagnostic ratio suggests diesel emissions as the prime source of PAHs at this sampling site.

  11. Propellers in Saturn's rings

    NASA Astrophysics Data System (ADS)

    Sremcevic, M.; Stewart, G. R.; Albers, N.; Esposito, L. W.

    2013-12-01

    Theoretical studies and simulations have demonstrated the effects caused by objects embedded in planetary rings. Even if the objects are too small to be directly observed, each creates a much larger gravitational imprint on the surrounding ring material. These strongly depend on the mass of the object and range from "S" like propeller-shaped structures for about 100m-sized icy bodies to the opening of circumferential gaps as in the case of the embedded moons Pan and Daphnis and their corresponding Encke and Keeler Gaps. Since the beginning of the Cassini mission many of these smaller objects (~<500m in size) have been indirectly identified in Saturn's A ring through their propeller signature in the images. Furthermore, recent Cassini observations indicate the possible existence of objects embedded even in Saturn's B and C ring. In this paper we present evidence for the existence of propellers in Saturn's B ring by combining data from Cassini Ultraviolet Imaging Spectrograph (UVIS) and Imaging Science Subsystem (ISS) experiments. We show evidence that B ring seems to harbor two distinct populations of propellers: "big" propellers covering tens of degrees in azimuth situated in the densest part of B ring, and "small" propellers in less dense inner B ring that are similar in size and shape to known A ring propellers. The population of "big" propellers is exemplified with a single object which is observed for 5 years of Cassini data. The object is seen as a very elongated bright stripe (40 degrees wide) in unlit Cassini images, and dark stripe in lit geometries. In total we report observing the feature in images at 18 different epochs between 2005 and 2010. In UVIS occultations we observe this feature as an optical depth depletion in 14 out of 93 occultation cuts at corrotating longitudes compatible with imaging data. Combining the available Cassini data we infer that the object is a partial gap located at r=112,921km embedded in the high optical depth region of the B

  12. Mapping Ring Particle Cooling across Saturn's Rings with Cassini CIRS

    NASA Astrophysics Data System (ADS)

    Brooks, Shawn M.; Spilker, L. J.; Edgington, S. G.; Pilorz, S. H.; Deau, E.

    2010-10-01

    Previous studies have shown that the rings' thermal inertia, a measure of their response to changes in the thermal environment, varies from ring to ring. Thermal inertia can provide insight into the physical structure of Saturn's ring particles and their regoliths. Low thermal inertia and quick temperature responses are suggestive of ring particles that have more porous or fluffy regoliths or that are riddled with cracks. Solid, coherent particles can be expected to have higher thermal inertias (Ferrari et al. 2005). Cassini's Composite Infrared Spectrometer has recorded millions of spectra of Saturn's rings since its arrival at Saturn in 2004 (personal communication, M. Segura). CIRS records far infrared radiation between 10 and 600 cm-1 (16.7 and 1000 µm) at focal plane 1 (FP1), which has a field of view of 3.9 mrad. Thermal emission from Saturn's rings peaks in this wavelength range. FP1 spectra can be used to infer ring temperatures. By tracking how ring temperatures vary, we can determine the thermal inertia of the rings. In this work we focus on CIRS observations of the shadowed portion of Saturn's rings. The thermal budget of the rings is dominated by the solar radiation absorbed by its constituent particles. When ring particles enter Saturn's shadow this source of energy is abruptly cut off. As a result, ring particles cool as they traverse Saturn's shadow. From these shadow observations we can create cooling curves at specific locations across the rings. We will show that the rings' cooling curves and thus their thermal inertia vary not only from ring to ring, but by location within the individual rings. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with NASA. Copyright 2010 California Institute of Technology. Government sponsorship acknowledged.

  13. Saturn's Other Ring Current

    NASA Astrophysics Data System (ADS)

    Crary, F. J.

    2014-04-01

    Saturn's main rings orbit the planet within an atmosphere and ionosphere of water, oxygen and hydrogen, produced by meteoritic impacts on and ultraviolet photodesorbtion of the ring particles [Johnson et al., 2006; Luhmann et al., 2006; Tseng et al., 2010]. The neutral atmosphere itself has only been tentatively detected through ultraviolet fluorescents of OH [Hall et al., 1996] while the ionosphere was observed in situ by the Cassini spacecraft shortly after orbital insertion [Coates et al.,2005; Tokar et al. 2005, Waite et al. 2005]. Although the plasma flow velocity of this ionosphere is not well-constrained, but the close association with the rings suggests that its speed would be couppled to the keplarian velocity of the rings themselves. As a result, the motion of the plasma through Saturn's magnetic field would produce an induced voltage, oriented away from the planet outside synchronous orbit and towards the planet inside synchronous orbit. Such a potential could result in currents flowing across the ring plane and closeing along magnetic field lines and through Saturn's ionosphere at latitudes between 36o and 48o. Cassini observations of whistler-mode plasma wave emissions [Xin et al.,2006] centered on synchronous orbit (1.76 Rs, mapping to 41o latitude) have been interpreted as a product of field-aligned electron beams associated with such a current. This presentation will investigate the magnitude of these currents and the resulting Joule heating of the ionosphere. An important constraint is that no auroral ultraviolet emissions have been observed at the relevant latitudes. In contrast, Joule heating could affect infrared emissions from H3+. Variations in H3+ emission associated with Saturn's rings have been reported by O'Donoghue et al., 2013, and interpreted as a result of ring "rain", i.e. precipitating water group species from the rings which alter ionosphereic chemistry and H3+ densities. As noted by O'Donoghue et al., this interpretation may be

  14. Piston Ring Pressure Distribution

    NASA Technical Reports Server (NTRS)

    Kuhn, M.

    1943-01-01

    The discovery and introduction of the internal combustion engine has resulted in a very rapid development in machines utilizing the action of a piston. Design has been limited by the internal components of the engine, which has been subjected to ever increasing thermal and mechanical stresses, Of these internal engine components, the piston and piston rings are of particular importance and the momentary position of engine development is not seldom dependent upon the development of both of the components, The piston ring is a well-known component and has been used in its present shape in the steam engine of the last century, Corresponding to its importance, the piston ring has been a rich field for creative activity and it is noteworthy that in spite of this the ring has maintained its shape through the many years. From the many and complicated designs which have been suggested as a packing between piston and cylinder wall hardly one suggestion has remained which does not resemble the original design of cast iron rectangular ring.

  15. Stacked Corrugated Horn Rings

    NASA Technical Reports Server (NTRS)

    Sosnowski, John B.

    2010-01-01

    This Brief describes a method of machining and assembly when the depth of corrugations far exceeds the width and conventional machining is not practical. The horn is divided into easily machined, individual rings with shoulders to control the depth. In this specific instance, each of the corrugations is identical in profile, and only differs in diameter and outer profile. The horn is segmented into rings that are cut with an interference fit (zero clearance with all machining errors biased toward contact). The interference faces can be cut with a reverse taper to increase the holding strength of the joint. The taper is a compromise between the interference fit and the clearance of the two faces during assembly. Each internal ring is dipped in liquid nitrogen, then nested in the previous, larger ring. The ring is rotated in the nest until the temperature of the two parts equalizes and the pieces lock together. The resulting assay is stable, strong, and has an internal finish that cannot be achieved through other methods.

  16. Two F Ring Views

    NASA Technical Reports Server (NTRS)

    2005-01-01

    These views, taken two hours apart, demonstrate the dramatic variability in the structure of Saturn's intriguing F ring.

    In the image at the left, ringlets in the F ring and Encke Gap display distinctive kinks, and there is a bright patch of material on the F ring's inner edge. Saturn's moon Janus (181 kilometers, or 113 miles across) is shown here, partly illuminated by reflected light from the planet.

    At the right, Prometheus (102 kilometers, or 63 miles across) orbits ahead of the radial striations in the F ring, called 'drapes' by scientists. The drapes appear to be caused by successive passes of Prometheus as it reaches the greatest distance (apoapse) in its orbit of Saturn. Also in this image, the outermost ringlet visible in the Encke Gap displays distinctive bright patches.

    These views were obtained from about three degrees below the ring plane.

    The images were taken in visible light with the Cassini spacecraft narrow-angle camera on June 29, 2005, when Cassini was about 1.5 million kilometers (900,000 miles) from Saturn. The image scale is about 9 kilometers (6 miles) per pixel.

  17. Steam turbine with improved blade ring and cylinder interface

    SciTech Connect

    Huang, K.P.

    1992-10-06

    This patent describes a steam turbine having a cylinder with a plurality of steam inlets which feed a plurality of nozzle blocks and a curtis stage blade ring disposed adjacent the nozzle blocks. This patent describes improvement in a kerf extending from each port through an inner circumferential margin of the tongue to reduce heat induced stresses between the ports and inner circumferential margin of the tongue and prevent cracking thereof.

  18. Rings in the solar system

    SciTech Connect

    Pollack, J.B.; Cuzzi, J.N.

    1981-11-01

    Saturn, Jupiter, and Uranus have rings with different structure and composition. The rings consist of tiny masses in independent orbits. Photographs and data obtained by the Voyager project have aided in the understanding of Saturn's rings. Spokes have been found in B ring and boards, knots, and twist in F ring. Particles on the order of a micrometer in size are believed to occur in F, B, and A rings. The dominant component is water ice. The rings of Uranus are narrow and separated by broad empty regions. The technique used to study them has been stellar occulation. Nothing is known of particle size. The dominant component is believed to be silicates rich in compounds that absorb sunlight. Jupiter's rings consist of 3 main parts: a bright ring, a diffuse disk, and a halo. Use of Pioneer 10 data and other techniques have indicated particle sizes on the order of several micrometers and some at least a centimeter in diameter. The architecture of the ring system results from the interplay of a number of forces. These include gravitational forces due to moons outside the rings and moonlets embedded in them, electromagnetic forces due to the planet's rotating magnetic field, and even the gentle forces exerted by the dilute gaseous medium in which the rings rotate. Each of these forces is discussed. Several alternative explanations of how the rings arose are considered. The primary difference in these hypotheses is the account of the relationship between the ring particles of today and the primordial ring material. (SC)

  19. Physics of planetary rings

    NASA Astrophysics Data System (ADS)

    Gorkavyi, N.

    2007-08-01

    It is difficult to enumerate all the surprises presented by the planetary rings. The Saturnian rings are stratified into thousands of ringlets and the Uranian rings are compressed into narrow streams, which for some reason or other differ from circular orbits like the wheel of an old bicycle. The edge of the rings is jagged and the rings themselves are pegged down under the gravitational pressure of the satellites, bending like a ship's wake. There are spiral waves, elliptical rings, strange interlacing of narrow ringlets, and to cap it all one has observed in the Neptunian ring system three dense, bright arcs - like bunches of sausages on a transparent string. For celestial mechanics this is a spectacle as unnatural as a bear's tooth in the necklace of the English queen. In the dynamics of planetary rings the physics of collective interaction was supplemented by taking collisions between particles into account. One was led to study a kinetic equation with a rather complex collision integral - because the collisions are inelastic - which later on made it possible, both by using the Chapman-Enskog method and by using the solution of the kinetic equation for a plasma in a magnetic field, to reduce it to a closed set of (hydrodynamical) moment equations [1]. The hydrodynamical instabilities lead to the growth of short-wavelength waves and large-scale structures of the Saturnian rings [1]. We have shown that the formation of the existing dense Uranian rings is connected with the capture of positively drifting ring particles in inner Lindblad resonances which arrest this drift [1]. After the formation of dense rings at the positions of satellite resonances the collective interaction between resonant particles is amplified and the rings can leave the resonance and drift away from the planet and the parent resonance. We can expect in the C ring an appreciable positive ballistic particle drift caused by the erosion of the B ring by micrometeorites. It is therefore natural

  20. Double Ring Craters

    NASA Technical Reports Server (NTRS)

    1974-01-01

    A faint double ring crater is seen at upper right in this picture of Mercury (FDS 166601) taken one hour and 40 minutes before Mariner 10's second rendezvous with the planet September 21. Located 35 degrees S. Lat. The outer ring is 170 kilometers (10 miles) across. Double ring craters are common features on Mercury. This particular feature and the bright rayed crater to its left were seen from a different viewing angle in pictures taken by Mariner 10 during its first Mercury flyby last March 29.

    The Mariner 10 mission, managed by the Jet Propulsion Laboratory for NASA's Office of Space Science, explored Venus in February 1974 on the way to three encounters with Mercury-in March and September 1974 and in March 1975. The spacecraft took more than 7,000 photos of Mercury, Venus, the Earth and the Moon.

    Image Credit: NASA/JPL/Northwestern University

  1. Deployable Fresnel Rings

    NASA Technical Reports Server (NTRS)

    Kennedy, Timothy F.; Fink, Patrick W.; Chu, Andrew W.; Lin, Gregory Y.

    2014-01-01

    Deployable Fresnel rings (DFRs) significantly enhance the realizable gain of an antenna. This innovation is intended to be used in combination with another antenna element, as the DFR itself acts as a focusing or microwave lens element for a primary antenna. This method is completely passive, and is also completely wireless in that it requires neither a cable, nor a connector from the antenna port of the primary antenna to the DFR. The technology improves upon the previous NASA technology called a Tri-Sector Deployable Array Antenna in at least three critical aspects. In contrast to the previous technology, this innovation requires no connector, cable, or other physical interface to the primary communication radio or sensor device. The achievable improvement in terms of antenna gain is significantly higher than has been achieved with the previous technology. Also, where previous embodiments of the Tri-Sector antenna have been constructed with combinations of conventional (e.g., printed circuit board) and conductive fabric materials, this innovation is realized using only conductive and non-conductive fabric (i.e., "e-textile") materials, with the possible exception of a spring-like deployment ring. Conceptually, a DFR operates by canceling the out-of-phase radiation at a plane by insertion of a conducting ring or rings of a specific size and distance from the source antenna, defined by Fresnel zones. Design of DFRs follow similar procedures to those outlined for conventional Fresnel zone rings. Gain enhancement using a single ring is verified experimentally and through computational simulation. The experimental test setup involves a microstrip patch antenna that is directly behind a single-ring DFR and is radiating towards a second microstrip patch antenna. The first patch antenna and DFR are shown. At 2.42 GHz, the DFR improves the transmit antenna gain by 8.6 dB, as shown in Figure 2, relative to the wireless link without the DFR. A figure illustrates the

  2. Oligomeric ferrocene rings

    NASA Astrophysics Data System (ADS)

    Inkpen, Michael S.; Scheerer, Stefan; Linseis, Michael; White, Andrew J. P.; Winter, Rainer F.; Albrecht, Tim; Long, Nicholas J.

    2016-09-01

    Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1‧-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e- waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (˜107 s-1), these molecules can be considered as uniformly charged nanorings (diameter ˜1-2 nm).

  3. Oligomeric ferrocene rings

    NASA Astrophysics Data System (ADS)

    Inkpen, Michael S.; Scheerer, Stefan; Linseis, Michael; White, Andrew J. P.; Winter, Rainer F.; Albrecht, Tim; Long, Nicholas J.

    2016-09-01

    Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1‧-disubstituted ferrocene units (cyclo[n], n = 5–7, 9). Due to the close proximity and connectivity of centres (covalent Cp–Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e– waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼107 s‑1), these molecules can be considered as uniformly charged nanorings (diameter ∼1–2 nm).

  4. Child sex rings.

    PubMed

    Wild, N J; Wynne, J M

    1986-07-19

    Details of 11 child sex rings identified in one working class community were obtained by interviewing investigating police officers and examining health and social services records. The rings contained 14 adult male perpetrators and 175 children aged 6-15 years. Most perpetrators used child ringleaders to recruit victims; others became a "family friend" or obtained a position of authority over children. Secrecy was encouraged and bribery, threats, and peer pressure used to induce participation in sexual activities. Offences reported included fondling, masturbation, pornography, and oral, vaginal, and anal intercourse. Eleven perpetrators were successfully prosecuted; all but one received a sentence of three years or less. Behavioural problems were common among those children who had participated for a long time. Child sex rings are difficult to detect and may be common. Many children are seriously abused as a consequence of them. PMID:3730803

  5. Rings dominate western Gulf

    NASA Astrophysics Data System (ADS)

    Vidal L., Francisco V.; Vidal L., Victor M. V.; Molero, José María Pérez

    Surface and deep circulation of the central and western Gulf of Mexico is controlled by interactions of rings of water pinched from the gulf's Loop Current. The discovery was made by Mexican oceanographers who are preparing a full-color, 8-volume oceanographic atlas of the gulf.Anticyclonic warm-core rings pinch off the Loop Current at a rate of about one to two per year, the scientists of the Grupo de Estudios Oceanográficos of the Instituto de Investigaciones Eléctricas (GEO-IIE) found. The rings migrate west until they collide with the continental shelf break of the western gulf, almost always between 22° and 23°N latitude. On their westward travel they transfer angular momentum and vorticity to the surrounding water, generating cyclonic circulations and vortex pairs that completely dominate the entire surface and deep circulation of the central and western gulf.

  6. Polycyclic Aromatic Hydrocarbons with Armchair Edges and the 12.7 μm Band

    NASA Astrophysics Data System (ADS)

    Candian, A.; Sarre, P. J.; Tielens, A. G. G. M.

    2014-08-01

    In this Letter, we report the results of density functional theory calculations on medium-sized neutral polycyclic aromatic hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 μm and in the fingerprint region (10-15 μm), and also strong ring deformation modes around 12.7 μm. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common, although generally weak. Therefore, we propose that armchair PAHs with NC > 65 are responsible for the 12.7 μm aromatic infrared band in H II regions and discuss the astrophysical implications in the context of the PAH life cycle.

  7. POLYCYCLIC AROMATIC HYDROCARBONS WITH ARMCHAIR EDGES AND THE 12.7 μm BAND

    SciTech Connect

    Candian, A.; Tielens, A. G. G. M.; Sarre, P. J.

    2014-08-10

    In this Letter, we report the results of density functional theory calculations on medium-sized neutral polycyclic aromatic hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 μm and in the fingerprint region (10-15 μm), and also strong ring deformation modes around 12.7 μm. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common, although generally weak. Therefore, we propose that armchair PAHs with N{sub C} > 65 are responsible for the 12.7 μm aromatic infrared band in H II regions and discuss the astrophysical implications in the context of the PAH life cycle.

  8. Sliding-Ring Catenanes.

    PubMed

    Fernando, Isurika R; Frasconi, Marco; Wu, Yilei; Liu, Wei-Guang; Wasielewski, Michael R; Goddard, William A; Stoddart, J Fraser

    2016-08-17

    Template-directed protocols provide a routine approach to the synthesis of mechanically interlocked molecules (MIMs), in which the mechanical bonds are stabilized by a wide variety of weak interactions. In this Article, we describe a strategy for the preparation of neutral [2]catenanes with sliding interlocked electron-rich rings, starting from two degenerate donor-acceptor [2]catenanes, consisting of a tetracationic cyclobis(paraquat-p-phenylene) cyclophane (CBPQT(4+)) and crown ethers containing either (i) hydroquinone (HQ) or (ii) 1,5-dioxynaphthalene (DNP) recognition units and carrying out four-electron reductions of the cyclophane components to their neutral forms. The donor-acceptor interactions between the CBPQT(4+) ring and both HQ and DNP units present in the crown ethers that stabilize the [2]catenanes are weakened upon reduction of the cyclophane components to their radical cationic states and are all but absent in their fully reduced states. Characterization in solution performed by UV-vis, EPR, and NMR spectroscopic probes reveals that changes in the redox properties of the [2]catenanes result in a substantial decrease of the energy barriers for the circumrotation and pirouetting motions of the interlocked rings, which glide freely through one another in the neutral states. The solid-state structures of the fully reduced catenanes reveal profound changes in the relative dispositions of the interlocked rings, with the glycol chains of the crown ethers residing in the cavities of the neutral CBPQT(0) rings. Quantum mechanical investigations of the energy levels associated with the four different oxidation states of the catenanes support this interpretation. Catenanes and rotaxanes with sliding rings are expected to display unique properties. PMID:27398609

  9. A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames

    SciTech Connect

    Wang, H.; Frenklach, M.

    1997-07-01

    A computational study was performed for the formation and growth of polycyclic aromatic hydrocarbons (PAHs) in laminar premixed acetylene and ethylene flames. A new detailed reaction mechanism describing fuel pyrolysis and oxidation, benzene formation, and PAH mass growth and oxidation is presented and critically tested. It is shown that the reaction model predicts reasonably well the concentration profiles of major and intermediate species and aromatic molecules in a number of acetylene and ethylene flames reported in the literature. It is demonstrated that reactions of n-C{sub 4}H{sub x} + C{sub 2}H{sub 2} leading to the formation of one-ring aromatics are as important as the propargyl recombination, and hence must be included in kinetic modeling of PAH formation in hydrocarbon flames. It is further demonstrated that the mass growth of PAHs can be accounted for by the previously proposed H-abstraction-C{sub 2}H{sub 2}-addiction mechanism.

  10. The covariant chiral ring

    NASA Astrophysics Data System (ADS)

    Bourget, Antoine; Troost, Jan

    2016-03-01

    We construct a covariant generating function for the spectrum of chiral primaries of symmetric orbifold conformal field theories with N = (4 , 4) supersymmetry in two dimensions. For seed target spaces K3 and T 4, the generating functions capture the SO(21) and SO(5) representation theoretic content of the chiral ring respectively. Via string dualities, we relate the transformation properties of the chiral ring under these isometries of the moduli space to the Lorentz covariance of perturbative string partition functions in flat space.

  11. GUARD RING SEMICONDUCTOR JUNCTION

    DOEpatents

    Goulding, F.S.; Hansen, W.L.

    1963-12-01

    A semiconductor diode having a very low noise characteristic when used under reverse bias is described. Surface leakage currents, which in conventional diodes greatly contribute to noise, are prevented from mixing with the desired signal currents. A p-n junction is formed with a thin layer of heavily doped semiconductor material disposed on a lightly doped, physically thick base material. An annular groove cuts through the thin layer and into the base for a short distance, dividing the thin layer into a peripheral guard ring that encircles the central region. Noise signal currents are shunted through the guard ring, leaving the central region free from such currents. (AEC)

  12. Unidirectional ring lasers

    DOEpatents

    Hohimer, John P.; Craft, David C.

    1994-01-01

    Unidirectional ring lasers formed by integrating nonreciprocal optical elements into the resonant ring cavity. These optical elements either attenuate light traveling in a nonpreferred direction or amplify light traveling in a preferred direction. In one preferred embodiment the resonant cavity takes the form of a circle with an S-shaped crossover waveguide connected to two points on the interior of the cavity such that light traveling in a nonpreferred direction is diverted from the cavity into the crossover waveguide and reinjected out of the other end of the crossover waveguide into the cavity as light traveling in the preferred direction.

  13. Unidirectional ring lasers

    DOEpatents

    Hohimer, J.P.; Craft, D.C.

    1994-09-20

    Unidirectional ring lasers formed by integrating nonreciprocal optical elements into the resonant ring cavity is disclosed. These optical elements either attenuate light traveling in a nonpreferred direction or amplify light traveling in a preferred direction. In one preferred embodiment the resonant cavity takes the form of a circle with an S-shaped crossover waveguide connected to two points on the interior of the cavity such that light traveling in a nonpreferred direction is diverted from the cavity into the crossover waveguide and reinjected out of the other end of the crossover waveguide into the cavity as light traveling in the preferred direction. 21 figs.

  14. Saturn's Rings, the Yarkovsky Effects, and the Ring of Fire

    NASA Technical Reports Server (NTRS)

    Rubincam, David Parry

    2004-01-01

    The dimensions of Saturn's A and B rings may be determined by the seasonal Yarkovsky effect and the Yarkovsky-Schach effect; the two effects confine the rings between approximately 1.68 and approximately 2.23 Saturn radii, in reasonable agreement with the observed values of 1.525 and 2.267. The C ring may be sparsely populated because its particles are transients on their way to Saturn; the infall may create a luminous Ring of Fire around Saturn's equator. The ring system may be young: in the past heat flow from Saturn's interior much above its present value would not permit rings to exist.

  15. Transition-Metal Planar Boron Clusters: a New Class of Aromatic Compounds with High Coordination

    NASA Astrophysics Data System (ADS)

    Wang, Lai-Sheng

    2012-06-01

    Photoelectron spectroscopy in combination with computational studies over the past decade has shown that boron clusters possess planar or quasi-planar structures, in contrast to that of bulk boron, which is dominated by three-dimensional cage-like building blocks. All planar or quasi-planar boron clusters are observed to consist of a monocyclic circumference with one or more interior atoms. The propensity for planarity has been found to be due to both σ and π electron delocalization throughout the molecular plane, giving rise to concepts of σ and π double aromaticity. We have found further that the central boron atoms can be substituted by transition metal atoms to form a new class of aromatic compounds, which consist of a central metal atom and a monocyclic boron ring (M B_n). Eight-, nine-, and ten-membered rings of boron have been observed, giving rise to octa-, ennea-, and deca-coordinated aromatic transition metal compounds [1-3]. References: [1] ``Aromatic Metal-Centered Monocyclic Boron Rings: Co B_9^- and Ru B_9^-" (Constantin Romanescu, Timur R. Galeev, Wei-Li Li, A. I. Boldyrev, and L. S. Wang), Angew. Chem. Int. Ed. {50}, 9334-9337 (2011). [2] ``Transition-Metal-Centered Nine-Membered Boron Rings: M B_9 and M B_9^- (M = Rh, Ir)" (Wei-Li Li, Constantin Romanescu, Timur R. Galeev, Zachary Piazza, A. I. Boldyrev, and L. S. Wang), J. Am. Chem. Soc. {134}, 165-168 (2012). [3] ``Observation of the Highest Coordination Number in Planar Species: Decacoordinated Ta B10^- and Nb B_9^- Anions" (Timur R. Galeev, Constantin Romanescu, Wei-Li Li, L. S. Wang, and A. I. Boldyrev), Angew. Chem. Int. Ed. {51}, 2101-2105 (2012).

  16. Concise, aromatization-based approach to an elaborate C2-symmetric pyrenophane.

    PubMed

    Nandaluru, Penchal Reddy; Dongare, Prateek; Kraml, Christina M; Pascal, Robert A; Dawe, Louise N; Thompson, David W; Bodwell, Graham J

    2012-08-11

    A very short synthesis (5 steps), the crystal structure and resolution of an elaborate, inherently chiral [n](1,6)pyrenophane is reported. The synthesis hinges upon two very productive events: a multicomponent reaction and an unprecedented double-McMurry/valence isomerization/dehydrogenation step. Aromatization reactions are involved in the formation of all four of the rings of the pyrene system. PMID:22760162

  17. Gadolinium-Catalyzed Regio- and Enantioselective Aminolysis of Aromatic trans-2,3-Epoxy Sulfonamides.

    PubMed

    Wang, Chuan; Yamamoto, Hisashi

    2015-07-20

    The first enantioselective aminolysis of aromatic trans-2,3-epoxy sulfonamides has been accomplished, which was efficiently catalyzed by a Gd-N,N'-dioxide complex. Under the directing effect of the sulfonamide moiety the ring-opening reaction proceeded selectively at the C-3 position in a highly enantioselective manner furnishing various Ts- and SES-protected 3-amino-3-phenylpropan-2-olamines as products.

  18. Prediscovery evidence of planetary rings

    NASA Technical Reports Server (NTRS)

    Mclaughlin, W. I.

    1980-01-01

    The discoveries of the Uranian and Jovian ring systems were surprising events to most of the scientific community. However, as far back as 1787 reports of observations of rings about a planet other than Saturn were made; Herschel, the discoverer of Uranus, thought he had detected rings about that planet on several occasions. Although Herschel's observations were almost certainly due to defects in the optical system of his telescope, several valid observations and predictions have been made in the last two hundred years. This paper focuses on such prediscovery evidence for the Uranian and Jovian rings and for the newly designated F ring of Saturn. Some new work of the author on the structure of the Saturnian rings is included which is relevant to the F ring. The prospects for rings about Neptune and Pluto and a ring close to the Sun are also reviewed. The relevance of the prediscovery evidence to aspects of scientific methodology is discussed.

  19. Crystal Structure And Functional Analysis of Tetracenomycin Aro/Cyc: Implications for Cyclization Specificity of Aromatic Polyketides

    SciTech Connect

    Ames, B.D.; Korman, T.P.; Zhang, W.; Smith, P.; Vu, T.; Tang, Y.; Tsai, S.-C.

    2009-05-11

    Polyketides are a class of natural products with highly diverse chemical structures and pharmaceutical activities. Polyketide cyclization, promoted by the aromatase/cyclase (ARO/CYC), helps diversify aromatic polyketides. How the ARO/CYC promotes highly specific cyclization is not well understood because of the lack of a first-ring ARO/CYC structure. The 1.9 {angstrom} crystal structure of Tcm ARO/CYC reveals that the enzyme belongs to the Bet v1-like superfamily (or STAR domain family) with a helix-grip fold, and contains a highly conserved interior pocket. Docking, mutagenesis, and an in vivo assay show that the size, shape, and composition of the pocket are important to orient and specifically fold the polyketide chain for C9-C14 first-ring and C7-C16 second-ring cyclizations. Two pocket residues, R69 and Y35, were found to be essential for promoting first- and second-ring cyclization specificity. Different pocket residue mutations affected the polyketide product distribution. A mechanism is proposed based on the structure-mutation-docking results. These results strongly suggest that the regiospecific cyclizations of the first two rings and subsequent aromatizations take place in the interior pocket. The chemical insights gleaned from this work pave the foundation toward defining the molecular rules for the ARO/CYC cyclization specificity, whose rational control will be important for future endeavors in the engineered biosynthesis of novel anticancer and antibiotic aromatic polyketides.

  20. Experimental support for the role of dispersion forces in aromatic interactions.

    PubMed

    Lima, Carlos F R A C; Rocha, Marisa A A; Gomes, Lígia R; Low, John N; Silva, Artur M S; Santos, Luís M N B F

    2012-07-16

    Herein a core scaffold of 1-phenylnaphthalenes and 1,8-diphenylnaphthalenes with different substituents on the phenyl rings was used to study substituent effects on parallel-displaced aromatic π⋅⋅⋅π interactions. The energetics of the interaction was evaluated in gas phase based on the standard molar enthalpies of formation, at T=298.15 K, for the compounds studied; these values were derived from the combination of the results obtained by combustion calorimetry and Knudsen/Quartz crystal effusion. A homodesmotic gas-phase reaction scheme was used to quantify and compare the intramolecular interaction enthalpies in various substituted 1,8-diphenylnaphthalenes. The application of this methodology allowed a direct evaluation of aromatic interactions, and showed that substituent effects on the interaction enthalpy cannot be rationalized solely on classical electrostatic grounds, because no correlation with the σ(meta) or σ(para) Hammett constants was observed. Moreover, the results obtained indicate that aromatic π⋅⋅⋅π interactions are significantly enhanced by substitution, in a way that correlates with the ability of the interacting aryl rings to establish dispersive interactions. A combined experimental and computational approach for calculation of the true aromatic π⋅⋅⋅π interaction energies in these systems, free of secondary effects, was employed, and corroborates the rationale derived from the experimental results. These findings clearly emphasize the role of dispersion and dilute the importance of electrostatic forces on this type of interactions. PMID:22729996

  1. Self-assembled electrical materials from contorted aromatics

    NASA Astrophysics Data System (ADS)

    Xiao, Shengxiong

    This thesis describes the design, synthesis, self-assembly and electrical properties of new types of contorted polycyclic aromatic hydrocarbons. These topologically interesting contorted aromatics show promising transistor characteristics as new building blocks for organic field-effect transistors (OFETs) at different length scales. In chapter 2, a class of pentacenes that are substituted along their long edges with aromatic rings were synthesized. Their solid-state assemblies were studied by X-ray crystallography. Their performance as thin film transistors (TFTs) and single crystal field effect transistors (SCFETs) were systematically evaluated. A structure-property relationship between these highly phenylated pentacenes was found. Chapter 3 explores the new concept of whether a non-planar aromatic core could yield efficacious electronic materials, as the ultimate success in the organic electronics will require a holistic approach to creating new building blocks. Synthesis, functionalization and assembly of a new type of contorted hexabenzocoronene (HBC) whose aromatic core is heavily distorted away from planarity due to the steric congestion around its proximal carbons were discussed. Structural studies by X-ray crystallography showed that these HBC molecules stack into columnar structures in the solid state, which are ideal for conduction. Chapter 4 describes that microscale liquid crystalline thin film OFETs of tetradodecyloxy HBC showed the best transistor properties of all discotic columnar materials. Chapter 5 details the fabrication and characterization of nanoscale single crystalline fiber OFETs of octadodecyloxyl HBC. In Chapter 6 we show that a molecular scale monolayer of HBC acid chlorides could be self-assembled on SiO2 insulating layer and could be organized laterally between the ends of 2 nm carbon nanotube gaps to form high quality FETs that act as environmental and chemical sensors. Chapter 7 details the enforced one-dimensional photoconductivity

  2. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  3. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  4. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  5. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  6. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  7. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  8. Planar homotropenylium cation: a transition state with reversed aromaticity.

    PubMed

    Gibson, Christopher M; Havenith, Remco W A; Fowler, Patrick W; Jenneskens, Leonardus W

    2015-02-01

    In contrast to the equilibrium structure of the homoaromatic C(s) homotropenylium cation, C8H9(+) (1), which supports a pinched diatropic ring current, the C(2v) transition state (2) for inversion of the methylene bridge of 1 is antiaromatic and supports a two-lobe paratropic π current, as detected by plotting B3LYP/6-31G** ipsocentric current maps. Participation of the bridge CH bonds is crucial for the change in global character of the current in the transition state, as shown by the quenching of its paratropicity on substitution of H by F. Orbital-based arguments allow rationalization of this transition between homoaromaticity and hyper(conjugative) antiaromaticity. More generally, the hyperconjugative ring current in a family of C(2v) planar-constrained geometries of (CR2)C(N-1)H(N-1)(q) homoannulenes (R = H, F) can be switched from paratropic (antiaromatic) to diatropic (aromatic) by variation of ring size, charge, and bridge substituent. An orbital-based counting rule accounts for these systematic trends. PMID:25526524

  9. Outflow of polycyclic aromatic hydrocarbons from Guangdong, southern China.

    PubMed

    Lang, Chang; Tao, Shu; Zhang, Gang; Fu, Jiamo; Simonich, Staci

    2007-12-15

    The atmospheric outflow of polycyclic aromatic hydrocarbons (PAHs) from Guangdong, China, a region of high PAH emission, was modeled using a potential receptor influence function (PRIF) probabilistic model which was based on a spatially resolved PAH inventory and air mass forward-trajectory calculations. Photochemical degradation and deposition (dry and wet) of PAHs during atmospheric transport were taken into consideration. On average, 48% of the PAHs (by mass) remained in the atmosphere for a transport period of 5 days, staying within the boundary of the source region. The medium molecular weight PAHs (four rings) were predicted to travel longer distances in the atmosphere than the low (three rings) or high molecular weight PAHs (five rings) because they are less photodegradable than the lower molecular weight, gas-phase PAHs and less likelyto undergo wet and dry depositions than the higher molecular weight, particulate phase PAHs. Under the strong influence of the East Asian monsoons in winter, the predominant outflow pattern of PAHs from Guangdong was to the South China Sea and Southeast Asian countries. In summer, PAHs were transported primarily to northern mainland China. Under particular weather conditions in winter, the PAH-containing air masses were lifted by cold fronts or convection and transported toward the Pacific Ocean by westerly winds. In addition to the distinct seasonality in PAH dispersion and outflow, interannual long-term variation in the outflow is likely influenced by El Niño and southern oscillation.

  10. Tough, Soluble, Aromatic, Thermoplastic Copolyimides

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G. (Inventor)

    1998-01-01

    Tough, soluble, aromatic, thermoplastic copolyimides were prepared by reacting 4,4'-oxydiphthalic anhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride and 3,4'-oxydianiline. These copolyimides were found to be soluble in common amide solvents such as N,N'-dimethyl acetamide, N-methylpyrrolidinone, and dimethylformamide allowing them to be applied as the fully imidized copolymer and to be used to prepare a wide range of articles.

  11. Flushing Ring for EDM

    NASA Technical Reports Server (NTRS)

    Earwood, L.

    1985-01-01

    Removing debris more quickly lowers cutting time. Operation, cutting oil and pressurized air supplied to ring placed around workpiece. Air forces oil through small holes and agitates oil as it flows over workpiece. High flow rate and agitation dislodge and remove debris. Electrical discharge removes material from workpiece faster.

  12. Ring of Stellar Death

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This false-color image from NASA's Spitzer Space Telescope shows a dying star (center) surrounded by a cloud of glowing gas and dust. Thanks to Spitzer's dust-piercing infrared eyes, the new image also highlights a never-before-seen feature -- a giant ring of material (red) slightly offset from the cloud's core. This clumpy ring consists of material that was expelled from the aging star.

    The star and its cloud halo constitute a 'planetary nebula' called NGC 246. When a star like our own Sun begins to run out of fuel, its core shrinks and heats up, boiling off the star's outer layers. Leftover material shoots outward, expanding in shells around the star. This ejected material is then bombarded with ultraviolet light from the central star's fiery surface, producing huge, glowing clouds -- planetary nebulas -- that look like giant jellyfish in space.

    In this image, the expelled gases appear green, and the ring of expelled material appears red. Astronomers believe the ring is likely made of hydrogen molecules that were ejected from the star in the form of atoms, then cooled to make hydrogen pairs. The new data will help explain how planetary nebulas take shape, and how they nourish future generations of stars.

    This image composite was taken on Dec. 6, 2003, by Spitzer's infrared array camera, and is composed of images obtained at four wavelengths: 3.6 microns (blue), 4.5 microns (green), 5.8 microns (orange) and 8 microns (red).

  13. Reading, Writing, and Rings!

    ERIC Educational Resources Information Center

    Aschbacher, Pamela; Li, Erika; Hammon, Art

    2008-01-01

    "Reading, Writing, and Rings!" was created by a team of elementary teachers, literacy experts, and scientists in order to integrate science and literacy. These free units bring students inside NASA's Cassini-Huygens mission to Saturn. The authors--a science teacher and education outreach specialist and two evaluators of educational programs--have…

  14. Ring laser scatterometer

    SciTech Connect

    Ackermann, Mark; Diels, Jean-Claude

    2005-06-28

    A scatterometer utilizes the dead zone resulting from lockup caused by scatter from a sample located in the optical path of a ring laser at a location where counter-rotating pulses cross. The frequency of one pulse relative to the other is varied across the lockup dead zone.

  15. Making Molecular Borromean Rings

    ERIC Educational Resources Information Center

    Pentecost, Cari D.; Tangchaivang, Nichol; Cantrill, Stuart J.; Chichak, Kelly S.; Peters, Andrea J.; Stoddart, Fraser J.

    2007-01-01

    A procedure that requires seven 4-hour blocks of time to allow undergraduate students to prepare the molecular Borromean rings (BRs) on a gram-scale in 90% yield is described. The experiment would serve as a nice capstone project to culminate any comprehensive organic laboratory course and expose students to fundamental concepts, symmetry point…

  16. Neptune may have polar rings

    NASA Astrophysics Data System (ADS)

    Dobrovolskis, A. R.; Steiman-Cameron, T. Y.; Borderies, N. J.

    1989-08-01

    Perturbations from Neptune's highly inclined satellite Triton can maintain rings passing nearly over Neptune's poles. These hypothetical polar rings are nearly perpendicular to Triton's orbit as well, and lie within several degrees of the plane of Voyager II's trajectory through the Neptunian system. Polar rings can coexist with equatorial rings at different radii. A randomly oriented torus of debris around Neptune has a probability of several percent to settle into a polar ring. Voyager II stands a significant chance of encountering a polar ring.

  17. Narrow rings - Observations and theory

    NASA Astrophysics Data System (ADS)

    Porco, C. C.

    Voyager 1 and 2 observations have revealed that within the rings of Saturn lies a set of narrow, eccentric rings resembling those of Uranus. Voyager 2 observations have proven crucial in refining the Uranian ring orbit models to a remarkable level of precision. All these rings share some common structural and kinematical characteristics, such as spatially variable radial widths and uniform precession; however, interesting differences exist which provoke attention and may be related to the differing dynamical environments in which these rings dwell. The current state of the knowledge of the shape, behavior, and confinement of narrow rings is discussed.

  18. The direct aromatization of methane

    SciTech Connect

    Marcelin, G.; Oukaci, R.; Migone, R.A.; Kazi, A.M.

    1995-12-31

    The thermal decomposition of methane shows significant potential as a process for the production of higher unsaturated and aromatic hydrocarbons when the extent of the reaction is limited. Thermodynamic calculations have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that cooling the product and reacting gases as the reaction proceeds can significantly reduce or eliminate the formation of solid carbon and heavier (C{sub 10+}) materials. Much work remains to be done in optimizing the quenching process and this is one of the goals of this program. Means to lower the temperature of the reaction are being studied as this result in a more feasible commercial process due to savings realized in energy and material of construction costs. The use of free-radical generators and catalysts will be investigated as a means of lowering the reaction temperature thus allowing faster quenching. It is highly likely that such studies will lead to a successful direct methane to higher hydrocarbon process.

  19. Ring species as demonstrations of the continuum of species formation.

    PubMed

    Pereira, Ricardo J; Wake, David B

    2015-11-01

    In the mid-20th century, Ernst Mayr (1942) and Theodosius Dobzhansky (1958) championed the significance of 'circular overlaps' or 'ring species' as the perfect demonstration of the gradual nature of species formation. As an ancestral species expands its range, wrapping around a geographic barrier, derived taxa within the ring display interactions typical of populations, such as genetic and morphological intergradation, while overlapping taxa at the terminus of the ring behave largely as sympatric, reproductively isolated species. Are ring species extremely rare or are they just difficult to detect? What conditions favour their formation? Modelling studies have attempted to address these knowledge gaps by estimating the biological parameters that result in stable ring species (Martins et al. 2013), and determining the necessary topographic parameters of the barriers encircled (Monahan et al. 2012). However, any generalization is undermined by a major limitation: only a handful of ring species are known to exist in nature. In addition, many of them have been broken into multiple species presumed to be evolving independently, usually obscuring the evolutionary dynamics that generate diversity. A paper in this issue of Molecular Ecology by Fuchs et al. (2015), focused on the entire genealogy of a bulbul (Alophoixus) species complex, offers key insights into the evolutionary processes underlying diversification of this Indo-Malayan bird. Their findings fulfil most of the criteria that can be expected for ring species (Fig. ): an ancestor has colonized the mainland from Sundaland, expanded along the forested habitat wrapping around Thailand's lowlands, adjacent taxa intergrade around the ring distribution, and terminal taxa overlap at the ring closure. Although it remains unclear whether ring divergence has resulted in restrictive gene flow relative to that observed around the ring, their results suggest that circular overlaps might be more common in nature than

  20. Ring Bubbles of Dolphins

    NASA Technical Reports Server (NTRS)

    Shariff, Karim; Marten, Ken; Psarakos, Suchi; White, Don J.; Merriam, Marshal (Technical Monitor)

    1996-01-01

    The article discusses how dolphins create and play with three types of air-filled vortices. The underlying physics is discussed. Photographs and sketches illustrating the dolphin's actions and physics are presented. The dolphins engage in this behavior on their own initiative without food reward. These behaviors are done repeatedly and with singleminded effort. The first type is the ejection of bubbles which, after some practice on the part of the dolphin, turn into toroidal vortex ring bubbles by the mechanism of baroclinic torque. These bubbles grow in radius and become thinner as they rise vertically to the surface. One dolphin would blow two in succession and guide them to fuse into one. Physicists call this a vortex reconnection. In the second type, the dolphins first create an invisible vortex ring in the water by swimming on their side and waving their tail fin (also called flukes) vigorously. This vortex ring travels horizontally in the water. The dolphin then turns around, finds the vortex and injects a stream of air into it from its blowhole. The air "fills-out" the core of the vortex ring. Often, the dolphin would knock-off a smaller ring bubble from the larger ring (this also involves vortex reconnection) and steer the smaller ring around the tank. One other dolphin employed a few other techniques for planting air into the fluke vortex. One technique included standing vertically in the water with tail-up, head-down and tail piercing the free surface. As the fluke is waved to create the vortex ring, air is entrained from above the surface. Another technique was gulping air in the mouth, diving down, releasing air bubbles from the mouth and curling them into a ring when they rose to the level of the fluke. In the third type, demonstrated by only one dolphin, the longitudinal vortex created by the dorsal fin on the back is used to produce 10-15 foot long helical bubbles. In one technique she swims in a curved path. This creates a dorsal fin vortex since

  1. Rings from Close Encounters

    NASA Astrophysics Data System (ADS)

    Kohler, Susanna

    2016-09-01

    Weve recently discovered narrow sets of rings around two minor planets orbiting in our solar system. How did these rings form? A new study shows that they could be a result of close encounters between the minor planets and giants like Jupiter or Neptune.Unexpected Ring SystemsPositions of the centaurs in our solar system (green). Giant planets (red), Jupiter trojans (grey), scattered disk objects (tan) and Kuiper belt objects (blue) are also shown. [WilyD]Centaurs are minor planets in our solar system that orbit between Jupiter and Neptune. These bodies of which there are roughly 44,000 with diameters larger than 1 km have dynamically unstable orbits that cross paths with those of one or more giant planets.Recent occultation observations of two centaurs, 10199 Chariklo and 2060 Chiron, revealed that these bodies both host narrow ring systems. Besides our four giant planets, Chariklo and Chiron are the only other bodies in the solar system known to have rings. But how did these rings form?Scientists have proposed several models, implicating collisions, disruption of a primordial satellite, or dusty outgassing. But a team of scientists led by Ryuki Hyodo (Paris Institute of Earth Physics, Kobe University) has recently proposed an alternative scenario: what if the rings were formed from partial disruption of the centaur itself, after it crossed just a little too close to a giant planet?Tidal Forces from a GiantHyodo and collaborators first used past studies of centaur orbits to estimate that roughly 10% of centaurs experience close encounters (passing within a distance of ~2x the planetary radius) with a giant planet during their million-year lifetime. The team then performed a series of simulations of close encounters between a giant planet and a differentiated centaur a body in which the rocky material has sunk to form a dense silicate core, surrounded by an icy mantle.Some snapshots of simulation outcomes (click for a closer look!) for different initial states of

  2. Comparison of mussels and semi-permeable membrane devices as intertidal monitors of polycyclic aromatic hydrocarbons at oil spill sites.

    PubMed

    Boehm, Paul D; Page, David S; Brown, John S; Neff, Jerry M; Edward Bence, A

    2005-07-01

    Side-by-side comparisons of polycyclic aromatic hydrocarbon (PAH) concentrations in resident blue mussels (Mytilus trossulus) and in semi-permeable membrane devices (SPMDs) were made at four sites in Prince William Sound, Alaska. SPMDs were deployed for approximately 30 days on the surface of the beach sediment at three tidal elevations on each shore and in 0.5 m deep open pits in the middle intertidal zone. Total PAH (TPAH) concentrations in mussels and in SPMDs were correlated, but the PAH compositions were different. The lower molecular weight PAH were relatively more abundant in the SPMDs than in the mussels at oiled and HA sites. TPAH concentrations in SPMDs deployed in pits and mussels collected adjacent to those pits at oiled sites were higher than in SPMDs and mussels from non-pitted SPMD locations approximately 3-15 m from the pits. Pitting released buried oil making its PAH bioavailable. SPMDs deployed in the supratidal zone (+4.0 m tidal elevation) were exposed to atmospheric contaminants for a large fraction of the deployment time and accumulated primarily pyrogenic (combustion-sourced) PAH from the atmosphere. The SPMD strips supplied by the manufacturer contained significant amounts (approximately 125 ng/strip) of primarily alkylated 2-3 ring PAH. These blank levels make SPMDs unsuitable for shoreline assessments when environmental PAH concentrations are low. Consequently, where available, mussels are recommended for use in assessments of the bioavailability of buried oil residues sequestered in intertidal sediments following an oil spill. Mussels are the preferred monitoring tool when the assessments involve food-chain effects. At locations where the absence of mussels necessitates the use of SPMDs or other passive sampling devices, their limitations need to be carefully considered in the interpretation of results.

  3. Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Mahjoub, Ahmed; Schwell, Martin; Carrasco, Nathalie; Benilan, Yves; Cernogora, Guy; Szopa, Cyril; Gazeau, Marie-Claire

    2016-10-01

    The role of polycyclic aromatic hydrocarbons (PAH) and Nitrogen containing PAH (PANH) as intermediates of aerosol production in the atmosphere of Titan has been a subject of controversy for a long time. An analysis of the atmospheric emission band observed by the Visible and Infrared Mapping Spectrometer (VIMS) at 3.28 μm suggests the presence of neutral polycyclic aromatic species in the upper atmosphere of Titan. These molecules are seen as the counter part of negative and positive aromatics ions suspected by the Plasma Spectrometer onboard the Cassini spacecraft, but the low resolution of the instrument hinders any molecular speciation. In this work we investigate the specific aromatic content of Titan's atmospheric aerosols through laboratory simulations. We report here the selective detection of aromatic compounds in tholins, Titan's aerosol analogs, produced with a capacitively coupled plasma in a N2:CH4 95:5 gas mixture. For this purpose, Two-Step Laser Desorption Ionization Time-of-Flight Mass Spectrometry (L2DI-TOF-MS) technique is used to analyze the so produced analogs. This analytical technique is based on the ionization of molecules by Resonance Enhanced Multi-Photon Ionization (REMPI) using a λ=248 nm wavelength laser which is selective for aromatic species. This allows for the selective identification of compounds having at least one aromatic ring. Our experiments show that tholins contain a trace amount of small PAHs with one to three aromatic rings. Nitrogen containing PAHs (PANHs) are also detected as constituents of tholins. Molecules relevant to astrobiology are detected as is the case of the substituted DNA base adenine.

  4. Saturn ring temperature changes before and after ring equinox

    NASA Astrophysics Data System (ADS)

    Spilker, Linda; Flandes, Alberto; Morishima, Ryuji; Leyrat, Cedric; Altobelli, Nicolas; Ferrari, Cecile; Brooks, Shawn; Pilorz, Stu

    2010-05-01

    The Cassini Composite infrared spectrometer (CIRS) retrieved the temperatures of Saturn's main rings at solar elevations ranging from 24 degrees to zero degrees at equinox (August 2009) as the sun traversed from the south to north side of the rings. Over this broad range of solar elevation the CIRS data show that the ring temperatures vary as much as 29K- 38K for the A ring, 22K-34K for the B ring and 18K-23K for the C ring. Interestingly the unlit sides of the rings show a similar decrease in temperature with the decreasing solar elevation. As equinox approached, the main rings cooled to their lowest temperatures measured to date. At equinox the solar input is very small and the primary heat sources for the rings are Saturn thermal and visible energy. Temperatures are almost identical for similar geometries on the north and south sides of the rings. The ring temperatures at equinox were: C ring, 55-75 K; B ring, 45-60 K; Cassini Division, 45 - 58 K; and A ring, 43 - 52 K. After Saturn equinox the solar elevation angle began to increase again and the temperatures on both the lit (north) and unlit (south) sides of the rings have begun to increase as well. Ring thermal models developed by Flandes and Morishima are able to reproduce most of the equinox temperatures observed by CIRS. Results before and after equinox will be presented. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with NASA and at CEA Saclay supported by the "Programme National de Planetologie". Copyright 2010 California Institute of Technology. Government sponsorship acknowledged.

  5. Noncomparative scaling of aromaticity through electron itinerancy

    SciTech Connect

    Paul, Satadal; Goswami, Tamal; Misra, Anirban

    2015-10-15

    Aromaticity is a multidimensional concept and not a directly observable. These facts have always stood in the way of developing an appropriate theoretical framework for scaling of aromaticity. In the present work, a quantitative account of aromaticity is developed on the basis of cyclic delocalization of π-electrons, which is the phenomenon leading to unique features of aromatic molecules. The stabilization in molecular energy, caused by delocalization of π-electrons is obtained as a second order perturbation energy for archetypal aromatic systems. The final expression parameterizes the aromatic stabilization energy in terms of atom to atom charge transfer integral, onsite repulsion energy and the population of spin orbitals at each site in the delocalized π-electrons. An appropriate computational platform is framed to compute each and individual parameter in the derived equation. The numerical values of aromatic stabilization energies obtained for various aromatic molecules are found to be in close agreement with available theoretical and experimental reports. Thus the reliable estimate of aromaticity through the proposed formalism renders it as a useful tool for the direct assessment of aromaticity, which has been a long standing problem in chemistry.

  6. Noncomparative scaling of aromaticity through electron itinerancy

    NASA Astrophysics Data System (ADS)

    Paul, Satadal; Goswami, Tamal; Misra, Anirban

    2015-10-01

    Aromaticity is a multidimensional concept and not a directly observable. These facts have always stood in the way of developing an appropriate theoretical framework for scaling of aromaticity. In the present work, a quantitative account of aromaticity is developed on the basis of cyclic delocalization of π-electrons, which is the phenomenon leading to unique features of aromatic molecules. The stabilization in molecular energy, caused by delocalization of π-electrons is obtained as a second order perturbation energy for archetypal aromatic systems. The final expression parameterizes the aromatic stabilization energy in terms of atom to atom charge transfer integral, onsite repulsion energy and the population of spin orbitals at each site in the delocalized π-electrons. An appropriate computational platform is framed to compute each and individual parameter in the derived equation. The numerical values of aromatic stabilization energies obtained for various aromatic molecules are found to be in close agreement with available theoretical and experimental reports. Thus the reliable estimate of aromaticity through the proposed formalism renders it as a useful tool for the direct assessment of aromaticity, which has been a long standing problem in chemistry.

  7. Steroidal aromatic 'naphthenic acids' in oil sands process-affected water: structural comparisons with environmental estrogens.

    PubMed

    Rowland, Steven J; West, Charles E; Jones, David; Scarlett, Alan G; Frank, Richard A; Hewitt, L Mark

    2011-11-15

    The large volumes, acute toxicity, estrogenicity, and antiandrogenicity of process-affected waters accruing in tailings ponds from the operations of the Alberta oil sands industries pose a significant task for environmental reclamation. Synchronous fluorescence spectra (SFS) suggest that oil sands process-affected water (OSPW) may contain aromatic carboxylic acids, which are among the potentially environmentally important toxicants, but no such acids have yet been identified, limiting interpretations of the results of estrogenicity and other assays. Here we show that multidimensional comprehensive gas chromatography-mass spectrometry (GCxGC-MS) of methyl esters of acids in an OSPW sample produces mass spectra consistent with their assignment as C(19) and C(20) C-ring monoaromatic hydroxy steroid acids, D-ring opened hydroxy and nonhydroxy polyhydrophenanthroic acids with one aromatic and two alicyclic rings and A-ring opened steroidal keto acids. High resolution MS data support the assignment of several of the so-called 'O3' species. When fractions of distilled, esterified, OSPW acid-extractable organics were examined, the putative aromatics were mainly present in a high boiling fraction; when examined by argentation thin layer chromatography, some were present in a fraction with a retardation factor between that of the methyl esters of synthetic monoalicyclic and monoaromatic acids. Ultraviolet absorption spectra of these fractions indicated the presence of benzenoid moieties. SFS of model octahydro- and tetrahydrophenanthroic acids produced emissions at the characteristic excitation wavelengths observed in some OSPW extracts, consistent with the postulations from ultraviolet spectroscopy and mass spectrometry data. We suggest the acids originate from extensive biodegradation of C-ring monoaromatic steroid hydrocarbons and offer a means of differentiating residues at different biodegradation stages in tailings ponds. Structural similarities with estrone and

  8. Peptide hairpins with strand segments containing alpha- and beta-amino acid residues: cross-strand aromatic interactions of facing Phe residues.

    PubMed

    Roy, Rituparna S; Gopi, Hosahudya N; Raghothama, S; Gilardi, Richard D; Karle, Isabella L; Balaram, Padmanabhan

    2005-01-01

    The incporation of beta-amino acid residues into the strand segments of designed beta-hairpin leads to the formation of polar sheets, since in the case of beta-peptide strands, all adjacent carbonyl groups point in one direction and the amide groups orient in the opposite direction. The conformational analysis of two designed peptide hairpins composed of alpha/beta-hybrid segments are described: Boc-Leu-betaPhe-Val-(D)-Pro-Gly-Leu-betaPhe-Val-OMe (1) and Boc-betaLeu-Phe-betaVal-D-Pro-Gly-betaLeu-Phe-betaVal-OMe (2). A 500-MHz 1H-NMR (nuclear magnetic resonance) analysis in methanol supports a significant population of hairpin conformations in both peptides. Diagnostic nuclear Overhauser effects (NOEs) are observed in both cases. X-ray diffraction studies on single crystals of peptide 1 reveal a beta-hairpin conformation in both the molecules, which constitute the crystallographic asymmetric unit. Three cross-strand hydrogen bonds and a nucleating type II' beta-turn at the D-Pro-Gly segment are observed in the two independent molecules. In peptide 1, the betaPhe residues at positions 2 and 7 occur at the nonhydrogen-bonding position, with the benzyl side chains pointing on opposite faces of the beta-sheet. The observed aromatic centroid-to-centroid distances are 8.92 A (molecule A) and 8.94 A (molecule B). In peptide 2, the aromatic rings must occupy facing positions in antiparallel strands, in the NMR-derived structure. Peptide 1 yields a normal "hairpin-like" CD spectrum in methanol with a minimum at 224 nm. The CD spectrum of peptide 2 reveals a negative band at 234 nm and a positive band at 221 nm, suggestive of an exciton split doublet. Modeling of the facing Phe side chains at the hydrogen-bonding position of a canonical beta-hairpin suggests that interring separation is approximately 4.78 A for the gauche+ gauche- (g+ g-) rotamer. A previously reported peptide beta-hairpin composed of only alpha-amino acids, Boc-Leu-Phe-Val-D-Pro-Gly-Leu-Phe-Val-OMe also

  9. Polycyclic aromatic hydrocarbon emissions from motorcycles

    NASA Astrophysics Data System (ADS)

    Yang, Hsi-Hsien; Hsieh, Lien-Te; Liu, Hsu-Chung; Mi, Hsiao-Hsuan

    Emissions of polycyclic aromatic hydrocarbons (PAHs, 2-7 ring) and regulated air pollutants (CO, HC, NO x, PM) from 2-stroke carburetor (2-Stk/Cb), 4-stroke carburetor (4-Stk/Cb) and 4-stroke fuel injection (4-Stk/FI) motorcycles were investigated by testing these vehicles on a chassis dynamometer. Exhaust samplings were carried out on diluted exhausts in a dilution tunnel connected to a constant volume sampling system. Measurements were performed on a standard driving cycle. The results reveal that low molecular weight PAHs (especially naphthalene) dominated in the exhaust gas. The averages of soluble organic fractions were 86.4%, 46.3% and 48.9% for the 2-Stk/Cb, 4-Stk/Cb and 4-Stk/FI motorcycles, respectively. PAH emissions are greater from cold-start driving than those from hot-start driving cycle for all these three kinds of motorcycles. Total PAH emission factors were 8320, 5990 and 3390 μg km -1 for the in-used 2-Stk/Cb, 4-Stk/Cb and 4-Stk/FI motorcycles, respectively. PAH emission factors were the largest for the 2-Stk/Cb motorcycles. Besides, the 2-Stk/Cb motorcycle had the largest total BaP equivalent emission factor of 10.8 μg km -1, indicating that the emission exhaust from the 2-Stk/Cb motorcycle was most carcinogenic. HC, PM and PAH emissions were the lowest for the 4-Stk/FI motorcycles. The correlation coefficient between CO and total PAH emissions for all the test motorcycles was 0.51, indicating that CO and PAH emissions are not highly correlated.

  10. Inorganic glass ceramic slip rings

    NASA Technical Reports Server (NTRS)

    Glossbrenner, E. W.; Cole, S. R.

    1972-01-01

    Prototypes of slip rings have been fabricated from ceramic glass, a material which is highly resistant to deterioration due to high temperature. Slip ring assemblies were not structurally damaged by mechanical tests and performed statisfactorily for 200 hours.

  11. The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

    NASA Technical Reports Server (NTRS)

    Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

    1994-01-01

    Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

  12. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Weckhuysen, Bert M

    2011-03-21

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. PMID:21246746

  13. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Weckhuysen, Bert M

    2011-03-21

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin.

  14. Environmental diagnostic analysis of ground water bacteria and their involvement in utilization of aromatic compounds

    SciTech Connect

    Wear, J.E. Jr.

    1993-01-01

    This study examines the hypothesis that select functional groups of bacteria from pristine sites have an innate ability to degrade synthetic aromatics contaminating groundwater environments, due to exposure to naturally occurring recalcitrant aromatics in their environment. Ground water was pumped at monthly intervals from twelve wells at four different sites. Two of these sites could be considered pristine. The other two sites were contaminated, one with trichloroethylene, the other with polyaromatic hydrocarbons and possible sulfur compounds. There are great variations in physiological states and metabolic needs of bacteria in these different aquifers. All but one of the wells studied demonstrated higher counts on low nutrient media than high nutrient media, suggesting the oligotrophic nature of these groundwater environments. The subsurface microbial communities are capable of utilizing lignin and humic acid breakdown products. Highest counts for the aromatics tested were observed with the naturally occurring breakdown products of either lignin or humic acid. Carboxylic acids were found to be an important sole carbon source for groundwater bacteria possibly explained by the fact that they are produced by the oxidative cleavage of aromatic ring structures. Utilization of naturally occurring aromatic compounds in the subsurface is an important nutritional source for groundwater bacteria. In addition, adaptation to naturally occurring recalcitrant substrates is the origin of degradative pathways for xenobiotic compounds with analogous structure. This has important implications for in situ bioremediation as a method of environmental cleanup.

  15. Ring Opening of Naphthenic Molecules Over Metal Containing Mesoporous Y Zeolite Catalyst.

    PubMed

    Lee, You-Jin; Kim, Eun Sang; Kim, Tae-Wan; Kim, Chul-Ung; Jeong, Kwang-Eun; Lee, Chang-Ha; Jeong, Soon-Yong

    2015-07-01

    Mesoporous Y zeolite (Meso-Y) with a uniform mesopore was synthesized via pseudomorphic syn- thesis. The Meso-Y supported Ni-W catalyst (NiW/Meso-Y) was introduced as a catalyst for the selective ring opening of naphthenic rings. The catalytic test for the ring opening of naphthalene as a model compound of multi-ring aromatics was performed using a batch-type reaction system with both sulfided 20 wt% NiW/Meso-Y and NiW/Y catalysts under different reaction conditions. The catalytic results reveal that the Meso-Y supported NiW catalyst experiences a naphthalene conversion similar to the NiW/Y catalyst, but the NiW/Meso-Y catalyst has higher product yields for BTEX (benzene, toluene, ethyl benzene, and xylene) and the middle distillate than those of the NiW/Y catalyst at a low reaction temperature. These results suggest that the mesoporosity of the NiW/Meso-Y catalyst is more advantageous for the ring opening reaction of multi-ring aromatics due to the easier access for the bulky molecules compared to the NiW/Y catalyst.

  16. O-Ring-Testing Fixture

    NASA Technical Reports Server (NTRS)

    Turner, James E.; Mccluney, D. Scott

    1990-01-01

    Fixture used to evalute properties of O-rings of various materials. Hydraulic actuator positions plug in housing, creating controlled, variable gap in O-ring glands formed by grooves in plug and by inner wall of housing. Creates controlled axial and radial gaps between sealing surfaces around ring so effectiveness of material in maintaining seal determined under dynamic conditions.

  17. RINGED ACCRETION DISKS: EQUILIBRIUM CONFIGURATIONS

    SciTech Connect

    Pugliese, D.; Stuchlík, Z. E-mail: zdenek.stuchlik@physics.cz

    2015-12-15

    We investigate a model of a ringed accretion disk, made up by several rings rotating around a supermassive Kerr black hole attractor. Each toroid of the ringed disk is governed by the general relativity hydrodynamic Boyer condition of equilibrium configurations of rotating perfect fluids. Properties of the tori can then be determined by an appropriately defined effective potential reflecting the background Kerr geometry and the centrifugal effects. The ringed disks could be created in various regimes during the evolution of matter configurations around supermassive black holes. Therefore, both corotating and counterrotating rings have to be considered as being a constituent of the ringed disk. We provide constraints on the model parameters for the existence and stability of various ringed configurations and discuss occurrence of accretion onto the Kerr black hole and possible launching of jets from the ringed disk. We demonstrate that various ringed disks can be characterized by a maximum number of rings. We present also a perturbation analysis based on evolution of the oscillating components of the ringed disk. The dynamics of the unstable phases of the ringed disk evolution seems to be promising in relation to high-energy phenomena demonstrated in active galactic nuclei.

  18. DC-Powered Jumping Ring

    ERIC Educational Resources Information Center

    Jeffery, Rondo N.; Farhang, Amiri

    2016-01-01

    The classroom jumping ring demonstration is nearly always performed using alternating current (AC), in which the ring jumps or flies off the extended iron core when the switch is closed. The ring jumps higher when cooled with liquid nitrogen (LN2). We have performed experiments using DC to power the solenoid and find similarities and significant…

  19. Vortex Rings in Superfluid Helium

    NASA Astrophysics Data System (ADS)

    Alamri, Sultan Z.; Barenghi, Carlo F.

    2008-11-01

    We present results of numerical simulations of large-scale vortex rings in superfluid helium. These large-scale vortex rings consists of many discrete (quantized) vortex filaments which interact with each other moving according to the Biot-Savart law. Lifetime, structural stability and speed of large-scale vortex rings will be discussed and compared to experimental results.

  20. Uranus: the rings are black.

    PubMed

    Sinton, W M

    1977-11-01

    An upper limit of 0.05 is established for the geometric albedo of the newly discovered rings of Uranus. In view of this very low albedo, the particles of the rings cannot be ice-covered as are those of rings A and B of Saturn.

  1. Reflectance spectroscopy (350-2500 nm) of solid-state polycyclic aromatic hydrocarbons (PAHs)

    NASA Astrophysics Data System (ADS)

    Izawa, M. R. M.; Applin, D. M.; Norman, L.; Cloutis, E. A.

    2014-07-01

    Polycyclic aromatic hydrocarbons (PAHs) are organic compounds based on fused aromatic rings, and are formed in a variety of astrophysical, solar nebula and planetary processes. Polycyclic aromatic hydrocarbons are known or suspected to occur in a wide variety of planetary settings including icy satellites, Titan’s hazes, carbonaceous meteorites, comet nuclei, ring particles; and terrestrial organic-rich lithologies such as coals, asphaltites, and bituminous sands. Relatively few measurements of the visible and near-infrared spectra of PAHs exist, yet this wavelength region (350-2500 nm) is widely used for remote sensing. This study presents detailed analyses of the 350-2500 nm reflectance spectra of 47 fine-grained powders of different high-purity solid-state PAHs. Spectral properties of PAHs change with variations in the number and connectivity of linked aromatic rings and the presence and type of side-groups and heterocycles. PAH spectra are characterized by three strong features near ∼880 nm, ∼1145 nm, and ∼1687 nm due to overtones of νCH fundamental stretching vibrations. Some PAHs are amenable to remote detection due to the presence of diagnostic spectral features, including: Nsbnd H stretching overtones at 1490-1515 nm in NH- and NH2-bearing PAHs, aliphatic or saturated bond Csbnd H overtone vibrations at ∼1180-1280 nm and ∼1700-1860 nm; a broad asymmetric feature between ∼1450 nm and ∼1900 nm due to Osbnd H stretching overtones in aromatic alcohols, Csbnd H and Cdbnd O combinations near ∼2000-2010 nm and ∼2060-2270 nm in acetyl and carboxyl-bearing PAHs. Other substituents such as sulphonyl, thioether ether and carboxyl heterocycles, or cyano, nitrate, and aromatic side groups, do not produce well-resolved diagnostic spectral features but do cause shifts in the positions of the aromatic Csbnd H vibrational overtone features. Fluorescence is commonly suppressed by the presence of heterocycles, side-groups and in many non-alternant PAHs

  2. Satellite Rings Movie

    NASA Technical Reports Server (NTRS)

    2000-01-01

    This brief movie clip (of which the release image is a still frame), taken by NASA's Cassini spacecraft as it approached Jupiter, shows the motions, over a 16 hour-period, of two satellites embedded in Jupiter's ring. The moon Adrastea is the fainter of the two, and Metis the brighter. Images such as these will be used to refine the orbits of the two bodies.

    The movie was made from images taken during a 40-hour sequence of the Jovian ring on December 11, 2000.

    Cassini is a cooperative mission of NASA, the European Space Agency and the Italian Space Agency. JPL, a division of the California Institute of Technology in Pasadena, manages Cassini for NASA's Office of Space Science, Washington, D.C.

  3. Oligomeric ferrocene rings.

    PubMed

    Inkpen, Michael S; Scheerer, Stefan; Linseis, Michael; White, Andrew J P; Winter, Rainer F; Albrecht, Tim; Long, Nicholas J

    2016-09-01

    Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category-differently sized rings comprising only 1,1'-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e(-) waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼10(7) s(-1)), these molecules can be considered as uniformly charged nanorings (diameter ∼1-2 nm). PMID:27554408

  4. Which Ringed Planet...!?

    NASA Astrophysics Data System (ADS)

    2002-12-01

    Don't worry - you are not the only one who thought this was a nice amateur photo of planet Saturn, Lord of the Rings in our Solar System! But then the relative brightness and positions of the moons may appear somewhat unfamiliar... and the ring system does look unusually bright when compared to the planetary disk...?? Well, it is not Saturn, but Uranus , the next giant planet further out, located at a distance of about 3,000 million km, or 20 times the distance between the Sun and the Earth. The photo shows Uranus surrounded by its rings and some of the moons, as they appear on a near-infrared image that was obtained in the K s -band (at wavelength 2.2 µm) with the ISAAC multi-mode instrument on the 8.2-m VLT ANTU telescope at the ESO Paranal Observatory (Chile) . The exposure was made on November 19, 2002 (03:00 hrs UT) during a planetary research programme. The observing conditions were excellent (seeing 0.5 arcsec) and the exposure lasted 5 min. The angular diameter of Uranus is about 3.5 arcsec. The observers at ISAAC were Emmanuel Lellouch and Thérése Encrenaz of the Observatoire de Paris (France) and Jean-Gabriel Cuby and Andreas Jaunsen (both ESO-Chile). The rings The rings of Uranus were discovered in 1977, from observations during a stellar occultation event by astronomer teams at the Kuiper Airborne Observatory (KAO) and the Perth Observatory (Australia). Just before and after the planet moved in front of the (occulted) star, the surrounding rings caused the starlight to dim for short intervals of time. Photos obtained from the Voyager-2 spacecraft in 1986 showed a multitude of very tenuous rings. These rings are almost undetectable from the Earth in visible light. However, on the present VLT near-infrared picture, the contrast between the rings and the planet is strongly enhanced. At the particular wavelength at which this observation was made, the infalling sunlight is almost completely absorbed by gaseous methane present in the planetary atmosphere

  5. Uranus rings and two moons

    NASA Technical Reports Server (NTRS)

    1986-01-01

    Voyager 2 has discovered two 'shepherd' satellites associated with the rings of Uranus. The two moons -- designated 1986U7 and 1986U8 -- are seen here on either side of the bright epsilon ring; all nine of the known Uranian rings are visible. The image was taken Jan. 21, 1986, at a distance of 4.1 million kilometers (2.5 million miles) and resolution of about 36 km (22 mi). The image was processed to enhance narrow features. The epsilon ring appears surrounded by a dark halo as a result of this processing; occasional blips seen on the ring are also artifacts. Lying inward from the epsilon ring are the delta, gamma and eta rings; then the beta and alpha rings; and finally the barely visible 4, 5 and 6 rings. The rings have been studied since their discovery in 1977, through observations of how they diminish the light of stars they pass in front of. This image is the first direct observation of all nine rings in reflected sunlight. They range in width from about 100 km (60 mi) at the widest part of the epsilon ring to only a few kilometers for most of the others. The discovery of the two ring moons 1986U7 and 1986U8 is a major advance in our understanding of the structure of the Uranian rings and is in good agreement with theoretical predictions of how these narrow rings are kept from spreading out. Based on likely surface brightness properties, the moons are of roughly 2O- and 3O-km diameter, respectively. The Voyager project is managed for NASA by the Jet Propulsion Laboratory.

  6. Quantum transport through aromatic molecules

    SciTech Connect

    Ojeda, J. H.; Rey-González, R. R.; Laroze, D.

    2013-12-07

    In this paper, we study the electronic transport properties through aromatic molecules connected to two semi-infinite leads. The molecules are in different geometrical configurations including arrays. Using a nearest neighbor tight-binding approach, the transport properties are analyzed into a Green's function technique within a real-space renormalization scheme. We calculate the transmission probability and the Current-Voltage characteristics as a function of a molecule-leads coupling parameter. Our results show different transport regimes for these systems, exhibiting metal-semiconductor-insulator transitions and the possibility to employ them in molecular devices.

  7. From Möbius aromaticity to gapped spin liquids

    NASA Astrophysics Data System (ADS)

    Chen, Cheng-Chien; Muechler, Lukas; Neupert, Titus; Maciejko, Joseph; Car, Roberto

    Motivated by the concept of Möbius aromatics in organic chemistry, the Hubbard model on ring-shaped molecules has been shown previously to support a fragile Mott insulator (FMI) ground state, which is distinct from a conventional insulator through its nontrivial transformation properties under point-group symmetry operations. In this talk, we discuss two-dimensional lattices of weakly-coupled FMI molecules belonging to multi-dimensional irreducible representations of the molecular point group. The low-energy effective Hamiltonians map onto quantum compass models with broken spin SU(2) symmetry. On the triangular lattice, the ground state develops long-range magnetism, which corresponds to a charge-ordered state of the molecules. On the honeycomb lattice, interestingly, we find a non-degenerate gapped spin-liquid ground state that preserves all spatial symmetries but transforms nontrivially under point-group operations. Our microscopic model therefore realizes an intrinsically interacting fermionic symmetry protected topological (SPT) phase.

  8. Biodegradation for polynuclear aromatic hydrocarbons in the environment

    SciTech Connect

    Prince, R.C.; Brake, E.N.; Rothenburger, S.J.

    1996-10-01

    Bioremediation promises to be a cost-effective remediation option for hydrocarbon contaminated soils and sediments, but much remains to be determined about the molecular fate of specific molecules in spilled oil and refined products. We have examined the biodegradation of polynuclear aromatic hydrocarbons with two to five rings, in aqueous flask systems, and in soils where the hydrocarbons have been present for many years. We have used consortia of indigenous organisms, and have attempted to use optimal nutrient strategies to stimulate microbial growth. We find that all the alkylated forms of naphthalene with 0-4 methyl groups, and of phenanthrene and dibenzothiophene with 0-3 methyl groups are biodegradable, and that parent compounds such as naphthalene, phenanthrene, anthracene, dibenzothiophene, benz[a]anthracene, pyrene, chrysene and benz[a]anthracene are all degradable under conditions that mimic field application of nutrient-assisted bioremediation.

  9. The adsorption of aromatic acids onto the graphite basal surface

    NASA Astrophysics Data System (ADS)

    Martin, David S.

    2003-06-01

    The adsorption of benzoic acid, toluic acid, and salicylic acid from solution onto the graphite basal surface has been studied using atomic force microscopy (AFM). A systematic study of these three related planar aromatic acids is conducted in order to observe the influence of the functional side-group upon adsorption. It is found that upon adsorption all three acids orient with the benzene ring parallel to the graphite surface. On the graphite terraces, the benzoic acid decoration follows a Stranski-Krastanov growth mode whereas toluic acid follows Volmer-Weber growth. Salicylic acid forms a fibrous aggregate network. In addition to the terraces, graphite steps and near-surface bulk defects are found to be important sites for adsorption. The AFM tip is used to create irreversible nanoscale modifications of adsorbate structures.

  10. Transport of Polycyclic Aromatic Hydrocarbons in Unsaturated Porous Media

    NASA Astrophysics Data System (ADS)

    Chahal, Maninder; Flury, Markus

    2016-04-01

    Polycyclic aromatic hydrocarbons (PAHs) are complex organic molecules containing 2 or more fused benzene rings. Being hydrophobic and non-polar, PAHs tend to partition to the organic matter in the soil from bulk aqueous phase. Though transport of these contaminants has been well studied in saturated environment, interactive mechanisms of these fluorescent compounds in unsaturated (identified by presence of air-water interface) porous media is still not well understood. We studied is the transport of fluoranthene in unsaturated porous media as facilitated by moving air-water interfaces. Confocal microscopy was used to visualize the interactions of fluoranthene particles in a glass channel packed with quartz glass beads. The packed glass channel was used to mimic a porous media and effects of an advancing and receding capillary fringe on the detachment of fluoranthene.

  11. PAH and H2 emission in the Ring Nebula

    NASA Astrophysics Data System (ADS)

    Cox, N. L. J.; Pilleri, P.; Berné, O.; Cernicharo, J.; Joblin, C.

    2016-07-01

    This paper presents the Spitzer IRS (Infra Red Spectrograph) detection of mid-infrared polycyclic aromatic hydrocarbon (PAH) emission features and H2 associated with dense knots in the ring of the “oxygen-rich” (C/O∼⃒0.6-0.8) planetary nebula (PN) NGC6720 (Ring Nebula). We explored a further three oxygen-rich extended PNe with similar dataset available. These turned out to be non-detection of PAHs, although two of these do contain H2 emission knots. The presence of PAHs is discussed in the context of a bottom-up formation mechanism, in which first small hydrocarbons, and later PAHs, are formed in warm dense knots inside the ionised regions of PNe.

  12. Ius Chasma Tributary Valleys and Adjacent Plains

    NASA Technical Reports Server (NTRS)

    2006-01-01

    This image covers valley tributaries of Ius Chasma, as well as the plains adjacent to the valleys. Ius Chasma is one of several canyons that make up the Valles Marineris canyon system. Valles Marineris likely formed by extension associated with the growth of the large volcanoes and topographic high of Tharsis to the northwest. As the ground was pulled apart, large and deep gaps resulted in the valleys seen in the top and bottom of this HiRISE image. Ice that was once in the ground could have also melted to create additional removal of material in the formation of the valleys. HiRISE is able to see the rocks along the walls of both these valleys and also impact craters in the image. Rock layers that appear lower down in elevation appear rougher and are shedding boulders. Near the top of the walls and also seen in patches along the smooth plains are brighter layers. These brighter layers are not shedding boulders so they must represent a different kind of rock formed in a different kind of environment than those further down the walls. Because they are highest in elevation, the bright layers are youngest in age. HiRISE is able to see dozens of the bright layers, which are perhaps only a meter in thickness. Darker sand dunes and ripples cover most of the plains and fill the floors of impact craters.

    Image PSP_001351_1715 was taken by the High Resolution Imaging Science Experiment (HiRISE) camera onboard the Mars Reconnaissance Orbiter spacecraft on November 9, 2006. The complete image is centered at -8.3 degrees latitude, 275.4 degrees East longitude. The range to the target site was 254.3 km (158.9 miles). At this distance the image scale ranges from 25.4 cm/pixel (with 1 x 1 binning) to 101.8 cm/pixel (with 4 x 4 binning). The image shown here has been map-projected to 25 cm/pixel and north is up. The image was taken at a local Mars time of 3:32 PM and the scene is illuminated from the west with a solar incidence angle of 59 degrees, thus the sun was about

  13. Ideals of generalized matrix rings

    SciTech Connect

    Budanov, Aleksandr V

    2011-01-31

    Let R and S be rings, and {sub R}M{sub S} and {sub S}N{sub R} bimodules. In the paper, in terms of isomorphisms of lattices, relationships between the lattices of one-sided and two-sided ideals of the generalized matrix ring and the corresponding lattices of ideals of the rings R and S are described. Necessary and sufficient conditions for a pair of ideals I, J of rings R and S, respectively, to be the main diagonal of some ideal of the ring K are also obtained. Bibliography: 8 titles.

  14. O-Ring-Testing Fixture

    NASA Technical Reports Server (NTRS)

    Turner, James E.; Mccluney, D. Scott

    1991-01-01

    Fixture tests O-rings for sealing ability under dynamic conditions after extended periods of compression. Hydraulic cylinder moves plug in housing. Taper of 15 degrees on plug and cavity of housing ensures that gap created between O-ring under test and wall of cavity. Secondary O-rings above and below test ring maintain pressure applied to test ring. Evaluates effects of variety of parameters, including temperature, pressure, rate of pressurization, rate and magnitude of radial gap movement, and pretest compression time.

  15. New instability of Saturn's ring

    SciTech Connect

    Goertz, C.K.; Morfill, G.

    1988-05-01

    Perturbations in the Saturn ring's mass density are noted to be prone to instabilities through the sporadic elevation of submicron-size dust particles above the rings, which furnishes an effective angular momentum exchange between the rings and Saturn. The dust thus elevated from the ring settles back onto it at a different radial distance. The range of wavelength instability is determinable in light of the dust charge, the average radial displacement of the dust, and the fluctuation of these quantities. It is suggested that at least some of the B-ring's ringlets may arise from the instability.

  16. Helmet latching and attaching ring

    NASA Technical Reports Server (NTRS)

    Chase, E. W.; Viikinsalo, S. J. (Inventor)

    1970-01-01

    A neck ring releasably secured to a pressurized garment carries an open-ended ring normally in the engagement position fitted into an annular groove and adapted to fit into a complementary annular groove formed in a helmet. Camming means formed on the inner surface at the end of the helmet engages the open-ended ring to retract the same and allow for one motion donning even when the garment is pressurized. A projection on the end of the split ring is engageable to physically retract the split ring.

  17. Transmission performance of one waveguide and double micro-ring resonator using 3×3 optical fiber coupler

    NASA Astrophysics Data System (ADS)

    Zhao, Chao Ying; Tan, Wei Han

    2016-09-01

    This paper investigates theoretically the transmission characteristics of one waveguide and double micro-ring resonator using 3 × 3 optical fibre coupler. Our analytical solution of transmittance is suitable for either linearly distributed coupler or circularly symmetric distributed coupler. The all-optical analogue to electromagnetic inducted transparency spectrum of one waveguide and double micro-ring resonators can be controlled by changing the coupling strength between waveguide and micro-rings, the absorption coefficient around micro-rings, as well as the asymmetric coupling coefficients between non-adjacent waveguides. The curves show that the transitions of transmission spectra sensitively depend on asymmetric coupling coefficients.

  18. Learning Non-Adjacent Regularities at Age 0 ; 7

    ERIC Educational Resources Information Center

    Gervain, Judit; Werker, Janet F.

    2013-01-01

    One important mechanism suggested to underlie the acquisition of grammar is rule learning. Indeed, infants aged 0 ; 7 are able to learn rules based on simple identity relations (adjacent repetitions, ABB: "wo fe fe" and non-adjacent repetitions, ABA: "wo fe wo", respectively; Marcus et al., 1999). One unexplored issue is…

  19. View of north side from exterior stairs of adjacent building, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    View of north side from exterior stairs of adjacent building, bottom cut off by fringed buildings, view facing south-southwest - U.S. Naval Base, Pearl Harbor, Industrial X-Ray Building, Off Sixth Street, adjacent to and south of Facility No. 11, Pearl City, Honolulu County, HI

  20. Delayed Acquisition of Non-Adjacent Vocalic Distributional Regularities

    ERIC Educational Resources Information Center

    Gonzalez-Gomez, Nayeli; Nazzi, Thierry

    2016-01-01

    The ability to compute non-adjacent regularities is key in the acquisition of a new language. In the domain of phonology/phonotactics, sensitivity to non-adjacent regularities between consonants has been found to appear between 7 and 10 months. The present study focuses on the emergence of a posterior-anterior (PA) bias, a regularity involving two…

  1. Aromatic Anchor at an Invariant Hormone-Receptor Interface

    PubMed Central

    Pandyarajan, Vijay; Smith, Brian J.; Phillips, Nelson B.; Whittaker, Linda; Cox, Gabriella P.; Wickramasinghe, Nalinda; Menting, John G.; Wan, Zhu-li; Whittaker, Jonathan; Ismail-Beigi, Faramarz; Lawrence, Michael C.; Weiss, Michael A.

    2014-01-01

    Crystallographic studies of insulin bound to fragments of the insulin receptor have recently defined the topography of the primary hormone-receptor interface. Here, we have investigated the role of PheB24, an invariant aromatic anchor at this interface and site of a human mutation causing diabetes mellitus. An extensive set of B24 substitutions has been constructed and tested for effects on receptor binding. Although aromaticity has long been considered a key requirement at this position, MetB24 was found to confer essentially native affinity and bioactivity. Molecular modeling suggests that this linear side chain can serve as an alternative hydrophobic anchor at the hormone-receptor interface. These findings motivated further substitution of PheB24 by cyclohexanylalanine (Cha), which contains a nonplanar aliphatic ring. Contrary to expectations, [ChaB24]insulin likewise exhibited high activity. Furthermore, its resistance to fibrillation and the rapid rate of hexamer disassembly, properties of potential therapeutic advantage, were enhanced. The crystal structure of the ChaB24 analog, determined as an R6 zinc-stabilized hexamer at a resolution of 1.5 Å, closely resembles that of wild-type insulin. The nonplanar aliphatic ring exhibits two chair conformations with partial occupancies, each recapitulating the role of PheB24 at the dimer interface. Together, these studies have defined structural requirements of an anchor residue within the B24-binding pocket of the insulin receptor; similar molecular principles are likely to pertain to insulin-related growth factors. Our results highlight in particular the utility of nonaromatic side chains as probes of the B24 pocket and suggest that the nonstandard Cha side chain may have therapeutic utility. PMID:25305014

  2. [Syntheses and ring-closures of difunctional tetrahydroisoquinolines].

    PubMed

    Zalán, Zita

    2006-01-01

    Starting from homoveratrylamine and N-protected amino acids 1,2,3,4-tetrahydroisoquinoline diamines were prepared by a convenient four-step process. This synthetic method was successfully extended to substituted beta-alanine and homoveratrylamine derivatives. In the case of the 1'-methyl-substituted derivatives, the reducing agent applied and the sequence of the reduction and deprotection steps proved to have marked effects on the formation of the possible diamine diastereomers. By N-amination of the corresponding amino alcohols, tetrahydroisoquinoline hydrazino alcohol regioisomers were prepared. Condensation products of the prepared tetrahydroisoquinoline 1,2- and 1,3-diamines containing a primary amino group with aromatic aldehydes proved to participate in three-component ring-chain tautomeric equilibria. The tautomeric equilibrium was sensitive to the electronic effects of the aromatic substituents, the ring size and the methyl substituents of the skeleton. By N-substitution reactions of 1-(Cbz-aminomethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline with isocyanates and isothiocyanates, the corresponding urea or thiourea derivatives were obtained some derivatives of which showed a remarkable MDR modulating activity. By ring-closures of tetrahydroisoquinoline diamines and hydrazino alcohols with phosphorus-containing reagents, saturated 1,3,2-diazaphosphino[6,1-a]isoquinolines, and 1,3,4,2-oxadiazaphosphino[5,4-a]- and [4,5-b]isoquinolines as the first representatives of these ring systems were prepared. The conformational behaviour of these compounds was studied by NMR and X-ray diffractional analyses. PMID:17094664

  3. A season in Saturn's rings: Cycling, recycling and ring history

    NASA Astrophysics Data System (ADS)

    Esposito, L. W.; Meinke, B. K.; Albers, N.; Sremcevic, M.

    2012-04-01

    Cassini experiments have watched Saturn's ring system evolve before our eyes. Images and occultations show changes and transient events. The rings are a dynamic and complex geophysical system, incompletely modeled as a single-phase fluid. Key Cassini observations: High resolution images show straw, propellers, embedded moonlets, and F ring objects. Multiple UVIS, RSS and VIMS occutlations indicate multimodal ringlet and edge structure, including free and forced modes along with stochastic perturbations that are most likely caused by nearby mass concentrations. Vertical excursions are evident at ring edges and in other perturbed regions. The rings are occasionally hit by meteorites that leave a signature that may last centuries; meteoritic dust pollutes the rings. Temperature, reflectance and transmission spectra are influenced by the dynamical state of the ring particles. Saturn's Equinox 2009: Oblique lighting exposed vertical structure and embedded objects. The rings were the coldest ever. Images inspired new occultation and spectral analysis that show abundant structure in the perturbed regions. The rings are more variable and complex than we had expected prior to this seasonal viewing geometry. Sub-kilometer structure in power spectral analysis: Wavelet analysis shows features in the strongest density waves and at the shepherded outer edge of the B ring. Edges are variable as shown by multiple occultations and occultations of double stars. F ring kittens: 25 features seen in the first 102 occultations show a weak correlation with Prometheus location. We interpret these features as temporary aggregations. Simulation results indicate that accretion must be enhanced to match the kittens' size distribution. Images show that Prometheus triggers the formation of transient objects. Propellers and ghosts: Occulations and images provide evidence for small moonlets in the A, B and C rings. These indicate accretion occurs inside the classical Roche limit. Implications

  4. Large Abundances of Polycyclic Aromatic Hydrocarbons in Titan's Upper Atmosphere

    NASA Technical Reports Server (NTRS)

    Lopez-Puertas, M.; Dinelli, B. M.; Adriani, A.; Funke, B.; Garcia-Comas, M.; Moriconi, M. L.; D'Aversa, E.; Boersma, C.; Allamandola, L. J.

    2013-01-01

    In this paper, we analyze the strong unidentified emission near 3.28 micron in Titan's upper daytime atmosphere recently discovered by Dinelli et al.We have studied it by using the NASA Ames PAH IR Spectroscopic Database. The polycyclic aromatic hydrocarbons (PAHs), after absorbing UV solar radiation, are able to emit strongly near 3.3 micron. By using current models for the redistribution of the absorbed UV energy, we have explained the observed spectral feature and have derived the vertical distribution of PAH abundances in Titan's upper atmosphere. PAHs have been found to be present in large concentrations, about (2-3) × 10(exp 4) particles / cubic cm. The identified PAHs have 9-96 carbons, with a concentration-weighted average of 34 carbons. The mean mass is approx 430 u; the mean area is about 0.53 sq. nm; they are formed by 10-11 rings on average, and about one-third of them contain nitrogen atoms. Recently, benzene together with light aromatic species as well as small concentrations of heavy positive and negative ions have been detected in Titan's upper atmosphere. We suggest that the large concentrations of PAHs found here are the neutral counterpart of those positive and negative ions, which hence supports the theory that the origin of Titan main haze layer is located in the upper atmosphere.

  5. LARGE ABUNDANCES OF POLYCYCLIC AROMATIC HYDROCARBONS IN TITAN'S UPPER ATMOSPHERE

    SciTech Connect

    Lopez-Puertas, M.; Funke, B.; Garcia-Comas, M.; Dinelli, B. M.; Adriani, A.; D'Aversa, E.; Moriconi, M. L.; Boersma, C.; Allamandola, L. J.

    2013-06-20

    In this paper, we analyze the strong unidentified emission near 3.28 {mu}m in Titan's upper daytime atmosphere recently discovered by Dinelli et al. We have studied it by using the NASA Ames PAH IR Spectroscopic Database. The polycyclic aromatic hydrocarbons (PAHs), after absorbing UV solar radiation, are able to emit strongly near 3.3 {mu}m. By using current models for the redistribution of the absorbed UV energy, we have explained the observed spectral feature and have derived the vertical distribution of PAH abundances in Titan's upper atmosphere. PAHs have been found to be present in large concentrations, about (2-3) Multiplication-Sign 10{sup 4} particles cm{sup -3}. The identified PAHs have 9-96 carbons, with a concentration-weighted average of 34 carbons. The mean mass is {approx}430 u; the mean area is about 0.53 nm{sup 2}; they are formed by 10-11 rings on average, and about one-third of them contain nitrogen atoms. Recently, benzene together with light aromatic species as well as small concentrations of heavy positive and negative ions have been detected in Titan's upper atmosphere. We suggest that the large concentrations of PAHs found here are the neutral counterpart of those positive and negative ions, which hence supports the theory that the origin of Titan main haze layer is located in the upper atmosphere.

  6. Mutagenicity of photochemically-transformed polycyclic aromatic amines

    SciTech Connect

    Strniste, G.F.; Nickols, J.W.; Okinaka, R.T.; Whaley, T.W.

    1985-01-01

    Polycyclic aromatic amines (PAA) constitute a class of suspect genotoxic chemicals found in certain energy-related complex organic mixtures. A variety of studies are reported on the photochemical transformation (oxidation) of polycyclic aromatic amines and the increase in genotoxicity of the resulting complex mixtures of radiation-generated products. Biological endpoints of cytotoxicity and mutagenicity were measured in the Ames/Salmonella standard-plate assay. Chemical fractionation and identification of various photoproducts was accomplished with h.p.l.c., uv and ir spectroscopic and mass spectrometric techniques. The benchmark PAA in these studies was aminofluorene (2-AF). Photooxidation of 2-AF can occur at both the exocyclic nitrogen and certain ring positions resulting in the formation of direct-acting and potent bacterial mutagens, including 2-nitrosofluorene, 2-nitrofluorene, and 2-nitrofluoren-9-one. UVA-irradiated 2-AF solutions also contain promutagenic compounds, i.e., is 2-aminofluoren-9-one. These results support the hypothesis that the critical step in the activation of major, identified direct-acting mutagenic 2-AF photoproducts is their reduction by bacterial nitroreductase enzymes to reactive hydroxylamines. Photochemical oxidation is an alternative mechanism of transforming PAA into direct-acting genotoxins. 24 refs., 5 figs.

  7. Heterogeneous catalyzed benzylic acetoxylation of methylated aromatic hydrocarbons

    SciTech Connect

    Benazzi, E.; Mimoun, H.; Cameron, C.J. )

    1993-04-01

    The palladium-catalyzed acetoxylation of toluene to benzyl acetate is highly dependent on particle size. The rate of reaction is highest with 30--35 [Angstrom] particles corresponding to a 0.33 dispersion. Catalysts prepared and reduced by controlled methods before being contacted with the reaction medium, ex situ catalysts, were found to yield lower reaction rates than catalysts prepared in the reaction medium, in situ. Potassium ion-encapsulation in palladium during in situ preparation is a possible explanation for this result. Tin is required to reduce Pd[sup 2+] to Pd[sup 0] in the in situ system, but is not required for the ex situ catalyst. The improvement in activity of the ex situ catalyst in the presence of tin may be due to the reducibility of Sn[sup 4+] to Sn[sup 2+] during oxygen-poor regimes. Results obtained with diverse methylated aromatic hydrocarbons indicate that the aromatic ring interactions with the palladium surface via [pi]-donation before oxidation occurs. 37 refs., 7 figs., 5 tabs.

  8. Alkyl polycyclic aromatic hydrocarbons emissions in diesel/biodiesel exhaust

    NASA Astrophysics Data System (ADS)

    Casal, Carina S.; Arbilla, Graciela; Corrêa, Sergio M.

    2014-10-01

    Polycyclic aromatic hydrocarbons (PAHs) are widely studied in environmental matrices, such as air, water, soil and sediment, because of their toxicity, mutagenicity and carcinogenicity. Because of these properties, the environmental agencies of developed countries have listed sixteen PAHs as priority pollutants. Few countries have limits for these compounds for ambient air, but they only limit emissions from stationary and mobile sources and occupational areas. There are several studies to specifically address the 16 priority PAHs and very little for the alkyl PAHs. These compounds are more abundant, more persistent and frequently more toxic than the non-alkylated PAHs, and the toxicity increases with the number of alkyl substitutions on the aromatic ring. In this study, a method was developed for the analysis of PAHs and alkyl PAHs by using a GC-MS and large injection volume injection coupled with program temperature vaporisation, which allows for limits of detection below 1.0 ng μL-1. Several variables were tested, such as the injection volume, injection velocity, injector initial temperature, duration of the solvent split and others. This method was evaluated in samples from particulate matter from the emissions of engines employing standard diesel, commercial diesel and biodiesel B20. Samples were collected on a dynamometer bench for a diesel engine cycle and the results ranged from 0.5 to 96.9 ng mL-1, indicating that diesel/biodiesel makes a significant contribution to the formation of PAHs and alkyl PAHs.

  9. A DFT study on dihydropyrazine annulated linear polyacenes: aromaticity, stability and HOMO-LUMO energy modulation.

    PubMed

    Rakhi, Ramachandran; Suresh, Cherumuttathu H

    2016-09-21

    Linear polyacenes (LPAs) beyond pentacene are highly unstable and their application potential in the optoelectronics field is very limited. On the basis of theoretical studies at the M06L/6-311++G(d,p) level of DFT, we show that annulating dihydropyrazine units to LPA cores can yield large LPA mimics. This strategy enhances the aromaticity of the LPA core and also provides a way to modulate the HOMO-LUMO energy gap by choosing an appropriate LPA core and extending dihydropyrazine annulation. The study is conducted for LPA mimics containing up to six dihydropyrazine units annulated to benzene (pB1-pB6), naphthalene (pN1-pN6), anthracene (pA1-pA6) and tetracene (pT1-pT6) cores. The longest of them pT6 contains 34 linearly connected six-membered rings. The dehydrogenation energy (Edh) of the N-heterocycles of the LPA mimics showed endothermic character and indicated their higher stability than dehydrogenated N-heteroacenes. The total Edh (ΣEdh) is proportional to the increase in the number of heterocycles and the increase in the size of the LPA core. The aromaticity of individual rings of all the LPA mimics is assessed on the basis of the harmonic oscillator model of aromaticity (HOMA) and nucleus independent chemical shift (NICS) parameters. Both parameters showed strong linear correlation with ΣEdh, confirming the geometric, magnetic and energetic criteria of aromaticity. The electronic features of the LPA mimics assessed by analysing molecular electrostatic potential topography and molecular orbitals have shown that the LPA cores retain the reactivity of the parent LPA. Furthermore, significant mixing of the N-lone pairs of the heterocycle with carbon π-orbitals improves aromaticity and decreases the HOMO-LUMO energy gap. PMID:27546099

  10. Multi-element double ring infrared detector based on InSb

    NASA Astrophysics Data System (ADS)

    Li, Mo; Lv, Hui; Guo, Li; Liu, Zhu

    2015-10-01

    A multi-element double ring infrared detector based on InSb p-n photodiodes is presented. The presented detector includes an outer ring detector and an inner ring detector. Each ring consist 10 detector elements, five mid-wave infrared detector elements and five short wave infrared detector elements. Two wavebands of 3.5-5 μm and 1.5-3 μm in mid-wave infrared and short wave infrared are adopted. The mid-wave infrared and short wave infrared detector elements are arranged alternately and close to each other to form detection pair. Between the adjacent detector elements, there is an interval to avoid cross talk. Dual band filter thin films are directly coated on the photodiode surface to form a dual band infrared detector. The double ring detector which can perform dual band IR counter-countermeasures can track target effectively under infrared countermeasure conditions.

  11. VIS-IR spectrophotometric indicators for Saturn's rings and spokes

    NASA Astrophysics Data System (ADS)

    Filacchione, G.; Capaccioni, F.; Cerroni, P.; D'Aversa, E.; Clark, R. N.; Cuzzi, J. N.; Nicholson, P. D.; Brown, R. H.; Coradini, A.

    2009-12-01

    The composition of Saturn's main rings can be inferred through the application of VIS-IR spectral indicators applied to Cassini-VIMS observations and comparison of these properties with those of other icy bodies in the Saturn system and in the outer solar system. We have selected several rings mosaics taken at observation geometries at which the contamination of the rings spectra by saturnshine in negligible. Main ring particles are composed of almost pure crystalline water ice: at VIS wavelengths <0.52 µm the rings have a distinctive reddish color indicative of a non-icy component that must not exceed (based on microwave observations) a few percent. No other IR absorption feature of CO2, CH4, silicates or C-H organics (i.e. tholins) are detected in VIMS spectra. By using several spectral indicators (visible colors, water ice band depths and particle albedo) we map the radial variation of the rings composition, showing how it correlates with the local surface mass density and/or optical depth: C ring and Cassini Division are more contaminated by non-icy material than the A and B rings. The degree of visual “redness” is highly correlated with ice band strengths, suggesting the presence of a UV absorber, still unidentified, intimately mixed within the icy component. We have also applied the spectral indicators to several observations of the B ring in which spokes are visible. These shadowy radial structures, first discovered by Voyager, were almost absent during the Cassini nominal mission (2004-2008) but have become more and more frequent as Saturn approaches equinox. When observed in reflectance in the 0.35 to 3 µm range, the region of the B ring intersected by the spoke has a lower reflectance than adjacent points at the same radial distance, as seen by Voyager and HST, and interpreted as local overabundance of submicron-sized grains. The presence of the spoke don't influence the rings spectra in the 3-5 µm range nor introduce variations in the distribution

  12. Genetics Home Reference: aromatic l-amino acid decarboxylase deficiency

    MedlinePlus

    ... aromatic l-amino acid decarboxylase deficiency aromatic l-amino acid decarboxylase deficiency Enable Javascript to view the expand/ ... PDF Open All Close All Description Aromatic l-amino acid decarboxylase (AADC) deficiency is an inherited disorder that ...

  13. Beyond organic chemistry: aromaticity in atomic clusters.

    PubMed

    Boldyrev, Alexander I; Wang, Lai-Sheng

    2016-04-28

    We describe joint experimental and theoretical studies carried out collaboratively in the authors' labs for understanding the structures and chemical bonding of novel atomic clusters, which exhibit aromaticity. The concept of aromaticity was first discovered to be useful in understanding the square-planar unit of Al4 in a series of MAl4(-) bimetallic clusters that led to discoveries of aromaticity in many metal cluster systems, including transition metals and similar cluster motifs in solid compounds. The concept of aromaticity has been found to be particularly powerful in understanding the stability and bonding in planar boron clusters, many of which have been shown to be analogous to polycyclic aromatic hydrocarbons in their π bonding. Stimulated by the multiple aromaticity in planar boron clusters, a design principle has been proposed for stable metal-cerntered aromatic molecular wheels of the general formula, M@Bn(k-). A series of such borometallic aromatic wheel complexes have been produced in supersonic cluster beams and characterized experimentally and theoretically, including Ta@B10(-) and Nb@B10(-), which exhibit the highest coordination number in two dimensions.

  14. Heterogeneous photocatalytic reactions of sulfur aromatic compounds.

    PubMed

    Samokhvalov, Alexander

    2011-11-18

    Sulfur aromatic compounds, such as mono-, di-, tri-, and tetraalkyl-substituted thiophene, benzothiophenes, dibenzothiophenes, are the molecular components of many fossils (petroleum, oil shale, tar sands, bitumen). Structural units of natural, cross-linked heteroaromatic polymers present in brown coals, turf, and soil are similar to those of sulfur aromatic compounds. Many sulfur aromatic compounds are found in the streams of petroleum refining and upgrading (naphthas, gas oils) and in the consumer products (gasoline, diesel, jet fuels, heating fuels). Besides fossils, the structural fragments of sulfur aromatic compounds are present in molecules of certain organic semiconductors, pesticides, small molecule drugs, and in certain biomolecules present in human body (pheomelanin pigments). Photocatalysis is the frontier area of physical chemistry that studies chemical reactions initiated by absorption of photons by photocatalysts, that is, upon electronic rather than thermal activation, under "green" ambient conditions. This review provides systematization and critical review of the fundamental chemical and physicochemical information on heterogeneous photocatalysis of sulfur aromatic compounds accumulated in the last 20-30 years. Specifically, the following topics are covered: physicochemical properties of sulfur aromatic compounds, major classes of heterogeneous photocatalysts, mechanisms and reactive intermediates of photocatalytic reactions of sulfur aromatic compounds, and the selectivity of these reactions. Quantum chemical calculations of properties and structures of sulfur aromatic compounds, their reactive intermediates, and the structure of adsorption complexes formed on the surface of the photocatalysts are also discussed.

  15. Aromatic Polyimides With Group VI Linkages

    NASA Technical Reports Server (NTRS)

    St. Clair, T. L.; Burks, H. D.; Ely, R. M.

    1983-01-01

    New polymer system combines thermal and solvent resistant properties of aromatic polyimides with processability of PPX polymers. PPX polymers include polyphenylene oxide, polyphenylene sulfide, and polyphenylene sulfone classes. Generally more processable by hot melt or thermoplastic techniques than aromatic polyimides. PPX systems more susceptible to attack by solvents and have lower glass transition temperatures than PI group.

  16. Continuous ring furnaces

    SciTech Connect

    De Stefani, G.; Genevois, J.L.; Paolo, P.

    1981-01-06

    A smoke conducting apparatus for use particularly with continuous ring furnaces (e.g., Hoffman furnaces) wherein each furnace chamber is connected to the smoke channel, the latter being a metal pipe inclined slightly from horizontal and provided with one or more traps along the length of its bottom surface, each trap containing a removable receptacle, and heating means being disposed along the bottom of the channel to fluidize tarry deposits of combustion products so that such deposits will flow by gravity into the removable receptacle.

  17. On Organic Material in E Ring Ice Grains

    NASA Astrophysics Data System (ADS)

    Postberg, F.; Khawaja, N.; Reviol, R.; Nölle, L.; Klenner, F.; Hsu, H. W.; Horanyi, M.

    2015-12-01

    Pure water ice dominates the composition of the micron and sub-micron sized dust particles in Saturn's E-ring, a ring constantly replenished by active ice jets of the moon Enceladus [1]. Details about the composition of this tenuous, optically thin ring can only be constrained by in situ measurements. The Cosmic Dust Analyzer (CDA) onboard Cassini investigates the composition of these grains by cationic time-of-flight mass spectra of individual ice grains hitting the instruments target surface. From these spectra three compositional types of E ring ice grains have been identified previously [2,3]: Type-1: Almost pure water, Type-2: Enriched in organics, and Type-3: Enriched in salt. Unlike Type-1 and 3, organic-enriched Type-2 spectra have not yet been investigated in depth. Here we report the first detailed compositional analysis of this type. The spectra analysis is supported by a large-scale laboratory ground campaign yielding a library of analogue spectra for organic material embedded in a water ice matrix. In contrast to Type 1 and 3, Type-2 spectra display a great compositional diversity, which indicates varying contributions of several organic species. So far we have identified characteristic fragment patterns of at least three classes of organic compounds: aromatic species, amines, and carbonyl group species. Work is in progress to quantify concentrations of the identified species and to assign yet un-specified organic mass lines in Type 2 spectra. Due to the dynamical evolution of the orbital elements of E ring grains a large fraction collides with the icy moons embedded in the E ring. Therefore, the organic components identified by CDA can accumulate on the surfaces of these bodies over time. Ref: :[1]Kempf et al., Icarus-206, 2010. [2]Postberg et al., Nature-459, 2009. [3]Postberg et al., Icarus-193, 2008.

  18. Spiral and Rotor Patterns Produced by Fairy Ring Fungi

    NASA Astrophysics Data System (ADS)

    Karst, N.; Dralle, D.; Thompson, S. E.

    2014-12-01

    Soil fungi fill many essential ecological and biogeochemical roles, e.g. decomposing litter, redistributing nutrients, and promoting biodiversity. Fairy ring fungi offer a rare glimpse into the otherwise opaque spatiotemporal dynamics of soil fungal growth, because subsurface mycelial patterns can be inferred from observations at the soil's surface. These observations can be made directly when the fungi send up fruiting bodies (e.g., mushrooms and toadstools), or indirectly via the effect the fungi have on neighboring organisms. Grasses in particular often temporarily thrive on the nutrients liberated by the fungus, creating bands of rich, dark green turf at the edge of the fungal mat. To date, only annular (the "ring" in fairy ring) and arc patterns have been described in the literature. We report observations of novel spiral and rotor pattern formation in fairy ring fungi, as seen in publically available high-resolution aerial imagery of 22 sites across the continental United States. To explain these new behaviors, we first demonstrate that a well-known model describing fairy ring formation is equivalent to the Gray-Scott reaction-diffusion model, which is known to support a wide range of dynamical behaviors, including annular traveling waves, rotors, spirals, and stable spatial patterns including spots and stripes. Bifurcation analysis and numerical simulation are then used to define the region of parameter space that supports spiral and rotor formation. We find that this region is adjacent to one within which typical fairy rings develop. Model results suggest simple experimental procedures that could potentially induce traditional ring structures to exhibit rotor or spiral dynamics. Intriguingly, the Gray-Scott model predicts that these same procedures could be used to solicit even richer patterns, including spots and stripes, which have not yet been identified in the field.

  19. Spiral and Rotor Patterns Produced by Fairy Ring Fungi

    NASA Astrophysics Data System (ADS)

    Karst, N.; Dralle, D.; Thompson, S. E.

    2015-12-01

    Soil fungi fill many essential ecological and biogeochemical roles, e.g. decomposing litter, redistributing nutrients, and promoting biodiversity. Fairy ring fungi offer a rare glimpse into the otherwise opaque spatiotemporal dynamics of soil fungal growth, because subsurface mycelial patterns can be inferred from observations at the soil's surface. These observations can be made directly when the fungi send up fruiting bodies (e.g., mushrooms and toadstools), or indirectly via the effect the fungi have on neighboring organisms. Grasses in particular often temporarily thrive on the nutrients liberated by the fungus, creating bands of rich, dark green turf at the edge of the fungal mat. To date, only annular (the "ring" in fairy ring) and arc patterns have been described in the literature. We report observations of novel spiral and rotor pattern formation in fairy ring fungi, as seen in publically available high-resolution aerial imagery of 22 sites across the continental United States. To explain these new behaviors, we first demonstrate that a well-known model describing fairy ring formation is equivalent to the Gray-Scott reaction-diffusion model, which is known to support a wide range of dynamical behaviors, including annular traveling waves, rotors, spirals, and stable spatial patterns including spots and stripes. Bifurcation analysis and numerical simulation are then used to define the region of parameter space that supports spiral and rotor formation. We find that this region is adjacent to one within which typical fairy rings develop. Model results suggest simple experimental procedures that could potentially induce traditional ring structures to exhibit rotor or spiral dynamics. Intriguingly, the Gray-Scott model predicts that these same procedures could be used to solicit even richer patterns, including spots and stripes, which have not yet been identified in the field.

  20. The trigonal bipyramidal MN3M species: a new kind of aromatic complex containing a multiple-fold aromatic N3 subunit.

    PubMed

    Li, Ying; Li, Zhi-Ru; Wu, Di; Chen, Wei; Sun, Chia-Chung

    2005-12-01

    A new kind of aromatic trigonal bipyramidal MN3M (M=Be, B, Mg, Al, and Ca) species, with all real frequencies, is obtained at the MP2/6-311+G(3d) level. The nucleus-independent chemical shift values are -102.16 ppm for the N3 (3-) ring, and -74.09, -79.39, -65.06, -74.44, and -62.33 ppm (at the geometrical center of the trigonal bipyramid) for BeN3Be, BN3B, MgN3Mg, AlN3Al, and CaN3Ca, respectively. Molecular orbital analysis indicates that the regular triangular N3 (3-) ring and each MN3M species have three aromatic six-electron systems (pi, sigma(p), and sigma(s)) and exhibit threefold aromaticity. The CaN3Ca species has a very low vertical ionization energy of 3.64 eV at the CCSD(T)/6-311+G(3d) level, which is even lower than the ionization energy (3.9 eV) of the Cs atom. Therefore, CaN3Ca can be considered as a new superalkali species. A further study on the CaN3CaCl molecule confirms the superalkali characteristics of CaN3Ca. Two interesting phenomena are explored in the MN3M species: the delocalized electron cloud of the N3 subunit is elongated by two M cations, and the electron clouds of two M cations are distended by the N3 (3-) ring.