Sample records for aromatic nucleophilic displacement

  1. Dehalogenation of aromatics by nucleophilic aromatic substitution. (United States)

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


    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.

  2. Nucleophilic fluorination of aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Satyamurthy, Nagichettiar; Barrio, Jorge R


    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.

  3. Concerted nucleophilic aromatic substitution with 19F- and 18F- (United States)

    Neumann, Constanze N.; Hooker, Jacob M.; Ritter, Tobias


    Nucleophilic aromatic substitution (SNAr) is widely used by organic chemists to functionalize aromatic molecules, and it is the most commonly used method to generate arenes that contain 18F for use in positron-emission tomography (PET) imaging. A wide range of nucleophiles exhibit SNAr reactivity, and the operational simplicity of the reaction means that the transformation can be conducted reliably and on large scales. During SNAr, attack of a nucleophile at a carbon atom bearing a ‘leaving group’ leads to a negatively charged intermediate called a Meisenheimer complex. Only arenes with electron-withdrawing substituents can sufficiently stabilize the resulting build-up of negative charge during Meisenheimer complex formation, limiting the scope of SNAr reactions: the most common SNAr substrates contain strong π-acceptors in the ortho and/or para position(s). Here we present an unusual concerted nucleophilic aromatic substitution reaction (CSNAr) that is not limited to electron-poor arenes, because it does not proceed via a Meisenheimer intermediate. We show a phenol deoxyfluorination reaction for which CSNAr is favoured over a stepwise displacement. Mechanistic insights enabled us to develop a functional-group-tolerant 18F-deoxyfluorination reaction of phenols, which can be used to synthesize 18F-PET probes. Selective 18F introduction, without the need for the common, but cumbersome, azeotropic drying of 18F, can now be accomplished from phenols as starting materials, and provides access to 18F-labelled compounds not accessible through conventional chemistry.

  4. Driving force and nucleophilicity in SN2 displacements


    Streitwieser, Andrew


    The free energies of activation for reaction of six anionic nucleophiles with methyl iodide in dimethylformamide correlate linearly with the overall heats of reaction in the gas phase. The result indicates that nucleophilicity in this SN2 displacement reaction is dominated by electron affinity and bond-strength effects.

  5. Nucleophilic Aromatic Substitution Between Halogenated Benzene Dopants and Nucleophiles in Atmospheric Pressure Photoionization. (United States)

    Kauppila, Tiina J; Haack, Alexander; Kroll, Kai; Kersten, Hendrik; Benter, Thorsten


    In a preceding work with dopant assisted-atmospheric pressure photoionization (DA-APPI), an abundant ion at [M + 77](+) was observed in the spectra of pyridine and quinoline with chlorobenzene dopant. This contribution aims to reveal the identity and route of formation of this species, and to systematically investigate structurally related analytes and dopants. Compounds containing N-, O-, and S-lone pairs were investigated with APPI in the presence of fluoro-, chloro-, bromo-, and iodobenzene dopants. Computational calculations on a density functional theory (DFT) level were carried out to study the reaction mechanism for pyridine and the different halobenzenes. The experimental and computational results indicated that the [M + 77](+) ion was formed by nucleophilic aromatic ipso-substitution between the halobenzene radical cation and nucleophilic analytes. The reaction was most efficient for N-heteroaromatic compounds, and it was weakened by sterical effects and enhanced by resonance stabilization. The reaction was most efficient with chloro-, bromo-, and iodobenzenes, whereas with fluorobenzene the reaction was scarcely observed. The calculated Gibbs free energies for the reaction between pyridine and the halobenzenes were shown to increase in the order I < Br < Cl < F. The reaction was found endergonic for fluorobenzene due to the strong C-F bonding, and exergonic for the other halobenzenes. For fluoro- and chlorobenzenes the reaction was shown to proceed through an intermediate state corresponding to [M + dopant](+), which was highly stable for fluorobenzene. For the bulkier bromine and iodine, this intermediate did not exist, but the halogens were shown to detach already during the approach by the nucleophile.

  6. Continuous Flow Nucleophilic Aromatic Substitution with Dimethylamine Generated in Situ by Decomposition of DMF

    DEFF Research Database (Denmark)

    Petersen, Trine P; Larsen, Anders Foller; Ritzén, Andreas;


    A safe, practical, and scalable continuous flow protocol for the in situ generation of dimethylamine from DMF followed by nucleophilic aromatic substitution of a broad range of aromatic and heteroaromatic halides is reported....

  7. Ionic Liquid Solvent Based on Cyclic Guanidinium Cation for Nucleophilic Displacement Reactions

    Institute of Scientific and Technical Information of China (English)

    LIN Ying-jie; QIU Zhi-ming; DUAN Hai-feng; LI Sheng-hai; ZHANG Suo-bo


    The nucleophilic displacement reaction of n-bromooctane and potassium iodide in ionic liquid based on cyclic guanidinium cation(2) was investigated. The kinetic reasult shows that the rate of the reaction is enhanced in ionic liquid (2). The same reaction in [bmim][PF6](1)(where bmim=1-butyl-3-methylimidazolium) was also studied. It was found that as a reaction medium ionic liquid (2) is better than (1) for nucelophilic displacement reactions.

  8. Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

    Directory of Open Access Journals (Sweden)

    Magnus Liljenberg


    Full Text Available A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the “σ-complex approach”, has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirements for predictive reactivity models for the pharmaceutical industry. We also present new results regarding the reaction rates and regioselectivities in nucleophilic substitution of fluorinated aromatics. They were rationalized by investigating linear correlations between experimental rate constants (k from the literature with a theoretical quantity, which we call the sigma stability (SS. The SS is the energy change associated with formation of the intermediate σ-complex by attachment of the nucleophile to the aromatic ring. The correlations, which include both neutral (NH3 and anionic (MeO− nucleophiles are quite satisfactory (r = 0.93 to r = 0.99, and SS is thus useful for quantifying both global (substrate and local (positional reactivity in SNAr reactions of fluorinated aromatic substrates. A mechanistic analysis shows that the geometric structure of the σ-complex resembles the rate-limiting transition state and that this provides a rationale for the observed correlations between the SS and the reaction rate.

  9. A mild and efficient method for nucleophilic aromatic fluorination using tetrabutylammonium fluoride as fluorinating reagent

    Institute of Scientific and Technical Information of China (English)


    Anhydrous tetrabutylammonium fluoride(TBAF_(anh).) has been found to be a highly efficient fluorinating reagent for nucleophilic aromatic fluorinations such as fluorodenitration or halogen exchange(Halex) reaction.The products were formed in high to excellent yields under surprisingly mild reaction conditions and no phenol or ether side-products were detected in these reactions.

  10. Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides. (United States)

    Liljenberg, Magnus; Brinck, Tore; Rein, Tobias; Svensson, Mats


    A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the "σ-complex approach", has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirements for predictive reactivity models for the pharmaceutical industry. We also present new results regarding the reaction rates and regioselectivities in nucleophilic substitution of fluorinated aromatics. They were rationalized by investigating linear correlations between experimental rate constants (k) from the literature with a theoretical quantity, which we call the sigma stability (SS). The SS is the energy change associated with formation of the intermediate σ-complex by attachment of the nucleophile to the aromatic ring. The correlations, which include both neutral (NH3) and anionic (MeO(-)) nucleophiles are quite satisfactory (r = 0.93 to r = 0.99), and SS is thus useful for quantifying both global (substrate) and local (positional) reactivity in SNAr reactions of fluorinated aromatic substrates. A mechanistic analysis shows that the geometric structure of the σ-complex resembles the rate-limiting transition state and that this provides a rationale for the observed correlations between the SS and the reaction rate.

  11. Use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Graczyk, D.G.; Taylor, J.W.; Turnquist, C.R.


    Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables.

  12. Temperature-dependent regioselectivity of nucleophilic aromatic photosubstitution. Evidence that activation energy controls reactivity. (United States)

    Wubbels, Gene G; Tamura, Ryo; Gannon, Emmett J


    Irradiation (λ > 330 nm) of 2-chloro-4-nitroanisole (1) at 25 °C in aqueous NaOH forms three substitution photoproducts: 2-methoxy-5-nitrophenol (2), 2-chloro-4-nitrophenol (3), and 3-chloro-4-methoxyphenol (4), in chemical yields of 69.2%, 14.3%, and 16.5%. The activation energies for the elementary steps from the triplet state at 25 °C were determined to be 1.8, 2.4, and 2.7 kcal/mol, respectively. The chemical yields of each of the three products were determined for exhaustive irradiations at 0, 35, and 70 °C. The variation with temperature of the experimental yields is reproduced almost exactly by the yields calculated with the Arrhenius equation. This indicates that activation energy is the fundamental property related to regioselectivity in nucleophilic aromatic photosubstitution of the S(N)2 Ar* type. The many methods proposed for predicting regioselectivity in reactions of this type have had limited success and have not been related to activation energy.

  13. NCA nucleophilic radiofluorination on substituted benzaldehydes for the preparation of [18F]fluorinated aromatic amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Wadsak, Wolfgang [Department of Nuclear Medicine, Medical University of Vienna (Austria)]. E-mail:; Wirl-Sagadin, Barbara [Department of Nuclear Medicine, Medical University of Vienna (Austria); Department of Inorganic Chemistry, University of Vienna (Austria); Mitterhauser, Markus [Department of Nuclear Medicine, Medical University of Vienna (Austria); Department of Pharmaceutical Technology and Biopharmaceuticals, University of Vienna (Austria); Hospital Pharmacy of the General Hospital of Vienna (Austria); Mien, Leonhard-Key [Department of Nuclear Medicine, Medical University of Vienna (Austria); Department of Pharmaceutical Technology and Biopharmaceuticals, University of Vienna (Austria); Department of Psychiatry, Medical University of Vienna (Austria); Ettlinger, Dagmar E. [Department of Nuclear Medicine, Medical University of Vienna (Austria); Keppler, Bernhard K. [Department of Inorganic Chemistry, University of Vienna (Austria); Dudczak, Robert [Department of Nuclear Medicine, Medical University of Vienna (Austria); Kletter, Kurt [Department of Nuclear Medicine, Medical University of Vienna (Austria)


    Nucleophilic aromatic substitution is a challenging task in radiochemistry. Therefore, a thorough evaluation and optimisation of this step is needed to provide a satisfactory tool for the routine preparation of [{sup 18}F]fluorinated aromatic amino acids. Two methods, already proposed elsewhere, were evaluated and improved. The yields for the radiofluorination were increased whereas activity loss during solid phase extraction was observed. Radiochemical yields for the two methods were 92.7{+-}5.5% (method 1) and 92.1{+-}12.3% (method 2) for conversion and 11.1{+-}2.8% (method 1) and 34.8{+-}0.6% (method 2) for purification, respectively. In total, we demonstrate an optimised method for the preparation of this important class of [{sup 18}F]fluorinated synthons for PET.

  14. Synthesis of Aryl-Substituted 2,4-Dinitrophenylamines: Nucleophilic Aromatic Substitution as a Problem-Solving and Collaborative-Learning Approach (United States)

    Santos, Elvira Santos; Garcia, Irma Cruz Gavilan; Gomez, Eva Florencia Lejarazo; Vilchis-Reyes, Miguel Angel


    A series of experiments based on problem-solving and collaborative-learning pedagogies are described that encourage students to interpret results and draw conclusions from data. Different approaches including parallel library synthesis, solvent variation, and leaving group variation are used to study a nucleophilic aromatic substitution of…

  15. Poly(ether-imide-benzoxazole) via Nucleophilic Aromatic Substitution with Fluorophenyl/phenolic Precursor (United States)


    mixture cooled, and 1 equivalent of HCI Polyimides and polybenzoxazoles have good mechanical and added to give 3b; 255-257*C. Ammonium formate was reacted...synthesis and 2a: 216T0, 3a: 225- 227CC and 4a: 325- 3270C. 4-Fluorobenzoyl processing. For these reasons, polybenzoxazoles have only recently chloride...Characterization and Applications: Pie .jm Press: New York, 1989. 3. Yang, H. H., Aromatic High Strength Fibers : Wiley- lnterscience: New York, 1989

  16. Microwave-induced nucleophilic [18F]fluorination on aromatic rings: synthesis and effect of halogen on [18F]fluoride substitution of meta-halo (F, Cl, Br, I)-benzonitrile derivatives. (United States)

    Guo, Ning; Alagille, David; Tamagnan, Gilles; Price, Ronald R; Baldwin, Ronald M


    The meta-halo-3-methylbenzonitrile derivatives (-F, -Cl, -Br, -I) were synthesized as model compounds to study reactivity towards aromatic nucleophilic substitution. A single-mode microwave system was incorporated into a commercial radiochemical synthetic module for (18)F labeling. Labeling yields of 64% for fluoro-, 13% for bromo- and 9% for chloro-precursors were achieved in DMSO in Br>Cl>I.

  17. A quantitative approach to nucleophilic organocatalysis

    Directory of Open Access Journals (Sweden)

    Herbert Mayr


    Full Text Available The key steps in most organocatalytic cyclizations are the reactions of electrophiles with nucleophiles. Their rates can be calculated by the linear free-energy relationship log k(20 °C = sN(E + N, where electrophiles are characterized by one parameter (E and nucleophiles are characterized by the solvent-dependent nucleophilicity (N and sensitivity (sN parameters.Electrophilicity parameters in the range –10 E N N parameters of enamines derived from phenylacetaldehyde and MacMillan’s imidazolidinones one can rationalize why only strong electrophiles, such as stabilized carbenium ions (–8 E E = –6.75, are suitable electrophiles for enamine activated reactions with imidazolidinones. Several mechanistic controversies concerning iminium and enamine activated reactions could thus be settled by studying the reactivities of independently synthesized intermediates.Kinetic investigations of the reactions of N-heterocyclic carbenes (NHCs with benzhydrylium ions showed that they have similar nucleophilicities to common organocatalysts (e.g., PPh3, DMAP, DABCO but are much stronger (100–200 kJ mol–1 Lewis bases. While structurally analogous imidazolylidenes and imidazolidinylidenes have comparable nucleophilicities and Lewis basicities, the corresponding deoxy Breslow intermediates differ dramatically in reactivity. The thousand-fold higher nucleophilicity of 2-benzylidene-imidazoline relative to 2-benzylidene-imidazolidine is explained by the gain of aromaticity during electrophilic additions to the imidazoline derivatives. O-Methylated Breslow intermediates are a hundred-fold less nucleophilic than deoxy Breslow intermediates.

  18. Sparing the ortho-position in nucleophilic aromatic substitution-specific displacement of the 4-SePh group in 2,4-bis(phenylseleno)nitrobenzene

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Götze, Thorstein Finn; Henriksen, Lars;


    -(phenylseleno)nitrobenzene 3 was observed. This product remained unreactive toward an excess of sodium methoxide, thus preventing the for-mation of 2,4-dimethoxynitrobenzene 6. The nature of the reactants and of the intermediate Meisenheimer complexes was examined by synthetic investigations, x......-ray crystallography, and DFT calculations. We found that the observed selectivity can be understood in terms of traditional resonance considerations. (C) 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:101-108, 2009; Published online in Wiley InterScience ( DOI 10.1002/hc.20519...

  19. Aromatic fluorine compounds. VI. Displacement of aryl fluorine in diazonium salts (United States)

    Finger, G.C.; Oesterling, R.E.


    Several chlorofluorobenzenes have been isolated from the Schiemann synthesis of fluorobenzenes. These have been shown to be the products of two side reactions occurring during thermal decomposition of the dry benzenediazonium fluoborate salt containing coprecipitated sodium chloride, an unavoidable contaminant in large preparations involving the use of hydrochloric acid and sodium fluoborate. The major side reaction and its chloro product were unexpected; a unique displacement of fluorine ortho to the diazonium group was observed. Replacement of the diazo group with chlorine was the predicted side reaction which proved to be minor. Conditions causing the side reactions and the isolation and identification of the products are described.

  20. Nucleophilic substitution as a mechanism of atrazine sequestration in soil

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Junhe, E-mail: [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Shao, Juan [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China)


    Highlights: • Atrazine tends to form nonextractable bound residue in soil. • Nucleophilic substitution is a pathway leading to atrazine sequestration in soil. • Sulfur containing amino acids are likely to play an important role as nucleophiles during this process. - Abstract: Formation of nonextractable residue was widely observed as a sink of atrazine (ATZ) in soil. However, the mechanisms by which ATZ binds to soil organic matter remain unclear. In this study, we demonstrated that neucleophilic substitution could serve an important pathway causing ATZ sequestration. The carbon bonded to the chlorine in ATZ molecule is partially positively charged due to the strong electronegativity of chlorine and is susceptible to the attack of nucleophiles such as aniline. Since aromatic amines are relatively rare in natural soils, amino acids/peptides were hypothesized to act as the main nucleophiles in real environment. However, substantially ATZ transformation was only observed in the presence of those species containing thiol functionality. Thus, we speculated that it was the thiol group in amino acids/peptides acting as the nucleophile. Nitrogen in amino acids was in fact not an active nucleophile toward ATZ. In addition to the sulfur-containing amino acids, other thiol compounds, and sulfide were also proved to be reactive to ATZ. Thus, the sequestration potential of ATZ probably correlates to the availability of thiol compounds in soil.

  1. Nucleophilic Substitution by Benzodithioate Anions. (United States)

    Bonnans-Plaisance, Chantal; Gressier, Jean-Claude


    Describes a two-session experiment designed to provide a good illustration of, and to improve student knowledge of, the Grignard reaction and nucleophilic substitution. Discusses the procedure, experimental considerations, and conclusion of this experiment. (CW)

  2. Unprecedented reactivity of an aluminium hydride complex with ArNH2BH3 : nucleophilic substitution versus deprotonation

    NARCIS (Netherlands)

    Harder, Sjoerd; Spielmann, Jan


    Reaction of DIPPnacnacAlH(2) with DIPPNH2BH3 did not give the anticipated deprotonation but nucleophilic substitution at B was observed instead. The product DIPPnacnacAl(BH4)(2) was isolated and structurally characterized. Nucleophilic displacement at B might play a role in mechanistic pathways rela

  3. Conjugate Addition of Nucleophiles to the Vinyl Function of 2-Chloro-4-vinylpyrimidine Derivatives

    Directory of Open Access Journals (Sweden)

    Lucjan Strekowski


    Full Text Available Conjugate addition reaction of various nucleophiles across the vinyl group of 2-chloro-4-vinylpyrimidine, 2-chloro-4-(1-phenylvinylpyrimidine and 2-chloro-4-vinylquinazoline provides the corresponding 2-chloro-4-(2-substituted ethylpyrimidines and 2-chloro-4-(2-substituted ethylquinazolines. Treatment of these products, without isolation, with N-methylpiperazine results in nucleophilic displacement of chloride and yields the corresponding 2,4-disubstituted pyrimidines and quinazolines.

  4. Detection of Electrophilic and Nucleophilic Chemical Agents

    Energy Technology Data Exchange (ETDEWEB)

    McElhanon, James R. (Manteca, CA); Shepodd, Timothy J. (Livermore, CA)


    A "real time" method for detecting electrophilic and nucleophilic species generally by employing tunable, precursor sensor materials that mimic the physiological interaction of these agents to form highly florescent berberine-type alkaloids that can be easily and rapidly detected. These novel precursor sensor materials can be tuned for reaction with both electrophilic (chemical species, toxins) and nucleophilic (proteins and other biological molecules) species.

  5. Nucleophilic fluorination of triflates by tetrabutylammonium bifluoride. (United States)

    Kim, Kyu-Young; Kim, Bong Chan; Lee, Hee Bong; Shin, Hyunik


    Careful examination of nucleophilicity, basicity, and leaving group ability led us to discover the nucleophilic fluorination of triflates by weakly basic tetrabutylammonium bifluoride, which provides excellent yields with minimal formation of elimination-derived side products. Primary hydroxyl groups as well as secondary hydroxyl groups in acyclic chains or in five-membered rings are excellent substrates, whereas benzylic and aldol-type secondary hydroxyl groups give poor yields as a result of the instability of their triflates.

  6. EXAFS structural study of platinum-based anticancer drugs degradation in presence of sulfur nucleophilic species. (United States)

    Provost, Karine; Bouvet-Muller, Diane; Crauste-Manciet, Sylvie; Moscovici, Jacques; Olivi, Luca; Vlaic, Gilberto; Michalowicz, Alain


    Three platinum complexes, cisplatin, carboplatin and oxaliplatin are currently used worldwide. Investigation of their main structural modifications in presence of sulfur nucleophiles is of particular interest because of the implication of thiol and thioether groups in biochemical mechanism of action, resistance mechanism and in vivo or in vitro detoxification. We present the main structural results we have obtained concerning the reaction of these drugs with diverse sulfur nucleophiles (cysteine, glutathione, methionine, thiosulfate and thiocyanate), monitored in solution or as precipitates by EXAFS spectroscopy. The reactivities of the carboxylate and amine ligands of both carboplatin and oxaliplatin are compared, on the basis of first-coordination sphere modeling. Among the new results of this EXAFS study, we present the first observation of oxaliplatin diaminocyclohexane ligand displacement by sulfur nucleophiles.

  7. Palladium-Catalyzed Nucleophilic Substitution of Alcohols : Mechanistic Studies and Synthetic Applications


    Sawadjoon, Supaporn


    This thesis deals with the palladium-catalyzed nucleophilic substitution of π-activated alcohols in which the C–O bond of a non-manipulated hydroxyl group is cleaved. The thesis is divided in two chapters describing two different catalytic systems. Chapter 2 describes a heterogeneous palladium-catalyzed transfer hydrogenolysis of primary, secondary, and tertiary benzylic alcohols to generate the corresponding aromatic hydrocarbons using formic acid as the hydrogen donor. A detailed mechanisti...

  8. Efficient synthesis of novel 9H-xanthen-9-yl derivatives of bidentate heterocyclic nucleophiles by Fe(HSO4)3 as a catalyst

    Institute of Scientific and Technical Information of China (English)

    Hossein Eshghi; Mehdi Bakavoli; Javad Abedini-Torghabeh; Mohammad Rahimizadeh


    We have demonstrated the direct substitution of 9H-xanthen-9-ol with different nucleophilic reagents such as thiazoles,triazoles,tetrazoles,hydrazines and hydrazinecarboxamides in good to high yields.This reaction catalyzed by ferric hydrogensulfate as a heterogeneous acid catalyst in ethanol through SN1 type reaction of pyrylium with a nucleophilic reagent afforded the heterocycle-and aromatic-N-substituted xanthene derivatives as simple marked molecules in short reaction times.

  9. Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles. (United States)

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen


    The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

  10. Detection of electrophilic and nucleophilic chemical agents

    Energy Technology Data Exchange (ETDEWEB)

    McElhanon, James R.; Shepodd, Timothy J.


    A "real time" method for detecting chemical agents generally and particularly electrophilic and nucleophilic species by employing tunable, precursor sensor materials that mimic the physiological interaction of these agents to form highly florescent berberine-type alkaloids that can be easily and rapidly detected. These novel precursor sensor materials can be tuned for reaction with both electrophilic (chemical species, toxins) and nucleophilic (proteins and other biological molecules) species. By bonding or otherwise attaching these precursor molecules to a surface or substrate they can be used in numerous applications.


    Institute of Scientific and Technical Information of China (English)

    Gui-long Wu; Jin-gang Liu; Zuo-bang Li; Zi-yi Ge; Lin Fan; Shi-yong Yang


    An aromatic diamine monomer, 4,4'-bis(3-amino-5-trifluoromethyl phenoxy)-biphenyl (TFBPDA), was synthesized via the nucleophilic displacement reaction of 3,5-dinitrobenzotrifluoride and 4,4'-biphenol. The monomer was reacted with various aromatic dianhydrides via the high temperature polycondensation procedure to provide a series of polyimides. The polyimides, PI-1 to PI-4, show good solubility not only in aprotic solvents, such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide, but also in many common solvents, such as m-cresol, chloroform and cyclopentanone. PI-4, derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and TFBPDA, was even soluble in toluene. Moreover, PI films exhibit good thermal stability, outstanding transparency in the visible light region and acceptable mechanical and electrical properties. The excellent combined properties of the polyimides make them as a good candidate for fabricating microelectronics.

  12. Study of quinones reactions with wine nucleophiles by cyclic voltammetry. (United States)

    Oliveira, Carla M; Barros, António S; Ferreira, António C S; Silva, Artur M S


    Quinones are electrophilic species which can react with various nucleophiles, like wine antioxidants, such as sulfur dioxide or ascorbic acid, thiols, amino acids, and numerous polyphenols. These reactions are very important in wine aging because they mediate oxygen reactions during both production and bottle aging phases. In this work, the major challenge was to determine the interaction between ortho-quinones and wine nucleophiles (amino acids, thiols, and the antioxidants SO2 and ascorbic acid), by cyclic voltammetry. Wine-model solutions with gallic acid, caffeic acid, or (+)-catechin and nucleophilic compounds were used. To understand the effect of nucleophilic addition in wine, a white wine with the same added nucleophiles was also analysed. Cyclic voltammograms were taken with glassy carbon electrode or screen-printed carbon electrodes, respectively, for wine-model and white wines solutions, in the absence and in the presence of nucleophiles. A nucleophilic order profile related to the cathodic current intensity decrease was observed.

  13. Direct no-carrier-added {sup 18}F-labelling of arenes via nucleophilic substitution on aryl(2-thienyl)iodonium salts

    Energy Technology Data Exchange (ETDEWEB)

    Ross, T.L.


    For in vivo imaging of molecular processes via positron emission tomography (PET) radiotracers of high specific activity are demanded. In case of the most commonly used positron emitter fluorine-18, this is only achievable with no-carrier-added [{sup 18}F]fluoride, which implies nucleophilic methods of {sup 18}F-substitution. Whereas electron deficient aromatic groups can be labelled in one step using no-carrier-added [{sup 18}F]fluoride, electron rich {sup 18}F-labelled aromatic molecules are only available by multi-step radiosyntheses or carrier-added electrophilic reactions. Here, diaryliodonium salts represent an alternative, since they have been proven as potent precursor for a direct nucleophilic {sup 18}F-introduction into aromatic molecules. Furthermore, as known from non-radioactive studies, the highly electron rich 2-thienyliodonium leaving group leads to a high regioselectivity in nucleophilic substitution reactions. Consequently, a direct nucleophilic no-carrier-added {sup 18}F-labelling of electron rich arenes via aryl(2-thienyl)iodonium precursors was developed in this work. The applicability of direct nucleophilic {sup 18}F-labelling was examined in a systematic study on eighteen aryl(2-thienyl)iodonium salts. As electron rich precursors the ortho-, meta- and para-methoxyphenyl(2-thienyl)iodonium bromides, iodides, tosylates and triflates were synthesised. In addition, para-substituted (R=BnO, CH{sub 3}, H, Cl, Br, I) aryl(2-thienyl)iodonium bromides were prepared as precursors with a systematically varying electron density. As first approach, the general reaction conditions of the nucleophilic {sup 18}F-substitution procedure were optimised. The best conditions for direct nucleophilic no-carrier-added {sup 18}F-labelling via aryl(2-thienyl)iodonium salts were found with dimethylformamide as solvent, a reaction temperature of 130{+-}3 C and 25 mmol/l as concentration of the precursor. (orig.)

  14. Studies on the Nucleophilicity and Scavenge of Superoxide Ion by Cyclic Voltammetry

    Institute of Scientific and Technical Information of China (English)

    Wei Ying-liang; Dang Xue-ping; Hu Sheng-shui


    Superoxide ion was generated by the electrochemical reduction of oxygen at a platinum electrode in dimethylsulphoxide (DMSO). This work was focused on the nucleophilicity and scavenge of electrogenerated-superoxide ion by cyclic voltammetry. The nucleophilic displacement reactions of superoxide ion with ethyl acetate and diethyl adipate were discussed and the reason for remarkable influence of diethyl adipate was elucidated. The scavenging activity of ascorbic acid was evaluated and the result allowed the conclusion that the scavenging ability of ascorbic acid is much lower in DMSO than in aqueous phase. UV-spectrum of electrogenerated superoxide ion in DMSO exhibited a single absorption band with λmax at 275 nm, which certified further that the method of electrogeneration was reliable and superoxide ion was stable in DMSO.

  15. Studies on the Nucleophilicity and Scavenge of Superoxide Ion by Cyclic Voltammetry

    Institute of Scientific and Technical Information of China (English)

    WeiYing-liang; DangXue-ping; HuSheng-shui


    Superoxide ion was generated by the electro-chemical reduction of oxygen at a platinum electrode in dimethylsulphoxide (DMSO). This work was focused on the nucleophilicity and scavenge of electrogenemted-superoxide ion by cyclic voltammetry. The nucleophilic displacement reactions of superoxide ion with ethyl acetate and diethyl adipate were discussed and the reason for remarkable influence of diethyl adipate was elucidated. The scavenging activity of ascorbic acid was evaluated and the result allowed the conclusion that the scavenging ability of ascorbic acid is much lower in DMSO than in aqueous phasc UV-spectrum of electrogenerated superoxide ion in DMSO exhibited a single absorption band with λmax at 275 nm, which certified further that the method of electrogeneration was reliable and superoxide ion was stable in DMSO.

  16. Nucleophilic Substitution Reactions Using Phosphine Nucleophiles: An Introduction to Phosphorus-31 NMR (United States)

    Sibbald, Paul A.


    Nuclear magnetic resonance (NMR) spectroscopy is commonly used in modern synthetic chemistry to monitor the conversion of reactants to products. Since instruction in the use of NMR spectroscopy typically does not occur until after the introduction of nucleophilic substitution reactions, organic chemistry students are not able to take advantage of…

  17. Displacement Ventilation

    DEFF Research Database (Denmark)

    Nielsen, Peter Vilhelm

    Displacement ventilation is an interesting new type of air distribution principle which should be considered in connection with design of comfort ventilation in both smal1 and large spaces. Research activities on displacement ventilation are large all over the world and new knowledge of design...... methods appears continuously. This book gives an easy introduction to the basis of displacement ventilation and the chapters are written in the order which is used in a design procedure. The main text is extended by five appendices which show some of the new research activities taking place at Aalborg...

  18. Hyperbranched Polycarbosilanes via Nucleophilic Substitution Reactions (United States)

    Interrante, L.; Shen, Q.

    Nucleophilic substitution reactions involving organomagnesium (Grignard) [1] and organolithium reagents have been used extensively for many years to form Si—C bonds (see Reaction Scheme 12.1). However, their use for the construction of hyperbranched polymers whose backbone contains, as a major structural component, silicon—carbon bonds, i.e., polycarbosilanes [2] is relatively more recent. (12.1) begin{array}{l} {{R}}_3 {{SiX + MR'}} to {{R}}_3 {{SiR' + MX}} \\ left({{{R,R' = alkyl}} {{or aryl;}} {{M = Mg(X),}} {{Li,}} {{Na}};{{X = halogen, OR''}}} right) \\ This chapter focuses on the application of such nucleophilic substitution reactions toward the synthesis of hyperbranched polycarbosilanes, with particular emphasis on those preparations that have resulted in relatively well characterized products. These syntheses are organized by the type of ABn monomer unit used (see Section 1.2), where A and B refer to the (C)X and (Si)Xn, respectively, functional ends of the monomer unit and where the nature of the coupling reaction leads to entirely or primarily Si—C bond formation. In most cases, these are “one-pot” reactions that employ monomers that bear halogen or alkoxy groups on the C and Si ends of the unit. Indeed, hyperbranched polycarbosilanes have been described, in general, as “obtained in one synthetic step via a random, one-pot polymerization of multifunctional monomers of AB n type” [2]. Treatment of the ABn monomer with either elemental Mg or an organolithium reagent, ideally (but not always) forms a complexed carbanion (the nucleophile) by reaction with the C-X end of the monomer unit, resulting in an intermediate of the type, (XxM)CSiXn, where M = Mg or Li, X = halogen or alkoxy, and x = 1 (Mg) or 0 (Li). Self-coupling of this reagent via reactions of the type shown in Reaction Scheme 12.1 leads to oligomeric and polymeric products that are connected primarily through Si—C bonds and yield an inorganic MXx by-product.

  19. Mechanism of SN2 disulfide bond cleavage by phosphorus nucleophiles. Implications for biochemical disulfide reducing agents. (United States)

    Dmitrenko, Olga; Thorpe, Colin; Bach, Robert D


    The B3LYP variant of DFT has been used to study the mechanism of S-S bond scission in dimethyl disulfide by a phosphorus nucleophile, trimethylphospine (TMP). The reaction is highly endothermic in the gas phase and requires significant external stabilization of the charged products. DFT calculations (B3LYP) were performed with explicit (water molecules added) and implicit solvent corrections (COSMO model). The transition structures for this SN2 displacement reaction in a number of model systems have been located and fully characterized. The reaction barriers calculated with different approaches for different systems are quite close (around 11 kcal/mol). Remarkably, the calculations suggest that the reaction is almost barrierless with respect to the preorganized reaction complex and that most of the activation energy is required to rearrange the disulfide and TMP to its most effective orientation for the SMe group transfer way. Different reactivities of different phosphorus nucleophiles were suggested to be the result of steric effects, as manifested largely by varying amounts of hindrance to solvation of the initial product phosphonium ion. These data indicate that the gas-phase addition of a phosphine to the disulfide moiety will most likely form a phosphonium cation-thiolate anion salt, in the presence of four or more water molecules, that provide sufficient H-bonding stabilization to allow displacement of the thiolate anion, a normal uncomplicated SN2 transition state is to be expected.

  20. Displacement Ventilation

    DEFF Research Database (Denmark)

    Bjørn, Erik; Mattsson, Magnus; Sandberg, Mats

    Full-scale experiments were made in a displacement ventilated room with two breathing thermal manikins to study the effect of movements and breathing on the vertical contaminant distribution, and on the personal exposure of occupants. Concentrations were measured with tracer gas equipment...

  1. Nucleophilic Substitution Reactions in Organic Chemistry%有机化学中的亲核取代反应

    Institute of Scientific and Technical Information of China (English)

    孙金鱼; 赵三虎; 赵明根


    亲核取代反应是有机化学中的一类非常重要的反应,可分为四种类型:①饱和碳原子上的亲核取代反应(SN1和SN2);②不饱和碳原子(主要是芳环)上的亲核取代反应;③经苯炔中间体的亲核取代反应;④底物为羧酸衍生物(酰卤、酸酐、酯、酰胺)的亲核取代反应。这些亲核取代反应在有机合成上有着极其广泛的应用,但因反应机理的差异性较大,学生学买并掌握起来困难较大。文章拟将上述四种类型的亲核取代反应进行系统分析和比较,找出反应的规律性,以期帮助学生学习之需要。%As a kind of very important organic chemistry reactions, nucleophilic substitution reactions are generally di- vided into four types: ①nucleophilic substitution reactions on the saturated carbon atoms(SN1 and SN2);②nucleophilic substitution reactions on the unsaturated carbon atoms (mainly aromatic ring); ③nucleophilic substitution reactions through such intermediate as benzyne, ④nucleophilic substitution reactions which substrates are carboxylic derivatives (acyl halides, anhydrides, esters, amides). These nucleophilic substitution reactions have an extremely wide range of ap- plications, but due to the differences of reaction mechanisms, we have found it difficult for students to learn and master these reactions. In this paper, we will analyse and compare the four types of nucleophilic substitution reactions systemati- cally and find out their regularities so as to meet the need of students.

  2. Tertiary amines nucleophilicity in quaternization reaction with benzyl chloride

    Directory of Open Access Journals (Sweden)

    Ksenia S. Yutilova


    Full Text Available Quaternization reaction of tertiary amines with benzyl chloride was investigated. Reaction orders with respect to the reactants were determined. Kinetic scheme of quaternization reaction was found to be corresponding to reversible process. An influence of amines basicity and steric factor of alkyl substituent bound to the nitrogen atom on tertiary amines reactivity as nucleophiles was studied. It was shown that the rate constants of direct reaction step may serve as a measure of nucleophilicity of amines.

  3. Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent. (United States)

    Ashtekar, Kumar Dilip; Vetticatt, Mathew; Yousefi, Roozbeh; Jackson, James E; Borhan, Babak


    Emerging work on organocatalytic enantioselective halocyclizations naturally draws on conditions where both new bonds must be formed under delicate control, the reaction regime where the concerted nature of the AdE3 mechanism is of greatest importance. Without assistance, many simple alkene substrates react slowly or not at all with conventional halenium donors under synthetically relevant reaction conditions. As demonstrated earlier by Shilov, Cambie, Williams, Fahey, and others, alkenes can undergo a concerted AdE3-type reaction via nucleophile participation, which sets the configuration of the newly created stereocenters at both ends in one step. Herein, we explore the modulation of alkene reactivity and halocyclization rates by nucleophile proximity and basicity, through detailed analyses of starting material spectroscopy, addition stereopreferences, isotope effects, and nucleophile-alkene interactions, all obtained in a context directly relevant to synthesis reaction conditions. The findings build on the prior work by highlighting the reactivity spectrum of halocyclizations from stepwise to concerted, and suggest strategies for design of new reactions. Alkene reactivity is seen to span the range from the often overgeneralized "sophomore textbook" image of stepwise electrophilic attack on the alkene and subsequent nucleophilic bond formation, to the nucleophile-assisted alkene activation (NAAA) cases where electron donation from the nucleophilic addition partner activates the alkene for electrophilic attack. By highlighting the factors that control reactivity across this range, this study suggests opportunities to explain and control stereo-, regio-, and organocatalytic chemistry in this important class of alkene additions.

  4. Chromo- and fluorophoric water-soluble polymers and silica particles by nucleophilic substitution reaction of poly(vinyl amine)


    Katja Hofmann; Ingolf Kahle; Frank Simon; Stefan Spange


    Novel chromophoric and fluorescent carbonitrile-functionalized poly(vinyl amine) (PVAm) and PVAm/silica particles were synthesized by means of nucleophilic aromatic substitution of 8-oxo-8H-acenaphtho[1,2-b]pyrrol-9-carbonitrile (1) with PVAm in water. The water solubility of 1 has been mediated by 2,6-O-β-dimethylcyclodextrin or by pre-adsorption onto silica particles. Furthermore, 1 was converted with isopropylamine into the model compound 1-M. All new compounds were characterized by N...

  5. Displacing use

    DEFF Research Database (Denmark)

    Kelly, Janet; Matthews, Ben


    -centred design process. We identified alternative design-relevant relationships between people and devices that are not specifically tied to the functions/uses of the devices, e.g. relationships between the healthcare professional and the device, between doctors and patients, and between patients and their own......This paper critically discusses the concept of use in design, suggesting that relevant relationships other than use are sometimes obscured by the usercentredness of design processes. We present a design case from the medical device domain that displaced the concept of use from the centre of a human...

  6. Study of improved resins for advanced supersonic technology composites. Part 1: Heteroaromatic polymers containing ether groups. Part 2: Curing chemistry of aromatic polymers and composite studies (United States)

    Takekoshi, T.; Hillig, W. B.; Mellinger, G. A.


    Fourteen ether-containing, aromatic dianhydrides have been synthesized from N-phenyl-3 or 4-nitrophthalimide and various bisphenols. The process involves nucleophilic displacement of activated nitro groups with bisphenolate ions. Ether-containing dianhydrides were indefinitely stable in the presence of atmospheric moisture. One-step, high temperature solution polymerization of the ether-containing dianhydrides with m-phenylene diamine, 4,4'-oxydianiline and 1, 3-bis(4-aminophenoxy)benzene afforded 42 polyetherimides. The polyetherimides were all soluble in m-cresol except two which were found to be crystalline. The glass transition temperatures of the polyetherimides ranged from 178 to 277 C. Soluble polybenzimidazopyrrolones containing ether groups were also prepared from the same ether-containing dianhydrides and aromatic tetraamines by one-step solution polymerization. Using low molecular weight polyetherimides, various thermoset resin systems were developed and tested as matrices for fiber-reinforced composites. The curing chemistry involving reaction of the phthalonitrile group and the o-diaminophenyl group was found to be generally applicable to crosslinking various aromatic polymers other than polyimides.

  7. (Hetero)aromatics from dienynes, enediynes and enyne-allenes. (United States)

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


    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.

  8. Nucleophilic Addition of Reactive Dyes on Amidoximated Acrylic Fabrics

    Directory of Open Access Journals (Sweden)

    Reda M. El-Shishtawy


    Full Text Available Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% owf of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics.

  9. Nucleophilic addition of reactive dyes on amidoximated acrylic fabrics. (United States)

    El-Shishtawy, Reda M; El-Zawahry, Manal M; Abdelghaffar, Fatma; Ahmed, Nahed S E


    Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% of of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics.

  10. Ring transformation of chromone-3-carboxamide under nucleophilic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, Magdy A., E-mail: [Department of Chemistry, Faculty of Education, Ain Shams University, Cairo(Egypt)


    The chemical reactivity of chromone-3-carboxamide was studied towards a series of nitrogen and carbon nucleophiles. Treatment of carboxamide with some primary amines gave chromane-2,4-diones. Condensation of carboxamide with hydrazine hydrate, phenyl hydrazine and hydroxylamine hydrochloride afforded chromenopyrazoles and chromenoisoxazole, respectively. Reaction of carboxamide with guanidine hydrochloride, cyanoguanidine and thiourea resulted in ring transformation producing chromenopyridines. The chemical behavior of carboxamide was also studied towards ethylenediamine, o-phenylenediamine, 2-aminophenol and 2-aminothiophenol. A variety of products were isolated from the reaction of carboxamide with some carbon nucleophiles. (author)

  11. Chloromethyl chlorosulfate: a new, catalytic method of preparation and reactions with some nucleophiles. (United States)

    Power, Nicholas P; Bethell, Donald; Proctor, Lee; Latham, Elliot; Dawson, Paul


    -metal salts in conjunction with a phase-transfer catalyst. In both situations the products (ClCH2X) arise by rapid nucleophilic displacement of the chlorosulfate moiety; this then more slowly liberates chloride ion, which converts further CMCS into CH2Cl2. The reactivity of CMCS has been compared with that of MBCS and methyl chlorosulfate (MCS) in competitive experiments; the reactivity order is MCS > MBCS > CMCS > CH2Cl2. Evidence is also presented suggesting that, in contrast to the halide nucleophiles, reaction of CMCS with sodium phenoxide in tetrahydrofuran solution leads to nucleophilic displacement of the sulfur-bound chloride.

  12. A Substrate-Assisted Mechanism of Nucleophile Activation in a Ser-His-Asp Containing C-C Bond Hydrolase

    Energy Technology Data Exchange (ETDEWEB)

    Ruzzini, Antonio C.; Bhowmik, Shiva; Ghosh, Subhangi; Yam, Katherine C.; Bolin, Jeffrey T.; Eltis, Lindsay D. [Purdue; (UBC)


    The meta-cleavage product (MCP) hydrolases utilize a Ser–His–Asp triad to hydrolyze a carbon–carbon bond. Hydrolysis of the MCP substrate has been proposed to proceed via an enol-to-keto tautomerization followed by a nucleophilic mechanism of catalysis. Ketonization involves an intermediate, ESred, which possesses a remarkable bathochromically shifted absorption spectrum. We investigated the catalytic mechanism of the MCP hydrolases using DxnB2 from Sphingomonas wittichii RW1. Pre-steady-state kinetic and LC ESI/MS evaluation of the DxnB2-mediated hydrolysis of 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid to 2-hydroxy-2,4-pentadienoic acid and benzoate support a nucleophilic mechanism catalysis. In DxnB2, the rate of ESred decay and product formation showed a solvent kinetic isotope effect of 2.5, indicating that a proton transfer reaction, assigned here to substrate ketonization, limits the rate of acylation. For a series of substituted MCPs, this rate was linearly dependent on MCP pKa2nuc ~ 1). Structural characterization of DxnB2 S105A:MCP complexes revealed that the catalytic histidine is displaced upon substrate-binding. The results provide evidence for enzyme-catalyzed ketonization in which the catalytic His–Asp pair does not play an essential role. The data further suggest that ESred represents a dianionic intermediate that acts as a general base to activate the serine nucleophile. This substrate-assisted mechanism of nucleophilic catalysis distinguishes MCP hydrolases from other serine hydrolases.

  13. HBF4-Catalysed Nucleophilic Substitutions of Propargylic Alcohols


    Barreiro, Elena; Sanz-Vidal, Alvaro; Tan, Eric; Lau, Shing-Hing; Sheppard, Tom D; Díez-González, Silvia


    The activity of HBF4 (aqueous solution) as a catalyst in propargylation reactions is presented. Diverse types of nucleophiles were employed in order to form new C–O, C–N and C–C bonds in technical acetone and in air. Good to excellent yields and good chemoselectivities were obtained using low acid loading (typically 1 mol-%) under simple reaction conditions.

  14. Aerobic dehydrogenative α-diarylation of benzyl ketones with aromatics through carbon-carbon bond cleavage. (United States)

    More, Nagnath Yadav; Jeganmohan, Masilamani


    Substituted benzyl ketones reacted with aromatics in the presence of K2S2O8 in CF3COOH at room temperature, yielding α-diaryl benzyl ketones through a carbon-carbon bond cleavage. In the reaction, two new carbon-carbon bonds were formed and one carbon-carbon bond was cleaved. It is very interesting that two different nucleophiles such as benzyl ketones and aromatics were coupled together without metal, which is unusual in organic synthesis.

  15. A study of diazonium couplings with aromatic nucleophiles both in solution and on a polymer surface (United States)

    Chng, Shuyun; Parker, Emily M.; Griffiths, Jon-Paul; Moloney, Mark G.; Wu, Linda Y. L.


    Diazonium coupling is a technique finding wider application to materials and biological science, for hybridization and linking processes, and for the construction of responsive surface functionality. For this reason, detailed examination of solution and surface processes was warranted, and results of such a study are reported here. The modification of polystyrene surfaces was examined as a model, and the process compared to a solution mimic using N,N-dimethylaniline. It was confirmed that solution and solid surface reactions proceed in a similar manner in terms of the chemical functionality generated, but with lower chemical efficiency and reaction times slower for the latter, in a reaction which was pH dependent. The solution process was shown to give only the trans-azo para- coupled products. Whilst there are clear similarities between the solution and surface chemistry, the efficiency of coupling at a surface is not necessarily replicated in the chemical yield of the mimicking solution processes, but nonetheless provides an alternative to other Click-type surface modifications. It should not be assumed that such couplings occur with quantitative efficiency at the surface.

  16. Aromatic graphene (United States)

    Das, D. K.; Sahoo, S.


    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.

  17. HBF4-Catalysed Nucleophilic Substitutions of Propargylic Alcohols (United States)

    Barreiro, Elena; Sanz-Vidal, Alvaro; Tan, Eric; Lau, Shing-Hing; Sheppard, Tom D; Díez-González, Silvia


    The activity of HBF4 (aqueous solution) as a catalyst in propargylation reactions is presented. Diverse types of nucleophiles were employed in order to form new C–O, C–N and C–C bonds in technical acetone and in air. Good to excellent yields and good chemoselectivities were obtained using low acid loading (typically 1 mol-%) under simple reaction conditions. PMID:26693210

  18. Nucleophilic Addition of Reactive Dyes on Amidoximated Acrylic Fabrics



    Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% owf of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophi...

  19. DFT analysis of the nucleophilicity of substituted pyridines and prediction of new molecules having nucleophilic character stronger than 4-pyrrolidino pyridine

    Indian Academy of Sciences (India)

    Kaustavmoni Deka; Prodeep Phukan


    Some commonly used 3-substituted, 4-substituted and 3,4,5-substituted pyridines were examined using DFT to predict the nucleophilicity behavior based on four different methods known in the literature. HOMO-LUMO energy calculations were done using DFT/B3LYP/6-311G+(d,p) level of theory. To establish the most suitable nucleophilicity scale for all the ranges of pyridines covered herein, either Hammett substituent constant () or experimental nucleophilicity values were computed. On the basis of this study, some new 4-substituted pyridines with enhanced nucleophilicity have been proposed. Nucleophilic behaviour of a few predicted molecules was found to be better than that of 4-pyrrolidino pyridine.

  20. Job Displacement and Crime

    DEFF Research Database (Denmark)

    Bennett, Patrick; Ouazad, Amine

    individuals, i.e. high-tenure workers with strong attachment to their firm, who lose employment during a mass-layoff event. Pre-displacement data suggests no evidence of endogenous selection of workers for displacement during mass-layoffs: displaced workers’ propensity to commit crime exhibits...... theory of crime. Marital dissolution is more likely post-displacement, and we find small intra-family externalities of adult displacement on younger family members’ crime. The impact of displacement on crime is stronger in municipalities with higher capital and labor income inequalities....

  1. On the regiochemistry of nucleophilic attack on 2-halo pi-allyl complexes. 4. The effect of silver acetate and nucleophile concentrations in competitive nucleophilic attack with malonate and phenoxide nucleophiles. (United States)

    Organ, Michael G; Arvanitis, Elena A; Hynes, Stephen J


    2,3-Dibromo-1-propene or its allyl carbonate analogue are ionized under Pd catalysis to generate the 2-bromo Pd-pi-allyl complex (triphenylphosphine ligand), which alkylates with malonate nucleophile at the terminal position. The presence of acetate ion in the reaction mixture results in some malonate attack being redirected to the central carbon. The acetate ion can come from the ionization of 1-acetoxy-2-bromo-2-propene or by the addition of silver acetate to the reaction mixture. The addition of phenoxide ion to the reaction also causes the same regiochemical phenomena, although harder anions such as methoxide exert no such effect.

  2. Multiple nucleophilic elbows leading to multiple active sites in a single module esterase from Sorangium cellulosum

    DEFF Research Database (Denmark)

    Udatha, D.B.R.K. Gupta; Madsen, Karina Marie; Panagiotou, Gianni;


    The catalytic residues in carbohydrate esterase enzyme families constitute a highly conserved triad: serine, histidine and aspartic acid. This catalytic triad is generally located in a very sharp turn of the protein backbone structure, called the nucleophilic elbow and identified by the consensus...... sequence GXSXG. An esterase from Sorangium cellulosum Soce56 that contains five nucleophilic elbows was cloned and expressed in Escherichia coli and the function of each nucleophilic elbowed site was characterized. In order to elucidate the function of each nucleophilic elbow, site directed mutagenesis...... was used to generate variants with deactivated nucleophilic elbows and the functional promiscuity was analyzed. In silico analysis together with enzymological characterization interestingly showed that each nucleophilic elbow formed a local active site with varied substrate specificities and affinities...

  3. Statelessness and environmental displacement

    Directory of Open Access Journals (Sweden)

    Jessie Connell


    Full Text Available Stateless people and migrants are at greater risk of displacement and are less likely to receive assistance; in turn, environmental displacement (especially multiple migrations heightens the risk of becoming stateless.

  4. General-base catalysed hydrolysis and nucleophilic substitution of activated amides in aqueous solutions

    NARCIS (Netherlands)

    Buurma, NJ; Blandamer, MJ; Engberts, JBFN; Buurma, Niklaas J.


    The reactivity of 1-benzoyl-3-phenyl-1,2,4-triazole (1a) was studied in the presence of a range of weak bases in aqueous solution. A change in mechanism is observed from general-base catalysed hydrolysis to nucleophilic substitution and general-base catalysed nucleophilic substitution. A slight tend

  5. The Use of Tertiary Alkylmagnesium Nucleophiles in Ni-Catalyzed Cross-Coupling Reactions. (United States)

    Joshi-Pangu, Amruta; Biscoe, Mark R


    Nickel-catalyzed cross-coupling reactions of unactivated tertiary alkyl nucleophiles and aryl bromides have been developed using N-heterocyclic carbene ligands. These processes are reviewed alongside earlier attempts to employ unactivated tertiary alkyl nucleophiles in cross-coupling reactions. Potential mechanisms for the transformations, and future challenges in this field are discussed.

  6. Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media

    Directory of Open Access Journals (Sweden)

    Haldon Carl Harris


    Full Text Available Rate constants and activations parameters are reported for solvolyses of p-Z-substituted benzoyl chlorides (1, Z = OMe, Me, H, and Cl in 97% w/w hexafluoroisopropanol-water (97H. Additional kinetic data are reported for solvolyses in acetic and formic acids. Plots of log k vs. σp in 97H are consistent with previous research showing that a cationic reaction channel is dominant, even for solvolyses of 1, Z = NO2. A benzoyl cation intermediate was trapped by Friedel-Crafts reaction with 1,3,5-trimethoxybenzene in hexafluoroisopropanol. The results are explained by an SN2-SN1 spectrum of mechanisms with variations in nucleophilic solvent assistance. Ab initio calculations of heterolytic bond dissociation energies of various chloro- and fluoro-substituted and other benzoyl chlorides are correlated with log k for solvolyses.

  7. Nucleophilic reactivities of the anions of nucleobases and their subunits. (United States)

    Breugst, Martin; Corral Bautista, Francisco; Mayr, Herbert


    The kinetics of the reactions of different heterocyclic anions derived from imidazoles, purines, pyrimidines, and related compounds with benzhydrylium ions and structurally related quinone methides have been studied in DMSO and water. The second-order rate constants (log k(2)) correlated linearly with the electrophilicity parameters E of the electrophiles according to the correlation log k(2) = s(N)(N+E) (H. Mayr, M. Patz, Angew. Chem. 1994, 106, 990-1010; Angew. Chem. Int. Ed. Engl. 1994, 33, 938-957) allowing us to determine the nucleophilicity parameters N and s(N) for these anions. In DMSO, the reactivities of these heterocyclic anions vary by more than six orders of magnitude and are comparable to carbanions, amide and imide anions, or amines. The azole anions are generally four to five orders of magnitude more reactive than their conjugate acids.

  8. Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics. (United States)

    Eberhart, Andrew J; Shrives, Harry J; Álvarez, Estela; Carrër, Amandine; Zhang, Yuntong; Procter, David J


    A sulfoxide-directed, metal-free ortho-propargylation of aromatics and heteroaromatics exploits intermolecular delivery of a propargyl nucleophile to sulfur followed by an intramolecular relay to carbon. The operationally simple cross-coupling procedure is general, regiospecific with regard to the propargyl nucleophile, and shows complete selectivity for products of ortho-propargylation over allenylation. The use of secondary propargyl silanes allows metal-free ortho-coupling to form carbon-carbon bonds between aromatic and heteroaromatic rings and secondary propargylic centres. The 'safety-catch' nature of the sulfoxide directing group is illustrated in a selective, iterative double cross-coupling process. The products of propargylation are versatile intermediates and they have been readily converted into substituted benzothiophenes.

  9. Bonding, aromaticity and reactivity patterns in some all-metal and non-metal clusters

    Indian Academy of Sciences (India)

    S Duley; S Giri; A Chakraborty; P K Chattaraj


    Several sandwich-like metal clusters have been studied at the B3LYP/6-311 + G∗ level of theory. Bonding and reactivity have been analysed through various geometrical parameters and conceptual density functional theory based global reactivity descriptors. Aromaticity patterns have been understood in terms of the associated nucleus independent chemical shift values. Possibility of bond-stretch isomerism in some doped clusters is explored. Preferable sites for electrophilic and nucleophilic attacks have been identified using different local reactivity descriptors.

  10. Displacement data assimilation (United States)

    Rosenthal, W. Steven; Venkataramani, Shankar; Mariano, Arthur J.; Restrepo, Juan M.


    We show that modifying a Bayesian data assimilation scheme by incorporating kinematically-consistent displacement corrections produces a scheme that is demonstrably better at estimating partially observed state vectors in a setting where feature information is important. While the displacement transformation is generic, here we implement it within an ensemble Kalman Filter framework and demonstrate its effectiveness in tracking stochastically perturbed vortices.

  11. XY displacement device

    NARCIS (Netherlands)

    Heerens, W.C.; Laham, C.D.; Holman, A.E.


    An XY-displacement device (1) with a four-fold symmetry comprises a reference frame (10); an object mount (20) for holding an object (22) to be displaced; an X-manipulator (100) coupled between the reference frame (10) and the object mount (20), which provides a rigid coupling between the object mou

  12. The electrochemical oxidation of dimethyl disulfide-Anodic methylsulfanylation of phenols and aromatic ethers

    Energy Technology Data Exchange (ETDEWEB)

    Quang Tho Do [Laboratoire d' Electrochimie et Environnement, CEREA, Universite Catholique de l' Ouest, BP 10808, 49008 ANGERS Cedex 01 (France); Elothmani, Driss [Laboratoire GRAPPE, Ecole Superieure d' Agriculture d' Angers, BP 30748, 49007 ANGERS Cedex 01 (France); Simonet, Jacques [Laboratoire d' Electrochimie Moleculaire (UMR CNRS 6510), Universite de RENNES 1, 35042 RENNES Cedex (France); Guillanton, Georges Le [Laboratoire d' Electrochimie et Environnement, CEREA, Universite Catholique de l' Ouest, BP 10808, 49008 ANGERS Cedex 01 (France)]. E-mail:


    The electrochemical oxidation of dimethyl disulfide was investigated in acetonitrile and dichloromethane. The nature of the oxidation strongly depends on the nucleophilicity of the solvent. In acetonitrile a one-electron oxidation is observed and the consecutive species did not exhibit any reactivity towards aromatic compounds subject to electrophile substitution. On the contrary, the oxidation of dimethyl disulfide in methylene chloride afforded a two-electron process with the formation of a species consistent with CH{sub 3} -S{sup +}. Its reactivity towards phenols and aromatic ethers was confirmed and showed a selective monomethylsulfanylation in most of the cases.

  13. Stereoselective Addition of Nucleophiles to Aziridinyl-2-carboxaldimine

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sang Woo; Noh, Heui Yoon; Paek, Seong In; Ha, Hyun Joon [Hankuk University of Foreign Studies, Yongin (Korea, Republic of); Lee, Won Koo [Sogang University, Seoul (Korea, Republic of)


    The addition of various nucleophiles to enantiomerically pure (p-methoxyphenyl)-[1'(R)-α-methylbenzyl] aziridin-2(R)-ylmethylene]amine was successful in highly stereoselective manner to give 2-aminomethylaziridine in the presence of BF{sub 3}·OEt{sub 2}. Commercial success to produce both enantiomers of aziridine-2-carboxylates in optically pure forms prompts us to extend their synthetic utilities for the preparation of enantiopure nitrogen containing molecules. In last few years we have studied with chiral aziridine-2-carboxylates to provide enantiomerically pure α- or β-amino ester and their derivatives. Synthetic study has been extended to construct diamine compounds based on the reaction with the substrate, aziridinyl-2-carboxaldimine. Recently we successfully prepared aminomethylaziridine and 4,5-disubstitued imidazolidin-2-ones by the addition of organomagnesium reagents to aziridinyl-2-carboxaldimine. The additions of alkyl- and arylmagnesium reagents to the chiral [1'(R)-α-methylbenzyl]aziridine-2(R)-carboxaldimine were highly stereoselective in most cases with chelation controlled transition states. The subsequent treatment of theses adducts with triphosgen and NaH afforded enantiopure 5-alkyl- or 5-aryl-4-chloromethylimidazolidin-2-ones.

  14. Dramatic effects of halogen substitution and solvent on the rates and mechanisms of nucleophilic substitution reactions of aziridines. (United States)

    Banks, Harold D


    In a previous study we reported that fluorine substitution at the carbon positions of aziridine results in profound enhancements of the rate of reaction with ammonia, a typical nucleophile, in the gas phase. In this study the investigation is extended to include chloro- and bromoaziridines. Because syntheses are largely performed in the condensed phase, the present computational investigation [(MP2(Full)/6-311++G(d,p)//MP2(Full)/6-31+G(d) level] was conducted with three typical solvents that cover a wide range of polarity: THF, CH3CN, and H2O. Nucleophiles can react with haloaziridines 1 by displacing a substituted amide ion by means of an SN2 mechanism (pathway a), producing 1,2-diaminohaloethanes (from the initially formed dipolar species 2). Alternatively, a rearrangement mechanism involving rate-determining departure of a halide ion (pathway b) to form an imidoyl halide, 3, is possible. Transition-state theory was used to compute relative reaction rates of these mechanistic possibilities and to assess the role of the halogen substituents and the reaction solvent. Gas-phase results provided the basis of mechanistic insights that were more apparent in the absence of intermolecular interactions. Fluoroaziridines were found to react at accelerated rates relative to aziridine exclusively by means of the a Menshutkin-type mechanism (SN2) in each solvent tested, while the reactions of the chloro- and bromoaziridines could be directed toward 2 in the highly nonpolar solvent, cyclohexane, or toward 3 in the more polar solvents. An assessment is made of the feasibility of using this chemistry of the haloazirdines in the synthetic laboratory.

  15. Displacement Data Assimilation

    CERN Document Server

    Rosenthal, W Steven; Mariano, Arthur J; Restrepo, Juan M


    We show that modifying a Bayesian data assimilation scheme by incorporating kinematically-consistent displacement corrections produces a scheme that is demonstrably better at estimating partially observed state vectors in a setting where feature information important. While the displacement transformation is not tied to any particular assimilation scheme, here we implement it within an ensemble Kalman Filter and demonstrate its effectiveness in tracking stochastically perturbed vortices.

  16. Advanced Triangulation Displacement Sensors (United States)

    Poteet, Wade M.; Cauthen, Harold K.


    Advanced optoelectronic triangulation displacement sensors undergoing development. Highly miniaturized, more stable, more accurate, and relatively easy to use. Incorporate wideband electronic circuits suitable for real-time monitoring and control of displacements. Measurements expected to be accurate to within nanometers. In principle, sensors mass-produced at relatively low unit cost. Potential applications numerous. Possible industrial application in measuring runout of rotating shaft or other moving part during fabrication in "zero-defect" manufacturing system, in which measured runout automatically corrected.

  17. Internal displacement in Burma. (United States)

    Lanjouw, S; Mortimer, G; Bamforth, V


    The internal displacement of populations in Burma is not a new phenomenon. Displacement is caused by numerous factors. Not all of it is due to outright violence, but much is a consequence of misguided social and economic development initiatives. Efforts to consolidate the state by assimilating populations in government-controlled areas by military authorities on the one hand, while brokering cease-fires with non-state actors on the other, has uprooted civilian populations throughout the country. Very few areas in which internally displaced persons (IDPs) are found are not facing social turmoil within a climate of impunity. Humanitarian access to IDP populations remains extremely problematic. While relatively little information has been collected, assistance has been focused on targeting accessible groups. International concern within Burma has couched the problems of displacement within general development modalities, while international attention along its borders has sought to contain displacement. With the exception of several recent initiatives, few approaches have gone beyond assistance and engaged in the prevention or protection of the displaced.

  18. Platinum Catalyzed Ring-Opening of 1,2-Cyclopropanated Sugars with O-Nucleophiles

    DEFF Research Database (Denmark)

    Beyer, Jürgen; Skaanderup, Philip Robert; Madsen, Robert


    In the presence of a catalytic amount of Zeise's dimer 1,2-cyclopropanated sugars undergo regioselective ring-opening at C-1 with O-nucleophiles including alcohols, phenols and water to produce 2-C-branched carbohydrates....

  19. Chromo- and fluorophoric water-soluble polymers and silica particles by nucleophilic substitution reaction of poly(vinyl amine

    Directory of Open Access Journals (Sweden)

    Katja Hofmann


    Full Text Available Novel chromophoric and fluorescent carbonitrile-functionalized poly(vinyl amine (PVAm and PVAm/silica particles were synthesized by means of nucleophilic aromatic substitution of 8-oxo-8H-acenaphtho[1,2-b]pyrrol-9-carbonitrile (1 with PVAm in water. The water solubility of 1 has been mediated by 2,6-O-β-dimethylcyclodextrin or by pre-adsorption onto silica particles. Furthermore, 1 was converted with isopropylamine into the model compound 1-M. All new compounds were characterized by NMR, FTIR, UV–vis and fluorescence spectroscopy. The solvent-dependent UV–vis absorption and fluorescence emission band positions of the model compound and the carbonitrile-functionalized PVAm were studied and interpreted using the empirical Kamlet–Taft solvent parameters π* (dipolarity/polarizability, α (hydrogen-bond donating capacity and β (hydrogen-accepting ability in terms of the linear solvation energy relationship (LSER. The solvent-independent regression coefficients a, b and s were determined using multiple linear correlation analysis. It is shown, that the chains of the polymer have a significant influence on the solvatochromic behavior of 1-P. The structure of the carbonitrile 1-Si bound to polymer-modified silica particles was studied by means of X-ray photoelectron spectroscopy (XPS and Brunauer–Emmett–Teller (BET measurements. Fluorescent silica particles were obtained as shown by fluorescence spectroscopy with a diffuse reflectance technique.

  20. Job Displacement and Crime

    DEFF Research Database (Denmark)

    Bennett, Patrick; Ouazad, Amine

    We use a detailed employer-employee data set matched with detailed crime information (timing of crime, fines, convictions, crime type) to estimate the impact of job loss on an individual's probability to commit crime. We focus on job losses due to displacement, i.e. job losses in firms losing...

  1. Aromater i drikkevand

    DEFF Research Database (Denmark)

    Nyeland, B. A.; Hansen, A. B.

    DMU har den 10. Juni 1997 afholdt en præstationsprøvning: Aromater i drikkevand. Der deltog 21 laboratorier i præstationsprøvningen. Prøvningen omfattede 6 vandige prøver og 6 ampuller indeholdende 6 aromater. Laboratorierne spikede de tilsendte vandprøver med indholdet fra ampullerne...

  2. Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Thiiranes%非对称环硫乙烷的区域选择性亲核开环反应

    Institute of Scientific and Technical Information of China (English)

    周婵; 许家喜


    Thiiranes are a class of important intermediates in organic synthesis, as well in pharmaceutical and agrochemieal industries as their oxygen analogs oxiranes and nitrogen analogs aziridines. They have been widely applied in the preparation of sulfur-containing compounds, such as diverse thiols and thioethers and so on, via ring opening reaction and isomerization. Nucleophilic ring opening reactions of unsymmetric thiiranes and their regioseleetivity with various widely used nueleophiles are reviewed. Generally, nucleophilic ring opening reactions of unsymmetrie thiiranes occur on their less substituted carbon atom, controlled by the steric hindrance. 2- Alkenyhhiiranes can undergo an SN2' ring opening reaction in some cases via the attack on the β-carbon atom of their alkenyl group. Strong nucleophiles easily lead to desulfurization of thiiranes to afford the corresponding olefins, while the relatively weak nueleophiles readily result in polymerization of thiiranes, affording polythioethers. In the presence of Lewis acid, the electronic effect affects the regioselectivity in ring opening reactions, even as the prominent effect in the reactions. Although aliphatic thiiranes are still attacked predominantly on their less substituted carbon atom with nucleophiles (the steric hindrance control) , aromatic thiiranes and 2-alkenylthiiranes are attacked on their more substituted carbon atom with nucleophiles (the electronic effect control). The current review provides a general rule for the regioselectivity of the nucleophilic ring opening reaction of unsymmetric thiiranes.%环硫乙烷与它的氧类似物环氧乙烷和氮类似物氮杂环丙烷一样,是一类重要的有机合成中间体,在医药和农用化学品工业领域也得到广泛应用。通过开环和异构化反应,还广泛用于制备硫醇和硫醚等含硫化合物。本文总结了常用亲核试剂对非对称环硫乙烷的亲核开环反应及其区域选择性。环硫乙烷

  3. Nucleophilic phosphine organocatalysis: a practical synthetic strategy for the drug-like nitrogen heterocyclic framework construction. (United States)

    Wang, Yurong; Pan, Jingjing; Chen, Zhidong; Sun, Xiaoqiang; Wang, Zhiming


    Nucleophilic phosphine catalysis has proven to be a practical and powerful synthetic strategy in organic chemistry, which can provide easy access to five-, six-, seven-, and eight-membered nitrogen heterocyclic compounds. The reaction topologies can be controlled by a proper choice of the phosphine catalysts, as well as the functionalization of the reaction substrates. In many cases, the reactions take place smoothly at room temperature, with high efficiency and atom economy. This mini-review presents the recent advances in nucleophilic phosphine catalysis for the synthesis of drug-like nitrogen heterocylic compounds. The nitrogen heterocyclic compounds with significant biological activities derived from the library based on nucleophilic phosphine-catalyzed annulation reactions are also highlighted.

  4. Ring-opening of cis-3-Substituted-2-vinylaziridines with Heteroatom Nucleophiles

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Gaeun; Shin, Miri; Kang, Hanyoung [Chungbuk National Univ., Cheongju (Korea, Republic of)


    The results of the ring opening reaction of N-protected-cis-2-vinyl-3-(benzyloxymethyl)aziridines as model compounds for cis-3-substituted-2-vinylaziridines with various heteroatom nucleophiles are summarized in Table 1. Methanol is a good nucleophile to provide the desired 1,2-amino-alcohol derivative as a single product in excellent yield. We analyzed briefly the effect of solvents with methanol. Although other solvents such as DMF and THF also gave the product, CH{sub 2}Cl{sub 2} was employed as a preferred solvent because of the high yield and ease of handling. All the reactions were, therefore, examined in CH{sub 2}Cl{sub 2} in the presence of BF{sub 3}·OEt{sub 2} as a Lewis acid unless mentioned otherwise. All alcohols behaved as good nucleophiles to exclusively give the desired products (entry 1-7)

  5. Alternative nucleophilic substrates for the endonuclease activities of human immunodeficiency virus type 1 integrase

    Energy Technology Data Exchange (ETDEWEB)

    Ealy, Julie B. [Department of Medicine, Penn State College of Medicine, Milton S. Hershey Medical Center, 500 University Drive, PO Box 850, Mail Services H036, Hershey, PA 17033 (United States); Department of Chemistry, Penn State Lehigh Valley, 2809 E. Saucon Valley Road, Center Valley, PA 18034 (United States); Sudol, Malgorzata [Department of Medicine, Penn State College of Medicine, Milton S. Hershey Medical Center, 500 University Drive, PO Box 850, Mail Services H036, Hershey, PA 17033 (United States); Krzeminski, Jacek; Amin, Shantu [Department of Pharmacology, Penn State College of Medicine, Milton S. Hershey Medical Center, 500 University Drive, Hershey, PA 17033 (United States); Katzman, Michael, E-mail: [Department of Medicine, Penn State College of Medicine, Milton S. Hershey Medical Center, 500 University Drive, PO Box 850, Mail Services H036, Hershey, PA 17033 (United States); Department of Microbiology and Immunology, Penn State College of Medicine, Milton S. Hershey Medical Center, 500 University Drive, Hershey, PA 17033 (United States)


    Retroviral integrase can use water or some small alcohols as the attacking nucleophile to nick DNA. To characterize the range of compounds that human immunodeficiency virus type 1 integrase can accommodate for its endonuclease activities, we tested 45 potential electron donors (having varied size and number or spacing of nucleophilic groups) as substrates during site-specific nicking at viral DNA ends and during nonspecific nicking reactions. We found that integrase used 22 of the 45 compounds to nick DNA, but not all active compounds were used for both activities. In particular, 13 compounds were used for site-specific and nonspecific nicking, 5 only for site-specific nicking, and 4 only for nonspecific nicking; 23 other compounds were not used for either activity. Thus, integrase can accommodate a large number of nucleophilic substrates but has selective requirements for its different activities, underscoring its dynamic properties and providing new information for modeling and understanding integrase.

  6. The photoelectric displacement converter (United States)

    Dragoner, Valeriu V.


    In the article are examined questions of constructing photoelectric displacement converter satisfying demands that are stated above. Converter has channels of approximate and precise readings. The approximate reading may be accomplished either by the method of reading from a code mask or by the method of the consecutive calculation of optical scale gaps number. Phase interpolator of mouar strips" gaps is determined as a precise measuring. It is shown mathematical model of converter that allow evaluating errors and operating speed of conversion.


    Institute of Scientific and Technical Information of China (English)

    Xu Longxiang; Zhang Jinyu; Schweitzer Gerhard


    A high temperature displacement sensor based on the principle of eddy-current is investigated. A new temperature compensation technique by using eddy-current effect is presented to satisfy the special requirement at high temperature up to 550℃. The experiment shows that the temperature compensation technique leads to good temperature stability for the sensors. The variation of the sensitivity as well as the temperature drift of the sensor with temperature compensation technique is only about 7.4% and 90~350 mV at 550℃ compared with that at room temperature, and that of the sensor without temperature compensation technique is about 31.2% and 2~3 V at 550℃ compared with that at room temperature. A new dynamic calibration method for the eddy-current displacement sensor is presented, which is very easy to be realized especially in high frequency and at high temperatures. The high temperature displacement sensors developed are successfully used at temperature up to 550℃ in a magnetic bearing system for more than 100 h.

  8. Theoretical Study of the Iodine-catalyzed Nucleophilic Addition by Halogen Bond

    Institute of Scientific and Technical Information of China (English)


    The iodine-catalyzed nucleophilic addition of pyrrole to acetone has been studied by density functional theory at the level of Lanl2DZ*. It has been shown that the first iodine molecule appears to have a remarkable catalytic effect on this reaction by halogen bond between carbonyl oxygen and iodine molecule, but the second one does not improve the reaction largely. In general, the nucleophilic addition at the C(2) site of pyrrole is more favorable than that at the C(3)site;however, this trend is not prominent or even changed in acetronitrile solvent for the indole system, which is consistent with the experimental result by Bandgar.

  9. Advances in nucleophilic phosphine catalysis of alkenes, allenes, alkynes, and MBHADs. (United States)

    Fan, Yi Chiao; Kwon, Ohyun


    In nucleophilic phosphine catalysis, tertiary phosphines undergo conjugate additions to activated carbon-carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis.

  10. Double Nucleophilic Addition of Ketene Silyl (THIO)Acetals and Trimethylsilyl Cyanide to N-Allylideneamine

    Institute of Scientific and Technical Information of China (English)

    Isao; Mizoia; Iwao; Hachiya; Makoto; Shimizu


    1 Results We have already published a double nucleophilic addition reaction of α,β-unsaturated imines with several nucleophiles such as ketene silyl acetals, trimethylsilyl cyanides, trimethylsilyl azides and thiols[1]. However, it was not easy to use N-allylideneamine 2 derived from acrolein for such reactions. Since there is no substituent at the β-position, imine 2 has high reactivity and are prone to be polymerization. We report the first synthesis of N-allylideneamines 2 using the isomerization of ...

  11. The Studies of Rhodium-catalyzed Ring Opening Reaction of N-Boc azabenzonorbornadiene with Heteroatom Nucleophiles

    Institute of Scientific and Technical Information of China (English)

    Er Chang LIU; Ding Qiao YANG; Ying Feng HAN; Jian Xia DONG


    A rhodium-catalyzed ring opening reaction of N-Boc-azabenzonorbornadiene with heteroatom nucleophiles was described. Piperidine and piperazine's derivatives were nucleophiles in this reaction. The yields of the products 2a-f are good and the regioselectivity are excellent.

  12. Metabolic activation of aromatic amines and azo dyes. (United States)

    Bartsch, H


    Aromatic amines, amides and nitro compounds are a class of chemicals that produce tumors in a wide variety of tissues in experimental animals, including liver, urinary bladder, forestomach, small intestine, Zymbal's gland, subcutaneous tissue or skin. In man, exposure to some aromatic amines is associated with tumours of the urinary bladder and carcinoma of the renal pelvis. Their biological activity as carcinogens or genotoxic agents is, in all the cases that have been studied in detail, dependent on metabolic activation in vivo, occurring by multiple pathways. Differences in these metabolic pathways may largely account for the differences in tissues and species susceptibilities to cancer induction. Carcinogenicity of aromatic amines or amides is dependent on their oxidation to N-hydroxy derivatives, whilst the carcinogenicity of aromatic nitro compounds is linked to their reduction to hydroxylamines. Further conversion of the N-hydroxylamine or N-hydroxyamide to reactive intermediates can occur in several ways, which include (i) esterification of the N-hydroxy group, (ii) non-enzymic protonation of the nitrogen of the hydroxylamine and (iii) oxidation to a free radical of arylhydroxamic acids. Following generation of such reactive electrophilic intermediates in tissues or cells, macromolecular binding has been observed to nucleic acids and proteins. In many cases, arylamidated and arylaminated products are formed with nucleic acid bases; in the case of the well-studied 2-acetylaminofluorene, nucleophilic atoms of guanine are the predominant site of reaction. Relatively little is known of the structure and biological consequences of DNA adducts formed from other aromatic amines, amides or nitro compounds; more research in these directions is warranted.

  13. Second Order Darboux Displacements

    CERN Document Server

    Samsonov, B F; Negro, J; Nieto, L M


    The potentials for a one dimensional Schroedinger equation that are displaced along the x axis under second order Darboux transformations, called 2-SUSY invariant, are characterized in terms of a differential-difference equation. The solutions of the Schroedinger equation with such potentials are given analytically for any value of the energy. The method is illustrated by a two-soliton potential. It is proven that a particular case of the periodic Lame-Ince potential is 2-SUSY invariant. Both Bloch solutions of the corresponding Schroedinger equation equation are found for any value of the energy. A simple analytic expression for a family of two-gap potentials is derived.

  14. Rhodium-catalyzed Asymmetric Ring Opening Reaction of Oxabenzo-norbornadiene with Substituted Phenolic Nucleophiles

    Institute of Scientific and Technical Information of China (English)


    We have developed an asymmetric ring opening reaction of oxabenzonorbornadienes with substituted phenolic nucleophiles. Under the reaction conditions ( [Rh(COD)Cl]2 (1 mol%),(S)-(R)-PPF-ptBu2 (2 mol%), THF, reflux), the reaction products were obtained with high yield and enantiomeric excesses ( up to 99% ee).

  15. Preparation of 6-Substituted Quinoxaline JSP-1 Inhibitors by Microwave Accelerated Nucleophilic Substitution

    Directory of Open Access Journals (Sweden)

    Jingkang Shen


    Full Text Available A small library of 6-aminoquinoxalines has been prepared by nucleophilic substitution of 6-fluoroquinoxaline with amines and nitrogen-containing heterocycles under computer-controlled microwave irradiation. Some compounds were found to be potent inhibitors of JNK Stimulatory Phosphatase-1 (JSP-1 in an in vitro biological assay.

  16. Ring opening of a resin-bound chiral aziridine with phenol nucleophiles

    DEFF Research Database (Denmark)

    Ottesen, Lars Korsgaard; Jaroszewski, Jerzy W; Franzyk, Henrik


    An efficient and versatile solid-phase route for the preparation of aryl-alkyl ethers is described. Regioselective ring opening of a resin-bound chiral aziridine with phenolic nucleophiles constitutes the key feature of the present protocol that allows incorporation of fluorescent moieties...

  17. Organic Chemistry Students' Ideas about Nucleophiles and Electrophiles: The Role of Charges and Mechanisms (United States)

    Anzovino, Mary E.; Bretz, Stacey Lowery


    Organic chemistry students struggle with reaction mechanisms and the electron-pushing formalism (EPF) used by practicing organic chemists. Faculty have identified an understanding of nucleophiles and electrophiles as one conceptual prerequisite to mastery of the EPF, but little is known about organic chemistry students' knowledge of nucleophiles…

  18. Heterocyclic analogs of pleiadiene. 57. Reactions of aceperimidylenes with some nucleophiles

    Energy Technology Data Exchange (ETDEWEB)

    Kashparov, I.S.; Pozharskii, A.F.


    N-Substituted aceperimidylenes were subjected for the first time to a recyclization reaction (the action of aroyl chlorides in the presence of triethylamine). As a result, their 2-aryl and 2-styryl derivatives were obtained in good yields. The reactions of the N-substituted aceperimidylenes and their quaternary salts with some other nucleophiles were studied.


    NARCIS (Netherlands)



    Dialkylcarbodiimides in the presence of a Cu-I catalyst react cleanly with the hydroxyl group of N-methylated (1R,2S)-ephedrine and (1S,2S)-pseudoephedrine. These adducts react with nucleophiles like alkyl and aryl thiols as well as thioic acids and phthalimide to form the substitution products with

  20. Displacing the Patient

    DEFF Research Database (Denmark)

    Pors, Anja Svejgaard


    The analysis is based on an empirical study of a hospital’s communication strategy entitled: 'The Perspective of the Patient'. The paper asks how the strategy organizes communication work as situated displacements of the patient. Based on methodological elements from situational analysis (Clarke ...... and market as mutually exclusive (Mol 2008), care and market appear to be intertwined in political patient figures through which the organization is trying to manage and transform itself from the inside......The analysis is based on an empirical study of a hospital’s communication strategy entitled: 'The Perspective of the Patient'. The paper asks how the strategy organizes communication work as situated displacements of the patient. Based on methodological elements from situational analysis (Clarke...... 2005) the analysis examines how the hospital’s patient communication is not just about disease treatment, but rather about information treatment of the patient in order to attain a high level of patient satisfaction. The goal of patient satisfaction addresses care-oriented understandings of the patient...

  1. Variable displacement blower (United States)

    Bookout, Charles C.; Stotts, Robert E.; Waring, Douglass R.; Folsom, Lawrence R.


    A blower having a stationary casing for rotatably supporting a rotor assembly having a series of open ended chambers arranged to close against the surrounding walls of the casing. Pistons are slidably mounted within each chamber with the center of rotation of the pistons being offset in regard to the center of rotation of the rotor assembly whereby the pistons reciprocate in the chambers as the rotor assembly turns. As inlet port communicates with the rotor assembly to deliver a working substance into the chamber as the pistons approach a top dead center position in the chamber while an outlet port also communicates with the rotor to exhaust the working substance as the pistons approach a bottom dead center position. The displacement of the blower is varied by adjusting the amount of eccentricity between the center of rotation of the pistons and the center of rotation of the rotor assembly.

  2. Activation of Aromatic C-C Bonds of 2,2'-Bipyridine Ligands. (United States)

    Fombona, Sergio; Espinal-Viguri, Maialen; Huertos, Miguel A; Díaz, Jesús; López, Ramón; Menéndez, M Isabel; Pérez, Julio; Riera, Lucía


    4,4'-Disubstituted-2,2'-bipyridine ligands coordinated to Mo(II) and Re(I) cationic fragments become dearomatized by an intramolecular nucleophilic attack from a deprotonated N-alkylimidazole ligand in cis disposition. The subsequent protonation of these neutral complexes takes place on a pyridine carbon atom rather than at nitrogen, weakening an aromatic C-C bond and affording a dihydropyridyl moiety. Computational calculations allowed for the rationalization of the formation of the experimentally obtained products over other plausible alternatives.

  3. Displacement Parameter Inversion for a Novel Electromagnetic Underground Displacement Sensor

    Directory of Open Access Journals (Sweden)

    Nanying Shentu


    Full Text Available Underground displacement monitoring is an effective method to explore deep into rock and soil masses for execution of subsurface displacement measurements. It is not only an important means of geological hazards prediction and forecasting, but also a forefront, hot and sophisticated subject in current geological disaster monitoring. In previous research, the authors had designed a novel electromagnetic underground horizontal displacement sensor (called the H-type sensor by combining basic electromagnetic induction principles with modern sensing techniques and established a mutual voltage measurement theoretical model called the Equation-based Equivalent Loop Approach (EELA. Based on that work, this paper presents an underground displacement inversion approach named “EELA forward modeling-approximate inversion method”. Combining the EELA forward simulation approach with the approximate optimization inversion theory, it can deduce the underground horizontal displacement through parameter inversion of the H-type sensor. Comprehensive and comparative studies have been conducted between the experimentally measured and theoretically inversed values of horizontal displacement under counterpart conditions. The results show when the measured horizontal displacements are in the 0–100 mm range, the horizontal displacement inversion discrepancy is generally tested to be less than 3 mm under varied tilt angles and initial axial distances conditions, which indicates that our proposed parameter inversion method can predict underground horizontal displacement measurements effectively and robustly for the H-type sensor and the technique is applicable for practical geo-engineering applications.

  4. Measuring vulnerability to disaster displacement (United States)

    Brink, Susan A.; Khazai, Bijan; Power, Christopher; Wenzel, Friedemann


    Large scale disasters can cause devastating impacts in terms of population displacement. Between 2008 and 2013, on average 27 million people were displaced annually by disasters (Yonetani 2014). After large events such as hurricane Katrina or the Port-au-Prince earthquake, images of inadequate public shelter and concerns about large scale and often inequitable migration have been broadcast around the world. Population displacement can often be one of the most devastating and visible impacts of a natural disaster. Despite the importance of population displacement in disaster events, measures to understand the socio-economic vulnerability of a community often use broad metrics to estimate the total socio-economic risk of an event rather than focusing on the specific impacts that a community faces in a disaster. Population displacement is complex and multi-causal with the physical impact of a disaster interacting with vulnerability arising from the response, environmental issues (e.g., weather), cultural concerns (e.g., expectations of adequate shelter), and many individual factors (e.g., mobility, risk perception). In addition to the complexity of the causes, population displacement is difficult to measure because of the wide variety of different terms and definitions and its multi-dimensional nature. When we speak of severe population displacement, we may refer to a large number of displaced people, an extended length of displacement or associated difficulties such as poor shelter quality, risk of violence and crime in shelter communities, discrimination in aid, a lack of access to employment or other difficulties that can be associated with large scale population displacement. We have completed a thorough review of the literature on disaster population displacement. Research has been conducted on historic events to understand the types of negative impacts associated with population displacement and also the vulnerability of different groups to these impacts. We

  5. Point Coupled Displacement Sensor Project (United States)

    National Aeronautics and Space Administration — Real-time displacement measurement techniques are needed to acquire aerodynamic and structural system characteristics in flight. This proposal describes the...

  6. Theoretical Studies on the Iodine-catalyzed Nucleophilic Addition of Acetone with Five-membered Heterocycles

    Institute of Scientific and Technical Information of China (English)

    WANG Yan-hua; LI Li; CHEN Xue-song


    The iodine-catalyzed nucleophilic addition reactions of pyrrole,furan,or thiophene with acetone were studied in gas and solvent by the density functional theory at the level of Lan12DZ*,It was seen that the halogen bond between iodine and carbonyl oxygen appeared to have an important catalytic effect on such reactions,and the first iodine molecule maximally diminished the barrier height by 41 kJ/mol,while the second iodine molecule could not improve such reactions largely,It was concluded that the C2-addition was generally more favorable than the C3-addition for the three heterocycles;however,iodine considerably more effectively catalyzed the C3-addition than the C2-addition for pyrrole,It was also revealed by PCM calculation that the iodine-catalyzed nucleophilic additions occurred more easily in solvent than in gas,which explained the experiment performed by Bandgar et al..

  7. Nucleophilic reactivity and electrocatalytic reduction of halogenated organic compounds by nickel o-phenylenedioxamidate complexes. (United States)

    Das, Siva Prasad; Ganguly, Rakesh; Li, Yongxin; Soo, Han Sen


    A growing number of halogenated organic compounds have been identified as hazardous pollutants. Although numerous advanced oxidative processes have been developed to degrade organohalide compounds, reductive and nucleophilic molecular approaches to dehalogenate organic compounds have rarely been reported. In this manuscript, we employ nickel(ii)-ate complexes bearing the o-phenylenebis(N-methyloxamide) (Me2opba) tetraanionic ligand as nucleophilic reagents that can react with alkyl halides (methyl up to the bulky isobutyl) by O-alkylation to give their respective imidate products. Four new nickel(ii) complexes have been characterized by X-ray crystallography, and the salient structural parameters and FT-IR vibrational bands (∼1655 cm(-1)) concur with their assignment as the imidate tautomeric form. To the best of our knowledge, this is the first report on the nucleophilic reactivity of Ni(II)(Me2opba) with halogenated organic compounds. The parent nickel(ii) Me2opba complex exhibits reversible electrochemical oxidation and reduction behavior. As a proof of concept, Ni(II)(Me2opba) and its alkylated congeners were utilized for the electrocatalytic reduction of chloroform, as a representative, simple polyhalogenated organic molecule that could arise from the oxidative treatment of organic compounds by chlorination. Modest turnover numbers of up to 6 were recorded, with dichloromethane identified as one of the possible products. Future efforts are directed towards bulkier -ate complexes that possess metal-centered instead of ligand-centered nucleophilic activity to create more effective electrocatalysts for the reduction of halogenated organic compounds.

  8. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    Directory of Open Access Journals (Sweden)

    A. W. Birdsall


    Full Text Available Recently, methacrylic acid epoxide (MAE has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA: 2-methylglyceric acid (2-MG and a set of oligomers, nitric acid esters and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG, and acids (including MAE and 2-MG in their reactions with MAE were found to be of a similar magnitude, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water; this finding is consistent with previous environmental chamber investigations of the relative humidity-dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  9. Displacement, Substitution, Sublimation: A Bibliography. (United States)

    Pedrini, D. T.; Pedrini, Bonnie C.

    Sigmund Freund worked with the mechanisms of displacement, substitution, and sublimation. These mechanisms have many similarities and have been studied diagnostically and therapeutically. Displacement and substitution seem to fit in well with phobias, hysterias, somatiyations, prejudices, and scapegoating. Phobias, prejudices, and scapegoating…

  10. Novel nucleophiles enhance the human serum paraoxonase 1 (PON1)-mediated detoxication of organophosphates. (United States)

    Chambers, Janice E; Chambers, Howard W; Meek, Edward C; Funck, Kristen E; Bhavaraju, Manikanthan H; Gwaltney, Steven R; Pringle, Ronald B


    Paraoxonase 1 (PON1) is a calcium-dependent hydrolase associated with serum high-density lipoprotein particles. PON1 hydrolyzes some organophosphates (OPs), including some nerve agents, through nucleophilic attack of hydroxide ion (from water) in the active site. Most OPs are hydrolyzed inefficiently. This project seeks to identify nucleophiles that can enhance PON1-mediated OP degradation. A series of novel nucleophiles, substituted phenoxyalkyl pyridinium oximes, has been synthesized which enhance the degradation of surrogates of sarin (nitrophenyl isopropyl methylphosphonate; NIMP) and VX (nitrophenyl ethyl methylphosphonate; NEMP). Two types of in vitro assays have been conducted, a direct assay using millimolar concentrations of substrate with direct spectrophotometric quantitation of a hydrolysis product (4-nitrophenol) and an indirect assay using submicromolar concentrations of substrate with quantitation by the level of inhibition of an exogenous source of acetylcholinesterase from non-hydrolyzed substrate. Neither NIMP nor NEMP is hydrolyzed effectively by PON1 if one of these novel oximes is absent. However, in the presence of eight novel oximes, PON1-mediated degradation of both surrogates occurs. Computational modeling has created a model of PON1 embedded in phospholipid and has indicated general agreement of the binding enthalpies with the relative efficacy as PON1 enhancers. PON1 enhancement of degradation of OPs could be a unique and unprecedented mechanism of antidotal action.


    Directory of Open Access Journals (Sweden)

    Ivanka Juttner


    Full Text Available After primary oil recovery in reservoirs remains about 70% of unexploited oil. To improve the recovery of the remaining reserves, injection of a fluid provide the extra energy in a mchunical form. Oil displacement can he achieved by gas injection of lean natural gas, mainly methane, carbon dioxide etc. Oil displacement can be in immiscible or miscible conditions. This paper deals with mechanism of miscible gas drive. On the basis of simulation of the oil displacement process by gas injection into oil field Žutica the character of process, i. c. a degree of miscibility or immiscibility between the injected fluid and reservoir oil was determined.

  12. 2,3,6 Trioxypentafulrene, 5(1): reactivity to primary-amines, nucleophilic substitution and ring expansion; 2,3,6 trioxipentafulvenos, 5(1): reactividad frente a aminas primarias: sustitucion nucleofilica y expansion de anillo

    Energy Technology Data Exchange (ETDEWEB)

    Victory, P.; Alvarez-Larena, A.; Pinilla, J.F.; Germain, G.; Solar, E.; Munoz, M. [Departamento de Quimica Organica, Instituto Quimico de Sarria, Barcelona (Spain)


    The reaction between dimethyl 2,3,6-trihydroxypenta-fulvene-1,4-dicarboxylate and primary alkyl or cycloalkylamines (methylamine, butylamine, cyclooactylamine, cyclohexylamine) affords the corresponding 6-aminopentafulvenes (nucleophilic substitution of the C6 hydroxyl group by the amine) or dimethyl 5-amino-2,3-dihydroxyterephthalates (ring expansion) depending on the reaction conditions. For the two kinds of compounds both a spectroscopic study and a single crystal X-ray analysis have been carried out. Different hydrogen bondings have been observed. Only the substitution products are obtained in the reaction between dimethyl 2,3,6-trihydroxypentafulvene-1,4-dicarboxylate and primary aromatic amines (aniline, 4-sec-butylaniline, p-anisidine). When p-nitroaniline or p-aminobenzonitrile are used the reaction does not progress. 26 refs.

  13. To prevent or pursue displacement?



    The repertoire of survival actions of at-risk civilians includes bothavoiding and attempting displacement. But there are also overlaps,combinations and tacking back and forth between the two, whiletrying to mitigate the risks that any choice entails.

  14. Internal displacement in eastern Burma


    Heather Rae


    The history of post-independent Burma is characterisedby numerous conflicts in this extraordinarily heterogeneous country. Since military rule began in 196 2 Burmahas witnessed gross human rights abuses andmassive displacement.

  15. Internal displacement in eastern Burma

    Directory of Open Access Journals (Sweden)

    Heather Rae


    Full Text Available The history of post-independent Burma is characterisedby numerous conflicts in this extraordinarily heterogeneous country. Since military rule began in 196 2 Burmahas witnessed gross human rights abuses andmassive displacement.

  16. Aromaticity Competition in Differentially Fused Borepin-Containing Polycyclic Aromatics. (United States)

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


    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.

  17. Tyrosyl-DNA phosphodiesterase I catalytic mutants reveal an alternative nucleophile that can catalyze substrate cleavage. (United States)

    Comeaux, Evan Q; Cuya, Selma M; Kojima, Kyoko; Jafari, Nauzanene; Wanzeck, Keith C; Mobley, James A; Bjornsti, Mary-Ann; van Waardenburg, Robert C A M


    Tyrosyl-DNA phosphodiesterase I (Tdp1) catalyzes the repair of 3'-DNA adducts, such as the 3'-phosphotyrosyl linkage of DNA topoisomerase I to DNA. Tdp1 contains two conserved catalytic histidines: a nucleophilic His (His(nuc)) that attacks DNA adducts to form a covalent 3'-phosphohistidyl intermediate and a general acid/base His (His(gab)), which resolves the Tdp1-DNA linkage. A His(nuc) to Ala mutant protein is reportedly inactive, whereas the autosomal recessive neurodegenerative disease SCAN1 has been attributed to the enhanced stability of the Tdp1-DNA intermediate induced by mutation of His(gab) to Arg. However, here we report that expression of the yeast His(nuc)Ala (H182A) mutant actually induced topoisomerase I-dependent cytotoxicity and further enhanced the cytotoxicity of Tdp1 His(gab) mutants, including H432N and the SCAN1-related H432R. Moreover, the His(nuc)Ala mutant was catalytically active in vitro, albeit at levels 85-fold less than that observed with wild type Tdp1. In contrast, the His(nuc)Phe mutant was catalytically inactive and suppressed His(gab) mutant-induced toxicity. These data suggest that the activity of another nucleophile when His(nuc) is replaced with residues containing a small side chain (Ala, Asn, and Gln), but not with a bulky side chain. Indeed, genetic, biochemical, and mass spectrometry analyses show that a highly conserved His, immediately N-terminal to His(nuc), can act as a nucleophile to catalyze the formation of a covalent Tdp1-DNA intermediate. These findings suggest that the flexibility of Tdp1 active site residues may impair the resolution of mutant Tdp1 covalent phosphohistidyl intermediates and provide the rationale for developing chemotherapeutics that stabilize the covalent Tdp1-DNA intermediate.

  18. Enhanced Reactivity in Nucleophilic Acyl Substitution Ion/Ion Reactions Using Triazole-Ester Reagents (United States)

    Bu, Jiexun; Peng, Zhou; Zhao, Feifei; McLuckey, Scott A.


    The acyl substitution reactions between 1-hydroxy-7-aza-benzotriazole (HOAt)/1-hydroxy-benzotriazole (HOBt) ester reagents and nucleophilic side chains on peptides have been demonstrated in the gas phase via ion/ion reactions. The HOAt/HOBt ester reagents were synthesized in solution and ionized via negative nano-electrospray ionization. The anionic reagents were then reacted with doubly protonated model peptides containing amines, guanidines, and imidazoles in the gas phase. The complexes formed in the reaction cell were further probed with ion trap collision induced dissociation (CID) yielding either a covalently modified analyte ion or a proton transfer product ion. The covalent reaction yield of HOAt/HOBt ester reagents was demonstrated to be higher than the yield with N-hydroxysuccinimide (NHS) ester reagents over a range of equivalent conditions. Density functional theory (DFT) calculations were performed with a primary amine model system for both triazole-ester and NHS-ester reactants, which indicated a lower transition state barrier for the former reagent, consistent with experiments. The work herein demonstrates that the triazole-ester reagents are more reactive, and therefore less selective, than the analogous NHS-ester reagent. As a consequence, the triazole-ester reagents are the first to show efficient reactivity with unprotonated histidine residues in the gas phase. For all nucleophilic sites and all reagents, covalent reactions are favored under long time, low amplitude activation conditions. This work presents a novel class of reagents capable of gas-phase conjugation to nucleophilic sites in analyte ions via ion/ion chemistry.

  19. Stereoselective nucleophilic fluoromethylation of aryl ketones: dynamic kinetic resolution of chiral α-fluoro carbanions. (United States)

    Shen, Xiao; Miao, Wenjun; Ni, Chuanfa; Hu, Jinbo


    Although many methods are available for the synthesis of optically enriched monofluoromethyl secondary alcohols, synthesizing optically enriched monofluoromethyl tertiary alcohols remains a challenge. An efficient and easy-to-handle nucleophilic fluoromethylation protocol was developed. The current monofluoromethylation showed much higher facial selectivity than the corresponding difluoromethylation and proceeded via a different type of transition state. Excellent stereoselective control at the fluorinated carbon chiral center was found, an effect believed to be facilitated by the dynamic kinetic resolution of the chiral α-fluoro carbanions.

  20. Cyclization of ortho-hydroxycinnamates to coumarins under mild conditions: A nucleophilic organocatalysis approach

    Directory of Open Access Journals (Sweden)

    Florian Boeck


    Full Text Available (E-Alkyl ortho-hydroxycinnamates cyclize to coumarins at elevated temperatures of 140–250 °C. We find that the use of tri-n-butylphosphane (20 mol % as a nucleophilic organocatalyst in MeOH solution allows cyclization to take place under much milder conditions (60–70 °C. Several coumarins were prepared, starting from ortho-hydroxyarylaldehydes, by Wittig reaction with Ph3P=CHCO2Me to (E-methyl ortho-hydroxycinnamates, followed by the phosphane catalyzed cyclization.

  1. Bicyclo[3.2.1]octane synthons from cyclopropenes: functionalization of cycloadducts by nucleophilic additions. (United States)

    Orugunty, Ravi S; Wright, Dennis L; Battiste, Merle A; Helmich, Richard J; Abboud, Khalil


    It has been known for several decades that a highly functionalized family of tetrahalobicyclo[3.2.1]octadienes are readily available through the cycloaddition of furan or cyclopentadiene with either tetrachloro- or tetrabromocyclopropene. However, the application of these highly functionalized building blocks in synthesis has remained relatively unexplored in relation to their better-known counterparts derived through oxyallyl cation additions. As a first step toward utilizing these highly versatile intermediates in synthesis, a study of the addition of various nucleophiles to the halogenated nucleus has been conducted. It has been found that these halogenated systems are amenable to a wide range of functionalizations in high yields and with good selectivities.

  2. Micellar Effects on Nucleophilic Addition Reaction and Applicability of Enzyme Catalysis Model

    Directory of Open Access Journals (Sweden)

    R. K. London Singh


    Full Text Available This study describes the effect of anionic and cationic micelles on nucleophilic addition reaction of rosaniline hydrochloride (RH with hydroxide under pseudo-first order condition. Strong inhibitory effect is observed due to SDS micelle, whereas CTAB catalysed the reaction. This is explained on the basis of electrostatic and hydrophobic interactions which are simultaneously operating in the reaction system. The kinetic data obtained is quantitatively analysed by applying the positive cooperativity model of enzyme catalysis. Binding constants and influence of counterions on the reaction have also been investigated.

  3. Nucleophilic addition to the ethynyl group in ethynylestradiol catalyzed by crown ether-copper (1) iodide. (United States)

    Chen, S H; Luo, G R; Chang, X Z; Zhao, H M


    A new and convenient synthetic route to acetylation of estrogens is described. Benzo-15-crown-5 and cuprous iodide-mixed catalyst catalyzed the nucleophilic addition of 2,4-dibromoethynylestradiol, resulting in the formation of a new compound, 2,4-dibromo-17 alpha-acetylestradiol, of which the structure was characterized by infrared, UV, 1H nuclear magnetic resonance, mass spectra, and elemental analysis. It was found that the yield of this approach is much higher than that obtained in the hydration of usual acetylenic compounds.

  4. Contorted polycyclic aromatics. (United States)

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


    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

  5. Rapid and efficient copper-catalyzed Finkelstein reaction of (hetero)aromatics under continuous-flow conditions. (United States)

    Chen, Mao; Ichikawa, Saki; Buchwald, Stephen L


    A general, rapid, and efficient method for the copper-catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N-H and O-H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous-flow processes (amidation and Mg-I exchange/nucleophilic addition) to demonstrate the flexibility of this method.

  6. Petrochemistry - Aromatics; Petrochimie - Aromatiques

    Energy Technology Data Exchange (ETDEWEB)



    The assignment of Unipetrol chemical activities to the Czech group Agrofert by the Polish PKN Orlen is suspended and would be renegotiated. Oman Oil Company (OOC) is joining in the Korean LG International and in its subsidiary company Oman Refinery Company (ORC) for the construction of its new aromatics complex on its site of Sohar (Oman). This plan represents an investment of one milliard of dollars; it will produce 800000 t/year of para-xylene and 210000 t/year of benzene. The unit would be operational at the third trimester 2008. (O.M.)

  7. Fluorinated aromatic diamine (United States)

    Jones, Robert J. (Inventor); O'Rell, Michael K. (Inventor); Hom, Jim M. (Inventor)


    This invention relates to a novel aromatic diamine and more particularly to the use of said diamine for the preparation of thermally stable high-molecular weight polymers including, for example, polyamides, polyamideimides, polyimides, and the like. This diamine is obtained by reacting a stoichometric amount of a disodium salt of 2,2-bis(4-hydroxyphenyl) hexafluoropropane with 4-chloronitrobenzene to obtain an intermediate, 2,2-bis[4-(4-nitrophenoxy)phenyl] hexafluoropropane, which is reduced to the corresponding 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane.

  8. Displacement currents in geoelectromagnetic problems (United States)

    Mogilatov, Vladimir; Goldman, Mark; Persova, Marina; Soloveichik, Yury


    The influence of displacement currents in conventional geoelectromagnetic (GEM) methods using unimodal transversal electric (TE) or multimodal TE and TM (transversal magnetic) fields is only significant at very high frequencies in the frequency domain or at extremely early times in the time domain. The transient process in the latter includes three stages: the propagation through air, the propagation through earth and the diffusion within the earth. The influence of displacement currents is significant mainly during the former two stages, normally up to several tens to a few hundreds of nanoseconds. The behavior is essentially different in novel GEM methods using a vertical electric dipole (VED) or circular electric dipole (CED) sources of unimodal TM-fields. Under certain geoelectric conditions, the influence of displacement currents in these methods might be crucial at late times as well. This happens, if the model consists of insulating layers. In the absence of displacement currents, such layers would totally mask underlying structures. However, TM-fields including displacement currents depend on geoelectric parameters below insulating layers at late times.

  9. Formation around planetary displaced orbit

    Institute of Scientific and Technical Information of China (English)

    GONG Sheng-ping; LI Jun-feng; BAOYIN He-xi


    The paper investigates the relative motion around the planetary displaced orbit. Several kinds of displaced orbits for geocentric and martian cases were discussed. First, the relative motion was linearized around the displaced orbits. Then, two seminatural control laws were investigated for each kind of orbit and the stable regions were obtained for each case. One of the two control laws is the passive control law that is very attractive for engineering practice. However, the two control laws are not very suitable for the Martian mission. Another special semi-natural control law is designed based on the requirement of the Martian mission. The results show that large stable regions exist for the control law.

  10. Nucleophilic substitution at silicon (SN2@Si) via a central reaction barrier. (United States)

    Bento, A Patrícia; Bickelhaupt, F Matthias


    It is textbook knowledge that nucleophilic substitution at carbon (SN2@C) proceeds via a central reaction barrier which disappears in the corresponding nucleophilic substitution reaction at silicon (SN2@Si). Here, we address the question why the central barrier disappears from SN2@C to SN2@Si despite the fact that these processes are isostructural and isoelectronic. To this end, we have explored and analyzed the potential energy surfaces (PES) of various Cl-+CR3Cl (R=H, CH3) and Cl-+SiR3Cl model reactions (R=H, CH3, C2H5, and OCH3). Our results show that the nature of the SN2 reaction barrier is in essence steric, but that it can be modulated by electronic factors. Thus, simply by increasing the steric demand of the substituents R around the silicon atom, the SN2@Si mechanism changes from its regular single-well PES (with a stable intermediate transition complex, TC), via a triple-well PES (with a pre- and a post-TS before and after the central TC), to a double-well PES (with a TS; R=OCH3), which is normally encountered for SN2@C reactions.

  11. Synthesis, Structure, and Reactivity of Anionic sp(2) -sp(3) Diboron Compounds: Readily Accessible Boryl Nucleophiles. (United States)

    Pietsch, Sabrina; Neeve, Emily C; Apperley, David C; Bertermann, Rüdiger; Mo, Fanyang; Qiu, Di; Cheung, Man Sing; Dang, Li; Wang, Jianbo; Radius, Udo; Lin, Zhenyang; Kleeberg, Christian; Marder, Todd B


    Lewis base adducts of tetra-alkoxy diboron compounds, in particular bis(pinacolato)diboron (B2 pin2 ), have been proposed as the active source of nucleophilic boryl species in metal-free borylation reactions. We report the isolation and detailed structural characterization (by solid-state and solution NMR spectroscopy and X-ray crystallography) of a series of anionic adducts of B2 pin2 with hard Lewis bases, such as alkoxides and fluoride. The study was extended to alternative Lewis bases, such as acetate, and other diboron reagents. The B(sp(2) )-B(sp(3) ) adducts exhibit two distinct boron environments in the solid-state and solution NMR spectra, except for [(4-tBuC6 H4 O)B2 pin2 ](-) , which shows rapid site exchange in solution. DFT calculations were performed to analyze the stability of the adducts with respect to dissociation. Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles-namely, aryl halides and diazonium salts-demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources.

  12. Perceived Displacement explains Wolfpack Effect

    Directory of Open Access Journals (Sweden)

    Matúš eŠimkovic


    Full Text Available We investigate the influence of perceived displacement of moving agent-like stimuli on the performance in dynamic interactive tasks. In order to reliably measure perceived displacement we utilize multiple tasks with different task demands. The perceived center of an agent’s body is displaced in the direction in which the agent is facing and this perceived displacement is larger than the theoretical position of the center of mass would predict. Furthermore, the displacement in the explicit judgment is dissociated from the displacement obtained by the implicit measures. By manipulating the location of the pivot point, we show that it is not necessary to postulate orientation as an additional cue utilized by perception, as has been suggested by earlier studies. These studies showed that the agent’s orientation influences the detection of chasing motion and the detection-related performance in interactive tasks. This influence has been labeled wolfpack effect. In one of the demonstrations of the wolfpack effect participants control a green circle on a display with a computer mouse. It has been shown that participants avoid display areas withagents pointing towards the green circle. Participants do so in favor of areas where the agents point in the direction perpendicular to the circle. We show that this avoidance behavior arises because the agent’s pivot point selected by the earlier studies is different from where people locate the center of agent’s body. As a consequence, the nominal rotation confounds rotation and translation. We show that the avoidance behavior disappears once the pivot point is set to the center of agent’s body.

  13. "Carbo-aromaticity" and novel carbo-aromatic compounds. (United States)

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


    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

  14. Displacement ventilation in lecture halls


    Egorov, Artem


    This thesis considers several important goals. The main purpose is to see how displacement ventilation sys-tem works in the lecture hall of M-building and compare obtained results with D2 and Indoor Climate Classi-fication. The second one is to analyze the function of the ventilation system. The last one is to realize when displacement ventilation is preferable to mixing ventilation. Analysis of the system was carried out with instruments from MUAS HVAC laboratory. In lecture hall were me...

  15. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li


    Full Text Available Aromatic compounds are among the most prevalent and persistent pollutants in the environment. Petroleum-contaminated soil and sediment commonly contain a mixture of polycyclic aromatic hydrocarbons (PAHs and heterocyclic aromatics. Aromatics derived from industrial activities often have functional groups such as alkyls, halogens and nitro groups. Biodegradation is a major mechanism of removal of organic pollutants from a contaminated site. This review focuses on bacterial degradation pathways of selected aromatic compounds. Catabolic pathways of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene are described in detail. Bacterial catabolism of the heterocycles dibenzofuran, carbazole, dibenzothiophene, and dibenzodioxin is discussed. Bacterial catabolism of alkylated PAHs is summarized, followed by a brief discussion of proteomics and metabolomics as powerful tools for elucidation of biodegradation mechanisms.


    Energy Technology Data Exchange (ETDEWEB)



    A research effort was undertaken to determine the need for any changes to USNRC's seismic regulatory practice to reflect the move, in the earthquake engineering community, toward using expected displacement rather than force (or stress) as the basis for assessing design adequacy. The research explored the extent to which displacement based seismic design methods, such as given in FEMA 273, could be useful for reviewing nuclear power stations. Two structures common to nuclear power plants were chosen to compare the results of the analysis models used. The first structure is a four-story frame structure with shear walls providing the primary lateral load system, referred herein as the shear wall model. The second structure is the turbine building of the Diablo Canyon nuclear power plant. The models were analyzed using both displacement based (pushover) analysis and nonlinear dynamic analysis. In addition, for the shear wall model an elastic analysis with ductility factors applied was also performed. The objectives of the work were to compare the results between the analyses, and to develop insights regarding the work that would be needed before the displacement based analysis methodology could be considered applicable to facilities licensed by the NRC. A summary of the research results, which were published in NUREGICR-6719 in July 2001, is presented in this paper.

  17. Displacement and difference in Lubumbashi

    Directory of Open Access Journals (Sweden)

    Aurelia Wa Kabwe-Segatti


    Full Text Available Signs on the outskirts of the second largest city in the Democratic Republic of Congo (DRC welcome visitors to ‘the city of peace’. Lubumbashi has a reputation as a haven of tolerance in a violent nation but how are displaced people treated?

  18. To prevent or pursue displacement?

    Directory of Open Access Journals (Sweden)

    Casey Barrs


    Full Text Available The repertoire of survival actions of at-risk civilians includes bothavoiding and attempting displacement. But there are also overlaps,combinations and tacking back and forth between the two, whiletrying to mitigate the risks that any choice entails.

  19. Quantification of Aromaticity Based on Interaction Coordinates: A New Proposal. (United States)

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


    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.

  20. Synthesis and structural studies of flavin and alloxazine adducts with O-nucleophiles (United States)

    Ménová, Petra; Eigner, Václav; Čejka, Jan; Dvořáková, Hana; Šanda, Miloslav; Cibulka, Radek


    Five flavin (isoalloxazine) and alloxazine adducts with O-nucleophiles, 5-ethyl-4a-hydroxy-3,7,8,10-tetramethyl-4a,5-dihydroisoalloxazine ( 1a-OH), 5-ethyl-4a-hydroxy-3,10-dimethyl-4a,5-dihydroisoalloxazine ( 1b-OH), 5-ethyl-4a-methoxy-3,10-dimethyl-4a,5-dihydroisoalloxazine ( 1b-OMe), 5-ethyl-4a-hydroxy-1,3-dimethyl-4a,5-dihydroalloxazine ( 2a-OH) and 5-ethyl-4a-methoxy-1,3-dimethyl-4a,5-dihydroalloxazine ( 2a-OMe) were prepared from the corresponding salts, 5-ethyl-3,7,8,10-tetramethylisoalloxazinium ( 1a), 5-ethyl-3,10-dimethylisoalloxazinium ( 1b) and 5-ethyl-1,3-dimethylalloxazinium ( 2a) perchlorates by the addition of a nucleophile (water or methanol) and triethylamine as a base. The prepared adducts represent artificial analogs of flavin cofactor derivatives which are essential for the functioning of flavoenzymes. They were characterized by 1H and 13C NMR, HR-MS and UV-VIS spectra. In the cases of 1a-OH, 1b-OH, and 2a-OMe, the crystal structures were determined by X-ray diffraction. Flavinium and alloxazinium salts are in rapid equilibria with their adducts in water or methanolic solutions without the presence of a base. It was found that the equilibrium constants for flavin adduct formation is higher by six orders of magnitude than those for alloxazine derivatives. The presence of the sp 3 hybridized C4a atom in the molecule of the adducts causes deviation from planarity. The interplanar angles between benzene and the pyrimidine ring were found to be 31.5°, 23.64° and 15.62° for 1a-OH, 1b-OH and 2a-OMe, respectively, which are much higher than those of previously published adducts of C-nucleophiles. In isoalloxazine adducts, delocalization of π electrons between the N10-C10a and C10a-N1 bonds was detected while the length of the N10-C10a and C10a-N1 bonds in the alloxazine adducts corresponds to a double and single bond, respectively.

  1. Friedel-Crafts alkylations of electron-rich aromatics with 3-hydroxy-2-oxindoles: scope and limitations. (United States)

    Kinthada, Lakshmana K; Ghosh, Santanu; Babu, K Naresh; Sharique, Mohd; Biswas, Soumava; Bisai, Alakesh


    A Lewis acid-catalyzed nucleophilic addition of electron rich aromatics with 3-hydroxy-2-oxindoles 5 was developed. The reaction is believed to proceed through the 2H-indol-2-one ring system 9, which eventually reacts with various electron-rich aromatics to afford a variety of 2-oxindoles with an all-carbon quaternary center at the pseudobenzylic position (4, 8, 13, and 16) in high yields. The methodology provides an expeditious route to the tetracyclic core (3) of diazonamide (1), and azonazine (2) as well as the tricyclic core of asperazine (6a), idiospermuline (6b), and calycosidine (6c) viz. C(3a)-arylpyrroloindolines 7 having an all-carbon quaternary center on further synthetic elaboration.

  2. Alkali metal ion catalysis and inhibition in nucleophilic displacement reactions at phosphorus centers: ethyl and methyl paraoxon and ethyl and methyl parathion. (United States)

    Um, Ik-Hwan; Shin, Young-Hee; Lee, Seung-Eun; Yang, Kiyull; Buncel, Erwin


    We report on the ethanolysis of the P=O and P=S compounds ethyl and methyl paraoxon (1a and 1b) and ethyl and methyl parathion (2a and 2b). Plots of spectrophotometrically measured rate constants, kobsd versus [MOEt], the alkali ethoxide concentration, show distinct upward and downward curvatures, pointing to the importance of ion-pairing phenomena and a differential reactivity of free ions and ion pairs. Three types of reactivity and selectivity patterns have been discerned: (1) For the P=O compounds 1a and 1b, LiOEt > NaOEt > KOEt > EtO-; (2) for the P=S compound 2a, KOEt > EtO- > NaOEt > LiOEt; (3) for P=S, 2b, 18C6-crown-complexed KOEt > KOEt = EtO(-) > NaOEt > LiOEt. These selectivity patterns are characteristic of both catalysis and inhibition by alkali-metal cations depending on the nature of the electrophilic center, P=O vs P=S, and the metal cation. Ground-state (GS) vs transition-state (TS) stabilization energies shed light on the catalytic and inhibitory tendencies. The unprecedented catalytic behavior of crowned-K(+) for the reaction of 2b is noteworthy. Modeling reveals an extreme steric interaction for the reaction of 2a with crowned-K(+), which is responsible for the absence of catalysis in this system. Overall, P=O exhibits greater reactivity than P=S, increasing from 50- to 60-fold with free EtO(-) and up to 2000-fold with LiOEt, reflecting an intrinsic P=O vs P=S reactivity difference (thio effect). The origin of reactivity and selectivity differences in these systems is discussed on the basis of competing electrostatic effects and solvational requirements as function of anionic electric field strength and cation size (Eisenman's theory).

  3. Interplay between interstitial displacement and displacive lattice transformations (United States)

    Zhang, Xie; Hickel, Tilmann; Rogal, Jutta; Neugebauer, Jörg


    Diffusionless displacive lattice rearrangements, which include martensitic transformations, are in real materials often accompanied by a displacive drag of interstitials. The interplay of both processes leads to a particular atomistic arrangement of the interstitials in the product phase, which is decisive for its performance. An archetype example is the martensitic transformation in Fe-C alloys. One of the puzzles for this system is that the deviation from the cubic symmetry (i.e., the tetragonality) in the martensite resulting from this interplay is lower than what thermodynamics dictates. In our ab initio approach, the relative motion of C in the transforming lattice is studied with the nudged elastic band method. We prove that an atomic shearlike shuffle mechanism of adjacent (11 2 ¯) Fe layers along the ±[111] bcc directions is essential to achieve a redistribution of C atoms during the fcc → bcc transition, which fully explains the abnormal behavior. Furthermore, the good agreement with experiment validates our method to treat a diffusionless redistribution of interstitials and a displacive rearrangement of the host lattice simultaneously.


    Institute of Scientific and Technical Information of China (English)

    Hossein Mahdavi; Mahdi Mahmoudian


    Cross-linked poly(diallyldimethylammonium chloride) and its derivative eopolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions. In addition, the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.

  5. Bis-tert-Alcohol-Functionalized Crown-6-Calix[4]arene: An Organic Promoter for Nucleophilic Fluorination. (United States)

    Jadhav, Vinod H; Choi, Wonsil; Lee, Sung-Sik; Lee, Sungyul; Kim, Dong Wook


    A bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA) was designed and prepared as a multifunctional organic promoter for nucleophilic fluorinations with CsF. By formation of a CsF/BACCA complex, BACCA could release a significantly active and selective fluoride source for SN2 fluorination reactions. The origin of the promoting effects of BACCA was studied by quantum chemical methods. The role of BACCA was revealed to be separation of the metal fluoride to a large distance (>8 Å), thereby producing an essentially "free" F(-). The synergistic actions of the crown-6-calix[4]arene subunit (whose O atoms coordinate the counter-cation Cs(+)) and the terminal tert-alcohol OH groups (forming controlled hydrogen bonds with F(-)) of BACCA led to tremendous efficiency in SN2 fluorination of base-sensitive substrates.

  6. Effect of solid particle loading on nucleophilic addition of epoxy-resin to isophorone diisocyanate

    Institute of Scientific and Technical Information of China (English)

    Wei Zhang; Richard S.Blackburn; Abbas A.Dehghani-Sanij


    In the preparation of surface coatings made of conductive composites consisting of conductive particulate fillers in a soft matrix, cracks will develop with increase of the particulate loading, which is believed to be related to the nucleophilic addition reaction between glycidyl end-capped poly (bisphenol A-co-epichlorohydrin) and isophorone diisocyanate molecules. This curing reaction is responsible for the generation of cross-linking network throughout the coatings. The influence of solid particle loading on the chemical reaction may be described as a volume-excluded effect, that is, the high solid particle loading will occupy the space between the functional groups thus preventing the chemical reaction to take place. As a direct consequence, the cross-linking network cannot develop properly due to the insufficiency of curing reaction. This will lead to the generation of cracks, as was supported by FT-IR analysis in this work.

  7. Nucleophilic addition/double cyclization cascade processes between enynyl Fischer carbene complexes and alkynyl malonates. (United States)

    Álvarez-Fernández, Ana; Suárez-Rodríguez, Tatiana; Suárez-Sobrino, Ángel L


    Two new selective cascade processes for enynyl Fischer carbene complexes 1 are described in their reaction with alkynyl malonates. When carbene complexes 1 react with the sodium enolate of homopropargyl malonates 3 a consecutive Michael-type addition/cyclopentannulation/6-exo cyclization takes place leading, in a regio- and stereoselective way, to n/5/6 angular tricyclic compounds 5. Furthermore, when propargylic malonates are used, a delayed protonation of the reaction mixture allows intermediate 1,4-addition adduct Ia to evolve through a 5-exo cyclization, consisting of an intramolecular nucleophilic attack from the central carbon of the allenylmetallate over the triple C-C bond. Further spontaneous cyclopentannulation of the resulting metallatriene gives rise to bicyclic and linear polycyclic compounds 6 and 7, some of them bearing a polyquinane framework.

  8. Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

    KAUST Repository

    Fetsch, Corinna


    Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Subclass-specific labeling of protein-reactive natural products with customized nucleophilic probes. (United States)

    Rudolf, Georg C; Koch, Maximilian F; Mandl, Franziska A M; Sieber, Stephan A


    Natural products represent a rich source of bioactive compounds that constitute a large fraction of approved drugs. Among those are molecules with electrophilic scaffolds, such as Michael acceptors, β-lactams, and epoxides that irreversibly inhibit essential enzymes based on their catalytic mechanism. In the search for novel bioactive molecules, current methods are challenged by the frequent rediscovery of known chemical entities. Herein small nucleophilic probes that attack electrophilic natural products and enhance their detection by HPLC-UV and HPLC-MS are introduced. A screen of diverse probe designs revealed one compound with a desired selectivity for epoxide- and maleimide-based antibiotics. Correspondingly, the natural products showdomycin and phosphomycin could be selectively targeted in extracts of their natural producing organism, in which the probe-modified molecules exhibited superior retention and MS detection relative to their unmodified counterparts. This method may thus help to discover small, electrophilic molecules that might otherwise easily elude detection in complex samples.

  10. Symmetry Analysis in Mechanistic Studies of Nucleophilic Substitution and β-Elimination Reactions

    Directory of Open Access Journals (Sweden)

    Xiaoping Sun


    Full Text Available A mechanistic study of the bimolecular nucleophilic substitution (SN2 reaction for halomethane CH3X (X = Cl, Br, or I is approached by using symmetry principles and molecular orbital theory. The electrophilicity of the functionalized sp3–carbon is attributable to a 2p-orbital-based antibonding MO along the C–X bond. This antibonding MO, upon accepting an electron pair from a nucleophile, gives rise to dissociation of the C–X bond and formation of a new Nuc–C bond. Correlations are made between the molecular orbitals of reactants (Nuc- and CH3X and products (NucCH3 and X-. Similar symmetry analysis has been applied to mechanistic study of the bimolecular b-elimination (E2 reactions of haloalkanes. It well explains the necessity of an anti-coplanar arrangement of the Cα–X and Cβ–H bonds for an E2 reaction (anti-elimination. Having this structural arrangement, the bonding Cα–X (σC-X and antibonding Cβ–H (σC-H* orbitals become symmetry–match. They can partially overlap resulting in increase in electron density in σC-H*, which weakens and polarizes the Cβ–H bond making the β-H acidic. An E2 reaction can readily take place in the presence of a base. The applications of symmetry analysis to the SN2 and E2 reactions represent a new approach to studying organic mechanisms.

  11. The development of catalytic nucleophilic additions of terminal alkynes in water. (United States)

    Li, Chao-Jun


    One of the major research endeavors in synthetic chemistry over the past two decades is the exploration of synthetic methods that work under ambient atmosphere with benign solvents, that maximize atom utilization, and that directly transform natural resources, such as renewable biomass, from their native states into useful chemical products, thus avoiding the need for protecting groups. The nucleophilic addition of terminal alkynes to various unsaturated electrophiles is a classical (textbook) reaction in organic chemistry, allowing the formation of a C-C bond while simultaneously introducing the alkyne functionality. A prerequisite of this classical reaction is the stoichiometric generation of highly reactive metal acetylides. Over the past decade, our laboratory and others have been exploring an alternative, the catalytic and direct nucleophilic addition of terminal alkynes to unsaturated electrophiles in water. We found that various terminal alkynes can react efficiently with a wide range of such electrophiles in water (or organic solvent) in the presence of simple and readily available catalysts, such as copper, silver, gold, iron, palladium, and others. In this Account, we describe the development of these synthetic methods, focusing primarily on results from our laboratory. Our studies include the following: (i) catalytic reaction of terminal alkynes with acid chloride, (ii) catalytic addition of terminal alkynes to aldehydes and ketones, (iii) catalytic addition of alkynes to C=N bonds, and (iv) catalytic conjugate additions. Most importantly, these reactions can tolerate various functional groups and, in many cases, perform better in water than in organic solvents, clearly defying classical reactivities predicated on the relative acidities of water, alcohols, and terminal alkynes. We further discuss multicomponent and enantioselective reactions that were developed. These methods provide an alternative to the traditional requirement of separate steps in

  12. Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide. (United States)

    Cuevasanta, Ernesto; Lange, Mike; Bonanata, Jenner; Coitiño, E Laura; Ferrer-Sueta, Gerardo; Filipovic, Milos R; Alvarez, Beatriz


    Hydrogen sulfide (H2S) is increasingly recognized to modulate physiological processes in mammals through mechanisms that are currently under scrutiny. H2S is not able to react with reduced thiols (RSH). However, H2S, more precisely HS(-), is able to react with oxidized thiol derivatives. We performed a systematic study of the reactivity of HS(-) toward symmetric low molecular weight disulfides (RSSR) and mixed albumin (HSA) disulfides. Correlations with thiol acidity and computational modeling showed that the reaction occurs through a concerted mechanism. Comparison with analogous reactions of thiolates indicated that the intrinsic reactivity of HS(-) is 1 order of magnitude lower than that of thiolates. In addition, H2S is able to react with sulfenic acids (RSOH). The rate constant of the reaction of H2S with the sulfenic acid formed in HSA was determined. Both reactions of H2S with disulfides and sulfenic acids yield persulfides (RSSH), recently identified post-translational modifications. The formation of this derivative in HSA was determined, and the rate constants of its reactions with a reporter disulfide and with peroxynitrite revealed that persulfides are better nucleophiles than thiols, which is consistent with the α effect. Experiments with cells in culture showed that treatment with hydrogen peroxide enhanced the formation of persulfides. Biological implications are discussed. Our results give light on the mechanisms of persulfide formation and provide quantitative evidence for the high nucleophilicity of these novel derivatives, setting the stage for understanding the contribution of the reactions of H2S with oxidized thiol derivatives to H2S effector processes.

  13. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions (United States)

    Mendes, Desiree E.; Schoffstall, Allen M.


    This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

  14. C-Terminally modified peptides via cleavage of the HMBA linker by O-, i>N>- or S-nucleophiles

    DEFF Research Database (Denmark)

    Hansen, Jonas; Diness, Frederik; Meldal, Morten Peter


    A large variety of C-terminally modified peptides was obtained by nucleophilic cleavage of the ester bond in solid phase linked peptide esters of 4-hydroxymethyl benzamide (HMBA). The developed methods provided peptides, C-terminally functionalized as esters, amides and thioesters, with high puri...

  15. Abnormal Nucleophilic Reaction of Ethyl Crotonate: An Easy Way to Form Novel Imidazo[1,5-a] pyridine derivatives

    Institute of Scientific and Technical Information of China (English)


    An abnormal intramolecular nucleophilic reaction of α-carbon of α,β-unsaturated ester was discovered and the reaction makes it very easy to form imidazo[1,5-a]pyridine derivatives. The mechanism of the reaction was discussed.

  16. Benchmark Study on the Smallest Bimolecular Nucleophilic Substitution Reaction: H−+CH4 →CH4+H−

    Directory of Open Access Journals (Sweden)

    Marcel Swart


    Full Text Available We report here a benchmark study on the bimolecular nucleophilic substitution (SN2 reaction between hydride and methane, for which we have obtained reference energies at the coupled cluster toward full configuration-interaction limit (CC-cf/CBS. Several wavefunction (HF, MP2, coupled cluster and density functional methods are compared for their reliability regarding these reference data.

  17. Organic Chemistry Students' Fragmented Ideas about the Structure and Function of Nucleophiles and Electrophiles: A Concept Map Analysis (United States)

    Anzovino, Mary E.; Bretz, Stacey Lowery


    Organic chemistry students struggle with multiple aspects of reaction mechanisms and the curved arrow notation used by organic chemists. Many faculty believe that an understanding of nucleophiles and electrophiles, among other concepts, is required before students can develop fluency with the electronpushing formalism (EPF). An expert concept map…

  18. Direct sp(3)C-H acroleination of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with nucleophilic catalysis. (United States)

    Feng, Zhu-Jia; Xuan, Jun; Xia, Xu-Dong; Ding, Wei; Guo, Wei; Chen, Jia-Rong; Zou, You-Quan; Lu, Liang-Qiu; Xiao, Wen-Jing


    Sequence catalysis merging photoredox catalysis (PC) and nucleophilic catalysis (NC) has been realized for the direct sp(3) C-H acroleination of N-aryl-tetrahydroisoquinoline (THIQ). The reaction was performed under very mild conditions and afforded products in 50-91% yields. A catalytic asymmetric variant was proved to be successful with moderate enantioselectivities (up to 83 : 17 er).

  19. Single-mode displacement sensor (United States)

    Duivenvoorden, Kasper; Terhal, Barbara M.; Weigand, Daniel


    We show that one can determine both parameters of a displacement acting on an oscillator with an accuracy which scales inversely with the square root of the number of photons in the oscillator. Our results are obtained by using a grid state as a sensor state for detecting small translations in phase space (displacements). Grid states were first proposed [D. Gottesman et al., Phys. Rev. A 64, 012310 (2001), 10.1103/PhysRevA.64.012310] for encoding a qubit into an oscillator: an efficient preparation protocol of such states, using a coupling to a qubit, was later developed [B. M. Terhal and D. Weigand, Phys. Rev. A 93, 012315 (2016), 10.1103/PhysRevA.93.012315]. We compare the performance of the grid state with the quantum compass or cat code state and place our results in the context of the two-parameter quantum Cramér-Rao lower bound on the variances of the displacement parameters. We show that the accessible information about the displacement for a grid state increases with the number of photons in the state when we measure and prepare the state using a phase estimation protocol. This is in contrast with the accessible information in the quantum compass state which we show is always upper bounded by a constant, independent of the number of photons. We present numerical simulations of a phase estimation based preparation protocol of a grid state in the presence of photon loss, nonlinearities, and qubit measurement, using no post-selection, showing how the two effective squeezing parameters which characterize the grid state change during the preparation. The idea behind the phase estimation protocol is a simple maximal-information gain strategy.

  20. Advances towards aromatic oligoamide foldamers

    DEFF Research Database (Denmark)

    Hjelmgaard, Thomas; Plesner, Malene; Dissing, Mette Marie;


    We have efficiently synthesized 36 arylopeptoid dimers with ortho-, meta-, and para-substituted aromatic backbones and tert-butyl or phenyl side chains. The dimers were synthesized by using a "submonomer method" on solid phase, by applying a simplified common set of reaction conditions. X......-ray crystallographic analysis of two of these dimers disclosed that the tert-butyl side chain invokes a cis amide conformation with a comparatively more closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation with a more open, extended structure...... of the surrounding aromatic backbone. Investigation of the X-ray structures of two arylopeptoid dimers disclosed that the tert-butyl side chain invokes a cis amide conformation with a closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation...

  1. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.


    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.

  2. 25 CFR 700.59 - Displaced person. (United States)


    ... 25 Indians 2 2010-04-01 2010-04-01 false Displaced person. 700.59 Section 700.59 Indians THE OFFICE OF NAVAJO AND HOPI INDIAN RELOCATION COMMISSION OPERATIONS AND RELOCATION PROCEDURES General Policies and Instructions Definitions § 700.59 Displaced person. Displaced person means a member of...

  3. Polycyclic Aromatic Hydrocarbons (United States)

    Salama, Farid


    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.

  4. Ground state destabilization by anionic nucleophiles contributes to the activity of phosphoryl transfer enzymes.

    Directory of Open Access Journals (Sweden)

    Logan D Andrews


    Full Text Available Enzymes stabilize transition states of reactions while limiting binding to ground states, as is generally required for any catalyst. Alkaline Phosphatase (AP and other nonspecific phosphatases are some of Nature's most impressive catalysts, achieving preferential transition state over ground state stabilization of more than 10²²-fold while utilizing interactions with only the five atoms attached to the transferred phosphorus. We tested a model that AP achieves a portion of this preference by destabilizing ground state binding via charge repulsion between the anionic active site nucleophile, Ser102, and the negatively charged phosphate monoester substrate. Removal of the Ser102 alkoxide by mutation to glycine or alanine increases the observed Pi affinity by orders of magnitude at pH 8.0. To allow precise and quantitative comparisons, the ionic form of bound P(i was determined from pH dependencies of the binding of Pi and tungstate, a P(i analog lacking titratable protons over the pH range of 5-11, and from the ³¹P chemical shift of bound P(i. The results show that the Pi trianion binds with an exceptionally strong femtomolar affinity in the absence of Ser102, show that its binding is destabilized by ≥10⁸-fold by the Ser102 alkoxide, and provide direct evidence for ground state destabilization. Comparisons of X-ray crystal structures of AP with and without Ser102 reveal the same active site and P(i binding geometry upon removal of Ser102, suggesting that the destabilization does not result from a major structural rearrangement upon mutation of Ser102. Analogous Pi binding measurements with a protein tyrosine phosphatase suggest the generality of this ground state destabilization mechanism. Our results have uncovered an important contribution of anionic nucleophiles to phosphoryl transfer catalysis via ground state electrostatic destabilization and an enormous capacity of the AP active site for specific and strong recognition of the

  5. Solvent-free functionalization of fullerene C60 and pristine multi-walled carbon nanotubes with aromatic amines (United States)

    Ramírez-Calera, Itzel J.; Meza-Laguna, Victor; Gromovoy, Taras Yu.; Chávez-Uribe, Ma. Isabel; Basiuk, Vladimir A.; Basiuk, Elena V.


    We employed a direct one-step solvent-free covalent functionalization of solid fullerene C60 and pristine multi-walled carbon nanotubes (MWCNTs) with aromatic amines 1-aminopyrene (AP), 2-aminofluorene (AF) and 1,5-diaminonaphthalene (DAN). The reactions were carried out under moderate vacuum, in a wide temperature range of 180-250 °C, during relatively short time of about 2 h. To confirm successful amine attachment, a large number of analytical techniques were used (depending on the nanomaterial functionalized) such as Fourier transform infrared, Raman, X-ray photoelectron, 13C cross-polarization magic angle spinning NMR spectroscopy, thermogravimetric analysis, laser-desorption ionization time-of-flight mass spectrometry, temperature-programmed desorption with mass spectrometric detection, as well as scanning and transmission electron microscopy. The nucleophilic addition of the aromatic amines to C60 molecule was studied theoretically by using density functional theory (PBE GGA functional with Grimme dispersion correction in conjunction with the DNP basis set). In the case of crystalline C60, the solvent-free technique has a limited applicability due to poor diffusion of vaporous aromatic amines into the bulk. Nevertheless, the approach proposed allows for a facile preparation of aromatic amine-functionalized pristine MWCNTs without contamination with other chemical reagents, detergents and solvents, which is especially important for a vast variety of nanotube applications spanning from nanoelectronics to nanomedicine.

  6. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora


    Full Text Available 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 compounds 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.

  7. Aromatic-Aromatic Interactions in Biological System: Structure Activity Relationships

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopal, Appavu; Deepa, Mohan [Molecular Biophysics Unit, Indian Institute of Sciences-Bangalore, Karnataka (India); Govindaraju, Munisamy [Bio-Spatial Technology Research Unit, Department of Environmental Biotechnology, School of Environmental Sciences, Bharathidasan University, Tiruchirappalli, Tamil Nadu (India)


    While, intramolecular hydrogen bonds have attracted the greatest attention in studies of peptide conformations, the recognition that several other weakly polar interactions may be important determinants of folded structure has been growing. Burley and Petsko provided a comprehensive overview of the importance of weakly polar interactions, in shaping protein structures. The interactions between aromatic rings, which are spatially approximate, have attracted special attention. A survey of the proximal aromatic residue pairs in proteins, allowed Burley and Petsko to suggest that, “phenyl ring centroids are separated by a preferential distance of between 4.5 and 7 Å, and dihedral angles approximately 90° are most common”.

  8. Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with secondary amine nucleophiles

    Directory of Open Access Journals (Sweden)

    Dingqiao Yang


    Full Text Available Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with various aliphatic and aromatic secondary amines are reported for the first time. The reaction gave the corresponding trans-1,2-dihydronaphthalenol derivatives in good yields with moderate enantioselectivities in the presence of 2.5 mol % [Ir(CODCl]2 and 5 mol % bisphosphine ligand (S-p-Tol-BINAP. The trans-configuration of 3f was confirmed by X-ray crystallography.

  9. Detoxification of biomass hydrolysates with nucleophilic amino acids enhances alcoholic fermentation. (United States)

    Xie, Rui; Tu, Maobing; Carvin, Jamarius; Wu, Yonnie


    Carbonyl compounds generated in biomass pretreatment hinder the biochemical conversion of biomass hydrolysates to biofuels. A novel approach of detoxifying hydrolysates with amino acids for ethanol production was developed. Among the 20 amino acids assessed for their detoxification efficiency and nucleophilicity, cysteine was the most effective one. It increased both ethanol productivity and final yield of biomass hydrolysates from 0.18 (untreated) to 1.77 g/L/h and from 0.02 to 0.42 g/g, respectively. Detoxification efficiency was followed by histidine and it increased the final yield to 0.42 g/g, then by lysine, tryptophan and asparagine. It was observed all five effective amino acids contained reactive side-chain functional groups, which played important roles in the amino acid detoxification reaction. The study further showed cysteine and glycine detoxifications were temperature and pH dependent. The mechanistic study using mass spectrometry revealed thiazolidine carboxylic acid, a Schiff base, was formed by condensation of aldehyde and cysteine.

  10. Theoretical study of nucleophilic halogenalkylation of propylene oxide with halogenmethane and dihalogenmethane anion

    Indian Academy of Sciences (India)

    Tao Liu; Xiang-Chen Yin; Guo-Dong Liu; Zhang-Yu Yu


    The nucleophilic halogenalkylation reactions of propylene oxide with halogenmethane anion (CH2X-) and dihalogenmethane anion (CHX$^{-}_{2}$) (X = F, Cl) in the gas phase and in the Et2O solvent are studied using the B3LYP method and the SCIPCM model for simulating solution effects. Our calculations predict the same reaction path for following reactions: (1) (X = F, Cl) and (2) (X = F) in the two phases, but there is a little difference in the relative energy of IM1(2Cl) in the gas phase and in the Et2O solvent for reaction (2) (X = Cl). All the four reactions proceed in two steps. Reactions (1) and (2) are predicted to be exothermic and thermodynamically favourable in both the gas phase and the Et2O solvent. The overall barrier energies for reaction (1) (X = F), reaction (1) (X = Cl), reaction (2) (X = F), and reaction (2) (X = Cl) are predicted to be 2.74 and 4.08 kcal mol-1, 3.35 and 5.20 kcal mol-1, 4.67 and 6.05 kcal mol-1, and 5.33 and 8.23 kcal mol-1 in the gas phase and in the Et2O solvent, respectively. The accurate calculation of results for the model systems would be useful for experimental researchers working in this field.

  11. Gramicidin S: a peptide model for protein glycation and reversal of glycation using nucleophilic amines. (United States)

    Shakkottai, V G; Sudha, R; Balaram, P


    Nonenzymatic glycation of proteins has been implicated in various diabetic complications and age-related disorders. Proteins undergo glycation at the N-terminus or at the epsilon-amino group of lysine residues. Glycation of proteins proceeds through the stages of Schiff base formation, conversion to ketoamine product and advanced glycation end products. Gramicidin S, which has two ornithine residues, was used as a model system to study the various stages of glycation of proteins using electrospray ionization mass spectrometry. The proximity of two ornithine residues in the peptide favors the glycation reaction. Formation of advanced glycation end products and diglycation on ornithine residues in gramicidin S were observed. The formation of Schiff base adduct is reversible, whereas the Amadori rearrangement to the ketoamine product is irreversible. Nucleophilic amines and hydrazines can deglycate the Schiff base adduct of glucose with peptides and proteins. Hydroxylamine, isonicotinic acid hydrazide and aminoguanidine effectively removed glucose from the Schiff base adduct of gramicidin S. Hydroxylamine is more effective in deglycating the adduct compared with isonicotinic acid hydrazide and aminoguanidine. The observation that the hydrazines are effective in deglycating the Schiff base adduct even in the presence of high concentrations of glucose, may have a possible therapeutic application in preventing complications of diabetes mellitus. Hydrazines may be used to distinguish between the Schiff base and the ketoamine products formed at the initial stages of glycation.

  12. sp(2)-sp(3) diboranes: astounding structural variability and mild sources of nucleophilic boron for organic synthesis. (United States)

    Dewhurst, Rian D; Neeve, Emily C; Braunschweig, Holger; Marder, Todd B


    Despite the widespread use of organoborane reagents in organic synthesis and catalysis, a major challenge still remains: very few boron-centered nucleophiles exist for the direct construction of B-C bonds. Perhaps the most promising emerging solution to this problem is the use of sp(2)-sp(3) diboranes, in which one boron atom of a conventional diborane(4) is quaternised by either a neutral or anionic nucleophile. These compounds, either isolated or generated in situ, serve as relatively mild and convenient sources of the boryl anion [BR2](-) for use in organic synthesis and have already proven their efficacy in metal-free as well as metal-catalysed borylation reactions. This Feature article documents the history of sp(2)-sp(3) diborane synthesis, their properties and surprising structural variability, and their burgeoning utility in organic synthesis.

  13. Nucleophilic Substitution on 2-Monosubstituted Quinoxalines Giving 2,3-Disubstituted Quinoxalines: Investigating the Effect of the 2-Substituent

    Directory of Open Access Journals (Sweden)

    Ndumiso Thamsanqa Ndlovu


    Full Text Available An investigation on the effect of substituent at the 2-position of mono-substituted quinoxalines in the synthesis of di-substituted quinoxaline derivatives via nucleophilic substitution reactions, is reported. Di-substituted quinoxalines bearing aryl-alky, aryl-aryl, aryl-heteroaryl, aryl-alkynyl, and amino-alkyl substituents were prepared in moderate to good yields. 2-Monosubstituted quinoxalines bearing a phenyl and butyl substituent reacted readily with alkyl-, aryl-, heteroaryl- and alkynyl- nucluephiles, giving di-substituted quinoxalines. 2-Monosubstituted quinoxalines bearing an amine and alkynyl substituent only reacted with alkyl nucleophiles. Oxidative rearomatization to give 2,3-disubstituted quinoxaline products occurred in atmospheric O2.

  14. Novel Substitution Reactions of 5-(4-Nitrophenyl)-10,15,20-triphenyl porphyrin with Nucleophilic Reagents

    Institute of Scientific and Technical Information of China (English)

    SHAO,Zhi-Jun; CHEN,Zhang-Ping; OUYANG,Yan; ZENG,Dan-Li


    @@ Substitution reactions of 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin (1)and its Ni(Ⅱ) complexe 2 with different nucleophilic reagents were studied for preparing asymmetric porphyrin. The reaction products are different with the nucleophilic reagents changing. Diporphyrin (3) was obtained when compound 1 reacted with sodium phenoxide or diphenoxide ion in DMF solution. Whereas the nitro group was reduced and 5-(4-amino-phenyl)-10,15,20-triphenylporphyrinato Nickel(Ⅱ) (4) was achieved when compound 2 reacted with above nuleophilic reagents in the same condition. The reductive product 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (5) was also achieved when 1 reacted with mercaptoethanol or thiophene and lithium hydroxide. While the nitro group was substituted by cyanide anion and 5-(4-nitrilephenyl)-10,15,20-triphenylporphyrin (6) was achieved when 1 reacted with sodium cyanide.

  15. Regio- and Diasteroselectivity of Rhodium-catalyzed Ring Opening Reaction of Oxabenzonorbornadienes with Heteroatom Nucleophiles

    Institute of Scientific and Technical Information of China (English)


    A new rhodium catalyzed ring opening reaction of oxabenzonorbornadienes and its derivatives was described. This reaction forms a new carbon-nitrogen bond via an intermolecular allylic displacement of the bridgehead oxygen with a piperazine's derivatives, which proceeds with very high regioselectivity.


    Energy Technology Data Exchange (ETDEWEB)



    The USNRC has initiated a project to determine if any of the likely revisions to traditional earthquake engineering practice are relevant to seismic design of the specialized structures, systems and components of nuclear power plants and of such significance to suggest that a change in design practice might be warranted. As part of the initial phase of this study, a literature survey was conducted on the recent changes in seismic design codes/standards, on-going activities of code-writing organizations/communities, and published documents on displacement-based design methods. This paper provides a summary of recent changes in building codes and on-going activities for future codes. It also discusses some technical issues for further consideration.

  17. Displacement Based Seismic Design Criteria

    Energy Technology Data Exchange (ETDEWEB)

    Costello, J.F.; Hofmayer, C.; Park, Y.J.


    The USNRC has initiated a project to determine if any of the likely revisions to traditional earthquake engineering practice are relevant to seismic design of the specialized structures, systems and components of nuclear power plants and of such significance to suggest that a change in design practice might be warranted. As part of the initial phase of this study, a literature survey was conducted on the recent changes in seismic design codes/standards, on-going activities of code-writing organizations/communities, and published documents on displacement-based design methods. This paper provides a summary of recent changes in building codes and on-going activities for future codes. It also discusses some technical issues for further consideration.

  18. Displaceable Gear Torque Controlled Driver (United States)

    Cook, Joseph S., Jr. (Inventor)


    Methods and apparatus are provided for a torque driver including a displaceable gear to limit torque transfer to a fastener at a precisely controlled torque limit. A biasing assembly biases a first gear into engagement with a second gear for torque transfer between the first and second gear. The biasing assembly includes a pressurized cylinder controlled at a constant pressure that corresponds to a torque limit. A calibrated gage and valve is used to set the desired torque limit. One or more coiled output linkages connect the first gear with the fastener adaptor which may be a socket for a nut. A gear tooth profile provides a separation force that overcomes the bias to limit torque at the desired torque limit. Multiple fasteners may be rotated simultaneously to a desired torque limit if additional output spur gears are provided. The torque limit is adjustable and may be different for fasteners within the same fastener configuration.

  19. Nucleophile-directed selectivity towards linear carbonates in the niobium pentaethoxide-catalysed cycloaddition of CO2 and propylene oxide

    KAUST Repository

    Dutta, Barnali


    Homoleptic Nb-complexes combined with selected organic nucleophiles generate very active catalytic systems for the cycloaddition of propylene oxide and CO2 under ambient conditions. An unprecedented reaction pathway towards an acyclic organic carbonate is observed when extending the study to [Nb(OEt)5] in combination with 4-dimethylamino-pyridine (DMAP) or tetra-n-butylammonium bromide (TBAB). Mechanistic insights of the reaction are provided based on experimental and spectroscopic evidences. This journal is © the Partner Organisations 2014.

  20. Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Brønsted acids. (United States)

    Motokura, Ken; Nakagiri, Nobuaki; Mizugaki, Tomoo; Ebitani, Kohki; Kaneda, Kiyotomi


    We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na+-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the alpha-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces.

  1. Aromaticity of group 14 organometallics: experimental aspects. (United States)

    Lee, Vladimir Ya; Sekiguchi, Akira


    The long story of aromatic compounds has extended over almost two centuries, since the discovery by Faraday of "bicarburet of hydrogen", or C(6)H(6), now called benzene. Since then, the chemistry of aromatic compounds has been developed extensively; this is reflected in the synthesis of novel classes of aromatic derivatives including charged species, nonclassical (Möbius, three-dimensional, homo-, metalla-) aromatics, and fullerenes. The theory of aromaticity has also undergone a spectacular evolution since the first definition of aromaticity by Hückel; the classification of aromaticity now requires the consideration of versatile criteria: energetic, structural, magnetic, among others. In this Review, we discuss the current state of affairs in the chemistry of aromatic compounds of the heavier Group 14 elements, the latest experimental achievements, as well as future prospects in the field.

  2. High Brønsted beta nuc values in SNAr displacement. An indicator of the SET pathway? (United States)

    Terrier, François; Mokhtari, Malika; Goumont, Régis; Hallé, Jean-Claude; Buncel, Erwin


    Nucleophilic substitutions of 4-chloro-7-nitrobenzofurazan (NBD-Cl) and 3-methyl-1-(4-nitrobenzofurazanyl)-imidazolium ions (NBD-Im+) with a series of 4-X-substituted anilines have been kinetically investigated in 70-30 (v/v) and 20-80 (v/v) H2O-Me2SO mixtures. The rate-limiting step in these reactions is nucleophilic addition with formation of Meisenheimer-type sigma-adducts followed by fast expulsion of the leaving group (Cl- or Im). The reactions are characterized by a notable sensitivity to basicity of the aniline nucleophiles, with Hammett rho values of -2.68 and -3.82 in 30% and 80% Me2SO, respectively, for NBD-Cl and even more negative values, -3.43 and -5.27, respectively, for NBD-Im+. This is consistent with significant development of positive charge at the nitrogen atom of the zwitterionic sigma-adduct. Unexpectedly, the Brønsted-type plots reveal abnormally high beta nuc values, ca. 1.0 and 1.3-1.4, respectively. Satisfactory correlations between the rates of the reactions and the oxidation potentials of the respective anilines support a SET mechanism for this process, i.e. initial (fast) electron-transfer from the aniline donor to the nitrobenzofurazan acceptor moiety and subsequent (slow) coupling of the resulting cation and anion radicals within the solvent cage with formation of the sigma-adduct. An alternative possible explanation of the high beta nuc values being related to the strong--I effect exerted by the negatively charged 4-nitrobenzofurazanyl structure, which would induce a greater positive charge at the developing anilinium nitrogen atom in the sigma-adduct-like transition state as compared with the situation in the reference protonation equilibria of anilines, is considered less probable. It is thus proposed that obtention of abnormal beta nuc values may be an indicator of electron-transfer in nucleophilic aromatic substitution and highlights the transition from the polar (SNAr) to the single electron-transfer (SET) mechanism.

  3. Facial Selectivity in the Nucleophilic Additions of endo-Tricyclo[5.2.1.O2.6]deca-2(6),8-dien-3-one

    Institute of Scientific and Technical Information of China (English)


    Nucleophilic additions to endo-tricyclo[]deca-2(6),8-dien-3-one 4 are described.Experimental results show high preference for exo-facial attack to the enone moiety of tricyclodecadienone. Steric hindrance is the main kinetically controlling factor in the nucleophilic reaction. The shielding effect and the stabilizing effect of the norbornene double bond favor the exo-facial attack also.

  4. Modelling toehold-mediated RNA strand displacement

    CERN Document Server

    Šulc, Petr; Romano, Flavio; Doye, Jonathan P K; Louis, Ard A


    We study the thermodynamics and kinetics of an RNA toehold-mediated strand displacement reaction with a recently developed coarse-grained model of RNA. Strand displacement, during which a single strand displaces a different strand previously bound to a complementary substrate strand, is an essential mechanism in active nucleic acid nanotechnology and has also been hypothesized to occur in vivo. We study the rate of displacement reactions as a function of the length of the toehold and temperature and make two experimentally testable predictions: that the displacement is faster if the toehold is placed at the 5' end of the substrate and that the displacement slows down with increasing temperature for longer toeholds.

  5. Preventing re-displacement through genuine reintegration in Burundi

    Directory of Open Access Journals (Sweden)

    Lucy Hovil


    Full Text Available Displacement is often part of a cyclical process of conflict anddisplacement. Preventing displacement, therefore, is not only aboutpreventing new displacement but about ensuring that people do notget re-displaced.

  6. Displacement based multilevel structural optimization (United States)

    Striz, Alfred G.


    Multidisciplinary design optimization (MDO) is expected to play a major role in the competitive transportation industries of tomorrow, i.e., in the design of aircraft and spacecraft, of high speed trains, boats, and automobiles. All of these vehicles require maximum performance at minimum weight to keep fuel consumption low and conserve resources. Here, MDO can deliver mathematically based design tools to create systems with optimum performance subject to the constraints of disciplines such as structures, aerodynamics, controls, etc. Although some applications of MDO are beginning to surface, the key to a widespread use of this technology lies in the improvement of its efficiency. This aspect is investigated here for the MDO subset of structural optimization, i.e., for the weight minimization of a given structure under size, strength, and displacement constraints. Specifically, finite element based multilevel optimization of structures (here, statically indeterminate trusses and beams for proof of concept) is performed. In the system level optimization, the design variables are the coefficients of assumed displacement functions, and the load unbalance resulting from the solution of the stiffness equations is minimized. Constraints are placed on the deflection amplitudes and the weight of the structure. In the subsystems level optimizations, the weight of each element is minimized under the action of stress constraints, with the cross sectional dimensions as design variables. This approach is expected to prove very efficient, especially for complex structures, since the design task is broken down into a large number of small and efficiently handled subtasks, each with only a small number of variables. This partitioning will also allow for the use of parallel computing, first, by sending the system and subsystems level computations to two different processors, ultimately, by performing all subsystems level optimizations in a massively parallel manner on separate

  7. Tracking speckle displacement by double Kalman filtering

    Institute of Scientific and Technical Information of China (English)

    Donghui Li; Li Guo


    @@ A tracking technique using two sequentially-connected Kalman filter for tracking laser speckle displacement is presented. One Kalman filter tracks temporal speckle displacement, while another Kalman filter tracks spatial speckle displacement. The temporal Kalman filter provides a prior for the spatial Kalman filter, and the spatial Kalman filter provides measurements for the temporal Kalman filter. The contribution of a prior to estimations of the spatial Kalman filter is analyzed. An optical analysis system was set up to verify the double-Kalman-filter tracker's ability of tracking laser speckle's constant displacement.

  8. Displacement of Propagating Squeezed Microwave States (United States)

    Fedorov, Kirill G.; Zhong, L.; Pogorzalek, S.; Eder, P.; Fischer, M.; Goetz, J.; Xie, E.; Wulschner, F.; Inomata, K.; Yamamoto, T.; Nakamura, Y.; Di Candia, R.; Las Heras, U.; Sanz, M.; Solano, E.; Menzel, E. P.; Deppe, F.; Marx, A.; Gross, R.


    Displacement of propagating quantum states of light is a fundamental operation for quantum communication. It enables fundamental studies on macroscopic quantum coherence and plays an important role in quantum teleportation protocols with continuous variables. In our experiments, we have successfully implemented this operation for propagating squeezed microwave states. We demonstrate that, even for strong displacement amplitudes, there is no degradation of the squeezing level in the reconstructed quantum states. Furthermore, we confirm that path entanglement generated by using displaced squeezed states remains constant over a wide range of the displacement power.

  9. Study on biodegradable aromatic/aliphatic copolyesters

    Energy Technology Data Exchange (ETDEWEB)

    Yiwang Chen; Licheng Tan; Lie Chen; Yan, Yang; Xiaofeng Wang [Nanchang University, Nanchang (China). School of Materials Science and Engineering. Inst. of Polymer Materials]. E-mail:


    Progress on biodegradable aromatic/aliphatic copolyesters based on aliphatic and aromatic diacids, diols and ester monomers was reviewed. The aromatic/aliphatic copolyesters combined excellent mechanical properties with biodegradability. Physical properties and biodegradability of copolyesters varied with chain length of the aliphatic polyester segment and atacticity of copolyesters. The process ability of copolyesters could be improved significantly after incorporating a stiff chain segment through copolymerization of aliphatic polyesters with an aromatic liquid crystal element. The aromatic/aliphatic copolyesters as a new type of biodegradable materials could replace some general plastics in certain applications, namely biomedical and environmental friendly fields. (author)

  10. Microwave Assisted Condensation Reactions of 2-Aryl Hydrazonopropanals with Nucleophilic Reagents and Dimethyl Acetylenedicarboxylate

    Directory of Open Access Journals (Sweden)

    Rita M. Borik


    Full Text Available The reaction of methyl ketones 1a-g with dimethylformamide dimethylacetal (DMFDMA afforded the enaminones 2a-g, which were coupled with diazotized aromatic amines 3a,b to give the corresponding aryl hydrazones 6a-h. Condensation of compounds 6a-h with some aromatic heterocyclic amines afforded iminoarylhydrazones 9a-m. Enaminoazo compounds 12a,b could be obtained from condensation of 6c with secondary amines. The reaction of 6e,h with benzotriazolylacetone yielded 14a,b. Also, the reaction of 6a,b,d-f,h with glycine and hippuric acid in acetic anhydride afforded pyridazinone derivatives 17a-f. Synthesis of pyridazine carboxylic acid derivatives 22a,b from the reaction of 6b,e with dimethyl acetylenedicarboxylate (DMAD in the presence of triphenylphosphine at room temperature is also reported. Most of these reactions were conducted under irradiation in a microwave oven in the absence of solvent in an attempt to improve the product yields and to reduce the reaction times.

  11. Reactivity of silicon and germanium doped CNTs toward aromatic sulfur compounds: A theoretical approach

    Energy Technology Data Exchange (ETDEWEB)

    Galano, Annia [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, C.P. 09340 Mexico D.F. (Mexico); Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)], E-mail:; Francisco-Marquez, Misaela [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, C.P. 09340 Mexico D.F. (Mexico); Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)


    Adsorption processes of thiophene and benzothiophene on pristine carbon nanotubes (CNTs), and on CNTs doped with Si or Ge, have been modeled with Density Functional. This is the first study on the chemical reactivity of such doped tubes. The calculated data suggest that the presence of silicon or germanium atoms in CNTs increases their reactivity toward thiophene, and benzothiophene. The adsorption of these species on pristine CNTs seems very unlikely to occur, while the addition products involving doped CNTs were found to be very stable, with respect to the isolated reactants, in terms of Gibbs free energy. Several of these adsorption processes were found to be significantly exergonic ({delta}G < 0) in non-polar liquid phase. The results reported in this work suggest that Si and Ge defects on CNTs increase their reactivity toward unsaturated species, and could make them useful in the removal processes of aromatic sulfur compounds from oil-hydrocarbons. However, according to our results, CNTs doped with Si atoms are expected to be more efficient as aromatic sulfur compounds scavengers than those doped with Ge. These results also suggest that the presence of silicon and germanium atoms in the CNTs structures enhances their reactivity toward nucleophilic molecules, compared to pristine carbon nanotubes.

  12. Arizona: In Search of the Displaced Homemaker. (United States)

    Woods, Doris

    The model described offers information about displaced homemakers that, while specific to Arizona, can provide a guide to persons in any state responsible for program planning. The report presents results of an Arizona Department of Education study which was conducted to: (1) identify the "displaced homemaker;" (2) define the need for services;…

  13. Flow cell system for miscible displacement experiments

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, S.H.; Kirkham, D.


    The use of a continuous graphic recording system for flow-component measurement in miscible displacement experiments is described. This system measures and continuously records radioactive tracer concentrations of effluents of miscible displacement columns. The recordings are needed breakthrough curves. The use of the system obviates fraction collectors.

  14. Etiopathogenesis of abomasal displacement in cattle

    Directory of Open Access Journals (Sweden)

    Šamanc Horea


    Full Text Available Abomasal displacement presents topographic gastropathy, where this organ has changed its position, and there is simultaneous dilatation which can vary in intensity. The incidence of this disorder in herds of high-yield dairy cows varies to a great degree (1 to 18 %. Abomasal displacement was established in herds of East-Frisian cows in 1 to 3% animals, and in Holstein cow herds in 5 to 18 % animals. The most frequent abomasal displacement is to the left (88%. There is significant seasonal variation in the incidence of abomasal displacement. About two-thirds of cases of abomasal displacement are diagnosed from October until April. The disorder appears more frequently in cows with repeated lactations. It has been established that it appears after the first calving in 27.8% cases, after the second to fifth calving in 66.7% cases, and after the sixth and seventh calving in 5.5% of the cows. The response of endocrine pancreas B-cells for insulin secretion to hyperglycaemia caused by applying an excess-glucose test is reduced in cows with left abomasal displacement, and there is constant hyperglycaemia in cows with right abomasal displacement. The excess-glucose test indicates a disrupted function of the endocrine pancreas in diseased animals. It has been determined through examinations of Aml genotypes in Holstein cow herds in connection with the appearance of abomasal displacement, that the occurrence of this disorder cannot be attributed to a genetic predisposition.

  15. Nonsurgical gingival displacement in restorative dentistry. (United States)

    Thomas, Manuel S; Joseph, Robin Mathai; Parolia, Abhishek


    Gingival displacement is critical for obtaining accurate impressions for the fabrication of fixed restorations, especially when the finish line is at or just within the gingival sulcus. Displacement of the gingival tissue is also important when dealing with the restoration of cervical lesions due to their proximity to the periodontal tissue. The methods of gingival tissue displacement can be broadly classified as nonsurgical and surgical techniques, with nonsurgical being the more commonly practiced method. Dentists must alter their armamentarium and gingival displacement techniques to meet specific demands and obtain predictable results. Hence, the purpose of this article is to describe the different means by which nonsurgical gingival displacement can be achieved effectively under a variety of clinical situations.

  16. Internal displacement in Colombia: Fifteen distinguishing features. (United States)

    Shultz, James M; Ceballos, Ángela Milena Gómez; Espinel, Zelde; Oliveros, Sofia Rios; Fonseca, Maria Fernanda; Florez, Luis Jorge Hernandez


    This commentary aims to delineate the distinguishing features of conflict-induced internal displacement in the nation of Colombia, South America. Even as Colombia is currently implementing a spectrum of legal, social, economic, and health programs for "victims of armed conflict," with particular focus on internally displaced persons (IDPs), the dynamics of forced migration on a mass scale within this country are little known beyond national borders.   The authors of this commentary are embarking on a global mental health research program in Bogota, Colombia to define best practices for reaching the displaced population and implementing sustainable, evidence-based screening and intervention for common mental disorders. Presenting the defining characteristics of internal displacement in Colombia provides the context for our work and, more importantly, conveys the compelling and complex nature of this humanitarian crisis. We attempt to demonstrate Colombia's unique position within the global patterning of internal displacement.

  17. Alkylation of organic aromatic compounds (United States)

    Smith, L.A. Jr.


    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.

  18. Solvent-free functionalization of fullerene C{sub 60} and pristine multi-walled carbon nanotubes with aromatic amines

    Energy Technology Data Exchange (ETDEWEB)

    Ramírez-Calera, Itzel J. [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico); Meza-Laguna, Victor [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Gromovoy, Taras Yu. [O.O. Chuiko Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Chávez-Uribe, Ma. Isabel [Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Vladimir A., E-mail: [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Elena V., E-mail: [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico)


    Highlights: • Pristine multi-walled carbon nanotubes were functionalized with aromatic amines. • The amines add onto nanotube defects, likewise they add onto fullerene C{sub 60}. • The addition takes place at elevated temperature and without organic solvents. • Functionalized nanotubes were characterized by a number of instrumental techniques. - Abstract: We employed a direct one-step solvent-free covalent functionalization of solid fullerene C{sub 60} and pristine multi-walled carbon nanotubes (MWCNTs) with aromatic amines 1-aminopyrene (AP), 2-aminofluorene (AF) and 1,5-diaminonaphthalene (DAN). The reactions were carried out under moderate vacuum, in a wide temperature range of 180–250 °C, during relatively short time of about 2 h. To confirm successful amine attachment, a large number of analytical techniques were used (depending on the nanomaterial functionalized) such as Fourier transform infrared, Raman, X-ray photoelectron, {sup 13}C cross-polarization magic angle spinning NMR spectroscopy, thermogravimetric analysis, laser-desorption ionization time-of-flight mass spectrometry, temperature-programmed desorption with mass spectrometric detection, as well as scanning and transmission electron microscopy. The nucleophilic addition of the aromatic amines to C{sub 60} molecule was studied theoretically by using density functional theory (PBE GGA functional with Grimme dispersion correction in conjunction with the DNP basis set). In the case of crystalline C{sub 60}, the solvent-free technique has a limited applicability due to poor diffusion of vaporous aromatic amines into the bulk. Nevertheless, the approach proposed allows for a facile preparation of aromatic amine-functionalized pristine MWCNTs without contamination with other chemical reagents, detergents and solvents, which is especially important for a vast variety of nanotube applications spanning from nanoelectronics to nanomedicine.

  19. The direct aromatization of methane

    Energy Technology Data Exchange (ETDEWEB)

    Marcelin, G.; Oukaci, R.; Migone, R.A.; Kazi, A.M. [Altamira Instruments, Pittsburgh, PA (United States)


    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.

  20. Deuterated polycyclic aromatic hydrocarbons: Revisited

    CERN Document Server

    Doney, Kirstin D; Mori, Tamami; Onaka, Takashi; Tielens, A G G M


    The amount of deuterium locked up in polycyclic aromatic hydrocarbons (PAHs) has to date been an uncertain value. We present a near-infrared (NIR) spectroscopic survey of HII regions in the Milky Way, Large Magellanic Cloud (LMC), and Small Magellanic Cloud (SMC) obtained with AKARI, which aims to search for features indicative of deuterated PAHs (PAD or Dn-PAH) to better constrain the D/H ratio of PAHs. Fifty-three HII regions were observed in the NIR (2.5-5 {\\mu}m), using the Infrared Camera (IRC) on board the AKARI satellite. Through comparison of the observed spectra with a theoretical model of deuterated PAH vibrational modes, the aromatic and (a)symmetric aliphatic C-D stretch modes were identified. We see emission features between 4.4-4.8 {\\mu}m, which could be unambiguously attributed to deuterated PAHs in only six of the observed sources, all of which are located in the Milky Way. In all cases, the aromatic C-D stretching feature is weaker than the aliphatic C-D stretching feature, and, in the case o...

  1. Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers (United States)

    Kanavarioti, A.; Rosenbach, M. T.


    Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

  2. Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers (United States)

    Kanavarioti, A.; Rosenbach, M. T.


    Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

  3. Photochemical activation of extremely weak nucleophiles: highly fluorinated urethanes and polyurethanes from polyfluoro alcohols. (United States)

    Soto, Marc; Sebastián, Rosa María; Marquet, Jordi


    An efficient and environmentally friendly photoreaction between phenyl isocyanate or pentafluorophenyl isocyanate and polyfluorinated alcohols and diols is described for the first time. New highly fluorinated urethanes and diurethanes, derived from aromatic isocyanates, are produced in good yields in a photoreaction that is apparently governed by the acidic properties of the polyfluoro alcohols and diols. The wettability properties of the new polyfluorinated diurethanes have been tested, some of them showing significantly high values of hydrophobicity and oleophobicity. This new photoreaction has also been tested in the production of a model polyfluorinated polyurethane, establishing the influence of the irradiation power in the outcome of the process, and directly achieving a molecular weight distribution corresponding to a number-average DP(n) = 12 and a highest DP(n) = 20 after 4 h of irradiation (DP(n): "number-average degree of polymerization").

  4. Scalable Synthesis of the Amber Odorant 9-epi-Ambrox through a Biomimetic Cationic Cyclization/Nucleophilic Bromination Reaction. (United States)

    Fontaneda, Raquel; Alonso, Pedro; Fañanás, Francisco J; Rodríguez, Félix


    A novel biomimetic nucleophilic bromocyclization reaction is used in the key step of a new and straightforward synthesis of 9-epi-Ambrox, an organic compound of high interest and value in the context of fragrances. This strategic reaction allows access to 9-epi-Ambrox on a gram scale from a dienyne derivative, easily available from geraniol, following a sequence of seven steps (35% global yield) with just one purification process. Both enantiomers of the molecule were obtained by a challenging enzymatic resolution.

  5. Tandem SN2' nucleophilic substitution/oxidative radical cyclization of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds. (United States)

    Zhang, Zhen; Li, Cheng; Wang, Shao-Hua; Zhang, Fu-Min; Han, Xue; Tu, Yong-Qiang; Zhang, Xiao-Ming


    A novel and efficient tandem SN2' nucleophilic substitution/oxidative radical cyclization reaction of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds has been developed by using Mn(OAc)3 as an oxidant, which enables the expeditious synthesis of polysubstituted dihydrofuran (DHF) derivatives in moderate to high yields. The use of weakly acidic hexafluoroisopropanol (HFIP) as the solvent rather than AcOH has successfully improved the yields and expanded the substrate scope of this type of radical cyclization reactions. Mechanistic studies confirmed the cascade reaction process involving a final radical cyclization.

  6. Noncomparative scaling of aromaticity through electron itinerancy

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Satadal [Department of Chemistry, University of North Bengal, Raja Rammohunpur, Darjeeling 734013, West Bengal (India); Darjeeling Polytechnic, Kurseong, Darjeeling 734203, West Bengal (India); Goswami, Tamal; Misra, Anirban, E-mail: [Department of Chemistry, University of North Bengal, Raja Rammohunpur, Darjeeling 734013, West Bengal (India)


    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. Variable displacement alpha-type Stirling engine (United States)

    Homutescu, V. M.; Bălănescu, D. T.; Panaite, C. E.; Atanasiu, M. V.


    The basic design and construction of an alpha-type Stirling engine with on load variable displacement is presented. The variable displacement is obtained through a planar quadrilateral linkage with one on load movable ground link. The physico-mathematical model used for analyzing the variable displacement alpha-type Stirling engine behavior is an isothermal model that takes into account the real movement of the pistons. Performances and power adjustment capabilities of such alpha-type Stirling engine are calculated and analyzed. An exemplification through the use of the numerical simulation was performed in this regard.

  8. Etiopathogenesis of abomasal displacement in cattle


    Šamanc Horea; Damnjanović Z.; Janković Dušan; Vujanac I.; Radaković Radomir; Mandić L.


    Abomasal displacement presents topographic gastropathy, where this organ has changed its position, and there is simultaneous dilatation which can vary in intensity. The incidence of this disorder in herds of high-yield dairy cows varies to a great degree (1 to 18 %). Abomasal displacement was established in herds of East-Frisian cows in 1 to 3% animals, and in Holstein cow herds in 5 to 18 % animals. The most frequent abomasal displacement is to the left (88%). There is significant seasonal v...

  9. Revisiting the Dielectric Constant Effect on the Nucleophile and Leaving Group of Prototypical Backside Sn2 Reactions: a Reaction Force and Atomic Contribution Analysis. (United States)

    Pedraza-González, Laura Milena; Galindo, Johan Fabian; Gonzalez, Ronald; Reyes, Andrés


    The solvent effect on the nucleophile and leaving group atoms of the prototypical F(-) + CH3Cl → CH3F + Cl(-) backside bimolecular nucleophilic substitution reaction (SN2) is analyzed employing the reaction force and the atomic contributions methods on the intrinsic reaction coordinate (IRC). Solvent effects were accounted for using the polarizable continuum solvent model. Calculations were performed employing eleven dielectric constants, ε, ranging from 1.0 to 78.5, to cover a wide spectrum of solvents. The reaction force data reveals that the solvent mainly influences the region of the IRC preceding the energy barrier, where the structural rearrangement to reach the transition state occurs. A detailed analysis of the atomic role in the reaction as a function of ε reveals that the nucleophile and the carbon atom are the ones that contribute the most to the energy barrier. In addition, we investigated the effect of the choice of nucleophile and leaving group on the ΔE0 and ΔE(↕) of Y(-) + CH3X → YCH3 + X(-) (X,Y= F, Cl, Br, I) in aqueous solution. Our analysis allowed us to find relationships between the atomic contributions to the activation energy and leaving group ability and nucleophilicity.

  10. Displacement and deformation analysis for uplift piles

    Institute of Scientific and Technical Information of China (English)


    On the assumptions that the shear resistance increases linearly with increasing shear displacement between the uplift pile and surrounding soil,that the axis force is distributed as parabola along the pile length,that elastic distortion occurs when the pile is loaded,that the displacement of pile is in accord with that of the soil,and that the uplift pile failure is regarded as the soil failure,arational calculation method was proposed for calculating the deformation,ultimate displacement and shear resistance of piles.The distributions of frictional resistance and the shear displacement along the pile length were obtained with the method.The comparisons were made between the measurement results and the present results.The present theoretical results agree well with the measurement results,with the average difference being less than 12% before failure.The comparisons show that the proposed method is reasonable for uplift design and engineering construction of piles.

  11. Assisting the return of displaced Dinka Bor

    Directory of Open Access Journals (Sweden)

    Paul Murphy


    Full Text Available The issues involved in supporting the return of internally displaced Dinka Bor communities highlight the complex, and often ignored, challenges of addressing the consequencesof South-South conflict.

  12. Epitaxial growth by monolayer restricted galvanic displacement

    Directory of Open Access Journals (Sweden)

    Vasilić Rastko


    Full Text Available The development of a new method for epitaxial growth of metals in solution by galvanic displacement of layers pre-deposited by underpotential deposition (UPD was discussed and experimentally illustrated throughout the lecture. Cyclic voltammetry (CV and scanning tunneling microscopy (STM are employed to carry out and monitor a “quasi-perfect”, two-dimensional growth of Ag on Au(111, Cu on Ag(111, and Cu on Au(111 by repetitive galvanic displacement of underpotentially deposited monolayers. A comparative study emphasizes the displacement stoichiometry as an efficient tool for thickness control during the deposition process and as a key parameter that affects the deposit morphology. The excellent quality of layers deposited by monolayer-restricted galvanic displacement is manifested by a steady UPD voltammetry and ascertained by a flat and uniform surface morphology maintained during the entire growth process.

  13. Comprehensive study of the organic-solvent-free CDI-mediated acylation of various nucleophiles by mechanochemistry. (United States)

    Métro, Thomas-Xavier; Bonnamour, Julien; Reidon, Thomas; Duprez, Anthony; Sarpoulet, Jordi; Martinez, Jean; Lamaty, Frédéric


    Acylation reactions are ubiquitous in the synthesis of natural products and biologically active compounds. Unfortunately, these reactions often require the use of large quantities of volatile and/or toxic solvents, either for the reaction, purification or isolation of the products. Herein we describe and discuss the possibility of completely eliminating the use of organic solvents for the synthesis, purification and isolation of products resulting from the acylation of amines and other nucleophiles. Thus, utilisation of N,N'-carbonyldiimidazole (CDI) allows efficient coupling between carboxylic acids and various nucleophiles under solvent-free mechanical agitation, and water-assisted grinding enables both the purification and isolation of pure products. Critical parameters such as the physical state and water solubility of the products, milling material, type of agitation (vibratory or planetary) as well as contamination from wear are analysed and discussed. In addition, original organic-solvent-free conditions are proposed to overcome the limitations of this approach. The calculations of various green metrics are included, highlighting the particularly low environmental impact of this strategy.

  14. 2014 and beyond: implications for displacement

    Directory of Open Access Journals (Sweden)

    Aidan O’Leary


    Full Text Available 2014 marks a watershed for Afghanistan, with the withdrawal of the International Security Assistance Force after twelve years, and the very real risks this withdrawal poses to the capacity of the Afghan state to meet the many internal and external challenges faced by the country. These challenges have significant implications for displaced and returning Afghans and for the potential for displacement in the future.

  15. Monolithically integrated interferometer for optical displacement measurement (United States)

    Hofstetter, Daniel; Zappe, Hans P.


    We discuss the fabrication of a monolithically integrated optical displacement sensors using III-V semiconductor technology. The device is configured as a Michelson interferometer and consists of a distributed Bragg reflector laser, a photodetector and waveguides forming a directional coupler. Using this interferometer, displacements in the 100 nm range could be measured at distances of up to 45 cm. We present fabrication, device results and characterization of the completed interferometer, problems, limitations and future applications will also be discussed.

  16. Compactness Aromaticity of Atoms in Molecules

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz


    Full Text Available A new aromaticity definition is advanced as the compactness formulation through the ratio between atoms-in-molecule and orbital molecular facets of the same chemical reactivity property around the pre- and post-bonding stabilization limit, respectively. Geometrical reactivity index of polarizability was assumed as providing the benchmark aromaticity scale, since due to its observable character; with this occasion new Hydrogenic polarizability quantum formula that recovers the exact value of 4.5 a03 for Hydrogen is provided, where a0 is the Bohr radius; a polarizability based–aromaticity scale enables the introduction of five referential aromatic rules (Aroma 1 to 5 Rules. With the help of these aromatic rules, the aromaticity scales based on energetic reactivity indices of electronegativity and chemical hardness were computed and analyzed within the major semi-empirical and ab initio quantum chemical methods. Results show that chemical hardness based-aromaticity is in better agreement with polarizability based-aromaticity than the electronegativity-based aromaticity scale, while the most favorable computational environment appears to be the quantum semi-empirical for the first and quantum ab initio for the last of them, respectively.

  17. Attempts to prevent displacement in the occupied Palestinian territories


    Karim Khalil


    Prevention has become a strategy increasingly adopted by the humanitarian community in addressing forced displacement in the occupied Palestinian territories, as well as responding to immediate emergency needs for families displaced or at risk of displacement.

  18. Threshold Energies for Single Carbon Knockout from Polycyclic Aromatic Hydrocarbons

    CERN Document Server

    Stockett, M H; Chen, T; de Ruette, N; Giacomozzi, L; Wolf, M; Schmidt, H T; Zettergren, H; Cederquist, H


    We have measured absolute cross sections for ultrafast (fs) single-carbon knockout from Polycyclic Aromatic Hydrocarbon (PAH) cations as functions of He-PAH center-of-mass collision energy in the range 10-200 eV. Classical Molecular Dynamics (MD) simulations cover this range and extend up to 10$^5$ eV. The shapes of the knockout cross sections are well described by a simple analytical expression yielding experimental and MD threshold energies of $E_{th}^{Exp}=32.5\\pm 0.4$ eV and $E_{th}^{MD}=41.0\\pm 0.3$ eV, respectively. These are the first measurements of knockout threshold energies for molecules isolated \\emph{in vacuo}. We further deduce semi-empirical (SE) and MD displacement energies --- \\emph{i.e.} the energy transfers to the PAH molecules at the threshold energies for knockout --- of $T_{disp}^{SE}=23.3\\pm 0.3$ eV and $T_{disp}^{MD}=27.0\\pm 0.3$ eV. The semi-empirical results compare favorably with measured displacement energies for graphene $T_{disp}=23.6$ eV [Meyer \\emph{et al.} Phys. Rev Lett. \\tex...

  19. Birds and polycyclic aromatic hydrocarbons (United States)

    Albers, P.H.


    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.

  20. Hückel's Rule of Aromaticity Categorizes Aromatic Closo Boron Hydride Clusters


    Poater i Teixidor, Jordi; Solà i Puig, Miquel; Viñas, Clara; Teixidor, Francesc


    A direct connection is established between tridimensional aromatic closo boron hydride clusters and planar aromatic [n]annulenes for medium and large size boron clusters. In particular, our results prove the existence of a link between the two-dimensional Hückel rule followed by aromatic [n]-annulenes and Wade-Mingos' rule of three-dimensional aromaticity applied to the aromatic [BnHn]2- closo boron hydride clusters. Our results show that closo boron hydride clusters can be categorized into d...

  1. Beyond organic chemistry: aromaticity in atomic clusters. (United States)

    Boldyrev, Alexander I; Wang, Lai-Sheng


    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.

  2. Heterogeneous photocatalytic reactions of sulfur aromatic compounds. (United States)

    Samokhvalov, Alexander


    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.

  3. 3-Nucleophilic substitution reaction research of GCLE%GCLE3-位亲核取代反应研究

    Institute of Scientific and Technical Information of China (English)

    张静; 范继业; 翟少华


    Objective To improve the semi-synthetic technics of cephalosporin and study the nucleophilic substitution reaction kinetics of GCLE with pyridine, N-methylpyrrolidine and triazine. Methods The reaction process was monitored by HPLC, and the solvent effects were also stuided . Results The nucleophilic substitution reaction of GCLE iodid with pyridine, N-methylpyrrolidine and triazine were all SN2 course , activity order of the nucleophilicity in different solvents were as follows: acetone>tetrahydrofuran>dichloromethane>the mixture of ethyl acetate and DMF, dichloromethane>acetone>acetonitrile,acetonitrile>tetrahydrofuran. Conclusion The results of this study have certain instruction significance in improving the quality of products and guiding the fourth generation products of the production.%目的 为改进现有半合成头孢菌素类抗生素的生产工艺,研究GCLE与吡啶、N-甲基四氢吡咯和三嗪环发生亲核取代反应的动力学过程.方法 用高效液相色谱仪对该反应过程进行了监测,并进一步研究了反应的溶剂效应.结果 GCLE碘取代物与吡啶、N-甲基四氢吡咯、三嗪环的反应为SN2历程.在不同溶剂中,GCLE碘取代物与与吡啶、N-甲基四氢吡咯、三嗪环反应的活性顺序为:丙酮>四氢呋喃>乙酸乙酯-DMF>二氯乙烷,二氯乙烷>丙酮>乙腈,乙腈>四氢呋喃.结论 本研究结果对提高产品质量,指导第四代产品的生产具有一定的指导意义.

  4. Atomic displacements in bcc dilute alloys

    Indian Academy of Sciences (India)

    Hitesh Sharma; S Prakash


    We present here a systematic investigation of the atomic displacements in bcc transition metal (TM) dilute alloys. We have calculated the atomic displacements in bcc (V, Cr, Fe, Nb, Mo, Ta and W) transition metals (TMs) due to 3d, 4d and 5d TMs at the substitutional site using the Kanzaki lattice static method. Wills and Harrison interatomic potential is used to calculate the atomic force constants, the dynamical matrix and the impurity-induced forces. We have thoroughly investigated the atomic displacements using impurities from 3d, 4d and 5d series in the same host metal and the same impurity in different hosts. We have observed a systematic pattern in the atomic displacements for Cr-, Fe-, Nb-, Mo-, Ta- and W-based dilute alloys. The atomic displacements are found to increase with increase in the number of d electrons for all alloys considered except for V dilute alloys. The 3d impurities are found to be more easily dissolved in the 3d host metals than 4d or 5d TMs whereas 4d and 5d impurities show more solubility in 4d and 5d TMs. In general, the relaxation energy calculation suggests that impurities may be easily solvable in 5d TM hosts when compared to 3d or 4d TMs.

  5. Quantification of the vocal folds’ dynamic displacements (United States)

    del Socorro Hernández-Montes, María; Muñoz, Silvino; De La Torre, Manuel; Flores, Mauricio; Pérez, Carlos; Mendoza-Santoyo, Fernando


    Fast dynamic data acquisition techniques are required to investigate the motional behavior of the vocal folds (VFs) when they are subjected to a steady air-flow through the trachea. High-speed digital holographic interferometry (DHI) is a non-invasive full-field-of-view technique that has proved its usefulness to study rapid and non-repetitive object movements. Hence it is an ideal technique used here to measure VF displacements and vibration patterns at 2000 fps. Analyses from a set of 200 displacement images showed that VFs’ vibration cycles are established along their width (y) and length (x). Furthermore, the maximum deformation for the right and left VFs’ area may be quantified from these images, which in itself represents an important result in the characterization of this structure. At a controlled air pressure, VF displacements fall within the range ~100-1740 nm, with a calculated precision and accuracy that yields a variation coefficient of 1.91%. High-speed acquisition of full-field images of VFs and their displacement quantification are on their own significant data in the study of their functional and physiological behavior since voice quality and production depend on how they vibrate, i.e. their displacement amplitude and frequency. Additionally, the use of high speed DHI avoids prolonged examinations and represents a significant scientific and technological alternative contribution in advancing the knowledge and working mechanisms of these tissues.

  6. Fingering phenomena during grain-grain displacement (United States)

    Mello, Nathália M. P.; Paiva, Humberto A.; Combe, G.; Atman, A. P. F.


    Spontaneous formation of fingered patterns during the displacement of dense granular assemblies was experimentally reported few years ago, in a radial Hele-Shaw cell. Here, by means of discrete element simulations, we have recovered the experimental findings and extended the original study to explore the control parameters space. In particular, using assemblies of grains with different geometries (monodisperse, bidisperse, or polydisperse), we measured the macroscopic stress tensor in the samples in order to confirm some conjectures proposed in analogy with Saffman-Taylor viscous fingering phenomena for immiscible fluids. Considering an axial setup which allows to control the discharge of grains and to follow the trajectory and the pressure gradient along the displacing interface, we have applied the Darcy law for laminar flow in fluids in order to measure an "effective viscosity" for each assembly combination, in an attempt to mimic variation of the viscosity ratio between the injected/displaced fluids in the Saffman-Taylor experiment. The results corroborate the analogy with the viscous fluids displacement, with the bidisperse assembly corresponding to the less viscous geometry. But, differently to fluid case, granular fingers only develop for a specific combination of displaced/injected geometries, and we have demonstrated that it is always related with the formation of a force chain network along the finger direction.

  7. Forced displacement and women's security in Colombia. (United States)

    Meertens, Donny


    In the protracted Colombian conflict, assistance to internally displaced persons has developed in the context of contradictory political processes. The Colombian government's launching of a transitional justice process in the midst of armed conflict has generated a complex situation displaying both conflict and post-conflict characteristics. The progressive Constitutional Court rulings on internal displacement, in particular the gender-sensitive Auto 092, constitute an attempt to bring together humanitarian interventions and transitional justice measures in a rights-based framework. However, the national government is reluctant to adopt them fully and local realities still hamper their integrated implementation. Displaced women, therefore, remain in an especially vulnerable position. This paper argues that gender-sensitive humanitarian interventions must take into account all of these complexities of scale and political process in order to make legal frameworks more effective at the local level. In these contexts, interventions should pay particular attention to strategies that contribute to transforming pre-existing gender regimes.

  8. Miscible, porous media displacements with density stratification. (United States)

    Riaz, Amir; Meiburg, Eckart


    High accuracy, three-dimensional numerical simulations of miscible displacements with gravity override, in both homogeneous and heterogeneous porous media, are discussed for the quarter five-spot configuration. The influence of viscous and gravitational effects on the overall displacement dynamics is described in terms of the vorticity variable. Density differences influence the flow primarily by establishing a narrow gravity layer, in which the effective Peclet number is enhanced due to the higher flow rate. Although this effect plays a dominant role in homogeneous flows, it is suppressed to some extent in heterogeneous displacements. This is a result of coupling between the viscous and permeability vorticity fields. When the viscous wavelength is much larger than the permeability wavelength, gravity override becomes more effective because coupling between the viscous and permeability vorticity fields is less pronounced. Buoyancy forces of a certain magnitude can lead to a pinch-off of the gravity layer, thereby slowing it down.

  9. Performance of displacement ventilation in practice

    DEFF Research Database (Denmark)

    Naidenov, K.; Pitchurov, G.; Langkilde, Gunnar


    This paper presents results of a field study in offices with displacement ventilation. It comprises detailed physical measurements of the thermal environment and collection of occupants´ response at 227 workplaces. The results, both physical measurements and human response, identified draught...... as the major local discomfort in the rooms with displacement ventilation. Twenty-three percent of the occupants were daily bothered by draught. In some buildings the maintenance personnel tried to improve occupants´ thermal comfort by raising the supply air temperature or office workers themselves blocked...... the diffusers by rearranging the furniture. Half of the surveyed occupants were not satisfied with the indoor air quality. The main conclusion is that displacement ventilation needs careful design and room furnishing in order to ensure a comfortable environment. Occupants must understand the underlying...

  10. Iminoboronate Formation Leads to Fast and Reversible Conjugation Chemistry of α-Nucleophiles at Neutral pH. (United States)

    Bandyopadhyay, Anupam; Gao, Jianmin


    Bioorthogonal reactions that are fast and reversible under physiological conditions are in high demand for biological applications. Herein, it is shown that an ortho boronic acid substituent makes aryl ketones rapidly conjugate with α-nucleophiles at neutral pH. Specifically, 2-acetylphenylboronic acid and derivatives were found to conjugate with phenylhydrazine with rate constants of 10(2) to 10(3) M(-1) s(-1) , comparable to the fastest bioorthogonal conjugations known to date. (11) B NMR analysis revealed the varied extent of iminoboronate formation of the conjugates, in which the imine nitrogen forms a dative bond with boron. The iminoboronate formation activates the imines for hydrolysis and exchange, rendering these oxime/hydrazone conjugations reversible and dynamic under physiological conditions. The fast and dynamic nature of the iminoboronate chemistry should find wide applications in biology.


    Institute of Scientific and Technical Information of China (English)


    A novel variable displacement compressor (VDC) for automotive air conditioner (AAC) is introduced, which inherits the advantages of common wobble plate type VDC. It has fewer parts and makes less noise, and inst ead of pneumatic valve the displacement is controlled by electronic control valv e. In order to know the control mechanism well and get a good control effect, a mathematical model for the variable displacement mechanism is developed accordin g to the geometrical and kinematical information of the compressor. Using the mo del, the effect of relevant parameters on variable displace control is estimated . It is helpful to make the optimum decision in the flow control of AAC. As the novel displacement control device, the structure and control rule of electronic control valve is introduced. It can get better effect than the conventional pneu matic valves. And by using this new electronic control device, the optimum syste mic control of AAC is available.

  12. The Costs of Displacement in Brazil


    Naercio Menezes-Filho


    This paper uses new data that combines information on workers’ education and earnings trajectories with information about their firms to estimate the costs of job displacement in Brazil. We find that high-tenure workers displaced from their firms during mass lay-offs suffer a long-term loss in monthly wages of about 20% per year. We show that this result is robust to different treatment of workers that leave the formal sector of the economy and is driven by the losses suffered by more educa...

  13. Histone displacement during nucleotide excision repair

    DEFF Research Database (Denmark)

    Dinant, C.; Bartek, J.; Bekker-Jensen, S.


    Nucleotide excision repair (NER) is an important DNA repair mechanism required for cellular resistance against UV light and toxic chemicals such as those found in tobacco smoke. In living cells, NER efficiently detects and removes DNA lesions within the large nuclear macromolecular complex called...... of histone variants and histone displacement (including nucleosome sliding). Here we review current knowledge, and speculate about current unknowns, regarding those chromatin remodeling activities that physically displace histones before, during and after NER. © 2012 by the authors; licensee MDPI, Basel...

  14. Maxillary tooth displacement in the infratemporal fossa

    Directory of Open Access Journals (Sweden)

    Korosh Roshanghias


    Full Text Available Wisdom tooth operations are sometimes accompanied by complications. This case report shows complications during upper jaw third molar removal. Expectable problems during oral surgery should be planned to be solved in advance. Displacement of the third molar during oral surgeries as a considerable complication is rarely discussed scientifically. A good design of flap, adequate power for extraction, and clear view on the surgical field are crucial. Three-dimensional radiographic diagnostics in terms of cone beam computed tomography is helpful after tooth displacement into the infratemporal fossa.

  15. Bucket Foundation Response Under Various Displacement Rates

    DEFF Research Database (Denmark)

    Vaitkunaite, Evelina; Nielsen, Benjaminn Nordahl; Ibsen, Lars Bo


    in a multi-bucket foundation system. The foundation model is at a scale of approximately 1:20 prototype foundation size. The tests are performed in a pressure tank with the foundation model installed in dense sand. Based on the data, the conclusion is that the bucket foundation design in a storm case should......The present testing program aims at showing the pore pressure response around a bucket foundation skirt as well as the load and displacement change due to ten different displacement rates. Research findings are useful for a numerical model calibration focusing on the design of the upwind foundation...

  16. Passive Smoking in a Displacement Ventilated Room

    DEFF Research Database (Denmark)

    Bjørn, Erik; Nielsen, Peter V.

    The aim of this research is to see if the displacement ventilation principle can protect a person from exposure to passive tobacco smoking. This is done by full-scale experiments with two breathing thermal manikins, smoke visualisations, and tracer gas measurements. In some situations, exhaled...... smoke will stratify in a certain height due to the vertical temperature gradient. This horizontal layer of exhaled tobacco smoke may lead to exposure. In other situations, the smoke is mixed into the upper zone, and the passive smoker is protected to some extent by the displacement principle...

  17. Personal Exposure in Displacement Ventilated Rooms

    DEFF Research Database (Denmark)

    Brohus, Henrik; Nielsen, Peter Vilhelm


    Personal exposure in a displacement ventilated room is examined. The stratified flow and the considerable concentration gradients necessitate an improvement of the widely used fully mixing compartmental approach. The exposure of a seated and a standing person in proportion to the stratification...... in the lower part of the room close to the occupant. A personal exposure model for displacement ventilated rooms is proposed. The model takes the influence of gradients and the human thermal boundary layer into account. Two new quantities describing the interaction between a person and the ventilation...

  18. Oxidative photoredox-catalytic activation of aliphatic nucleophiles for C(sp(3))-C(sp(2)) cross-coupling reactions. (United States)

    Jahn, Emanuela; Jahn, Ullrich


    In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions.

  19. Origin of Enhanced Reactivity of a Microsolvated Nucleophile in Ion Pair SN2 Reactions: The Cases of Sodium p-Nitrophenoxide with Halomethanes in Acetone. (United States)

    Li, Qiang-Gen; Xu, Ke; Ren, Yi


    In a kinetic experiment on the SN2 reaction of sodium p-nitrophenoxide with iodomethane in acetone-water mixed solvent, Humeres et al. (J. Org. Chem. 2001, 66, 1163) found that the reaction depends strongly on the medium, and the fastest rate constant was observed in pure acetone. The present work tries to explore why acetone can enhance the reactivity of the title reactions. Accordingly, we make a mechanistic study on the reactions of sodium p-nitrophenoxide with halomethanes (CH3X, X = Cl, Br, I) in acetone by using a supramolecular/continuum model at the PCM-MP2/6-311+G(d,p)//B3LYP/6-311+G(d,p) level, in which the ion pair nucleophile is microsolvated by one to three acetone molecules. We compared the reactivity of the microsolvated ion pair nucleophiles with solvent-free ion pair and anionic ones. Our results clearly reveal that the microsolvated ion pair nucleophile is favorable for the SN2 reactions; meanwhile, the origin of the enhanced reactivity induced by microsolvation of the nucleophile is discussed in terms of the geometries of transition state (TS) structures and activation strain model, suggesting that lower deformation energies and stronger interaction energies between the deformed reactants in the TS lead to the lower overall reaction barriers for the SN2 reaction of microsolvated sodium p-nitrophenoxide toward halomethanes in acetone.

  20. Synthesis of γ-Methoxy Carboxylic Acids via Nucleophilic Additions to Oxycarbenium Ions derived from 5-Methoxy-2(3H)-dihydrofuranones.

    NARCIS (Netherlands)

    Oeveren, Arjan van; Feringa, Bernard


    The Lewis acid induced addition of silylated nucleophiles to 5-methoxy-2(3H)-dihydrofuranones was studied. The methodology gives access to α,β-substituted-γ-alkoxy carboxylic acids with modest to high levels of acyclic diastereocontrol in the addition reaction.

  1. Base or nucleophile? DFT finally elucidates the origin of the selectivity between the competitive reactions triggered by MeLi or LDA on propanal. (United States)

    Marchois, J; Fressigné, C; Lecachey, B; Maddaluno, J


    The competition between basicity and nucleophilicity of two standard organolithium reagents was studied using DFT. Comparing the reactivity of solvated (MeLi)2 and (LDA)2 toward propanal finally explains why methyllithium adds onto the carbonyl while LDA deprotonates the α-position, in accord with experiment and Ireland's deprotonation TS.

  2. 24 CFR 42.350 - Relocation assistance for displaced persons. (United States)


    ... described in 49 CFR part 24. A displaced person must be advised of his or her rights under the Fair Housing... of 1974 § 42.350 Relocation assistance for displaced persons. A displaced person may choose to... safety of the person or the public; or (2) The person is displaced from a “lower-income dwelling...

  3. 24 CFR 92.353 - Displacement, relocation, and acquisition. (United States)


    ... U.S.C. 4201-4655) and 49 CFR part 24. A “displaced person” must be advised of his or her rights... assistance for displaced persons—(1) General. A displaced person (defined in paragraph (c)(2) of this section..., safe, and sanitary replacement dwellings not located in such areas. (2) Displaced Person. (i)...

  4. 24 CFR 882.810 - Displacement, relocation, and acquisition. (United States)


    ... CFR 24.2(g)(2); or (iv) HUD determines that the person was not displaced as a direct result of... section. (c) Relocation assistance for displaced persons. A “displaced person” (defined in paragraph (g... displaced person must be advised of his or her rights under the Fair Housing Act (42 U.S.C. 3601-19) and,...

  5. Ionic S(N)i-Si Nucleophilic Substitution in N-Methylaniline-Induced Si-Si Bond Cleavages of Si2Cl6. (United States)

    Zhang, Jie; Xie, Ju; Lee, Myong Euy; Zhang, Lin; Zuo, Yujing; Feng, Shengyu


    N-Methylaniline-induced Si-Si bond cleavage of Si2Cl6 has been theoretically studied. All calculations were performed by using DFT at the MPWB1K/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) levels. An ionic SN i-Si nucleophilic substitution mechanism, which is a newly found nucleophilic substitution in silicon-containing compounds, is proposed in the N-methylaniline-induced Si-Si bond cleavage in Si2Cl6. Unlike general S(N)i-Si nucleophilic substitutions that go through a pentacoordinated silicon transition state, ionic nucleophilic substitution goes through a tetracoordinated silicon transition state, in which the Si-Si bond is broken and siliconium ions are formed. Special cleavage of the Si-Si bond is presumably due to the good bonding strength between Si and N atoms, which leads to polarization of the Si-Si bond and eventually to heterolytic cleavage. Calculation results show that, in excess N-methylaniline, the final products of the reaction, including (NMePh)(3-n) SiHCl(n) (n=0-2) and (NMePh)(4-n) SiCl(n) (n=2-3), are the Si-Si cleavage products of Si2Cl6 and the corresponding amination products of the former. The ionic S(N)i-Si nucleophilic substitution mechanism can also be employed to describe the amination of chlorosilane by N-methylaniline. The suggested mechanisms are consistent with experimental data.

  6. Britain's Redundancy Payments for Displaced Workers. (United States)

    Root, Lawrence S.


    The Redundancy Payments Act of 1965 established the idea that an employee has property rights to a job based on years of company service. It instituted an entitlement program for displaced workers sponsored by firms and the government. The British layoff situtation differs from that of the United States. (Author/CH)

  7. Olympic scale of sport-induced displacement

    Directory of Open Access Journals (Sweden)

    Jean du Plessis


    Full Text Available The Olympic Games have displaced more than two million people in the last 20 years, disproportionately affecting particular groups such as the homeless, the poor, Roma and African-Americans. Mega-events such as the Olympic Games often leave a negative housing legacy for local populations.

  8. Comb-drive actuators for large displacements

    NARCIS (Netherlands)

    Legtenberg, Rob; Groeneveld, A.W.; Elwenspoek, M.


    The design, fabrication and experimental results of lateral-comb-drive actuators for large displacements at low driving voltages is presented. A comparison of several suspension designs is given, and the lateral large deflection behaviour of clamped - clamped beams and a folded flexure design is mod

  9. Heterodyne displacement interferometer, insensitive for input polarization

    NARCIS (Netherlands)

    Meskers, A.J.H.; Spronck, J.W.; Munnig Schmidt, R.H.


    Periodic nonlinearity (PNL) in displacement interferometers is a systematic error source that limits measurement accuracy. The PNL of coaxial heterodyne interferometers is highly influenced by the polarization state and orientation of the source frequencies. In this Letter, we investigate this error

  10. Displacement pile installation effects in sand

    NARCIS (Netherlands)

    Beijer-Lundberg, A.


    Installation effects govern the post-installation behaviour of displacement piles in sand. These effects are currently not completely understood. Suitable experimental techniques to model these installation effects include field, laboratory and experimental models. In the current thesis a small-scal

  11. Displacing Media: LCD LAB Artistic Residency

    Directory of Open Access Journals (Sweden)

    Filipe Pais


    Full Text Available This review refers to an artistic residency which took place at LCD LAB -  CAAA at Guimarães, in March, exploring a strategy for media art called Media Displacement. The text introduces the strategy very briefly and describes the residency's organization, structure, processses and the results produced.

  12. A new method for angular displacement measurement

    Institute of Scientific and Technical Information of China (English)

    Caini Zhang(张彩妮); Xiangzhao Wang(王向朝)


    We describe a new method for angular displacement measurements that is based on a Fabry-Perot inter-ferometer. A measurement accuracy of 10-s rad is obtained by use of the sinusoidal phase modulatinginterferometry. Another Fabry-Perot interferometer is used to obtain the key initial angle of incidence.

  13. A Personal Appearance Program for Displaced Homemakers. (United States)

    Fiore, Ann Marie; De Long, Marilyn Revell


    A career counseling program evaluated the self-esteem of 28 displaced homemakers, then presented 3 sessions on the importance of personal appearance in hiring practices, wardrobe management, nonverbal communication, professional image, and self-concept. Analysis of participant evaluations indicated improved levels of control and confidence and…

  14. Displacement Ventilation by Different Types of Diffusers

    DEFF Research Database (Denmark)

    Nielsen, Peter V.; Hoff, Lars; Pedersen, Lars Germann

    The paper describes measuring results of the air movement from three different types of diffusers for displacement ventilation. Two of the diffusers are lowlevel wall mounted diffusers, one with a low and one with a high initial entrainment. The third diffuser is of the floor mounted type....

  15. Conservation of medicinal and aromatic plants

    Directory of Open Access Journals (Sweden)

    Šveistytė, Laima


    Full Text Available The conservation of medicinal and aromatic plants includes ex situ and in situ methods. The genetic recourses of medicinal and aromatic plants are stored, studied and constantly maintained in the field collections of the Institute of Botany of Nature Research Centre, Kaunas Botanical Garden of Vytautas Magnus University and Aleksandras Stulginskis University of Agriculture. Presently seeds of 214 accessions representing 38 species of medicinal and aromatic plants are stored in a long-term storage in the Plant Gene Bank. The data about national genetic resources are collected and stored in the Central Database of the Plant Gene Bank.

  16. Reaction of carbon nucleophiles with alkylideneindazolium and alkylideneindolium ions generated from their 3-(1-arylsulfonylalkyl) indazole and indole precursors. (United States)

    Marsili, Laura; Palmieri, Alessandro; Petrini, Marino


    Lewis acid promoted elimination of p-toluenesulfinc acid from sulfonyl indazoles and sulfonyl indoles generates the corresponding iminium ion that reacts with allyltin reagents, silyl enol ethers, silyl ketene acetals and electron-rich aromatics leading to functionalized indazole and indole derivatives.

  17. On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

    Directory of Open Access Journals (Sweden)

    Malcolm J. D'Souza


    Full Text Available In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl-substituted derivatives have now been reported, where the application of the aromatic ring parameter (I removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term Grunwald-Winstein equations.

  18. Anion conductive aromatic block copolymers containing diphenyl ether or sulfide groups for application to alkaline fuel cells. (United States)

    Yokota, Naoki; Ono, Hideaki; Miyake, Junpei; Nishino, Eriko; Asazawa, Koichiro; Watanabe, Masahiro; Miyatake, Kenji


    A novel series of aromatic block copolymers composed of fluorinated phenylene and biphenylene groups and diphenyl ether (QPE-bl-5) or diphenyl sulfide (QPE-bl-6) groups as a scaffold for quaternized ammonium groups is reported. The block copolymers were synthesized via aromatic nucleophilic substitution polycondensation, chloromethylation, quaternization, and ion exchange reactions. The block copolymers were soluble in organic solvents and provided thin and bendable membranes by solution casting. The membranes exhibited well-developed phase-separated morphology based on the hydrophilic/hydrophobic block copolymer structure. The membranes exhibited mechanical stability as confirmed by DMA (dynamic mechanical analyses) and low gas and hydrazine permeability. The QPE-bl-5 membrane with the highest ion exchange capacity (IEC = 2.1 mequiv g(-1)) exhibited high hydroxide ion conductivity (62 mS cm(-1)) in water at 80 °C. A noble metal-free fuel cell was fabricated with the QPE-bl-5 as the membrane and electrode binder. The fuel cell operated with hydrazine as a fuel exhibited a maximum power density of 176 mW cm(-2) at a current density of 451 mA cm(-2).

  19. Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions. (United States)

    Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin


    The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

  20. Drinking and displacement: a systematic review of the influence of forced displacement on harmful alcohol use. (United States)

    Weaver, Heather; Roberts, Bayard


    This paper systematically reviews evidence about factors associated with harmful alcohol use amongst forcibly displaced persons, including refugees and internally displaced persons. Bibliographic and humanitarian-related databases were searched. The number of quantitative and qualitative studies that were screened and reviewed was 1108. Only 10 studies met inclusion criteria. Risk factors identified included gender, age, exposure to traumatic events and resulting posttraumatic stress disorder, prior alcohol consumption-related problems, year of immigration, location of residence, social relations, and postmigration trauma and stress. The evidence base was extremely weak, and there is a need to improve the quantity and quality of research about harmful alcohol use by forcibly displaced persons.

  1. Utilization of an ultrasound beam steering angle for measurements of tissue displacement vector and lateral displacement

    Directory of Open Access Journals (Sweden)

    Chikayoshi Sumi


    Full Text Available Chikayoshi SumiDepartment of Information and Communication Sciences, Faculty of Science and Technology, Sophia University, Tokyo, JapanAbstract: A number of ultrasonic displacement/velocity measurement methods have been extensively developed for measurements of blood flow, tissue motion, and strain. Lateral modulation (LM methods have also been reported using steered, crossed beams, and these methods permit measurements of displacement vectors. In this report, a new beam steering method for the transmission and reception of ultrasound is proposed, which can enable measurements of lateral displacements and of arbitrary displacement vectors with a very high degree of accuracy. Because this beam steering method uses only a steering angle, this method is referred to as ASTA. With ASTA, the number of available methods to obtain a displacement vector measurement is limited to previously developed block-matching methods, such as the multidimensional cross-spectrum phase gradient method, and the multidimensional autocorrelation method (MAM and the multidimensional Doppler method (MDM using a block-matching method (the methods using block matching are referred to as MAMb and MDMb, respectively. Being dependent on the measurement method, only a lateral displacement measurement can be made even if the methods are multidimensional, ie, previously developed MAM and MDM using a moving average and a mirror setting of the obtained steered beams, and one-dimensional (1D, such as an autocorrelation method. Considerations of beamforming schemes using LM and ASTA show that the simple ASTA beamforming method increases capabilities for real-time measurements and requires a small physical aperture when compared with LM. For lateral displacement measurements (eg, blood flow in a carotid artery, a lateral coordinate must correspond to the direction of the target’s lateral motion, and the steering angle used is as large as possible to increase the measurement accuracy

  2. Pulse shape discrimination in non-aromatic plastics

    Energy Technology Data Exchange (ETDEWEB)

    Paul Martinez, H.; Pawelczak, Iwona; Glenn, Andrew M.; Leslie Carman, M.; Zaitseva, Natalia; Payne, Stephen


    Recently it has been demonstrated that plastic scintillators have the ability to distinguish neutrons from gamma rays by way of pulse shape discrimination (PSD). This discovery has lead to new materials and new capabilities. Here we report our work with the effects of aromatic, non-aromatic, and mixed aromatic/non-aromatic matrices have on the performance of PSD plastic scintillators.

  3. Comments on Coulomb pairing in aromatic hydrocarbons

    CERN Document Server

    Huber, D L


    Recently reported anomalies in the double-photonionization spectra of aromatic molecules such as benzene, naphthalene, anthracene and coronene are attributed to Coulomb-pair resonances of pi electrons.

  4. Silicone elastomers with aromatic voltage stabilizers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Skov, Anne Ladegaard

    modifications. In order to increase the electrical breakdown strength of polymers for e.g. the cable industry, additives like aromatic voltage stabilizers are used. Earlier works on using voltage stabilizers in polymers have mainly focused on polyethylene with the purpose of reducing power loss for high voltage...... insulation cables.3–5 As an alternative to utilise additives as voltage stabilizers, grafting aromatic compounds to silicone backbones may overcome the common problem of insolubility of the aromatic voltage stabilizer in the silicone elastomers due to phase separation. Preventing phase separation during...... via hydrosilylation by a vinyl-functional crosslinker. The mechanism of electron-trapping by aromatic compounds grafted to silicone backbones in a crosslinked PDMS is illustrated in Fig. 1. The electrical breakdown strength, the storage modulus and the loss modulus of the elastomer were investigated...

  5. Graphite Oxide and Aromatic Amines : Size Matters

    NARCIS (Netherlands)

    Spyrou, Konstantinos; Calvaresi, Matteo; Diamanti, Evmorfi A. K.; Tsoufis, Theodoros; Gournis, Dimitrios; Rudolf, Petra; Zerbetto, Francesco


    Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molec

  6. Volatilisation of aromatic hydrocarbons from soil

    DEFF Research Database (Denmark)

    Lindhardt, B.; Christensen, T.H.


    The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic...... aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 mu g/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under...... saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch - by a factor of 8 to 25 - than expected for natural organic matter. The fluxes were also estimated using an analytical...

  7. Infrared Spectra of Polycyclic Aromatic Hydrocarbons (PAHs) (United States)

    Bauschlicher, Charles W., Jr.; Bakes, E. L. O.


    We have computed the synthetic infrared spectra of some polycyclic aromatic hydrocarbons containing up to 54 carbon atoms. The species studied include ovalene, circumcoronene, dicoronylene, and hexabenzocoronene. We report spectra for anions, neutrals, cations, and multiply charged cations.

  8. The Industrial Reduction of Aromatic Nitro Compounds. (United States)

    Gilbert, G.


    Describes methods for enriching an A-level chemistry course with a series of chemical company visits. The rationale is discussed for an emphasis of the visits on the industrial reduction of aromatic nitro compounds. (CS)

  9. Activity relationships for aromatic crown ethers

    CERN Document Server

    Wilson, M J


    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities...

  10. Dehydrogenative Aromatization of Saturated Aromatic Compounds by Graphite Oxide and Molecular Sieves

    Institute of Scientific and Technical Information of China (English)

    张轩; 徐亮; 王希涛; 马宁; 孙菲菲


    Graphite oxide (GO) has attracted much attention of material and catalysis chemists recently. Here we describe a combination of GO and molecular sieves for the dehydrogenative aromatization. GO prepared through improved Hummers method showed high oxidative activity in this reaction. Partially or fully saturated aromatic compounds were converted to their corresponding dehydrogenated aromatic products with fair to excellent conversions and selectivities. As both GO and molecular sieves are easily available, cheap, lowly toxic and have good tolerance to various functional groups, this reaction provides a facile approach toward aromatic compounds from their saturated precursors

  11. Thoughts on Optimization of Aromatic Feedstock

    Institute of Scientific and Technical Information of China (English)

    Cao Jian


    This article refers to four cases of process unit combinations with different throughputs of aromatics unit for production of 450 kt/a paraxylene at a certain petrochemical complex in order to against a representative case (provided with an 800-kt/a CCR unit and a 600-kt/a disproportionation unit) and the feasibility and advantage of using prolysis gasoline as aromatic feedstock is studied.

  12. Aromatic amines sources, environmental impact and remediation


    Pereira, Luciana; Mondal, P. K.; Alves, M. M.


    Aromatic amines are widely used industrial chemicals as their major sources in the environment include several chemical industry sectors such as oil refining, synthetic polymers, dyes, adhesives, rubbers, perfume, pharmaceuticals, pesticides and explosives. They result also from diesel exhaust, combustion of wood chips and rubber and tobacco smoke. Some types of aromatic amines are generated during cooking, special grilled meat and fish, as well. The intensive use and production of these comp...

  13. Precision optical displacement measurements using biphotons

    CERN Document Server

    Lyons, Kevin; Kwiat, Paul G; Jordan, Andrew N


    We propose and examine the use of biphoton pairs, such as those created in parametric down conversion or four-wave mixing, to enhance the precision and the resolution of measuring optical displacements by position-sensitive detection. We show that the precision of measuring a small optical beam displacement with this method can be significantly enhanced by the correlation between the two photons, given the same optical mode. The improvement is largest if the correlations between the photons are strong, and falls off as the biphoton correlation weakens. More surprisingly, we find that the smallest resolvable parameter of a simple split detector scales as the inverse of the number of biphotons for small biphoton number ("Heisenberg scaling"), because the Fisher information diverges as the parameter to be estimated decreases in value. One usually sees this scaling only for systems with many entangled degrees of freedom. We discuss the transition for the split-detection scheme to the standard quantum limit scalin...

  14. Comparing anisotropic displacement parameters in protein structures. (United States)

    Merritt, E A


    The increasingly widespread use of synchrotron-radiation sources and cryo-preparation of samples in macromolecular crystallography has led to a dramatic increase in the number of macromolecular structures determined at atomic or near-atomic resolution. This permits expansion of the structural model to include anisotropic displacement parameters U(ij) for individual atoms. In order to explore the physical significance of these parameters in protein structures, it is useful to be able to compare quantitatively the electron-density distribution described by the refined U(ij) values associated with corresponding crystallographically independent atoms. This paper presents the derivation of an easily calculated correlation coefficient in real space between two atoms modeled with anisotropic displacement parameters. This measure is used to investigate the degree of similarity between chemically equivalent but crystallographically independent atoms in the set of protein structural models currently available from the Protein Data Bank.

  15. Charge-displacement analysis for excited states

    Energy Technology Data Exchange (ETDEWEB)

    Ronca, Enrico, E-mail:; Tarantelli, Francesco, E-mail: [Istituto CNR di Scienze e Tecnologie Molecolari, via Elce di Sotto 8, I-06123 Perugia (Italy); Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, via Elce di Sotto 8, I-06123 Perugia (Italy); Pastore, Mariachiara, E-mail:; Belpassi, Leonardo; De Angelis, Filippo [Istituto CNR di Scienze e Tecnologie Molecolari, via Elce di Sotto 8, I-06123 Perugia (Italy); Angeli, Celestino; Cimiraglia, Renzo [Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, via Borsari 46, I-44100 Ferrara (Italy)


    We extend the Charge-Displacement (CD) analysis, already successfully employed to describe the nature of intermolecular interactions [L. Belpassi et al., J. Am. Chem. Soc. 132, 13046 (2010)] and various types of controversial chemical bonds [L. Belpassi et al., J. Am. Chem. Soc. 130, 1048 (2008); N. Salvi et al., Chem. Eur. J. 16, 7231 (2010)], to study the charge fluxes accompanying electron excitations, and in particular the all-important charge-transfer (CT) phenomena. We demonstrate the usefulness of the new approach through applications to exemplary excitations in a series of molecules, encompassing various typical situations from valence, to Rydberg, to CT excitations. The CD functions defined along various spatial directions provide a detailed and insightful quantitative picture of the electron displacements taking place.

  16. Intrinsic Mean Square Displacements in Proteins


    VURAL, Derya; Glyde, Henry R.


    The thermal mean square displacement (MSD) of hydrogen in proteins and its associated hydration water is measured by neutron scattering experiments and used an indicator of protein function. The observed MSD as currently determined depends on the energy resolution width of the neutron scattering instrument employed. We propose a method for obtaining the intrinsic MSD of H in the proteins, one that is independent of the instrument resolution width. The intrinsic MSD is defined as the infinite ...

  17. Experiments on chemically enhanced immiscible fluid displacements (United States)

    Soori, Tejaswi; Ward, Thomas


    This talk focuses on experiments conducted by displacing a vegetable oil within a capillary tube (diameter forms a stable micro-emulsion. We estimate the shear viscosity of the emulsion as a function of alkali and aqueous/oil concentrations. Separately we attempt to measure the average bulk diffusion coefficient of the emulsion in both phases which is necessary to estimate the Péclet number (Pé) and subsequent mass transport phenomena. American Chemical Society Petroleum Research Fund.

  18. Cooling airflow design tool for displacement ventilation.


    Schiavon, Stefano; Bauman, Fred


    These user notes describe how to use a spreadsheet-based (Excel 2007) version of the ASHRAE method (Chen and Glicksman 2003) for calculating the amount of design cooling airflow required for a displacement ventilation (DV) system that is providing all sensible cooling for a conditioned space. The design tool has been developed by CBE and is available on the CBE Partner website:

  19. A reference material for dynamic displacement calibration (United States)

    Davighi, A.; Hack, E.; Patterson, E.; Whelan, M.


    Calibration of displacement and strain measurement systems is an essential step in providing traceability and confidence in stress and strain distributions obtained from experiment and used to validate simulations employed in engineering design. Reference materials provide a simple, well-defined distribution of the measured quantity that can be traced to an international standard and can be used to assess the uncertainty associated with the measurement system. Previous work has established a reference material and procedure for calibrating optical systems for measuring static, in-plane strain distributions and also demonstrated its use. A new effort is in progress to extend this work to the measurement of three-dimensional displacement distributions induced by cyclic and dynamic loading, including transients and large-scale deformation. The first step in this effort has been to define both the essential and desirable attributes of a reference material for calibrating systems capable of measurements of dynamic displacement and strain. An international consortium of research laboratories, system designers, manufacturers and end-users has identified a list of attributes and members of the experimental mechanics community have been asked to weight the importance of these attributes. The attributes are being utilised to evaluate candidate designs for the reference material which have been generated through a series of brain-storming sessions within the consortium.

  20. Comparing Teaching Approaches About Maxwell's Displacement Current (United States)

    Karam, Ricardo; Coimbra, Debora; Pietrocola, Maurício


    Due to its fundamental role for the consolidation of Maxwell's equations, the displacement current is one of the most important topics of any introductory course on electromagnetism. Moreover, this episode is widely used by historians and philosophers of science as a case study to investigate several issues (e.g. the theory-experiment relationship). Despite the consensus among physics educators concerning the relevance of the topic, there are many possible ways to interpret and justify the need for the displacement current term. With the goal of understanding the didactical transposition of this topic more deeply, we investigate three of its domains: (1) The historical development of Maxwell's reasoning; (2) Different approaches to justify the term insertion in physics textbooks; and (3) Four lectures devoted to introduce the topic in undergraduate level given by four different professors. By reflecting on the differences between these three domains, significant evidence for the knowledge transformation caused by the didactization of this episode is provided. The main purpose of this comparative analysis is to assist physics educators in developing an epistemological surveillance regarding the teaching and learning of the displacement current.

  1. Digital image correlation: displacement accuracy estimation

    Directory of Open Access Journals (Sweden)

    Wattrisse B.


    Full Text Available The aim of this collaborative work is to study the uncertainties associated with Digital Image Correlation techniques (DIC. More specifically, the link between displacement uncertainties and several correlation parameters chosen by the user and relative to the image analysis software and several image characteristics like speckle size and image noise is emphasized. A previous work [1] has been done for situations with spatially fluctuating displacement fields which dealt with mismatch error linked to the discrepancy between the adopted shape function and the real displacement field in the subset. This present work is focused on the ultimate error regime. To ensure that there is no mismatch error, synthetic images of plane rigid body translation have been analysed. DIC softwares developed by or used in the French community were used to study a large number of settings. The first observations are: (a bias amplitude is almost always insensitive to the subset size, (b DIC formulations can be split up into two families. For the first one, the bias amplitude increases with the noise while it remains constant for the second one. For both families, the mean value of the random error increases with the noise level and with the inverse of the subset size. Furthermore, the random error decreases with the radius of the speckle for the first family, while it increases for the second one. These two different behaviours of the tested DIC package are probably due to their underlying DIC formulation (interpolation, correlation criteria, optimisation process.

  2. International Monetary Fund and aid displacement. (United States)

    Stuckler, David; Basu, Sanjay; McKee, Martin


    Several recent papers find evidence that global health aid is being diverted to reserves, education, military, or other sectors, and is displacing government spending. This is suggested to occur because ministers of finance have competing, possibly corrupt, priorities and deprive the health sector of resources. Studies have found that development assistance for health routed to governments has a negative impact on health spending and that similar assistance routed to private nongovernmental organizations has a positive impact. An alternative hypothesis is that World Bank and IMF macro-economic policies, which specifically advise governments to divert aid to reserves to cope with aid volatility and keep government spending low, could be causing the displacement of health aid. This article evaluates whether aid displacement was greater when countries undertook a new borrowing program from the IMF between 1996 and 2006. As found in existing studies, for each $1 of development assistance for health, about $0.37 is added to the health system. However, evaluating IMF-borrowing versus non-IMF-borrowing countries reveals that non-borrowers add about $0.45 whereas borrowers add less than $0.01 to the health system. On average, health system spending grew at about half the speed when countries were exposed to the IMF than when they were not. It is important to take account of the political economy of global health finance when interpreting data on financial flows.

  3. Aromatic metabolism of filamentous fungi in relation to the presence of aromatic compounds in plant biomass. (United States)

    Mäkelä, Miia R; Marinović, Mila; Nousiainen, Paula; Liwanag, April J M; Benoit, Isabelle; Sipilä, Jussi; Hatakka, Annele; de Vries, Ronald P; Hildén, Kristiina S


    The biological conversion of plant lignocellulose plays an essential role not only in carbon cycling in terrestrial ecosystems but also is an important part of the production of second generation biofuels and biochemicals. The presence of the recalcitrant aromatic polymer lignin is one of the major obstacles in the biofuel/biochemical production process and therefore microbial degradation of lignin is receiving a great deal of attention. Fungi are the main degraders of plant biomass, and in particular the basidiomycete white rot fungi are of major importance in converting plant aromatics due to their ability to degrade lignin. However, the aromatic monomers that are released from lignin and other aromatic compounds of plant biomass are toxic for most fungi already at low levels, and therefore conversion of these compounds to less toxic metabolites is essential for fungi. Although the release of aromatic compounds from plant biomass by fungi has been studied extensively, relatively little attention has been given to the metabolic pathways that convert the resulting aromatic monomers. In this review we provide an overview of the aromatic components of plant biomass, and their release and conversion by fungi. Finally, we will summarize the applications of fungal systems related to plant aromatics.

  4. Water-soluble constituents of caraway: aromatic compound, aromatic compound glucoside and glucides. (United States)

    Matsumura, Tetsuko; Ishikawa, Toru; Kitajima, Junichi


    From the water-soluble portion of the methanolic extract of caraway (fruit of Carum carvi L.), an aromatic compound, an aromatic compound glucoside and a glucide were isolated together with 16 known compounds. Their structures were clarified as 2-methoxy-2-(4'-hydroxyphenyl)ethanol, junipediol A 2-O-beta-D-glucopyranoside and L-fucitol, respectively.

  5. In situ nucleophilic substitution reaction of N,N-dialkylaminoethyl-2-chlorides monitored by gas chromatography/mass spectrometry. (United States)

    Lakshmi, V V S; Reddy, T Jagadeshwar; Murty, M R V S; Prabhakar, S; Vairamani, M


    The detection and identification of degradation products of scheduled chemicals, which are characteristic markers of Chemical Warfare agents (CWAs), plays a key role in verification analysis. Identification of such non-scheduled but specific markers of CWAs helps in deciphering the kind of agent that was present in the sample submitted for off-site analysis. This paper describes the stability of N,N-dialkylaminoethyl-2-chlorides, which are precursors for highly toxic chemicals like VX, in different solvents. These compounds are stable in chloroform, acetonitrile, hexane and dichloromethane but tend to undergo in situ nucleophilic substitution reaction in the presence of alcohols giving the corresponding alkyl ether. The study shows that N,N-dialkylaminoethyl alkyl ethers can be used as markers of N,N-dialkylaminoethyl-2-chlorides. A detailed degradation study of these compounds in the presence of alcohols was carried out and it was found that the reaction follows pseudo-first order kinetics. Electron ionization mass spectral data for the methyl ethers of all the compounds are briefly discussed.

  6. Ultrasonography for non-displaced and mini-displaced humeral lateral condyle fractures in children

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jing-dong; CHEN Hua


    Objective: To evaluate the value of ultrasonography in non-displaced and mini-displaced humeral lateral condyle fractures in children.Methods: Nine children aged 2-9 years with non-displaced or mini-displaced humeral lateral condyle fractures were examined by high-resolution ultrasonography.The fracture line through the joint surface was visualized by ultrasonography in 6 case,in which closed reduction and percutaneous pinning was performed on 3 patients and other 3 patients did not receive the treatment because of patients' or their parents'refusal.In the remaining 3 children,ultrasonography did not reveal the cartilaginous trochle involvement at the joint surface and conservative treatment was adopted.Results: The average follow-up period was 8 months.The sonographic findings were confirmed by magnetic resonance imaging in one child who received conservative treatment and another child who received percutaneous pinning.The elbow function and fractttre healing were good in cases received closed reduction and percutaneous pinning.Among the three cases who refused to receive closed reduction and internal f'txation,re-displacement occurred in 1 case and delayed union in 1 case.All three cases receiving conservative treatment had good results both in elbow function and fracture healing.Conclusion: High-resolution ultrasonography enable to reveal non-displaced and mini-displaced humeral lateral condyle fractures as well as to ascertain whether the cartilaginous trochlea humeri was involved.For these cases,arthrography or magnetic resonance imaging is unnecessary.

  7. Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl and Selectfluor/NH4SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition

    Directory of Open Access Journals (Sweden)

    A. Srinivas Reddy


    Full Text Available Reaction of benzyl and ethyl allenoates with TMSX (X = I, Br, Cl and with NH4SCN were investigated in MeCN, DMF, and in imidazolium ionic liquids [BMIM][NTf2] and [BMIM][PF6] as solvent, in the presence and absence of Selectfluor. Comparative product analysis studies demonstrate that the ability of Selectflour to promote oxidative/electrophilic dihalogenation/dithiocyanation with TMSX/NH4SCN (as observed previously for 1-arylallenes is diminished in allenoates, most significantly in reactions with TMSCl, and essentially disappearing in reactions with NH4SCN, in favor of nucleophilic/conjugate addition. The study underscores the contrasting reactivity patterns in 1-arylallenes and allenoates toward electrophilic and nucleophilic additions in halofunctionalization with TMSX/Selectfluor and thiocyanation reactions with NH4SCN/Selectfluor. These competing pathways are influenced by the nature of the anion, allene structure, and the choice of solvent.

  8. 非对称环氧乙烷的区域选择性亲核开环反应%Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Oxiranes

    Institute of Scientific and Technical Information of China (English)

    周婵; 许家喜


    本文总结了常用亲核试剂对非对称环氧乙烷的亲核开环反应及其区域选择性.强亲核性的亲核试剂通常只受空间效应影响,进攻非对称环氧乙烷位阻小的碳原子,对于烯基取代环氧乙烷还可以进攻烯基的β-碳原子发生Sn2'开环反应,其他亲核试剂同时受空间效应和电子效应的影响,对于烷基环氧乙烷通常进攻其取代少的碳原子,空间效应起主导作用,而对芳基和烯基取代环氧乙烷开环反应通常发生在环氧乙烷芳甲位和烯丙位的碳原子上,电子效应起主导作用.在质子酸或强Lewis酸存在下,虽然单烷基环氧乙烷的开环仍然发生在其取代少的碳原子上,但对于芳基、烯基和同碳双取代环氧乙烷,亲核开环反应将主要受电子效应控制,一般亲核试剂倾向于进攻环氧乙烷的芳甲位、烯丙位或多取代的碳原子.分子内的亲核开环反应主要受成环时环大小的控制,成环时的倾向是五元环>六元环>七元环.环氧乙烷亲核开环的区域选择性是环氧乙烷和亲核试剂空间效应和电子效应平衡的结果.%Nucleophilic ring opening reactions of unsymmetric oxiranes and their regioselectivity with widely used nucleophiles are reviewed. Strong nucleophiles attack the less substituted carbon atom of unsymmetric oxiranes, whatever alkyl, alkenyl, and aryloxiranes, controlled by the steric hindrance only. They can undergo an SN2' ring-opening reaction with alkenyloxiranes via the attack on the β-carbon atom of their alkenyl group. Other nucleophiles generally attack the less substituted carbon atom for alkyloxiranes, controlled by the steric hindrance,but attack the arylmethyl and allyl carbon atom for aryl and alkenyloxiranes, controlled by the electronic effect. In the presence of proton acids or strong Lewis acids, although monoalkyloxiranes are attacked on their less substituted carbon atom with nucleophiles (steric hindrance control), aryl, alkenyl

  9. 7 CFR 1944.667 - Relocation and displacement. (United States)


    ... permanent or temporary relocation of displaced persons for units repaired or rehabilitated or for individual... displaced persons. The applicant shall include in its statement of activities, a statement concerning...

  10. HIV and the internally displaced: Burundi in focus

    Directory of Open Access Journals (Sweden)

    Raquel Wexler


    Full Text Available "Special attention should also be given to the prevention of contagious and infectious diseases, including AIDS, among internally displaced persons." (Guiding Principles on InternalDisplacement, 19.3

  11. Displacement Mechanism of Polymer Flooding by Molecular Tribology

    Institute of Scientific and Technical Information of China (English)

    YANG Er-Long; SONG Kao-Ping


    @@ Whether polymer flooding can enhance displacement efficiency or not is still a problem under debate. Laboratory experiment, numerical simulation and core data analysis are the commonly used means to study polymer flooding displacement efficiency.

  12. The diverse behaviour of the P-Cl bonds in the spiro-cis-ansa spermidine derivative cyclotriphosphazene towards mono-functional nucleophilic reagents (United States)

    İbişoğlu, Hanife; Temur, Başak; Ün, İlker


    A number of new spiro-ansa spermidine derivative cyclotriphosphazenes ( 2- 10) is synthesized in order to provide insight into the reaction mechanism for nucleophilic substitution. The structures of the compounds were determined by elemental analysis, mass (MS), 1H, 19F (for 9) and 31P NMR spectroscopies. Compounds ( 2- 8) and 9, 10 can be formed by a proton abstraction-chloride elimination and both the SN1 and SN2 reaction mechanisms, respectively.

  13. Nucleophilic Additions of 2-Furyllithium to Carbonyl Derivatives of L-Serine. Formal Synthesis of (2R,3R-β-Hydroxy Aspartic Acid

    Directory of Open Access Journals (Sweden)

    T. Tejero


    Full Text Available The nucleophilic addition of 2-furyllithium to esters derived from L-serine is described. The obtained furyl ketone 5 is stereoselectively reduced (ds≥95% with sodium borohydride to afford the corresponding syn aminoalcohol 12 in enantiomerically pure form. Compound 12 was further converted into valuable α-hydroxy-β-amino acids by means of the furan-to-acid equivalence.

  14. Direct Nucleophilic Substitution of Free Allylic Alcohols in Water Catalyzed by FeCl3⋅6 H2O: Which is the Real Catalyst?


    Trillo Alarcón, María Paz; Baeza, Alejandro; Nájera Domingo, Carmen


    The allylic substitution reaction, and particularly the direct allylic amination reaction, of free allylic alcohols in water catalyzed by FeCl3⋅6 H2O is described. This novel environmentally-friendly methodology allows the use of a wide variety of nitrogenated nucleophiles such as sulfonamides, carbamates, benzamides, anilines, benzotriazoles, and azides, generally giving good yields of the corresponding substitution products. The synthetic applicability of the process is also demonstrated be...

  15. Glassy carbon electrode modified with horse radish peroxidase/organic nucleophilic-functionalized carbon nanotube composite for enhanced electrocatalytic oxidation and efficient voltammetric sensing of levodopa

    Energy Technology Data Exchange (ETDEWEB)

    Shoja, Yalda; Rafati, Amir Abbas, E-mail:; Ghodsi, Javad


    A novel and selective enzymatic biosensor was designed and constructed for voltammetric determination of levodopa (L-Dopa) in aqueous media (phosphate buffer solution, pH = 7). Biosensor development was on the basis of to physically immobilizing of horse radish peroxidase (HRP) as electrochemical catalyst by sol–gel on glassy carbon electrode modified with organic nucleophilic carbon nanotube composite which in this composite p-phenylenediamine (pPDA) as organic nucleophile chemically bonded with functionalized MWCNT (MWCNT-COOH). The results of this study suggest that prepared bioorganic nucleophilic carbon nanotube composite (HRP/MWCNT-pPDA) shows fast electron transfer rate for electro oxidation of L-Dopa because of its high electrochemical catalytic activity toward the oxidation of L-Dopa, more −NH{sub 2} reactive sites and large effective surface area. Also in this work we measured L-Dopa in the presence of folic acid and uric acid as interferences. The proposed biosensor was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), FT-IR spectroscopy and cyclic voltammetry (CV). The differential pulse voltammetry (DPV) was used for determination of L-Dopa from 0.1 μM to 1.9 μM with a low detection limit of 40 nM (for S/N = 3) and sensitivity was about 35.5 μA/μM. Also this biosensor has several advantages such as rapid response, high stability and reproducibility. - Highlights: • Glassy carbon electrode modified by a novel composite in which pPDA as nucleophile is chemically attached to MWCNTs. • The developed biosensor exhibited excellent electrocatalytic activity in electrochemically determination of L-Dopa. • The biosensor showed acceptable sensitivity, reproducibility, detection limit, selectivity and stability. • MWCNT-pPDA provides a good electrical conductivity and large effective surface area for enzyme immobilization.

  16. Inorganic base-catalyzed formation of antivirally active N-substituted benzamides from α-amido sulfones and N-nucleophile

    Directory of Open Access Journals (Sweden)

    Wang Zhenchao


    Full Text Available Abstract Background Heteronucleophiles as well as carbanionic reagents can be used to react with α-amido sulfones, thus giving the opportunity to prepare a large array of amino derivatives. Since, novel 1,3,4-oxadiazole-2-thiol derivatives can serve as potent nucleophiles, we employed 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the nucleophilic source of nitrogen in the reaction with α-amido sulfones. Results A series of N-substituted benzamides bearing 1,3,4-oxadiazol unit were prepared for the first time by the reaction of in situ generated protected imine from α-amido sulfones with 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the source of nitrogen nucleophile. Some of the synthesized products displayed favourable antiviral activity against cucumber mosaic virus (CMV in preliminary antiviral activity tests. The title compounds 5c, 5o and 5r revealed curative activity of 42.2%, 48.7% and 40.5%, respectively against CMV (inhibitory rate compared to the commercial standard Ningnanmycin (53.4% at 500 μg/mL. Conclusion A practical synthetic route to N-benzoyl-α-amido sulfones by the reaction of 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the source of nitrogen nucleophiles with in situ generated protected imine from N-benzoyl-α-amido sulfones is presented. The reaction catalyzed by an inorganic base has considerable significance to exploit the potential of α-amido sulfones in organic synthesis.

  17. Is competition needed for ecological character displacement? Does displacement decrease competition? (United States)

    Abrams, Peter A; Cortez, Michael H


    Interspecific competition for resources is generally considered to be the selective force driving ecological character displacement, and displacement is assumed to reduce competition. Skeptics of the prevalence of character displacement often cite lack of evidence of competition. The present article uses a simple model to examine whether competition is needed for character displacement and whether displacement reduces competition. It treats systems with competing resources, and considers cases when only one consumer evolves. It quantifies competition using several different measures. The analysis shows that selection for divergence of consumers occurs regardless of the level of between-resource competition or whether the indirect interaction between the consumers is competition (-,-), mutualism (+,+), or contramensalism (+,-). Also, divergent evolution always decreases the equilibrium population size of the evolving consumer. Whether divergence of one consumer reduces or increases the impact of a subsequent perturbation of the other consumer depends on the parameters and the method chosen for measuring competition. Divergence in mutualistic interactions may reduce beneficial effects of subsequent increases in the other consumer's population. The evolutionary response is driven by an increase in the relative abundance of the resource the consumer catches more rapidly. Such an increase can occur under several types of interaction.

  18. Glassy carbon electrode modified with horse radish peroxidase/organic nucleophilic-functionalized carbon nanotube composite for enhanced electrocatalytic oxidation and efficient voltammetric sensing of levodopa. (United States)

    Shoja, Yalda; Rafati, Amir Abbas; Ghodsi, Javad


    A novel and selective enzymatic biosensor was designed and constructed for voltammetric determination of levodopa (L-Dopa) in aqueous media (phosphate buffer solution, pH=7). Biosensor development was on the basis of to physically immobilizing of horse radish peroxidase (HRP) as electrochemical catalyst by sol-gel on glassy carbon electrode modified with organic nucleophilic carbon nanotube composite which in this composite p-phenylenediamine (pPDA) as organic nucleophile chemically bonded with functionalized MWCNT (MWCNT-COOH). The results of this study suggest that prepared bioorganic nucleophilic carbon nanotube composite (HRP/MWCNT-pPDA) shows fast electron transfer rate for electro oxidation of L-Dopa because of its high electrochemical catalytic activity toward the oxidation of L-Dopa, more--NH2 reactive sites and large effective surface area. Also in this work we measured L-Dopa in the presence of folic acid and uric acid as interferences. The proposed biosensor was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), FT-IR spectroscopy and cyclic voltammetry (CV). The differential pulse voltammetry (DPV) was used for determination of L-Dopa from 0.1 μM to 1.9 μM with a low detection limit of 40 nM (for S/N=3) and sensitivity was about 35.5 μA/μM. Also this biosensor has several advantages such as rapid response, high stability and reproducibility.

  19. 24 CFR 583.310 - Displacement, relocation, and acquisition. (United States)


    ... persons. A displaced person (defined in paragraph (f) of this section) must be provided relocation... “displaced person,” or the amount of relocation assistance for which the person is eligible, may file a... to the HUD field office. (f) Definition of displaced person. (1) For purposes of this section,...

  20. 24 CFR 941.207 - Displacement, relocation, and acquisition. (United States)


    ... CFR part 24. A “displaced person” shall be advised of his/her rights under the Fair Housing Act (42 U... paragraph (b)(1) of this section. (c) Relocation assistance for displaced persons. A “displaced person... and the standards for tenancy established in accordance with 24 CFR 960.204) who will not be...

  1. 24 CFR 886.138 - Displacement, relocation, and acquisition. (United States)


    ... regulations at 49 CFR part 24. A “displaced person” shall be advised of his or her rights under the Fair... person is ineligible under 49 CFR 24.2(g)(2); or (iv) HUD determines that the person was not displaced as... persons. A “displaced person” (as defined in paragraph (g) of this section) must be provided...

  2. From Word to Image: Displacement and Meaning in "Greed." (United States)

    Grindon, Leger


    Describes levels of displacement in Stroheim's film "Greed," including (1) the displacement of reason, pleasure, and life by the desire for gold; and (2) the displacement that points to a double movement in Stroheim's cinematic style. Argues that the film's sense of doom arises from the psychic nightmare operating through the mechanics…

  3. Rhetorics of Displacement: Constructing Identities in Forced Relocations (United States)

    Powell, Katrina M.


    Forced displacement has often involved the use of rhetoric, both by government institutions and by people who struggle not only to survive displacement, but also to resist it. In this article, the author offers first a theoretical framework that informs her thinking about displacement narratives. She briefly examines two published displacement…

  4. Year of displaced people’s rights in Colombia

    Directory of Open Access Journals (Sweden)

    Marco Alberto Romero


    Full Text Available A Campaign for the Rights of Displaced People in Colombia, launched in 2007 by UNHCR, Colombian NGO CODHES and the Catholic Church, has tried to raise awareness in Colombia and the international community about the severity of the country’s displacement crisis and its failure to guarantee the rights of displaced people.

  5. The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators and an unexpected intramolecular nucleophilic substitution reaction via a proposed Ni(III) NCP intermediate. (United States)

    Jiang, Hua-Wei; Chen, Qing-Yun; Xiao, Ji-Chang; Gu, Yu-Cheng


    The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators resulted in an unexpected intramolecular nucleophilic substitution reaction via a proposed Ni(III) NCP intermediate, which could be detected by HRMS.

  6. Binding Modes of Aromatic Ligands to Mammalian Heme Peroxidases with Associated Functional Implications (United States)

    Singh, Amit K.; Singh, Nagendra; Sinha, Mau; Bhushan, Asha; Kaur, Punit; Srinivasan, Alagiri; Sharma, Sujata; Singh, Tej P.


    The binding and structural studies of bovine lactoperoxidase with three aromatic ligands, acetylsalicylic acid (ASA), salicylhydoxamic acid (SHA), and benzylhydroxamic acid (BHA) show that all the three compounds bind to lactoperoxidase at the substrate binding site on the distal heme side. The binding of ASA occurs without perturbing the position of conserved heme water molecule W-1, whereas both SHA and BHA displace it by the hydroxyl group of their hydroxamic acid moieties. The acetyl group carbonyl oxygen atom of ASA forms a hydrogen bond with W-1, which in turn makes three other hydrogen-bonds, one each with heme iron, His-109 Nϵ2, and Gln-105 Nϵ2. In contrast, in the complexes of SHA and BHA, the OH group of hydroxamic acid moiety in both complexes interacts with heme iron directly with Fe-OH distances of 3.0 and 3.2Å respectively. The OH is also hydrogen bonded to His-109 Nϵ2 and Gln-105Nϵ2. The plane of benzene ring of ASA is inclined at 70.7° from the plane of heme moiety, whereas the aromatic planes of SHA and BHA are nearly parallel to the heme plane with inclinations of 15.7 and 6.2°, respectively. The mode of ASA binding provides the information about the mechanism of action of aromatic substrates, whereas the binding characteristics of SHA and BHA indicate the mode of inhibitor binding. PMID:19465478

  7. Two-Domain DNA Strand Displacement

    CERN Document Server

    Cardelli, Luca


    We investigate the computing power of a restricted class of DNA strand displacement structures: those that are made of double strands with nicks (interruptions) in the top strand. To preserve this structural invariant, we impose restrictions on the single strands they interact with: we consider only two-domain single strands consisting of one toehold domain and one recognition domain. We study fork and join signal-processing gates based on these structures, and we show that these systems are amenable to formalization and to mechanical verification.

  8. Atomic displacement energy in amorphous compounds (United States)

    Sanditov, D. S.; Mashanov, A. A.


    Atomic displacement energy Δɛe in multicomponent sheet and lead-silicate glasses is calculated from the free activation energy of a viscous flow. The value of Δɛe is shown to remain constant in a rather wide range of temperatures in the glass transition region. Satisfactory agreement with calculations of Δɛe using the current formula incorporating the glass transition temperature and the fluctuation volume fraction frozen at this temperature is obtained. The validity of the above formula not only at the glass transition temperature but also in the temperature region adjacent to it is confirmed.

  9. Uncovering deformation processes from surface displacements (United States)

    Stramondo, Salvatore; Trasatti, Elisa; Albano, Matteo; Moro, Marco; Chini, Marco; Bignami, Christian; Polcari, Marco; Saroli, Michele


    Today, satellite remote sensing has reached a key role in Earth Sciences. In particular, Synthetic Aperture Radar (SAR) sensors and SAR Interferometry (InSAR) techniques are widely used for the study of dynamic processes occurring inside our living planet. Over the past 3 decades, InSAR has been applied for mapping topography and deformation at the Earth's surface. These maps are widely used in tectonics, seismology, geomorphology, and volcanology, in order to investigate the kinematics and dynamics of crustal faulting, the causes of postseismic and interseismic displacements, the dynamics of gravity driven slope failures, and the deformation associated with subsurface movement of water, hydrocarbons or magmatic fluids.

  10. Galvanic displacement of metals on semiconductor nanocrystals (United States)

    Johnson, Melanie; Kelly, Joel A.; Henderson, Eric J.; Veinot, Jonathan G. C.


    We report the galvanic displacement (GD) of germanium from germanium nanocrystals (Ge-NCs) with silver. The Ge-NCs are synthesized by reductive thermal processing of germanium suboxide sol-gel prepolymers. Thermal processing yields size-controlled oxide-embedded Ge-NCs, which are liberated by dissolution of the germanium oxide matrix in water. Subsequent exposure of the freestanding Ge-NCs to aqueous solutions of AgNO3 leads to deposition of silver nanostructures by GD. The resulting metal structures were analyzed by XRD, XPS, TEM and EDX, confirming deposition of elemental silver in a variety of shapes and sizes.

  11. Galvanic displacement of metals on semiconductor nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Melanie; Kelly, Joel A; Henderson, Eric J; Veinot, Jonathan G C, E-mail: [University of Alberta, Department of Chemistry, Edmonton, AB, T6G 2G2 (Canada)


    We report the galvanic displacement (GD) of germanium from germanium nanocrystals (Ge-NCs) with silver. The Ge-NCs are synthesized by reductive thermal processing of germanium suboxide sol-gel prepolymers. Thermal processing yields size-controlled oxide-embedded Ge-NCs, which are liberated by dissolution of the germanium oxide matrix in water. Subsequent exposure of the freestanding Ge-NCs to aqueous solutions of AgNO{sub 3} leads to deposition of silver nanostructures by GD. The resulting metal structures were analyzed by XRD, XPS, TEM and EDX, confirming deposition of elemental silver in a variety of shapes and sizes.

  12. Simulating People Moving in Displacement Ventilated Rooms

    DEFF Research Database (Denmark)

    Mattsson, M.; Bjørn, Erik; Sandberg, M.

    A displacement ventilation system works better the more uni-directional the air flow through the ventilated room is: from floor to ceiling. Thus, from an air quality point of view, there should be as little vertical mixing of the room air as possible. It is therefore comprehensible that physical...... activity in the room -like peoples movements -in previous studies has been shown to influence the effectiveness of the ventilation. In this study we have compared results from previous tests, where a cylindrical person simulator was used, to results obtained when using a person simulator of more human...

  13. Can hydroxylamine be a more potent nucleophile for the reactivation of tabun-inhibited AChE than prototype oxime drugs? An answer derived from quantum chemical and steered molecular dynamics studies. (United States)

    Lo, Rabindranath; Ganguly, Bishwajit


    Organophosphorus nerve agents are highly toxic compounds which strongly inhibit acetylcholinesterase (AChE) in the blood and in the central nervous system (CNS). Tabun is one of the highly toxic organophosphorus (OP) compounds and is resistant to many oxime drugs formulated for the reactivation of AChE. The reactivation mechanism of tabun-conjugated AChE with various drugs has been examined with density functional theory and ab initio quantum chemical calculations. The presence of a lone-pair located on the amidic group resists the nucleophilic attack at the phosphorus center of the tabun-conjugated AChE. We have shown that the newly designed drug candidate N-(pyridin-2-yl)hydroxylamine, at the MP2/6-31+G*//M05-2X/6-31G* level in the aqueous phase with the polarizable continuum solvation model (PCM), is more effective in reactivating the tabun-conjugated AChE than typical oxime drugs. The rate determining activation barrier with N-(pyridin-2-yl)hydroxylamine was found to be ∼1.7 kcal mol(-1), which is 7.2 kcal mol(-1) lower than the charged oxime trimedoxime (one of the most efficient reactivators in tabun poisonings). The greater nucleophilicity index (ω(-)) and higher CHelpG charge of pyridinylhydroxylamine compared to TMB4 support this observation. Furthermore, we have also examined the reactivation process of tabun-inhibited AChE with some other bis-quaternary oxime drug candidates such as methoxime (MMB4) and obidoxime. The docking analysis suggests that charged bis-quaternary pyridinium oximes have greater binding affinity inside the active-site gorge of AChE compared to the neutral pyridinylhydroxylamine. The peripheral ligand attached to the neutral pyridinylhydroxylamine enhanced the binding with the aromatic residues in the active-site gorge of AChE through effective π-π interactions. Steered molecular dynamics (SMD) simulations have also been performed with the charged oxime (TMB4) and the neutral hydroxylamine. From protein-drug interaction

  14. Thermochemical factors affecting the dehalogenation of aromatics. (United States)

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


    Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.

  15. Structural Analysis of Aromatic Liquid Crystalline Polyesters

    Directory of Open Access Journals (Sweden)

    Arpad Somogyi


    Full Text Available Laboratory preparations of liquid crystalline prepolymers, distillates accompanying prepolymers, final polymers, and sublimates accompanying final polymers were examined. NaOD/D2O depolymerization of prepolymers and polymers back to monomers with integration of the 1H NMR spectra showed up to 6% excess of carboxyls over phenol groups, caused partly by loss of the low-boiling comonomer hydroquinone through distillation during prepolymerization and leaving anhydride units in the polymer chain. ESI− MS and MS/MS of hexafluoroisopropanol extracts of the prepolymer detected small molecules including some containing anhydride groups; ESI+ MS showed the presence of small cyclic oligomers. 1H NMR (including TOCSY spectra provided more quantitative analyses of these oligomers. The final polymerization increases the length of the polymer chains and sublimes out the small oligomers. Anhydride linkages remaining in the polymer must make LCP’s more susceptible to degradation by nucleophilic reagents such as water, alkalis, and amines.

  16. Synthesis and application of aryl-ferrocenyl(pseudo-biarylic) complexes. Part 5. Design and synthesis of a new type of ferrocene-based planar chiral DMAP analogues. A new catalyst system for asymmetric nucleophilic catalysis

    DEFF Research Database (Denmark)

    Seitzberg, J.G; Dissing, C; Søtofte, Inger;


    A new first-generation catalyst system for nucleophilic catalysis has been developed. It is based on a planar chiral ferrocene skeleton with either the potent nucleophile 4-(dimethylamino)pyridine (DMAP) or the related 4-nitropyridine N-oxide attached in either the 2- or the 3-position. The synth...... (selectivity) was studied using molecular modeling and the results pointed at new directions for future generations of catalysts based on this design....

  17. Regioselective photoamination of 4-nitroveratrole upon cyclodextrin complexation

    Indian Academy of Sciences (India)

    M C Durai Manickam; K Pitchumani; C Srinivasan


    Photoamination of 4-nitroveratrole in cyclodextrins with the nucleophiles ammonia, methylamine and hexylamine provides a new route to regioselectivity. This method gives a displaced product para to the nitro group as the predominant product, in contrast to the solution reaction wherein the meta-displaced product predominates. This is due to the change in the mechanistic shift from S2Ar∗, wherein the nitro group is meta-directing, to a mechanism involving electron transfer from the nucleophile to the excited aromatic substrate (S (ET)Ar∗) to give the para-displaced product.

  18. Production of aromatics from di- and polyoxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy


    Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Group VIII metal and a crystalline alumina support.

  19. Production of aromatics from di- and polyoxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy


    Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline alumina support.

  20. Global aromatics supply. Today and tomorrow

    Energy Technology Data Exchange (ETDEWEB)

    Bender, M. [BASF SE, Ludwigshafen (Germany)


    Aromatics are the essential building blocks for some of the largest petrochemical products in today's use. To the vast majority they are consumed to produce intermediates for polymer products and, hence, contribute to our modern lifestyle. Their growth rates are expected to be in line with GDP growth in future. This contrasts the significantly lower growth rates of the primary sources for aromatics - fuel processing and steam cracking of naphtha fractions. A supply gap can be expected to open up in future for which creative solutions will be required. (orig.)

  1. Precision optical displacement measurements using biphotons (United States)

    Lyons, Kevin; Pang, Shengshi; Kwiat, Paul G.; Jordan, Andrew N.


    We propose and examine the use of biphoton pairs, such as those created in parametric down-conversion or four-wave mixing, to enhance the precision and the resolution of measuring optical displacements by position-sensitive detection. We show that the precision of measuring a small optical beam displacement with this method can be significantly enhanced by the correlation between the two photons, given the same optical mode. The improvement is largest if the correlations between the photons are strong, and falls off as the biphoton correlation weakens. More surprisingly, we find that the smallest resolvable parameter of a simple split detector scales as the inverse of the number of biphotons for small biphoton number ("Heisenberg scaling"), because the Fisher information diverges as the parameter to be estimated decreases in value. One usually sees this scaling only for systems with many entangled degrees of freedom. We discuss the transition for the split-detection scheme to the standard quantum limit scaling for imperfect correlations as the biphoton number is increased. An analysis of an N -pixel detector is also given to investigate the benefit of using a higher resolution detector. The physical limit of these metrology schemes is determined by the uncertainty in the birth zone of the biphoton in the nonlinear crystal.

  2. Grating Loaded Cantilevers for Displacement Measurements (United States)

    Karademir, Ertugrul; Olcum, Selim; Atalar, Abdullah; Aydinli, Atilla


    A cantilever with a grating coupler engraved on its tip is used for measuring displacement. The coupled light in the cantilever is guided to a single mode optical waveguide defined at the base of the cantilever. The grating period is 550 nm and is fabricated on a SOI wafer using nanoimprint lithography. The waveguide and the cantilever are defined by an RIE and cantilevers released by KOH and HF solutions. Light with 1550 nm wavelength, is directed onto the grating coupler and detected at the cleaved end of the SOI waveguide. The angle of incidence is controlled by a motorized rotary stage. Light couples into the waveguide at a characteristic angle with a full width at half maximum of approximately 6.9 mrads translating into a Q factor of 87.5. The displacement sensitivity is measured by driving the cantilever with a frequency controlled piezoelectric element. The modulation of the light at the waveguide output is lock-in detected by a biased infrared detector. The resulting 43%mrad-1 sensitivity can be increased with further optimization.

  3. Estimating Hydrologic Processes from Subsurface Soil Displacements (United States)

    Freeman, C. E.; Murdoch, L. C.; Germanovich, L.; MIller, S.


    Soil moisture and the processes that control it are important components of the hydrologic cycle, but measuring these processes remains challenging. We have developed a new measurement method that offers flexibility compared to existing technology. The approach is to measure small vertical displacements in the soil which responds proportionally to distributed surface load changes such as variation in the near-surface water content. The instrument may be installed at a depth of several meters to hundreds of meters below the surface. Because the measurement averaging region scales with the depth of the displacement measurements, this approach provides the means for estimating the soil moisture time series over tens of square meters to tens of thousands of square meters. The instrument developed for this application is called a Sand-X, which is short for Sand Extensometer. It is designed for applications in unconsolidated material, ranging from clay to sand. The instrument is simple and relatively inexpensive, and it can be installed in a boring made with a hand auger or with a small drill rig. Studies at the field scale are ongoing at a field site near Clemson, SC. The site is underlain by saprolite weathered primarily from biotite gneiss. Several Sand-X devices are installed at a field site that is instrumented for validating soil moisture, precipitation, and evapotranspiration estimates. These instruments are emplaced at a depth of 6 m and respond to the weight of a vehicle out to 18 m from the well. Calibration is performed by comparing precipitation measurements to the soil displacement response. For example, the coefficient for one installation is roughly 185 nm soil displacement/mm water content change. The resolution of the instrument is approximately 10 nm, so the Sand-X is capable of detecting changes of soil moisture on the order of tenths of one mm in compliant soils like saprolite. A typical soil displacement time series shows alternating periods of

  4. Identification of glutamic acid 78 as the active site nucleophile in Bacillus subtilis xylanase using electrospray tandem mass spectrometry. (United States)

    Miao, S; Ziser, L; Aebersold, R; Withers, S G


    A new mechanism-based inactivator of beta-1,4-xylanases, 2',4'-dinitrophenyl 2-deoxy-2-fluoro-beta-xylobioside, has been synthesized and used to trap the covalent intermediate formed during catalysis by Bacillus subtilis xylanase. Electrospray mass spectrometry confirmed the 1:1 stoichiometry of the incorporation of inactivator into the enzyme. Inactivation of xylanase followed the expected pseudo-first-order kinetic behavior, and kinetic parameters were determined. The intermediate trapped was relatively stable toward hydrolytic turnover (t1/2 = 350 min). However, turnover could be facilitated by transglycosylation following the addition of the acceptor benzyl thio-beta-xylobioside, thus demonstrating the catalytic competence of the trapped intermediate. Reactivation kinetic parameters for this process of kre = 0.03 min-1 and Kre = 46 mM were determined. The nucleophilic amino acid was identified as Glu78 by a tandem mass spectrometric technique which does not require the use of radiolabels. The peptic digest of the labeled enzyme was separated by high-performance liquid chromatography and the eluent fed into a tandem mass spectrometer via an electrospray ionization device. The labeled peptide was identified as one of m/z = 826 (doubly charged) which fragmented in the collision chamber between the mass analyzers with loss of the mass of a 2-fluoroxylobiosyl unit. Confirmation of the peptide identity was obtained both by tandem mass spectrometric sequencing and by Edman degradation of the purified peptide. Glu78 is completely conserved in all members of this xylanase family and indeed is shown to be located in the active site in the recently determined X-ray crystal structure.

  5. Assessing aromaticity and the degree of aromatic condensation of pyrogenic carbon (United States)

    Wiedemeier, D. B.; Abiven, S.; Hockaday, W. C.; Keiluweit, M.; Kleber, M.; Masiello, C. A.; McBeath, A. V.; Nico, P. S.; Pyle, L. A.; Schneider, M. P.; Smernik, R. J.; Wiesenberg, G. L.; Schmidt, M. W.


    Fire-derived, pyrogenic carbon (PyC) is a persistent organic carbon fraction in soils because it is relatively resistant against chemical and biological degradation. PyC thus represents a carbon sequestration potential in the global carbon cycle and was also reported to be potentially beneficial for soil fertility. PyC is naturally added to soils during wildfires and anthropogenically in the form of biochar, after organic waste is pyrolyzed. Aromaticity and the degree of aromatic condensation are the two main quality properties of PyC that probably determine its persistence against degradation. Consequently, the two properties largely influence the PyC's carbon sequestration potential as well as the duration, during which it can provide benefits to the soil. Aromaticity and the degree of aromatic condensation of PyC should theoretically be dependent on pyrolysis conditions, such as highest heating temperature or pyrolysis time, and also depend on the feedstock. In this study, we used two different pyrolysis procedures and four different feedstocks to produce four thermosequences of 38 chars in total, with highest heating temperatures ranging from 100 - 1000° C. The chars were then analyzed with an extensive suite of seven different methods: solid state 13C nuclear magnetic resonance (13C NMR), diffuse infrared Fourier transform spectroscopy (DRIFT), synchrotron-based near-edge X-ray absorption fine structure analysis (NEXAFS), benzene polycarboxylic acid analysis (BPCA), lipid analysis, elemental analysis and helium pycnometry. These methods allowed to infer the aromaticity and the degree of aromatic condensation of the differently pyrolyzed materials. Using multivariate statistical methods, aromaticity and the degree of aromatic condensation could successfully be linked to highest heating temperature and other pyrolysis conditions because characteristic patterns of the two aromatic properties could be observed by different methods throughout all four

  6. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes (United States)

    Smith, R.E.; Dolbeare, F.A.


    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 4-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes. No Drawings

  7. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes (United States)

    Smith, Robert E.; Dolbeare, Frank A.


    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 5-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes.

  8. Attenuation of Scalar Fluxes Measured with Spatially-displaced Sensors (United States)

    Horst, T. W.; Lenschow, D. H.


    Observations from the Horizontal Array Turbulence Study (HATS) field program are used to examine the attenuation of measured scalar fluxes caused by spatial separation between the vertical velocity and scalar sensors. The HATS data show that flux attenuation for streamwise, crosswind, and vertical sensor displacements are each a function of a dimensionless, stability-dependent parameter n m multiplied by the ratio of sensor displacement to measurement height. The scalar flux decays more rapidly with crosswind displacements than for streamwise displacements and decays more rapidly for stable stratification than for unstable stratification. The cospectral flux attenuation model of Kristensen et al. agrees well with the HATS data for streamwise sensor displacements, although it is necessary to include a neglected quadrature spectrum term to explain the observation that flux attenuation is often less with the scalar sensor downwind of the anemometer than for the opposite configuration. A simpler exponential decay model provides good estimates for crosswind sensor displacements, as well as for streamwise sensor displacements with stable stratification. A model similar to that of Lee and Black correctly predicts flux attenuation for a combination of streamwise and crosswind displacements, i.e. as a function of wind direction relative to the sensor displacement. The HATS data for vertical sensor displacements extend the near-neutral results of Kristensen et al. to diabatic stratification and confirm their finding that flux attenuation is less with the scalar sensor located below the anemometer than if the scalar sensor is displaced an equal distance either horizontally or above the anemometer.

  9. The effect of base pair mismatch on DNA strand displacement

    CERN Document Server

    Broadwater, Bo


    DNA strand displacement is a key reaction in DNA homologous recombination and DNA mismatch repair and is also heavily utilized in DNA-based computation and locomotion. Despite its ubiquity in science and engineering, sequence-dependent effects of displacement kinetics have not been extensively characterized. Here, we measured toehold-mediated strand displacement kinetics using single-molecule fluorescence in the presence of a single base pair mismatch. The apparent displacement rate varied significantly when the mismatch was introduced in the invading DNA strand. The rate generally decreased as the mismatch in the invader was encountered earlier in displacement. Our data indicate that a single base pair mismatch in the invader stalls branch migration, and displacement occurs via direct dissociation of the destabilized incumbent strand from the substrate strand. We combined both branch migration and direct dissociation into a model, which we term, the concurrent displacement model, and used the first passage t...


    Neville, O.K.


    A selective complexing organic solvent extraction process is presented for the separation of uranium values from an aqueous nitric acid solution of neutron irradiated thorium. The process comprises contacting the solution with an organic aromatic dithiccarbamaie and recovering the resulting urancdithiccarbamate complex with an organic solvent such as ethyl acetate.

  11. Bacterial formation of hydroxylated aromatic compounds.

    NARCIS (Netherlands)

    Tweel, van den W.J.J.


    As stated in the introduction of this thesis, hydroxylated aromatic compounds in general are of great importance for various industries as for instance pharmaceutical, agrochemical and petrochemical industries. Since these compounds can not be isolated in sufficient amounts from natural resources, t


    Institute of Scientific and Technical Information of China (English)

    HUANG Zhitang


    This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of polymers.

  13. Fused aromatic thienopyrazines: structure, properties and function

    KAUST Repository

    Mondal, Rajib


    Recent development of a fused aromatic thieno[3.4-b]pyrazine system and their application in optoelectronic devices are reviewed. Introduction of a fused aromatic unit followed by side chain engineering, dramatically enhanced the charge carrier mobility in thin film transistor devices and mobilities up to 0.2 cm2/Vs were achieved. The optoelectronic properties of these fused aromatic thienopyrazine polymers (Eg = 1.3 to 1.6 eV, HOMO = -4.9 to -5.2 V) were tuned by introduction of various fused aromatic rings within thienopyrazine. By balancing the fundamental properties of these polymers, both high charge carrier mobilities and moderate PCEs in solar cells were achieved. Further, effects of copolymerizing units are discussed. Low band gap semiconducting polymer (Eg ∼ 1 eV) with high field effect mobility (0.044 cm2/Vs) was obtained using cyclopentadithiophene as copolymerizing unit. Finally, a molecular design approach to enhance the absorption coefficients is discussed, which resulted in improved power conversion efficiency in bulk heterojunction solar cells. © 2010 The Royal Society of Chemistry.

  14. Fate and biodegradability of sulfonated aromatic amines

    NARCIS (Netherlands)

    Tan, N.C.G.; Leeuwen, van A.; Voorthuizen, van E.M.; Slenders, P.; Prenafeta, F.X.; Temmink, H.; Lettinga, G.; Field, J.A.


    Ten sulfonated aromatic amines were tested for their aerobic and anaerobic biodegradability and toxicity potential in a variety of environmental inocula. Of all the compounds tested, only two aminobenzenesulfonic acid (ABS) isomers, 2- and 4-ABS, were degraded. The observed degradation occurred only

  15. Electronic Aromaticity Index for Large Rings

    CERN Document Server

    Matito, Eduard


    We introduce a new electronic aromaticity index, AV1245, consisting in the average of the 4-center MCI values along the ring that keep 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 a small computational cost that grows linearly with the number of ring members. Therefore, it is specially suitable to study the aromaticity of large molecular rings as those occurring in belt-shaped M\\"obius structures or porphyrins.

  16. Arylazoindazole Photoswitches: Facile Synthesis and Functionalization via SNAr Substitution (United States)


    A straightforward synthetic route to arylazoindazoles via nucleophilic aromatic substitution is presented. Upon deprotonation of the NH group, a C6F5-substituted formazan undergoes facile cyclization as a result of intermolecular nucleophilic substitution (SNAr). This new class of azo photoswitches containing an indazole five-membered heterocycle shows photochemical isomerization with high fatigue resistance. In addition, the Z-isomers have long thermal half-lives in the dark of up to several days at room temperature. The fluorinated indazole group offers a handle for further functionalization and tuning of its properties, as it is shown to be susceptible to a subsequent, highly selective nucleophilic displacement reaction. PMID:28218846

  17. 40 CFR 721.2673 - Aromatic epoxide resin (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aromatic epoxide resin (generic). 721... Substances § 721.2673 Aromatic epoxide resin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aromatic epoxide resin (PMN...

  18. 40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for...

  19. 40 CFR 721.2925 - Brominated aromatic ester. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  20. Analog Computation by DNA Strand Displacement Circuits. (United States)

    Song, Tianqi; Garg, Sudhanshu; Mokhtar, Reem; Bui, Hieu; Reif, John


    DNA circuits have been widely used to develop biological computing devices because of their high programmability and versatility. Here, we propose an architecture for the systematic construction of DNA circuits for analog computation based on DNA strand displacement. The elementary gates in our architecture include addition, subtraction, and multiplication gates. The input and output of these gates are analog, which means that they are directly represented by the concentrations of the input and output DNA strands, respectively, without requiring a threshold for converting to Boolean signals. We provide detailed domain designs and kinetic simulations of the gates to demonstrate their expected performance. On the basis of these gates, we describe how DNA circuits to compute polynomial functions of inputs can be built. Using Taylor Series and Newton Iteration methods, functions beyond the scope of polynomials can also be computed by DNA circuits built upon our architecture.

  1. An Alternative to Maxwell's Displacement Current

    CERN Document Server

    Wolsky, Alan M


    Though sufficient for local conservation of charge, we show that Maxwells displacement current is not necessary. An alternative to the Ampere Maxwell equation is exhibited and the alternative s electric and magnetic fields and scalar and vector potentials are expressed in terms of the charge and current densities. The alternative describes a theory in which action is instantaneous and so may provide a good approximation to Maxwells equations where and when the finite speed of light can be neglected. The result is reminiscent of the Darwin approximation which arose from the study classical charged point particles to order (v/c)2 in the Lagrangian. Unlike Darwin, this approach does not depend on the constitution of the electric current. Instead, this approach grows from a straightforward revision of the Ampere Equation which revision enforces the local conservation of charge.

  2. Axial flow positive displacement worm compressor (United States)

    Murrow, Kurt David (Inventor); Giffin, Rollin George (Inventor); Fakunle, Oladapo (Inventor)


    An axial flow positive displacement compressor has an inlet axially spaced apart and upstream from an outlet. Inner and outer bodies have offset inner and outer axes extend from the inlet to the outlet through first and second sections of a compressor assembly in serial downstream flow relationship. At least one of the bodies is rotatable about its axis. The inner and outer bodies have intermeshed inner and outer helical blades wound about the inner and outer axes respectively. The inner and outer helical blades extend radially outwardly and inwardly respectively. The helical blades have first and second twist slopes in the first and second sections respectively. The first twist slopes are less than the second twist slopes. An engine including the compressor has in downstream serial flow relationship from the compressor a combustor and a high pressure turbine drivingly connected to the compressor by a high pressure shaft.

  3. Axial flow positive displacement worm gas generator (United States)

    Murrow, Kurt David (Inventor); Giffin, Rollin George (Inventor); Fakunle, Oladapo (Inventor)


    An axial flow positive displacement engine has an inlet axially spaced apart and upstream from an outlet. Inner and outer bodies have offset inner and outer axes extend from the inlet to the outlet through first, second, and third sections of a core assembly in serial downstream flow relationship. At least one of the bodies is rotatable about its axis. The inner and outer bodies have intermeshed inner and outer helical blades wound about the inner and outer axes respectively. The inner and outer helical blades extend radially outwardly and inwardly respectively. The helical blades have first, second, and third twist slopes in the first, second, and third sections respectively. The first twist slopes are less than the second twist slopes and the third twist slopes are less than the second twist slopes. A combustor section extends axially downstream through at least a portion of the second section.

  4. Relativistic Lagrangian displacement field and tensor perturbations

    CERN Document Server

    Rampf, Cornelius


    We investigate the purely spatial Lagrangian coordinate transformation from the Lagrangian to the fundamental Eulerian frame. We demonstrate three techniques for extracting the relativistic displacement field from a given solution in the Lagrangian frame. These techniques are (a) from defining a local set of Eulerian coordinates embedded into the Lagrangian frame; (b) from performing a specific gauge transformation; and (c) from a fully non-perturbative approach based on the ADM split. The latter approach shows that this decomposition is not tied to a specific perturbative formulation for the solution of the Einstein equations. Rather, it can be defined at the level of the non-perturbative coordinate change from the Lagrangian to the Eulerian description. Studying such different techniques is useful because it allows us to compare and develop further the various approximation techniques available in the Lagrangian formulation. We find that one has to solve for gravitational waves in the relativistic analysis,...

  5. Dynamics of liquid-liquid displacement. (United States)

    Fetzer, Renate; Ramiasa, Melanie; Ralston, John


    Capillary driven liquid-liquid displacement in a system with two immiscible liquids of comparable viscosity was investigated by means of optical high speed video microscopy. For the first time, the impact of substrate wettability on contact line dynamics in liquid-liquid systems was studied. On all substrates, qualitatively different dynamics, in two distinct velocity regimes, were found. Hydrodynamic models apply to the fast stage of initial spreading, while nonhydrodynamic dissipation dominates contact line motion in a final stage at low speed, where the molecular kinetic theory (MKT) successfully captured the dynamics. The MKT model parameter values showed no systematic dependence on substrate wettability. This unexpected result is interpreted in terms of local contact line pinning.

  6. Displaced fracture through the anterior atlantal synchondrosis

    Energy Technology Data Exchange (ETDEWEB)

    Thakar, Chrishan; Allibone, James [Royal National Orthopaedic Hospital NHS Trust, Department of Spinal Deformity, Stanmore, Middlesex (United Kingdom); Harish, Srinivasan [Royal National Orthopaedic Hospital NHS Trust, Department of Radiology, Stanmore, Middlesex (United Kingdom); Saifuddin, Asif [Royal National Orthopaedic Hospital NHS Trust, Department of Radiology, Stanmore, Middlesex (United Kingdom); University College, The Institute of Orthopaedics and Musculoskeletal Sciences, London (United Kingdom)


    In the acute setting, accurate radiological interpretation of paediatric cervical spine trauma can be difficult due to a combination of normal variants and presence of multiple synchondroses. We present a rare case of a fracture through the anterior atlantal synchondrosis in a paediatric spine. A five-year-old boy, who fell backwards onto the top of his head while swinging across on a monkey bar frame, presented with neck pain, cervical muscle spasm and decreased right lateral rotation and extension of his neck. Computed tomography showed a displaced diastatic fracture through right anterior atlantal synchondrosis. There are only 12 cases of paediatric C1 fractures reported in the world literature. The importance of considering this diagnosis in the appropriate clinical setting, and the normal variants in the paediatric atlas that can cause diagnostic dilemma to the interpreting radiologist, are discussed in this case report. (orig.)

  7. Superconducting inductive displacement detection of a microcantilever

    Energy Technology Data Exchange (ETDEWEB)

    Vinante, A., E-mail: [Istituto di Fotonica e Nanotecnologie, CNR - Fondazione Bruno Kessler, I-38123 Povo, Trento (Italy)


    We demonstrate a superconducting inductive technique to measure the displacement of a micromechanical resonator. In our scheme, a type I superconducting microsphere is attached to the free end of a microcantilever and approached to the loop of a dc Superconducting Quantum Interference Device (SQUID) microsusceptometer. A local magnetic field as low as 100 μT, generated by a field coil concentric to the SQUID, enables detection of the cantilever thermomechanical noise at 4.2 K. The magnetomechanical coupling and the magnetic spring are in good agreement with image method calculations assuming pure Meissner effect. These measurements are relevant to recent proposals of quantum magnetomechanics experiments based on levitating superconducting microparticles.

  8. Can Monkeys (Macaca mulatta) Represent Invisible Displacement? (United States)

    Filion, Christine M.; Washburn, David A.; Gulledge, Jonathan P.


    Four experiments were conducted to assess whether or not rhesus macaques (Macaca mulatta) could represent the unperceived movements of a stimulus. Subjects were tested on 2 computerized tasks, HOLE (monkeys) and LASER (humans and monkeys), in which subjects needed to chase or shoot at, respectively, a moving target that either remained visible or became invisible for a portion of its path of movement. Response patterns were analyzed and compared between target-visible and target-invisible conditions. Results of Experiments 1, 2, and 3 demonstrated that the monkeys are capable of extrapolating movement. That this extrapolation involved internal representation of the target's invisible movement was suggested but not confirmed. Experiment 4, however, demonstrated that the monkeys are capable of representing the invisible displacements of a stimulus.

  9. Anisotropic permeability in deterministic lateral displacement arrays

    CERN Document Server

    Vernekar, Rohan; Loutherback, Kevin; Morton, Keith; Inglis, David


    We investigate anisotropic permeability of microfluidic deterministic lateral displacement (DLD) arrays. A DLD array can achieve high-resolution bimodal size-based separation of micro-particles, including bioparticles such as cells. Correct operation requires that the fluid flow remains at a fixed angle with respect to the periodic obstacle array. We show via experiments and lattice-Boltzmann simulations that subtle array design features cause anisotropic permeability. The anisotropy, which indicates the array's intrinsic tendency to induce an undesired lateral pressure gradient, can lead to off-axis flows and therefore local changes in the critical separation size. Thus, particle trajectories can become unpredictable and the device useless for the desired separation duty. We show that for circular posts the rotated-square layout, unlike the parallelogram layout, does not suffer from anisotropy and is the preferred geometry. Furthermore, anisotropy becomes severe for arrays with unequal axial and lateral gaps...

  10. Has multivessel angioplasty displaced surgical revascularization? (United States)

    King, S B; Ivanhoe, R J


    Over the years, PTCA has been proved a safe and effective therapy for single-vessel CAD. Given the record of favorable results for single-vessel angioplasty, the extension of angioplasty to multivessel CAD soon followed. The successful application of PTCA to multivessel disease has been facilitated by developments in balloon, guidewire, and guide catheter technology. Success rates have been satisfactory, and complications have remained acceptable. Furthermore, as an outgrowth of an understanding of the mechanism and effect of PTCA, guidelines have been developed to aid case selection. As emphasized earlier, these guidelines should weigh heavily in deciding whether to select PTCA as a treatment modality. Presently, in our opinion, PTCA has not yet completely displaced surgery for multivessel CAD. Surgical standby is required for safe PTCA, because emergency surgery can be lifesaving and limit myocardial infarction after failed angioplasty. It is doubtful that surgery will ever relinquish its position as the treatment of choice for left main coronary artery disease. Nor will elective surgery find wide application in single-vessel disease. Whether one mode of revascularization will emerge as the most efficacious for multivessel disease related to long-term survival, limitation of cardiac events, and cost will be addressed in the analysis of the ongoing randomized trials of surgery versus angioplasty. Andreas Gruentzig established that it was possible to work within the coronary artery in an alert and comfortable patient. Interventional cardiology has experienced rapid technologic growth. Many patients formerly treated with bypass surgery can be managed effectively with angioplasty. If effective bail-out methods for acute closure are proven effective and restenosis is limited to a small percentage of patients, angioplasty in some form will further displace CABG. Until those ultimate goals are achieved, the value of angioplasty compared with bypass surgery must rest

  11. Fluid trapping during capillary displacement in fractures (United States)

    Yang, Zhibing; Neuweiler, Insa; Méheust, Yves; Fagerlund, Fritjof; Niemi, Auli


    The spatial distribution of fluid phases and the geometry of fluid-fluid interfaces resulting from immiscible displacement in fractures cast decisive influence on a range of macroscopic flow parameters. Most importantly, these are the relative permeabilities of the fluids as well as the macroscopic irreducible saturations. They also influence parameters for component (solute) transport, as it usually occurs through one of the fluid phase only. Here, we present a numerical investigation on the critical role of aperture variation and spatial correlation on fluid trapping and the morphology of fluid phase distributions in a geological fracture. We consider drainage in the capillary dominated regime. The correlation scale, that is, the scale over which the two facing fracture walls are matched, varies among the investigated geometries between L/256 and L (self-affine fields), L being the domain/fracture length. The aperture variability is quantified by the coefficient of variation (δ), ranging among the various geometries from 0.05 to 0.25. We use an invasion percolation based model which has been shown to properly reproduce displacement patterns observed in previous experiments. We present a quantitative analysis of the size distribution of trapped fluid clusters. We show that when the in-plane curvature is considered, the amount of trapped fluid mass first increases with increasing correlation scale Lc and then decreases as Lc further increases from some intermediate scale towards the domain length scale L. The in-plane curvature contributes to smoothening the invasion front and to dampening the entrapment of fluid clusters of a certain size range that depends on the combination of random aperture standard deviation and spatial correlation.

  12. Systematic review of mini-implant displacement under orthodontic loading

    Institute of Scientific and Technical Information of China (English)

    Manuel Nienkemper; Jörg Handschel; Dieter Drescher


    A growing number of studies have reported that mini-implants do not remain in exactly the same position during treatment, although they remain stable. The aim of this review was to collect data regarding primary displacement immediately straight after loading and secondary displacement over time. A systematic review was performed to investigate primary and secondary displacement. The amount and type of displacement were recorded. A total of 27 studies were included. Sixteen in vitro studies or studies using finite element analysis addressed primary displacement, and nine clinical studies and two animal studies addressed secondary displacement. Significant primary displacement was detected (6.4-24.4 mm) for relevant orthodontic forces (0.5-2.5 N). The mean secondary displacement ranged from 0 to 2.7 mm for entire mini-implants. The maximum values for each clinical study ranged from 1.0 to 4.1 mm for the head, 1.0 to 1.5 for the body and 1.0 to 1.92 mm for the tail part. The most frequent type of movement was controlled tipping or bodily movement. Primary displacement did not reach a clinically significant level. However, clinicians can expect relevant secondary displacement in the direction of force. Consequently, decentralized insertion within the inter-radicular space, away from force direction, might be favourable. More evidence is needed to provide quantitative recommendations.

  13. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kostjukov, Viktor V.; Khomytova, Nina M. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine); Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas [Faculty of Chemical Sciences, Autonomous University of Puebla, Puebla (Mexico); Evstigneev, Maxim P., E-mail: [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)


    Graphical abstract: Highlights: > A protocol for decomposition of the free energy of aromatic stacking is developed. > The factors stabilizing/destabilizing stacking of aromatic molecules are defined. > Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  14. Microwave-assisted synthesis of α-hydroxy aromatic ketones from α-bromo aromatic ketones in water

    Institute of Scientific and Technical Information of China (English)

    Xiang Liu; Hai Bo Chen; Zheng Guang Pan; Jian He Xu; He Xing Li


    A reaction of α-bromo aromatic ketones in water with microwave irradiation gave the corresponding α-hydroxy aromatic ketones in good yields.The use of microwaves was found to significantly improve yields and shorten the reaction time.This reaction afforded a very clean,convenient method for the synthesis of α-hydroxy aromatic ketones.

  15. DENSE: Displacement Encoding with Stimulated Echoes in Cardiac Functional MRI (United States)

    Aletras, Anthony H.; Ding, Shujun; Balaban, Robert S.; Wen, Han


    Displacement encoding with stimulated echoes (DENSE) was developed for high-resolution myocardial displacement mapping. Pixel phase is modulated by myocardial displacement and data spatial resolution is limited only by pixel size. 2D displacement vector maps were generated for the systolic action in canines with 0.94 × 1.9 mm nominal in-plane resolution and 2.3 mm/π displacement encoding. A radial strain of 0.208 was measured across the free left ventricular wall over 105 ms during systole. DENSE displacement maps require small first-order gradient moments for encoding. DENSE magnitude images exhibit black-blood contrast which allows for better myocardial definition and reduced motion-related artifacts.

  16. Displacement desorption test of coalbed methane and its mechanism exploring

    Institute of Scientific and Technical Information of China (English)

    ZHANG Suian; HUO Yongzhong; YE Jianping; TANG Shuheng; MA Dongmin


    Through the test of CH4 displaced by CO2 using the coal sample as the adsorbent, this paper has found the coalbed methane (CBM) displacement desorption phenomenon under the natural conditions and CBM mining conditions. With the help of the adsorption theory of the modern physical chemistry and interfacial chemistry, the CBM competitive adsorption and displacement desorption mechanism are intensively discussed, and a new path for studying the CBM desorption mechanism in the CBM exploitation process is explored.

  17. Test Rig Design For Compact Variable Displacement Vane Pump


    Chawla, Pratik; Jenkins, Ryan; Ivantysynova, Monika


    Variable displacement vane pumps (VDVP) are one type of positive displacement pumps used in automatic transmission vehicles for lubricating the gears, cooling the transmission and actuating the clutches. Though fixed displacement pumps are widely used, they output a constant effective flow at a given speed. Depending on pump sizing considerations, the pump can be oversized at high speeds because flow demand of the transmission is independent of engine speed. The excess flow returns to the tan...

  18. Gingival displacement methods used by dental professionals: A survey


    S V Giridhar Reddy; M.Bharathi; B. Vinod; K Rajeev Kumar Reddy; N Simhachalam Reddy


    Aim: The aim of the present study was to identify the methods used by dental professionals for gingival displacement before making impressions for fixed prostheses. Materials and Methods: A printed questionnaire was distributed to over 600 dentists at a National Dental Conference held in Hyderabad. The questionnaire was designed to know the preferred method of gingival displacement, medicament used, frequency of performing gingival displacement, etc. The results were analyzed and represented ...

  19. Solid-phase Synthesis of Combinatorial 2,4-Disubstituted-1,3,5-Triazine via Amine Nucleophilic Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Sung Won [KIST Gangneung Institute, Gangneung (Korea, Republic of); Ham, Jungyeob [Gangneung-Wonju National University, Gangneung (Korea, Republic of); Chang, Young-Tae [National University of Singapore, Singapore (Singapore); Lee, Jae Wook [University of Science and Technology, Daejon (Korea, Republic of)


    In combinatorial chemistry, solid-phase synthesis is a popular approach formass production of small molecules. Compared to solution-phase synthesis, it is easy to prepare and purify a large number of heterocyclic small molecules via solid-phase chemistry; the overall reaction time is decreased as well. 1,3,5-Triazine is a nitrogen-containing heterocyclic aromatic scaffold that was shown to be a druggable scaffold in recent studies. These structures have been reported as anticancer, antimicrobial, and antiretroviral compounds, as CDKs and p38 MAP kinase inhibitors, as estrogen receptor modulators, and as inosine monophosphate dehydrogenase inhibitors. we designed and synthesized disubstituted triazine compounds as an analog of disubstituted pyrimidine compounds. These disubstituted triazine compounds possess a linear structure which may have biological activity similar to that of disubstituted pyrimidine. Here we report the solid-phase synthesis of disubstituted triazine compounds.

  20. Displacement spectra and displacement modification factors, based on records from Greece


    Athanassiadou, C. J.; Karakostas, C. Z.; Margaris, B. N.; Kappos, A. J.


    Elastic and inelastic displacement spectra (for periods up to 4.0 s) are derived, using a representative sample of acceleration records from Greece, carefully selected based on magnitude, distance and peak ground acceleration criteria, and grouped into three ground type categories according to the Eurocode 8 (EC8) provisions. The modification factor for the elastic design spectrum adopted in EC8 for accounting for damping is verified herein and is found to be satisfactory in the short to medi...

  1. Substituted quinolinones. Part 17: Some nucleophilic reactions with 4-hydroxy-1-methyl-3-[(2-oxo-2-chromen-3-yl)carbonyl]quinolin-2(1)-one

    Indian Academy of Sciences (India)

    Mohamed Abass; El-Hussain A Mohamed; Aisha S Mayas; Akram H Ibrahim


    The reactivity of 4-hydroxy-1-methyl-3-[(2-oxo-2-chromen-3-yl)carbonyl]-quinolin-2(1)-one (2), as a new asymmetric diheterocyclic ketone, towards different nucleophilic reagents, was examined. The reaction of the ketone 2 with hydrazine led to pyrazolinone 5, and excess of hydrazine pyrazolinopyrazole 7 was obtained. Treatment of the ketone 2 with 2,2-dimethoxyethanamine gave pyrrolocoumarin 12, while cyanoguanidine afforded pyrimidinone 15. Under PTC conditions, the ketone 2 was reacted with chloroacetonitrile, diethyl malonate, ethyl cyanoacetate, malononitrile, and cyanoacetamide to give coumarinyl furoquinoline 18, pyranoquinolines 20a, 20b, 21, and benzonaphthyridine 22, respectively.

  2. Performance study of magnesium-sulfur battery using a graphene based sulfur composite cathode electrode and a non-nucleophilic Mg electrolyte (United States)

    Vinayan, B. P.; Zhao-Karger, Zhirong; Diemant, Thomas; Chakravadhanula, Venkata Sai Kiran; Schwarzburger, Nele I.; Cambaz, Musa Ali; Behm, R. Jürgen; Kübel, Christian; Fichtner, Maximilian


    Here we report for the first time the development of a Mg rechargeable battery using a graphene-sulfur nanocomposite as the cathode, a Mg-carbon composite as the anode and a non-nucleophilic Mg based complex in tetraglyme solvent as the electrolyte. The graphene-sulfur nanocomposites are prepared through a new pathway by the combination of thermal and chemical precipitation methods. The Mg/S cell delivers a higher reversible capacity (448 mA h g-1), a longer cyclability (236 mA h g-1 at the end of the 50th cycle) and a better rate capability than previously described cells. The dissolution of Mg polysulfides to the anode side was studied by X-ray photoelectron spectroscopy. The use of a graphene-sulfur composite cathode electrode, with the properties of a high surface area, a porous morphology, a very good electronic conductivity and the presence of oxygen functional groups, along with a non-nucleophilic Mg electrolyte gives an improved battery performance.Here we report for the first time the development of a Mg rechargeable battery using a graphene-sulfur nanocomposite as the cathode, a Mg-carbon composite as the anode and a non-nucleophilic Mg based complex in tetraglyme solvent as the electrolyte. The graphene-sulfur nanocomposites are prepared through a new pathway by the combination of thermal and chemical precipitation methods. The Mg/S cell delivers a higher reversible capacity (448 mA h g-1), a longer cyclability (236 mA h g-1 at the end of the 50th cycle) and a better rate capability than previously described cells. The dissolution of Mg polysulfides to the anode side was studied by X-ray photoelectron spectroscopy. The use of a graphene-sulfur composite cathode electrode, with the properties of a high surface area, a porous morphology, a very good electronic conductivity and the presence of oxygen functional groups, along with a non-nucleophilic Mg electrolyte gives an improved battery performance. Electronic supplementary information (ESI) available

  3. Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations (United States)

    Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.


    Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

  4. Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles


    Chu, Crystal K.; Liang, Yufan; Fu, Gregory C.


    A wide array of cross-coupling methods for the formation of C–C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C–heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleophiles to form C–Si bonds. In this study, we address this challenge, establishing that a simple, comm...

  5. Dynamics of the NbCl5-catalyzed cycloaddition of propylene oxide and CO2: Assessing the dual role of the nucleophilic co-catalysts

    KAUST Repository

    D'Elia, Valerio


    A mechanistic study on the synthesis of propylene carbonate (PC) from CO2 and propylene oxide (PO) catalyzed by NbCl5 and organic nucleophiles such as 4-dimethylaminopyridine (DMAP) or tetra-n-butylammonium bromide (NBu4Br) is reported. A combination of in situ spectroscopic techniques and kinetic studies has been used to provide detailed insight into the reaction mechanism, the formation of intermediates, and interactions between the reaction partners. The results of DFT calculations support the experimental observations and allow us to propose a mechanism for this reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Emergence of electrophilic alumination as the counterpart of established nucleophilic lithiation: an academic sojourn in organometallics with William Kaska as fellow traveler. (United States)

    Eisch, John J


    William Kaska pursued doctoral studies with John Eisch in mechanistic organometallic chemistry, first with organolithium reactions at St. Louis University and then at the University of Michigan with organoaluminum reactions. Thereby he revealed the change in mechanism from nucleophilic lithiation and carbolithiation to that of electrophilic alumination, carboalumination and hydroalumination of organic substrates, which reactions were previously observed by Karl Ziegler in his empirical studies of organoaluminum reactions. Our findings were the first mechanistic studies attempting to set such Ziegler chemistry on a modern theoretical basis.

  7. Direct Substitution of the Hydroxy Group at the Allylic/propargylic Position with Carbon-and Heteroatomcentered Nucleophiles Catalyzed by Yb(OTf)3

    Institute of Scientific and Technical Information of China (English)

    HUANG Wen; SHEN Quan-Sheng; WANG Jia-Liang; ZHOU Xi-Geng


    An efficient and highly selective Yb(OTf)3-catalyzed direct substitution of the hydroxy group at the allylic and propargylic positions with a variety of heteroatom- and carbon-centered nucleophiles, such as alcohols, thiols,amines, amides and active methylene compounds has been developed. The advantages of the present catalytic system are wide availability of the starting materials, especially for tolerance to thiols, no need for dried solvents and additives, mild conditions, short time of reaction, simple manipulation and environmentally friendly catalyst that can be recovered and reused at least ten times without significant reduction of activity.

  8. Studying Landslide Displacements in Megamendung (Indonesia Using GPS Survey Method

    Directory of Open Access Journals (Sweden)

    Hasanuddin Z. Abidin


    Full Text Available Landslide is one of prominent geohazards that frequently affects Indonesia, especially in the rainy season. It destroys not only environment and property, but usually also causes deaths. Landslide monitoring is therefore very crucial and should be continuously done. One of the methods that can have a contribution in studying landslide phenomena is repeated GPS survey method. This paper presents and discusses the operational performances, constraints and results of GPS surveys conducted in a well known landslide prone area in West Java (Indonesia, namely Megamendung, the hilly region close to Bogor. Three GPS surveys involving 8 GPS points have been conducted, namely on April 2002, May 2003 and May 2004, respectively. The estimated landslide displacements in the area are relatively quite large in the level of a few dm to a few m. Displacements up to about 2-3 m were detected in the April 2002 to May 2003 period, and up to about 3-4 dm in the May 2003 to May 2004 period. In both periods, landslides in general show the northwest direction of displacements. Displacements vary both spatially and temporally. This study also suggested that in order to conclude the existence of real and significant displacements of GPS points, the GPS estimated displacements should be subjected to three types of testing namely: the congruency test on spatial displacements, testing on the agreement between the horizontal distance changes with the predicted direction of landslide displacement, and testing on the consistency of displacement directions on two consecutive periods.

  9. The Three Gorges: the unexamined toll of development-induced displacement


    Martin Stein


    In China, the context of forced displacement in its broadest sense centres on four issues: (1) coercive displacement for development; (2) political persecution resulting in controlled displacement; (3) massive labour dislocations; and (4) disaster-induced displacement. This article looks at the role of the state in displacement, focusing on the first of these issues: development-induced displacement.

  10. Displacement of the ventricular fold following cordectomy. (United States)

    Fukuda, H; Tsuji, D H; Kawasaki, Y; Kawaida, M; Sakou, T


    In order to avoid radiation and its undesirable side effects, we have employed surgical techniques for treatment of early glottic cancer when the lesion is confined to one membranous cord (Fukuda, Saito, Sato, and Kitahara: J. Jpn. Bronchoesophagol. Soc. 30: 7-14, 1979; Fukuda and Saito: Otologica 26: 434-436, 1980; Fukuda, Kawaida, Ohki, Kawasaki, Kita, and Tatehara: J. Jpn. Bronchoesophagaol. Soc. 39: 139-144, 1988). Laser is one of the most popular techniques and it has been accepted as the first choice by many authors (Annyas, Overbeek, Escajadillo, and Hoeksema: Laryngoscope 94: 836-838, 1984; Mcguirt and Koufman: Arch. Otolaryngol. Head Neck Surg. 113: 501-505, 1987; Tsuji, Fukuda, Kawaskai, Kawaida, and Kanzaki: Keio J. Med. 38: 413-418, 1989). However, some cases are difficult to approach by direct laryngoscopy, requiring an external way to expose the lesion. In these cases, cordectomy by laryngofissure is the method of choice, but the function of the glottis could be improved by replacing the excised cord displacing the ventricular fold. This technique, designed by the authors, was carried out in 22 patients and the results from the viewpoint of phonodynamics, voice quality, and cure rate are discussed in this study. The results are encouraging and we believe that this method is a very reasonable alternative to the laser when such equipment is not available. We also believe that late side effects and oncogenic problems associated with radiation are important points to be considered, especially in patients of relatively younger age.

  11. Motional displacements in proteins incorporating dynamical diversity (United States)

    Vural, Derya; Smith, Jeremy; Glyde, Henry

    The average mean square displacement (MSD), , of hydrogen H in proteins is measured using incoherent neutron scattering methods. The observed MSD shows a marked increase in magnitude at a temperature TD ~= 240 K. This is widely interpreted as a dynamical transition to large MSDs which make function possible in proteins. However, when the data is interpreted in terms of a single averaged MSD, the extracted depends on the neutron momentum transfer, ℏQ , used in the measurement. We have shown recently that this apparent dependence on Q arises because the dynamical diversity of the H in the protein is neglected[2]. We present models of the dynamical diversity of H in Lysosyme that when used in the analysis of simulated neutron data lead to consistent, Q independent values for the average MSD and for the diversity model.2. D. Vural and L. Hong, J. C. Smith and H. R. Glyde. Phys. Rev. E 91, 052705 (2015). Supported in part by Office of Basic Energy Sciences, USDOE, ER46680.

  12. Aromatic characterization of pot distilled kiwi spirits. (United States)

    López-Vázquez, Cristina; García-Llobodanin, Laura; Pérez-Correa, José Ricardo; López, Francisco; Blanco, Pilar; Orriols, Ignacio


    This study contributes fundamental knowledge that will help to develop a distillate of kiwi wine, made from kiwis of the Hayward variety grown in the southwest of Galicia (Spain). Two yeast strains, L1 (Saccharomyces cerevisiae ALB-6 from the EVEGA yeast collection) and L2 (S. cerevisiae Uvaferm BDX from Lallemand) were assessed to obtain a highly aromatic distillate. The kiwi spirits obtained were compared with other fruit spirits, in terms of higher alcohols, minor alcohols, monoterpenols, and other minor compounds, which are relevant in determining the quality and taste of the kiwi spirits. It was found that the kiwi juice fermented with yeast L1 produced a more aromatic distillate. In addition, kiwi distillates produced with both yeasts had the same ratio of trans-3-hexen-1-ol and cis-3-hexen-1-ol, which is lower than that found in other fruit distillates.

  13. Polyimides derived from non-aromatic monomers

    Energy Technology Data Exchange (ETDEWEB)

    Volksen, W.; Sanchez, M.I.; Cha, Hyuk-Jin; Yoon, D.Y. [IBM Almaden Research Center, San Jose, CA (United States)


    In recent years the shift in emphasis on high performance polymers, such as polyimides for microelectronic applications, has led to the search for other potential applications utilizing the unique properties of this class of polymers. In this context, polyimides incorporating non-aromatic units in the polymer backbone have been shown to exhibit excellent optical properties as well as significantly lower refractive indices. This lowering in the refractive index, of course, is also reflected in a lower dielectric constant of the material. For this reason, we have initiated a study of new polyimides, in which the traditional aromatic character is diluted with cycloaliphatic structures. One such example is the polyimide derived from hexafluoroisopropylidene diphthalic anhydride (6FDA) and 1,4-diaminocyclohexane (DACH). Preliminary data with respect to the preparation and solution behavior of the polyimide precursor as well as the characterization of relevant physical properties of the final polyimide will be presented.

  14. Side Chain Cyclized Aromatic Amino Acids

    DEFF Research Database (Denmark)

    Van der Poorten, Olivier; Knuhtsen, Astrid; Sejer Pedersen, Daniel


    Constraining the conformation of flexible peptides is a proven strategy to increase potency, selectivity, and metabolic stability. The focus has mostly been on constraining the backbone dihedral angles; however, the correct orientation of the amino acid side chains (χ-space) that constitute...... the peptide pharmacophore is equally important. Control of χ-space utilizes conformationally constrained amino acids that favor, disfavor, or exclude the gauche (-), the gauche (+), or the trans conformation. In this review we focus on cyclic aromatic amino acids in which the side chain is connected...... to the peptide backbone to provide control of χ(1)- and χ(2)-space. The manifold applications for cyclized analogues of the aromatic amino acids Phe, Tyr, Trp, and His within peptide medicinal chemistry are showcased herein with examples of enzyme inhibitors and ligands for G protein-coupled receptors....

  15. Aromatic compounds from three Brazilian Lauraceae species

    Energy Technology Data Exchange (ETDEWEB)

    Batista, Andrea Nastri de Luca; Batista Junior, Joao Marcos; Lopez, Silvia Noeli; Furlan, Maysa; Cavalheiro, Alberto Jose; Silva, Dulce Helena Siqueira; Bolzani, Vanderlan da Silva [UNESP, Araraquara, SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Nunomura, Sergio Massayoshi [Instituto Nacional de Pesquisa da Amazonia (INPA), Manaus, AM (Brazil). Dept. de Produtos Naturais; Yoshida, Massayoshi [Centro de Biotecnologia da Amazonia, Manaus, AM (Brazil)


    Phytochemical investigations on three Brazilian Lauraceae species from the Cerrado region of Sao Paulo State, Ocotea corymbosa (Meins) Mez., O. elegans Mez. and Persea pyrifolia Nees and Mart. ex Nees resulted in the isolation of flavonoids, an ester of the 4-O-E-caffeoylquinic acid, an aromatic sesquiterpene besides furofuran lignans. This is the first chemical study on the leaves of Ocotea elegans and O. corymbosa as well as the first report of non-volatile compounds from Persea pyrifolia. (author)

  16. Allylation of Aromatic Aldehyde under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu-Mei; JIA,Xue-Feng; WANG,Jin-Xian


    @@ Allylation of carbonyl compounds is one of the most interesting processes for the preparation of homoallylic alcohols. Over the past few decades, many reagents have been developed for such reactions[1~3]. In this paper, we first report allylic zinc reagent 1, which can be prepared from zinc dust and allyl bromide conveniently in THF, and reacted with aromatic aldehyde to give homo-allylic alcohols under microwave irradiation.

  17. Facile Synthesis of New Aromatic Polyamides Based on 1,2-Dihydro-2-(4-carboxylphenyl)-4-[4-(4-carboxyl- phenoxy)-3-methylphenyl]phthalazin-1-one

    Institute of Scientific and Technical Information of China (English)

    程琳; 应磊; 杨小玲; 蹇锡高


    A new monomer diacid, 1,2-dihydro-2-(4-carboxylphenyl)-4-[4-(4-carboxylphenoxy)-3-methylphenyl]phtha-lazin-1-one (3), was synthesized through the aromatic nucleophilic substitution reaction of a readily available unsymmetrical phthalazinone 1 bisphenol-like with p-chlorobenzonitrile in the presence of potassium carbonate in N,N-dimethylacetamide and alkaline hydrolysis. The diacid could be directly polymerized with various aromatic diamines 4a-4e using triphenyl phosphite and pyridine as condensing agents to give five new aromatic poly(ether amide)s 5a-5e containing the kink non-coplanar heterocyclic units with inherent viscosities of 1.30-1.54 dL/g.The polymers were readily soluble in a variety of solvents such as N,N-dimethylformamide (DMF), N,N-dimethyl-acetamide (DMA), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), and even in m-cresol and pyridine (Py). The transparent, flexible and tough films could be formed by solution casting. The glass transition tem-peratures Tg were in the range of 286-317℃.

  18. Aromatics Oxidation and Soot Formation in Flames

    Energy Technology Data Exchange (ETDEWEB)

    Howard, J. B.; Richter, H.


    This project is concerned with the kinetics and mechanisms of aromatics oxidation and the growth process to polycyclic aromatic hydrocarbons (PAH) of increasing size, soot and fullerenes formation in flames. The overall objective of the experimental aromatics oxidation work is to extend the set of available data by measuring concentration profiles for decomposition intermediates such as phenyl, cyclopentadienyl, phenoxy or indenyl radicals which could not be measured with molecular-beam mass spectrometry to permit further refinement and testing of benzene oxidation mechanisms. The focus includes PAH radicals which are thought to play a major role in the soot formation process while their concentrations are in many cases too low to permit measurement with conventional mass spectrometry. The radical species measurements are used in critical testing and improvement of a kinetic model describing benzene oxidation and PAH growth. Thermodynamic property data of selected species are determined computationally, for instance using density functional theory (DFT). Potential energy surfaces are explored in order to identify additional reaction pathways. The ultimate goal is to understand the conversion of high molecular weight compounds to nascent soot particles, to assess the roles of planar and curved PAH and relationships between soot and fullerenes formation. The specific aims are to characterize both the high molecular weight compounds involved in the nucleation of soot particles and the structure of soot including internal nanoscale features indicative of contributions of planar and/or curved PAH to particle inception.

  19. The organometallic fluorine chemistry of palladium and rhodium: studies toward aromatic fluorination. (United States)

    Grushin, Vladimir V


    analogue of Wilkinson's catalyst [(Ph(3)P)(3)RhF] and P-F bond-forming reactions at Pd(II) are insensitive to phosphine concentration and, because of the small size of fluorine, occur even with bulky phosphine ligands. These observations may guide further efforts toward metal-catalyzed nucleophilic fluorination of haloarenes. We have also developed aryne-mediated and CuF(2)/TMEDA-promoted aromatic fluorination reactions. The formation of fluoroarenes from the corresponding iodo- and bromoarenes in the presence of the CuF(2)/TMEDA system is the first example of a transition metal-mediated fluorination of nonactivated aryl halides in the liquid phase. Progress has also been made toward the development of aromatic trifluoromethylation. We have found unexpectedly facile and clean benzotrifluoride formation as a result of Ph-CF(3) reductive elimination from [(Xantphos)Pd(Ph)CF(3)]. This observation demonstrates for the first time that the notoriously strong and inert metal-CF(3) bond can be easily cleaved (at 50-80 degrees C) as a result of reductive elimination to produce the desired aryl-trifluoromethyl bond, the only previously missing link of the catalytic loop. Our study of the novel complex [(Ph(3)P)(3)RhCF(3)] has led to a rationale for the long-puzzling strong trans influence (electron donation) of the CF(3) group which, in complete contrast, is known to be an electron acceptor in organic chemistry.

  20. A quantum chemical study of molecular properties and QSPR modeling of oximes, amidoximes and hydroxamic acids with nucleophilic activity against toxic organophosphorus agents (United States)

    Alencar Filho, Edilson B.; Santos, Aline A.; Oliveira, Boaz G.


    The proposal of this work includes the use of quantum chemical methods and cheminformatics strategies in order to understand the structural profile and reactivity of α-nucleophiles compounds such as oximes, amidoximes and hydroxamic acids, related to hydrolysis rate of organophosphates. Theoretical conformational study of 41 compounds were carried out through the PM3 semiempirical Hamiltonian, followed by the geometry optimization at the B3LYP/6-31+G(d,p) level of theory, complemented by Polarized Continuum Model (PCM) to simulate the aqueous environment. In line with the experimental hypothesis about hydrolytic power, the strength of the Intramolecular Hydrogen Bonds (IHBs) at light of the Bader's Quantum Theory of Atoms in Molecules (QTAIM) is related to the preferential conformations of α-nucleophiles. A set of E-Dragon descriptors (1,666) were submitted to a variable selection through Ordered Predictor Selection (OPS) algorithm. Five descriptors, including atomic charges obtained from the Natural Bond Orbitals (NBO) protocol jointly with a fragment index associated to the presence/absence of IHBs, provided a Quantitative Structure-Property Relationship (QSPR) model via Multiple Linear Regression (MLR). This model showed good validation parameters (R2 = 0.80, Qloo2 = 0.67 and Qext2 = 0.81) and allowed the identification of significant physicochemical features on the molecular scaffold in order to design compounds potentially more active against organophosphorus poisoning.

  1. Part 1. Approaches to the total synthesis of the diterpene marrubin. Part II. Ligand assisted nucleophilic additions. Part III. Coal processing in a non-dissolving medium

    Energy Technology Data Exchange (ETDEWEB)

    Lipscombe, J.; Charles, W. II


    The total synthesis of the diterpene marrubiin was attempted using methodology previously developed in the Liotta laboratories. Ligand Assisted Nucleophilic Additions (LANA) comprise a new class of synthetic reactions involving the stereoselective addition of some group, usually in an intramolecular conjugate fashion. This group is itself derived from an earlier nucleophilic addition to a carbonyl moiety. Exchange of the original metal of the alkoxide with a second metal (which must be at least divalent) having a transferrable group demands that the stereochemistry of the first addition control the second. The general features of these types of processes are discussed. Initial work with substituted quinones is presented, and some mechanistic rationales are given. A novel method of coal processing at modest temperatures and hydrogen pressures (250-300/sup 0/C, 8.0 MPa) is discussed. Coals reacted with small amounts of tetrahydroquinoline in the presence of fluorocarbons or other non-dissolving media underwent astounding increases in pyridine solubility, a common standard in coal liquefaction studies. Several additives were employed, although only tetrahydroquinoline was found to effectively increase coal solubility. Coals having vastly different individual properties behaved similarly under these conditions. Kinetic and model studies were used in an attempt to clarify the reactions occurring under these novel conditions.

  2. Single Parent or Displaced Homemaker Program Management Guide. (United States)

    Utah State Office of Education, Salt Lake City. Div. of Vocational Education.

    This guide is designed to provide vocational education, single parent/displaced homemaker program directors, and other interested persons with information to help them support, establish, and conduct programs for single parents or displaced homemakers in the nine vocational education planning regions of Utah. It includes definitions and staff…

  3. 24 CFR 886.338 - Displacement, relocation, and acquisition. (United States)


    ... regulations at 49 CFR part 24. A “displaced person” shall be advised of his or her rights under the Fair... persons. A “displaced person” (defined in paragraph (g) of this section) must be provided relocation... the requirements described in 49 CFR part 24, subpart B. (e) Appeals. A person who disagrees with...

  4. The effect of bone displacement operations on facial soft tissues. (United States)

    Habib, Ali; Hisham, Ahmed


    A novel biomechanical model for face soft tissue (skin, mucosa, and muscles) is introduced to investigate the effect of mandible and chin bone displacement on the overall appearance of the patient's face. Nonlinear FE analysis is applied to the model and the results obtained are used to help surgeons to decide the amount of displacement required.

  5. Scaling of interface displacement in a microfluidic comparator

    NARCIS (Netherlands)

    Vanapalli, S.A.; Ende, van den D.; Duits, M.H.G.; Mugele, F.


    The authors quantify both experimentally and theoretically the scaling behavior between interface displacement and excess pressure drop in a microfluidic comparator. Unlike previous studies, the authors measure the interface displacement in the outlet channel of the comparator that yields a unique p

  6. Isothermal Gas assisted displacement of a polystyrene melt

    DEFF Research Database (Denmark)

    Eriksson, Torbjörn Gerhard; Rasmussen, Henrik K.


    Isothermal gas displacements of a polystyrene melt (shaped as circular cylinder with a radius of 2.5mm) placed inside a circular steel annulus were performed. A flow valve ensures a constant flow rate and rotational symmetric flow during the displacement. The experiments show an increase in the s...

  7. 24 CFR 236.1001 - Displacement, relocation, and acquisition. (United States)


    ... reasonable steps to minimize the displacement of persons (households, businesses, nonprofit organizations... temporarily to permit rehabilitation or other work for the assisted project. Such tenants must be provided: (1... shall maintain data on the race, ethnic, gender, and disability status of displaced persons....

  8. Displacement and Force Measurements with Quadrant Photodetector in Optical Tweezers

    Institute of Scientific and Technical Information of China (English)

    郭红莲; 刘春香; 李兆霖; 段建发; 韩学海; 程丙英; 张道中


    A technique of displacement and force measurements with a photodiode quadrant detector in an optical tweezers system is presented. The stiffness of optical trap is calibrated and the leukemia cell membrane tension is measured.The results show that the optical tweezers combined with the quadrant detector is a very useful tool for detecting the displacement and force with a millisecond-order response.

  9. Forced displacement: a development issue with humanitarian elements


    Niels Harild


    Work on conflict-induced forced displacement is at a crucial moment, at a tipping point. Now is the time to consolidate the shift towards full global recognition that the challenge of forced displacement is an integral part of the development agenda too.

  10. Employment protection and the consequences for displaced workers

    DEFF Research Database (Denmark)

    Albæk, Karsten; van Audenrode, Marc; Browning, Martin

    We compare the wage and employment consequences of a job displacement in Belgium and Denmark. These two countries both have generous unemployment insurance schemes but job protection laws vary dramatically between the two. Using comparable data we find that the incidence of displacement...

  11. The use of crosshead displacement in determining fracture parameters

    NARCIS (Netherlands)

    Walters, C.L.; Voormeeren, L.O.; Janssen, M.


    In determining the fracture toughness of a test specimen, standards currently require either locally-measured load-line displacements or clip gage displacements. In order to measure these parameters, secondary sensors generally need to be installed and calibrated, which often comes at a higher cost.

  12. Hyoid Displacement in Post-Treatment Cancer Patients: Preliminary Findings (United States)

    Zu, Yihe; Yang, Zhenyu; Perlman, Adrienne L.


    Purpose: Dysphagia after head and neck cancer treatment is a health care issue; in some cases, the cause of death is not cancer but, rather, the passage of food or liquid into the lungs. Hyoid displacement is known to be important to safe swallowing function. The purpose of this study was to evaluate hyoid displacement after cancer treatment.…

  13. A Reference Optical System of Laser Doppler Longitudinal Displacement Measurement

    Institute of Scientific and Technical Information of China (English)

    张存满; 赵洋; 李达成


    In this paper, a new reference optical system is put forward to achieve longitudinal displacement measurement. An optical grating is used for frequency mixing and getting high SNR signals in the measurement. Conditions and methods for getting Doppler beat signals are presented.The experiments indicate that this optical syetem can be used to measure the longitudinal displacement with high accuracy.

  14. Uniform stability of displacement coupled second-order equations

    Directory of Open Access Journals (Sweden)

    Abdelaziz Soufyane


    Full Text Available We prove that the uniform stability of semigroups associated to displacement coupled dissipator systems is equivalent to the uniform stability of velocity coupled dissipator systems. Using this equivalence, we give sufficient conditions for obtaining uniform stability and exact controllability of displacement coupled dissipator systems.

  15. Simple and economical capacitive displacement system for UHV operation. (United States)

    Chow, R; Tiller, W A


    A parallel plate capacitor was assembled as a displacement transducer for operation in an UHV environment. The capacitive displacement system was linear over a 2.5 mum range with a resolution of 0.051 mum. Components in the electric circuit were common laboratory instruments.

  16. Study on the applicability of the desk displacement ventilation concept

    NARCIS (Netherlands)

    Loomans, Marcel G.L.C.


    This paper summarizes an experimental and numerical study into a ventilation concept that combines displacement ventilation with task conditioning, the so-called desk displacement ventilation (DDV) concept. The study uses steady-state and transient results to discuss the applicability of the DDV con

  17. Displacement Ventilation in a Room with Low-Level Diffusers

    DEFF Research Database (Denmark)

    Nielsen, Peter V.

    Ventilation systems with vertical displacement flow have been used in industrial areas with high thermal loads for many years. Quite resently the vertical displacement flow systems have grown popular as comfort ventilation in rooms with thermal loads e.g. offices....

  18. Displacement, Outplacement, or Inplacement? Options for Business and Industry. (United States)

    Wiltzius, Thomas J.

    This report considers the differences among displacement, outplacement, and inplacement and looks at the risks, benefits, and costs of each. Displacement is defined as the termination of employment with little attention given to corporate or individual needs. Outplacement is defined as the pre-planned management of employee termination, addressing…

  19. Topology synthesis of large-displacement compliant mechanisms

    DEFF Research Database (Denmark)

    Pedersen, Claus B. Wittendorf; Buhl, Thomas; Sigmund, Ole


    This paper describes the use of topology optimization as a synthesis tool for the design of large-displacement compliant mechanisms. An objective function for the synthesis of large-displacement mechanisms is proposed together with a formulation for synthesis of path-generating compliant mechanisms...

  20. Fiber-coupled displacement interferometry without periodic nonlinearity

    NARCIS (Netherlands)

    Ellis, J.D.; Meskers, A.J.H.; Spronck, J.W.; Munnig Schmidt, R.H.


    Displacement interferometry is widely used for accurately characterizing nanometer and subnanometer displacements in many applications. In many modern systems, fiber delivery is desired to limit optical alignment and remove heat sources from the system, but fiber delivery can exacerbate common inter

  1. Forced displacement: a development issue with humanitarian elements

    Directory of Open Access Journals (Sweden)

    Niels Harild


    Full Text Available Work on conflict-induced forced displacement is at a crucial moment, at a tipping point. Now is the time to consolidate the shift towards full global recognition that the challenge of forced displacement is an integral part of the development agenda too.

  2. Displacement ventilation and passive cooling strategies

    Energy Technology Data Exchange (ETDEWEB)

    Carew, P.; Bekker, B. [PJCarew Consulting, Cape Town (South Africa)


    Displacement ventilation (DV) is widely used a passive cooling strategy because it requires less air supply for cooling compared to conventional mixing ventilation (MV). DV introduces air at low level and low velocity, and at high supply air temperature, usually around 18 degrees C. The slightly cooler air runs along the floor of a room until it reaches a heat load. The heat load induces a plume of warmer air that rises due to lower density. This induces stratification in room temperature with the occupied area of the room. The air near the ceiling is continually exhausted to prevent a build up of warm air into the occupied zone. This paper demonstrated the impacts of using DV in comparison to MV on the peak capacity, size and humidity levels associated with various passive cooling strategies, informed by the ASHRAE DV guidelines. A generic office building in Johannesburg, South Africa, was used as a model. The paper illustrated the extent to which DV can be used as a passive cooling strategy in spaces that were previously considered as having too high a heat load when calculated using MV system guidelines. A comparison of DV and MV also highlighted the risk of over-design when conventional MV guidelines are used to design cooling sources for DV applications. The DV was shown to significantly lower the amount of supply air needed to serve a room's heat load when compared to MV at the same temperatures. This reduction in air supply impacts the feasibility of using passive cooling strategies in evaporative cooling, 2-stage evaporative cooling, thermal storage and air to ground heat exchangers. However, passive cooling strategies are unlikely to be widely implemented until design guidelines are created by organizations such as ASHRAE. 8 refs., 2 tabs., 15 figs.

  3. Surgical treatment of displaced acetabular fractures

    Directory of Open Access Journals (Sweden)

    Milenković Saša


    Full Text Available Introduction. Acetabular fractures are severe injuries, generally caused by high-energy trauma, most frequently from traffic accidents or falls from heights. Fractures of the extremities, head injuries, chest, abdomen and pelvic ring injuries are most commonly associated injuries. Objective. The purpose of this study was to evaluate the results of open reduction and internal fixation of acetabular fractures. The open anatomical reduction of the articular surface combined with a rigid internal fixation and early mobilisation have become the standard treatment of these injuries. Methods. We conducted a retrospective analysis of 22 patients of average age 43.13 years. The patients were treated by open reduction and internal fixation at the Orthopaedic Clinic of Niš from 2005-2009. The follow-up was 12 to 60 months, with the average of 21.18 months after surgery. Results. All injured patients were operated on between 4 and 11 days (5.7 days on the average. According to the classification by Judet and Letournel, 15 (68.18% patients had an elementary acetabular fracture, whereas 7 (31.82% patients had associated fracture. A satisfactory postoperative reduction implying less than 2 mm of displacement was achieved in 19 (86.36% patients. The radiological status of the hip joint, determined according to Matta score, was excellent in 15 (68.18% patients, good in 4 (18.18% patients and moderate in 3 (13.63% patients. According to Merle d’Aubigné Scale, the final functional results of the treatment of all operated patients were excellent in 12 (54.54% patients, good in 7 (31.81% patients and moderate in 3 (13.63% patients. Conclusion. Surgical treatment of dislocated acetabular fractures requires an open reduction and a stable internal fixation. Excellent and good results can be expected only if anatomical reduction and stable internal fixation are achieved.

  4. [Vestibularly displaced flap with bone augmentation]. (United States)

    Bakalian, V L


    The aim of this study is to achieve esthetic gingival contours with the help of less traumatic mucogingival surgeries. 9 Patients were operated with horizontal deficiencies in 9 edentulous sites, planned to be restored with fixed partial dentures. In all cases there was lack of keratinized tissues. Temporary bridges were fabricated to all patients. Before surgery the bridges were removed and the abutment teeth were additionally cleaned with ultrasonic device. A horizontal incision was made from lingual (palatal) side between the abutment teeth, which was connected with two vertical releasing incisions to the mucogingival junction from the vestibular side. The horizontal incision was made on a distance 6-10 mm from the crest of the alveolar ridge. A partial thickness flap in the beginning 3-5 mm, then a full thickness flap up to the mucogingival junction, then a partial thickness flap was made. The flap was mobilized and displaced vestibularly. In the apical part the cortical bone was perforated, graft material was put and the flap was sutured. In all 9 cases the horizontal defect was partially or fully eliminated. The width of the keratinized tissues was also augmented in all cases. The postoperative healing was without complications, discomfort and painless. The donor sites also healed without complications. The application of Solcoseryl Dental Adhesive Paste 3 times a day for 7-10 days helped for painless healing of the donor site. The offered method of soft tissue and bone augmentation is effective in the treatment of horizontal defects of edentulous alveolar ridges of not big sizes. It makes possible to achieve esthetic results without traumatizing an additional donor-site.

  5. Displacement of soil pore water by trichloroethylene (United States)

    Wershaw, R. L.; Aiken, G.R.; Imbrigiotta, T.E.; Goldberg, M.C.


    Dense nonaqueous phase liquids (DNAPLS) are important pollutants because of their widespread use as chemical and industrial solvents. An example of the pollution caused by the discharge of DNAPLs is found at the Picatinny Arsenal, New Jersey, where trichloroethylene (TCE) has been discharged directly into the unsaturated zone. This discharge has resulted in the formation of a plume of TCE-contaminated water in the aquifer downgradient of the discharge. A zone of dark-colored groundwater containing a high dissolved organic C content has been found near the point of discharge of the TCE. The colored-water plume extends from the point of discharge at least 30 m (100 feet) downgradient. Fulvic acids isolated from the colored-waters plume, from water from a background well that has not been affected by the discharge of chlorinated solvents, and from soil pore water collected in a lysimeter installed at an uncontaminated site upgradient of the study area have been compared. Nuclear magnetic resonance spectra of the fulvic acids from the colored waters and from the lysimeter are very similar, but are markedly different from the nuclear magnetic resonance spectrum of the fulvic acid from the background well. The three-dimensional fluorescence spectrum and the DOC fractionation profile of the colored groundwater and the soil pore water are very similar to each other, but quite different from those of the background water. It is proposed from these observations that this colored water is soil pore water that has been displaced by a separate DNAPL liquid phase downward to the saturated zone.

  6. Dispersion-corrected density functional theory for aromatic interactions in complex systems. (United States)

    Ehrlich, Stephan; Moellmann, Jonas; Grimme, Stefan


    Aromatic interactions play a key role in many chemical and biological systems. However, even if very simple models are chosen, the systems of interest are often too large to be handled with standard wave function theory (WFT). Although density functional theory (DFT) can easily treat systems of more than 200 atoms, standard semilocal (hybrid) density functional approximations fail to describe the London dispersion energy, a factor that is essential for accurate predictions of inter- and intramolecular noncovalent interactions. Therefore dispersion-corrected DFT provides a unique tool for the investigation and analysis of a wide range of complex aromatic systems. In this Account, we start with an analysis of the noncovalent interactions in simple model dimers of hexafluorobenzene (HFB) and benzene, with a focus on electrostatic and dispersion interactions. The minima for the parallel-displaced dimers of HFB/HFB and HFB/benzene can only be explained when taking into account all contributions to the interaction energy and not by electrostatics alone. By comparison of saturated and aromatic model complexes, we show that increased dispersion coefficients for sp(2)-hybridized carbon atoms play a major role in aromatic stacking. Modern dispersion-corrected DFT yields accurate results (about 5-10% error for the dimerization energy) for the relatively large porphyrin and coronene dimers, systems for which WFT can provide accurate reference data only with huge computational effort. In this example, it is also demonstrated that new nonlocal, density-dependent dispersion corrections and atom pairwise schemes mutually agree with each other. The dispersion energy is also important for the complex inter- and intramolecular interactions that arise in the molecular crystals of aromatic molecules. In studies of hexahelicene, dispersion-corrected DFT yields "the right answer for the right reason". By comparison, standard DFT calculations reproduce intramolecular distances quite

  7. Relationship of polycyclic aromatic sulfur compounds and gold enrichment in the Kupferschiefer from Poland and Germany

    Institute of Scientific and Technical Information of China (English)


    The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Faule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.

  8. Land Restitution and Prevention of Forced Displacement in Colombia

    Directory of Open Access Journals (Sweden)

    Felipe Gómez-Isa


    Full Text Available The armed conflict in Colombia, which has generated over three million internally displaced persons, has dramatic humanitarian consequences and raises serious issues regarding the protection of displaced peoples’ rights. The underlying reasons for the displacement often lie in the dynamics associated with territorial control and land seizures undertaken for strategic, military or purely economic purposes. Domestic and international legal provisions have established the victims’ right to the restitution of their homes and property as the “preferred remedy” in cases of displacement. However, policies dealing with displacement, both those of the Colombian government and of several international institutions, fail to take this sufficiently into account. A comprehensive reparation policy for victims must necessarily entail the reversion of lands, territories and goods seized in Colombia under the pretext of the internal armed conflict.

  9. Displacement of maxillary third molar into the lateral pharyngeal space. (United States)

    Lee, Doksa; Ishii, Syoichiro; Yakushiji, Noboru


    Iatrogenic tooth displacement is a rare complication during extraction of impacted molars, but displacement of a maxillary third molar into the maxillary sinus, infratemporal fossa, buccal space, pterygomandibular space, and lateral pharyngeal space has been reported. Currently, 6 published reports describe third molar displacement into the lateral pharyngeal space, only 1 of which involved the loss of a maxillary third molar into this area, which occurred after an attempted self-extraction by the patient. There have been no reported cases of iatrogenic displacement of the maxillary third molar during an extraction procedure. This article describes the recovery, under general anesthesia, of a maxillary third molar from the lateral pharyngeal space after an iatrogenic displacement.

  10. Performance of ductless personalized ventilation in conjunction with displacement ventilation

    DEFF Research Database (Denmark)

    Dalewski, Mariusz; Melikov, Arsen Krikor; Vesely, Michal


    The performance of ductless personalized ventilation (DPV) in conjunction with displacement ventilation was studied and compared with displacement ventilation alone and mixing ventilation. Thirty subjects were exposed in a climate chamber to environmental conditions representing three levels...... perception of the environment. The subjects could control the position of the DPV supply diffuser and the personalized air flow (air velocity). The use of DPV improved perceived air quality and thermal comfort compared to displacement ventilation alone. At 26 °C and 29 °C the percentage dissatisfied with air...... movement decreased with DPV compared to corresponding conditions with displacement ventilation alone and reached the same level as mixing or displacement ventilation at 23 °C. Subjects were able to control the volume and speed of the personalized air flow in order to avoid eye irritation. However...

  11. Human response to ductless personalized ventilation coupled with displacement ventilation

    DEFF Research Database (Denmark)

    Dalewski, Mariusz; Veselý, Michal; Melikov, Arsen K.


    A human subject experiment was carried out to investigate the extent to which ductless personalized ventilation (DPV) in conjunction with displacement ventilation can improve perceived air quality (PAQ) and thermal comfort at elevated room air temperature in comparison with displacement ventilation...... alone. The experimental conditions comprised displacement ventilation alone (room air temperature of 23 °C, 26 °C, 29 °C) and DPV with displacement ventilation (26 °C, 29 °C), both operating at supply air temperatures 3, 5 or 6K lower than room air temperature, as well as mixing ventilation (23 °C, 3 K......). During one hour exposure participants answered questionnaires regarding PAQ and thermal comfort. PAQ was significantly better with DPV than without DPV at the same background conditions. Thermal comfort improved when DPV was used. Combining DPV with displacement ventilation showed the potential...

  12. Prediction of ground surface displacement caused by grouting

    Institute of Scientific and Technical Information of China (English)

    郭风琪; 刘晓潭; 童无期; 单智


    Ground surface displacement caused by grouting was calculated with stochastic medium theory. Ground surface displacement was assumed to be caused by the cavity expansion of grouting, slurry seepage, and slurry contraction. A prediction method of ground surface displacement was developed. The reliability of the presented method was validated through a comparison between theoretical results and results from engineering practice. Results show that the present method is effective. The effect of parameters on uplift displacement was illustrated under different grouting conditions. Through analysis, it can be known that the ground surface uplift is mainly caused by osmosis of slurry and the primary influence angle of stratum βdetermines the influence range of surface uplift. Besides, the results show that ground surface uplift displacement decreases notably with increasing depth of the grouting cavity but it increases with increasing diffusion radius of grout and increasing grouting pressure.

  13. CVN 68 Class Displacement Concerns; Dealing with the Differences between the Modeled and Actual Displacements (United States)


    It is the second case that is most important for a ship in the water. It has been referred to as a special case of Archimedes ’ Principle , or the...from the bottom of the block to the waterline. Figure 6. Wooden block in water As described above using Archimedes ’ Principle , the weight of the...carrier. Archimedes ’ Law was discussed, as well as how this principle is applied to the displacement of an object in a body of water. The application

  14. Investigation on modes of toxic action to rats based on aliphatic and aromatic compounds and comparison with fish toxicity based on exposure routes. (United States)

    He, Jia; Li, Jin J; Wen, Yang; Tai, Hong W; Yu, Yang; Qin, Wei C; Su, Li M; Zhao, Yuan H


    The modes of toxic action (MOAs) play an important role in the assessment of the ecotoxicity of organic pollutants. However, few studies have been reported on the MOAs in rat toxicity. In this paper, the toxic contributions of functional groups in 1255 aromatic compounds were calculated from regression and were then compared with the toxic contributions in aliphatic compounds. The results show that some functional groups have same toxic contributions both in aromatic and aliphatic compounds, but some have not. To investigate the MOAs in rat toxicity, the distribution of toxic ratio (TR) was examined for well-known baseline and less inert compounds and thresholds of log TR=0.3 and 0.5 were used to classify baseline, less inert and reactive compounds. The results showed that some compounds identified as baseline compounds in fish toxicity were also classified as baseline compounds in rat toxicity. Except for phenols and anilines which were identified as less inert compounds in fish toxicity, aromatic compounds with functional groups such as ether, nitrile, nitrophenol, isocyanatoe and chloro were identified as less inert chemicals in rat toxicity. Reactive compounds identified in fish toxicity exhibit greater toxicity to rats. These compounds can undergo nucleophilic substitution, acylation and Schiff base formation with biological macromolecules. The critical body residues (CBRs) calculated from absorption and bioconcentration show that log 1/CBRs in rat toxicity are not equal to that in fish for some compounds. It suggests that the exposure route can affect the identification of MOAs between these two species for these compounds.

  15. Determining Fault Geometries From Surface Displacements (United States)

    Volkov, D.; Voisin, C.; Ionescu, I. R.


    We introduce a new algorithm for determining the geometry of active parts of faults. This algorithm uses surface measurements of displacement fields and local modeling of the Earth's crust as a half-space elastic medium. The numerical method relies on iterations alternating non-linear steps for recovering the geometry and linear steps for reconstructing slip fields. Our algorithm greatly improves upon past attempts at reconstructing fault profiles. We argue that these past attempts suffered from either the restrictive assumption that the geometry of faults can be derived using only uniformly constant slips or that they relied on arbitrary assumptions on the statistics of the reconstruction error. We test this algorithm on the 2006 Guerrero, Mexico, slow slip event (SSE) and on the 2009 SSE for the same region. These events occurred on a relatively well-known subduction zone, whose geometry was derived from seismicity and gravimetric techniques, see Kostoglodov et al. (Geophys Res Lett 23(23):3385-3388, 1996), Pardo and Suarez (J Geophys Res 100(B7):357-373, 1995), Singh and Pardo (Geophys Res Lett 20(14):1483-1486, 1993), so our results can be compared to known benchmarks. Our derived geometry is found to be consistent with these benchmarks regarding dip and strike angles and the positioning of the North American Trench. In addition, our derived slip distribution is also consistent with previous studies (all done with an assumed fixed geometry), see Larson et al. (Geophys Res Lett 34(13), 2007), Bekaert et al. (J Geophys Res: Solid Earth 120(2):1357-1375, 2015), Radiguet et al. (Geophys J Int 184(2):816-828, 2011, J Geophys Res 2012), Rivet et al. (Geophys Res Lett 38(8), 2011), Vergnolle et al. (J Geophys Res: Solid Earth 115(B8), 2010), Walpersdorf et al. Geophys Res Lett 38(15), 2011), to name a few. We believe that the new computational inverse method introduced in this paper holds great promise for applications to blind inversion cases, where both geometry and

  16. Spectrometric study of α-methylene aromatic araminenone and aminoketone

    Institute of Scientific and Technical Information of China (English)


    Thirteen α-methylene aromatic araminenone and four α-methylene aromatic aminoketones were prepared by modified Mannich reaction. On the basis of isotopic labeling, a plausible way of cleavage was proposed for the formation of the M+- 17 fragment peak in the MS of the α-methylene aromatic araminenone and aminoketones. The characteristic chemical shift of the olefinic protons in 1H NMR is also discussed.

  17. Monobromination of Activated Aromatic Compounds withPolyvinylbenzyltriphenylphosphonium Supported Tribromide

    Institute of Scientific and Technical Information of China (English)

    WU Ming-Hu; YANG Gui-Chun; CHEN Zu-Xing


    Chloromethylated crosslinked co-polyvinylbenzene-divinylber-zene (2% DVB) was treated with triphenylphospbhie and then with sodium bromate and hydrobromic acid to afford red col-ored insoluble polyvinylbenzyltriphenylphosphon supportedtribromide.This reagent could be used as a mild and efficient monobrominating reagent for activated aromatic compounds such as phenols,aromatic,aromatic amines and acety-lanilines with good yields and high para-selectivity.

  18. Wide-range displacement expressions for standard fracture mechanics specimens (United States)

    Kapp, J. A.; Gross, B.; Leger, G. S.


    Wide-range algebraic expressions for the displacement of cracked fracture mechanics specimens are developed. For each specimen two equations are given: one for the displacement as a function of crack length, the other for crack length as a function of displacement. All the specimens that appear in ASTM Test for Plane-Strain Fracture Toughness of Metallic Materials (E 399) are represented in addition to the crack mouth displacement for a pure bending specimen. For the compact tension sample and the disk-shaped compact tension sample, the displacement at the crack mouth and at the load line are both considered. Only the crack mouth displacements for the arc-shaped tension samples are presented. The agreement between the displacements or crack lengths predicted by the various equations and the corresponding numerical data from which they were developed are nominally about 3 percent or better. These expressions should be useful in all types of fracture testing including fracture toughness, K-resistance, and fatigue crack growth.

  19. Development of a Wireless Displacement Measurement System Using Acceleration Responses

    Directory of Open Access Journals (Sweden)

    Billie F. Spencer Jr.


    Full Text Available Displacement measurements are useful information for various engineering applications such as structural health monitoring (SHM, earthquake engineering and system identification. Most existing displacement measurement methods are costly, labor-intensive, and have difficulties particularly when applying to full-scale civil structures because the methods require stationary reference points. Indirect estimation methods converting acceleration to displacement can be a good alternative as acceleration transducers are generally cost-effective, easy to install, and have low noise. However, the application of acceleration-based methods to full-scale civil structures such as long span bridges is challenging due to the need to install cables to connect the sensors to a base station. This article proposes a low-cost wireless displacement measurement system using acceleration. Developed with smart sensors that are low-cost, wireless, and capable of on-board computation, the wireless displacement measurement system has significant potential to impact many applications that need displacement information at multiple locations of a structure. The system implements an FIR-filter type displacement estimation algorithm that can remove low frequency drifts typically caused by numerical integration of discrete acceleration signals. To verify the accuracy and feasibility of the proposed system, laboratory tests are carried out using a shaking table and on a three storey shear building model, experimentally confirming the effectiveness of the proposed system.

  20. Two conceptual models of displacement transfer and examples

    Institute of Scientific and Technical Information of China (English)

    GUAN; Shuwei; WANG; Xin; YANG; Shufeng; HE; Dengfa; ZHAO; W


    This paper presents two conceptual models of displacement transfer, reverse symmetry model and infinitely equal division model, based on the fault-bend folding theory. If the fault shape is held constant in the trend, then the distribution of slip magnitude, geometry of imbricate structures and its axial surface map all display reverse symmetry on the process of displacement transfer, as called reverse symmetry model in this paper. However, if the ramp height of thrust fault decreases gradually along its strike, the displacement is postulated to be equally and infinitely divided to every thrust that is formed subsequently, this kinematic process is described using infinitely equal division model. In both models, displacement transfer is characterized by the regular changes of imbricate thrusting in the trend. Geometric analysis indicates that the displacement transfer grads can be estimated using the tangent of deflective angle of hinterland structures. Displacement transfer is often responsible for the distortion and branching of the surface anticlines, especially in the region where the multi-level detachment structures is developed. We also present some examples from the frontal structures of the Southern Tianshan fold-and-thrust belt, Xinjiang, China. Displacement transfer between deep imbricate thrusts in the middle segment of Qiulitag anticline zone causes the Kuqatawu and Southern Qiulitag deep anticlines left-lateral echelon. The region, where these two deep anticlines overlap, is characterized by duplex structures, and extends about 18 km. The shallow anticline is migrated southward displaying obvious "S" form in this area.

  1. A method to calculate displacement factors using SVM

    Institute of Scientific and Technical Information of China (English)

    Li Peixian; Tan Zhixiang; Yan Lili; Deng Kazhong


    In order to improve the precision of mining subsidence prediction,a mathematical model using Support Vector Machine (SVM) was established to calculate the displacement factor.The study is based on a comprehensive analysis of factors affecting the displacement factor,such as mechanical properties of the cover rock,the ratio of mining depth to seam thickness,dip angle of the coal seam and the thickness of loose layer.Data of 63 typical observation stations were used as a training and testing sample set.A SVM regression model of the displacement factor and the factors affecting it was established with a kernel function,an insensitive loss factor and a properly selected penalty factor.Given an accurate calculation algorithm for testing and analysis,the results show that an SVM regression model can calculate displacement factor precisely and reliable precision can be obtained which meets engineering requirements.The experimental results show that the method to calculation of the displacement factor,based on the SVM method,is feasible.The many factors affecting the displacement factor can be considered with this method.The research provides an efficient and accurate approach for the calculation of displacement in mining subsidence prediction.

  2. Phenylnaphthalenes: sublimation equilibrium, conjugation, and aromatic interactions. (United States)

    Lima, Carlos F R A C; Rocha, Marisa A A; Schröder, Bernd; Gomes, Lígia R; Low, John N; Santos, Luís M N B F


    In this work, the interplay between structure and energetics in some representative phenylnaphthalenes is discussed from an experimental and theoretical perspective. For the compounds studied, the standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were determined by the measurement of the vapor pressures as a function of T, using a Knudsen/quartz crystal effusion apparatus. The standard molar enthalpies of formation in the crystalline state were determined by static bomb combustion calorimetry. From these results, the standard molar enthalpies of formation in the gaseous phase were derived and, altogether with computational chemistry at the B3LYP/6-311++G(d,p) and MP2/cc-pVDZ levels of theory, used to deduce the relative molecular stabilities in various phenylnaphthalenes. X-ray crystallographic structures were obtained for some selected compounds in order to provide structural insights, and relate them to energetics. The thermodynamic quantities for sublimation suggest that molecular symmetry and torsional freedom are major factors affecting entropic differentiation in these molecules, and that cohesive forces are significantly influenced by molecular surface area. The global results obtained support the lack of significant conjugation between aromatic moieties in the α position of naphthalene but indicate the existence of significant electron delocalization when the aromatic groups are in the β position. Evidence for the existence of a quasi T-shaped intramolecular aromatic interaction between the two outer phenyl rings in 1,8-di([1,1'-biphenyl]-4-yl)naphthalene was found, and the enthalpy of this interaction quantified on pure experimental grounds as -(11.9 ± 4.8) kJ·mol(-1), in excellent agreement with the literature CCSD(T) theoretical results for the benzene dimer.

  3. Aromatic plant production on metal contaminated soils

    Energy Technology Data Exchange (ETDEWEB)

    Zheljazkov, Valtcho D. [Mississippi State, Department of Plant and Soil Sciences and North Mississippi Research and Extension Center, 5421 Highway 145 South, Verona, MS 38879 (United States)], E-mail:; Craker, Lyle E.; Xing Baoshan [Department of Plant and Soil Sciences, 12 Stockbridge Hall, University of Massachusetts, Amherst, MA 01003 (United States); Nielsen, Niels E. [Plant Nutrition and Soil Fertility Lab, Department of Agricultural Sciences, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK1871, Copenhagen (Denmark); Wilcox, Andrew [Harper Adams University College, Newport, Shropshire, TF10 8NB (United Kingdom)


    Field and container experiments were conducted to assess the feasibility of growing aromatic crops in metal contaminated areas and the effect of metals on herbage and oil productivity. The field experiments were conducted in the vicinities of the Non-Ferrous Metals Combine (Zn-Cu smelter) near Plovdiv, Bulgaria using coriander, sage, dill, basil, hyssop, lemon balm, and chamomile grown at various distances from the smelter. Herbage essential oil yields of basil, chamomile, dill, and sage were reduced when they were grown closer to the smelter. Metal removal from the site with the harvestable plant parts was as high as 180 g ha{sup -1} for Cd, 660 g ha{sup -1} for Pb, 180 g ha{sup -1} for Cu, 350 g ha{sup -1} for Mn, and 205 g ha{sup -1} for Zn. Sequential extraction of soil demonstrated that metal fractionation was affected by the distance to the smelter. With decreasing distance to the smelter, the transfer factor (TF) for Cu and Zn decreased but increased for Cd, while the bioavailability factor (BF) for Cd, Pb, Cu, Mn, and Zn decreased. Scanning electron microscopy and X-ray microanalyses of contaminated soil verified that most of the Pb, Cd, Mn, Cu, and Zn were in the form of small (< 1 {mu}m) particles, although there were larger particles (1-5 {mu}m) with high concentrations of individual metals. This study demonstrated that high concentrations of heavy metals in soil or growth medium did not result in metal transfer into the essential oil. Of the tested metals, only Cu at high concentrations may reduce oil content. Our results demonstrated that aromatic crops may not have significant phytoremediation potential, but growth of these crops in metal contaminated agricultural soils is a feasible alternative. Aromatic crops can provide economic return and metal-free final product, the essential oil.

  4. Metabolism of aromatic compounds by Caulobacter crescentus

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  5. Aromatics oxidation and soot formation in flames

    Energy Technology Data Exchange (ETDEWEB)

    Howard, J.B.; Pope, C.J.; Shandross, R.A.; Yadav, T. [Massachusetts Institute of Technology, Cambridge (United States)


    This project is concerned with the kinetics and mechanisms of aromatics oxidation and soot and fullerenes formation in flames. The scope includes detailed measurements of profiles of stable and radical species concentrations in low-pressure one-dimensional premixed flames. Intermediate species identifications and mole fractions, fluxes, and net reaction rates calculated from the measured profiles are used to test postulated reaction mechanisms. Particular objectives are to identify and to determine or confirm rate constants for the main benzene oxidation reactions in flames, and to characterize fullerenes and their formation mechanisms and kinetics.

  6. Photoinduced dynamics in protonated aromatic amino acid

    CERN Document Server

    Grégoire, Gilles; Barat, Michel; Fayeton, Jacqueline; Dedonder-Lardeux, Claude; Jouvet, Christophe


    UV photoinduced fragmentation of protonated aromatics amino acids have emerged the last few years, coming from a situation where nothing was known to what we think a good understanding of the optical properties. We will mainly focus this review on the tryptophan case. Three groups have mostly done spectroscopic studies and one has mainly been involved in dynamics studies of the excited states in the femtosecond/picosecond range and also in the fragmentation kinetics from nanosecond to millisecond. All these data, along with high level ab initio calculations, have shed light on the role of the different electronic states of the protonated molecules upon the fragmentation mechanisms.

  7. Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures

    NARCIS (Netherlands)

    Meindersma, G. Wytze; Podt, Anita (J.G.); Haan, de André B.


    The separation of aromatic hydrocarbons (benzene, toluene, ethyl benzene and xylenes) from C4 to C10 aliphatic hydrocarbon mixtures is challenging since these hydrocarbons have boiling points in a close range and several combinations form azeotropes. In this work, we investigated the separation of t

  8. Assessment of metal-assisted nucleophile activation in the hepatitis delta virus ribozyme from molecular simulation and 3D-RISM. (United States)

    Radak, Brian K; Lee, Tai-Sung; Harris, Michael E; York, Darrin M


    The hepatitis delta virus ribozyme is an efficient catalyst of RNA 2'-O-transphosphorylation and has emerged as a key experimental system for identifying and characterizing fundamental features of RNA catalysis. Recent structural and biochemical data have led to a proposed mechanistic model whereby an active site Mg(2+) ion facilitates deprotonation of the O2' nucleophile, and a protonated cytosine residue (C75) acts as an acid to donate a proton to the O5' leaving group as noted in a previous study. This model assumes that the active site Mg(2+) ion forms an inner-sphere coordination with the O2' nucleophile and a nonbridging oxygen of the scissile phosphate. These contacts, however, are not fully resolved in the crystal structure, and biochemical data are not able to unambiguously exclude other mechanistic models. In order to explore the feasibility of this model, we exhaustively mapped the free energy surfaces with different active site ion occupancies via quantum mechanical/molecular mechanical (QM/MM) simulations. We further incorporate a three-dimensional reference interaction site model for the solvated ion atmosphere that allows these calculations to consider not only the rate associated with the chemical steps, but also the probability of observing the system in the presumed active state with the Mg(2+) ion bound. The QM/MM results predict that a pathway involving metal-assisted nucleophile activation is feasible based on the rate-controlling transition state barrier departing from the presumed metal-bound active state. However, QM/MM results for a similar pathway in the absence of Mg(2+) are not consistent with experimental data, suggesting that a structural model in which the crystallographically determined Mg(2+) is simply replaced with Na(+) is likely incorrect. It should be emphasized, however, that these results hinge upon the assumption of the validity of the presumed Mg(2+)-bound starting state, which has not yet been definitively verified

  9. Inhomogeneous phase shifting: an algorithm for nonconstant phase displacements

    Energy Technology Data Exchange (ETDEWEB)

    Tellez-Quinones, Alejandro; Malacara-Doblado, Daniel


    In this work, we have developed a different algorithm than the classical one on phase-shifting interferometry. These algorithms typically use constant or homogeneous phase displacements and they can be quite accurate and insensitive to detuning, taking appropriate weight factors in the formula to recover the wrapped phase. However, these algorithms have not been considered with variable or inhomogeneous displacements. We have generalized these formulas and obtained some expressions for an implementation with variable displacements and ways to get partially insensitive algorithms with respect to these arbitrary error shifts.

  10. Displacement fields denoising and strains extraction by finite element method

    Institute of Scientific and Technical Information of China (English)


    Optical full-field measurement methods are now widely applied in various domains. In general,the displacement fields can be directly obtained from the measurement,however in mechanical analysis strain fields are preferred.To extract strain fields from noisy displacement fields is always a challenging topic.In this study,a finite element method for smoothing displacement fields and calculating strain fields is proposed.An experimental test case on a holed aluminum specimen under tension is applied to vali...

  11. Serial forced displacement in American cities, 1916-2010. (United States)

    Fullilove, Mindy Thompson; Wallace, Rodrick


    Serial forced displacement has been defined as the repetitive, coercive upheaval of groups. In this essay, we examine the history of serial forced displacement in American cities due to federal, state, and local government policies. We propose that serial forced displacement sets up a dynamic process that includes an increase in interpersonal and structural violence, an inability to react in a timely fashion to patterns of threat or opportunity, and a cycle of fragmentation as a result of the first two. We present the history of the policies as they affected one urban neighborhood, Pittsburgh's Hill District. We conclude by examining ways in which this problematic process might be addressed.

  12. Helium vs. Proton Induced Displacement Damage in Electronic Materials (United States)

    Ringo, Sawnese; Barghouty, A. F.


    In this project, the specific effects of displacement damage due to the passage of protons and helium nuclei on some typical electronic materials will be evaluated and contrasted. As the electronic material absorbs the energetic proton and helium momentum, degradation of performance occurs, eventually leading to overall failure. Helium nuclei traveling at the same speed as protons are expected to impart more to the material displacement damage; due to the larger mass, and thus momentum, of helium nuclei compared to protons. Damage due to displacement of atoms in their crystalline structure can change the physical properties and hence performance of the electronic materials.

  13. Perceived Air Quality in a Displacement Ventilated Room

    DEFF Research Database (Denmark)

    Brohus, Henrik; Knudsen, Henrik Nellemose; Nielsen, Peter V.

    In a displacement ventilated room the non-uniform contaminant distribution causes an improved indoor air quality in the occupied zone compared with conventional mixing ventilation. This has been demonstrated in numerous studies by chemical measurements. In this study the air quality...... in a displacement ventilated room was determined directly by asking humans about how they perceived the air quality. A trained sensory panel comprising 12 subjects assessed the perceived air quality immediately after entering a climate chamber. The experiments showed that the perceived air quality...... in the displacement ventilated chamber was substantially better than in the case of mixing ventilation....

  14. Uncovering deformation processes from surface displacements (United States)

    Stramondo, Salvatore


    The aim of this talk is to provide an overview about the most recent outcomes in Earth Sciences, describe the role of satellite remote sensing, together with GPS, ground measurement and further data, for geophysical parameter retrieval in well known case studies where the combined approach dealing with the use of two or more techniques/datasets have demonstrated their effectiveness. The Earth Sciences have today a wide availability of instruments and sensors able to provide scientists with an unprecedented capability to study the physical processes driving earthquakes, volcanic eruptions, landslides, and other dynamic Earth systems. Indeed measurements from satellites allow systematic observation of the Earth surface covering large areas, over a long time period and characterized by growing sample intervals. Interferometric Synthetic Aperture Radar (InSAR) technique has demonstrated its effectiveness to investigate processes responsible for crustal faulting stemming from the detection of surface deformation patterns. Indeed using satellite data along ascending and descending orbits, as well as different incident angles, it is possible in principle to retrieve the full 3D character of the ground motion. To such aim the use of GPS stations providing 3D displacement components is a reliable complementary instrument. Finally, offset tracking techniques and Multiple Aperture Interferometry (MAI) may provide a contribution to the analysis of horizontal and NS deformation vectors. The estimation of geophysical parameters using InSAR has been widely discussed in seismology and volcanology, and also applied to deformation associated with groundwater and other subsurface fluids. These applications often involve the solution of an inverse problem, which means the retrieval of optimal source parameters at depth for volcanoes and earthquakes, from the knowledge of surface deformation from InSAR. In recent years, InSAR measurements combined with traditional seismological and

  15. Multicenter bond index analysis of influence of metal cations on the aromaticity of aromatic amino acids: Phenylalanine and tyrosine (United States)

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


    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.

  16. Self-assembly of aromatic-functionalized amphiphiles: The role and consequences of aromatic-aromatic noncovalent interactions in building supramolecular aggregates and novel assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Whitten, D.G.; Chen, L.; Geiger, H.C.; Perlstein, J.; Song, X. [Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.]|[Univ. of Rochester, NY (United States)


    This feature article presents an overview of a study of several different aromatic-functionalized amphiphiles-fatty acid and phospholipid derivatives. These amphiphiles form organized assemblies when the fatty acids are spread as monolayers at the air-water interface or when the phospholipids are dispersed in aqueous solutions. For a wide range of aromatic chromophores--trans-stilbene derivatives and a series of vinylogues (1,4-diphenyl-1,3-butadiene and 1,6-diphenyl-1,3,5-hexatriene), diphenylacetylenes, and azobenzenes such as phenyl, biphenyl, and terphenyl derivatives and modified stilbenes (styryl thiophenes and styryl naphthalenes)--assembly formation is accompanied by formation of aggregates of the aromatic groups. Results of experimental studies and simulations indicate that in many cases the aromatics form a small, stable unit aggregate characterized by strong noncovalent edge-to-face interactions among adjacent aromatics. Although the unit aggregates exhibit characteristic spectral shifts and strong induced circular dichroism indicating a chiral pinwheel aggregate structure, they may be packed together in pure films or dispersions to form an extended glide or herringbone structure. Although the pinwheel unit aggregate and the extended glide or herringbone structure. Although the pinwheel unit aggregate and the extended glide structure is favored for the majority of aromatics studied, for certain aromatics (styrenes, styrylthiophenes, and {alpha}-styrylnaphthalenes) a translation layer, characterized by face-to-face noncovalent interactions, is preferred. The glide or herringbone aggregates are readily distinguished from the translation aggregates by different spectral signatures and different photochemical and photophysical behavior. Factors controlling the type of aggregate and hence extended structure formed from different aromatic functionalized aromatics include shape and steric factors and strength of the competing noncovalent edge-face and face

  17. Initial microbial degradation of polycyclic aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    Milić Jelena


    Full Text Available The group of polycyclic aromatic hydrocarbons (PAHs are very hazardous environmental pollutants because of their mutagenic, carcinogenic and toxic effects on living systems. The aim of this study was to examine and compare the ability and efficiency of selected bacterial isolates obtained from oil-contaminated areas to biodegrade PAHs. The potential of the bacteria to biodegrade various aromatic hydrocarbons was assessed using the 2,6-dichlorophenol-indophenol assay. Further biodegradation of PAHs was monitored by gravimetric and gas-chromatographic analysis. Among the eight bacterial isolates, identified on the basis of 16S rDNA sequences, two isolates, Planomicrobium sp. RNP01 and Rhodococcus sp. RNP05, had the ability to grow on and utilize almost all examined hydrocarbons. Those isolates were further examined for biodegradation of phenanthrene and pyrene, as single substrates, and as a mixture, in vitro for ten days. After three days, both isolates degraded a significant amount phenanthrene, which has a simpler chemical structure than pyrene. Planomicrobium sp.RNP01 commenced biodegradation of pyrene in the PAH mixture only after it had almost completly degraded phenanthrene. The isolated and characterized bacteria, Planomicrobium sp. RNP01 and Rhodococcus sp. RNP05, have shown high bioremediation potential and are likely candidates to be used for degradation of highly toxic PAHs in contaminated areas. [Projekat Ministarstva nauke Republike Srbije, br. III43004

  18. Enzyme catalytic nitration of aromatic compounds. (United States)

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


    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.

  19. An Aromatic Inventory of the Local Volume

    CERN Document Server

    Marble, A R; van Zee, L; Dale, D A; Smith, J D T; Gordon, K D; Wu, Y; Lee, J C; Kennicutt, R C; Skillman, E D; Johnson, L C; Block, M; Calzetti, D; Cohen, S A; Lee, H; Schuster, M D


    Using infrared photometry from the Spitzer Space Telescope, we perform the first inventory of aromatic feature emission (AFE, but also commonly referred to as PAH emission) for a statistically complete sample of star-forming galaxies in the local volume. The photometric methodology involved is calibrated and demonstrated to recover the aromatic fraction of the IRAC 8 micron flux with a standard deviation of 6% for a training set of 40 SINGS galaxies (ranging from stellar to dust dominated) with both suitable mid-infrared Spitzer IRS spectra and equivalent photometry. A potential factor of two improvement could be realized with suitable 5.5 and 10 micron photometry, such as what may be provided in the future by JWST. The resulting technique is then applied to mid-infrared photometry for the 258 galaxies from the Local Volume Legacy (LVL) survey, a large sample dominated in number by low-luminosity dwarf galaxies for which obtaining comparable mid-infrared spectroscopy is not feasible. We find the total LVL lum...

  20. Catalytic C-H imidation of aromatic cores of functional molecules: ligand-accelerated Cu catalysis and application to materials- and biology-oriented aromatics. (United States)

    Kawakami, Takahiro; Murakami, Kei; Itami, Kenichiro


    Versatile imidation of aromatic C-H bonds was accomplished. In the presence of copper bromide and 6,6'-dimethyl-2,2'-bipyridyl, a range of aromatics, such as polycyclic aromatic hydrocarbons, aromatic bowls, porphyrins, heteroaromatics, and natural products, can be imidated by N-fluorobenzenesulfonimide. A dramatic ligand-accelerated copper catalysis and an interesting kinetic profile were uncovered.

  1. Evolution of specialization and ecological character displacement: metabolic plasticity matters.

    NARCIS (Netherlands)

    Egas, C.J.M.; Reydon, Th.A.C.; Hemerik, L.


    An important question in evolutionary biology, especially with respect to herbivorous arthropods, is the evolution of specialization. In a previous paper, the combined evolutionary dynamics of specialization and ecological character displacement was studied, focusing on the role of herbivore foragin

  2. The displaced claiming their rights in fragile states

    Directory of Open Access Journals (Sweden)

    Antonia Mulvey


    Full Text Available To date, displaced persons in fragile and conflict-affected stateshave had little success in claiming their rights for housing, land andproperty violations. Creative legal thinking and strategic litigation has the potential to change this.

  3. Measurement of local relative displacements in large structures

    DEFF Research Database (Denmark)

    Tesauro, Angelo; Eder, Martin Alexander; Nielsen, Magda


    This paper presents a novel measurement technique to measure local relative displacements between parts of large-scale structures. The measured deformations can be of significant importance for fracture analyses in many different types of structures in general, and for adhesive connections...... in particular. The measurement of small local relative displacements in structures subjected to large global deformations is complex and hardly feasible with conventional measurement methods. Therefore, a Small Displacement Measurement System (SDMS) has been devised. The SDMS is based on stereo photogrammetry...... and capable of measuring 3D local displacements with a high degree of accuracy. In this article, the technique is used to measure local deformations in the vicinity of the adhesive trailing edge joint of a wind turbine rotor blade. The SDMS results correspond well with another independent measurement method....

  4. Health outcomes of crisis driven urban displacement: A conceptual framework. (United States)

    Deola, Claudio; Patel, Ronak B


    With urbanisation, cities are increasingly home to greater proportions of the world's population. As this transition has significant implications on human health, the epidemiology of diseases among relatively stable urban populations is growing. As humanitarian crises increasingly drive people to urban centers rather than traditional refugee camps, however, rapid and massive urban displacements will increase in frequency. This paper explores the idea that such urban displacements combine epidemiological features of forced migration, slum conditions and humanitarian disaster contexts. This paper highlights the lack of primary data and the consequent paucity of solid epidemiological literature in the aftermath of rapid massive urban displacements. A framework of health outcomes in urban displacement drawing from the above 3 phenomenon is presented and avenues for improved epidemiologic work described.

  5. Zooplankton Displacement Volume in Glacier Bay, Alaska, 2004 (United States)

    U.S. Geological Survey, Department of the Interior — This dataset includes zooplankton displacement volume sampled in Glacier Bay National Park during summer of 2004. Zooplankton were sampled with a multinet with a 0.5...

  6. General mechanism for helium blistering involving displaced atom transport

    Energy Technology Data Exchange (ETDEWEB)

    McDonell, W.R.


    A mechanism developed to account for formation of vertically elongated blisters in high displacement environments produced by /sup 252/Cf alpha particles and fission fragments has been extended to formation of done-shaped blisters in the low displacement environments produced by simple helium ion beams. In this mechanism, transport of displaced atoms to relieve compressive stresses in the helium-implanted layer allows interconnections of small, subsurface bubbles to form the blister cavity. The same transport may cause thickening of the blister caps at low implantation energies. The transition from dome-shaped to vertically elongated blistering occurs between the 300 and 3000 displacements per helium atom produced by simple helium ions and /sup 252/Cf radiations respectively.

  7. Analytical Modeling for the Grating Eddy Current Displacement Sensors

    Directory of Open Access Journals (Sweden)

    Lv Chunfeng


    Full Text Available As a new type of displacement sensor, grating eddy current displacement sensor (GECDS combines traditional eddy current sensors and grating structure in one. The GECDS performs a wide range displacement measurement without precision reduction. This paper proposes an analytical modeling approach for the GECDS. The solution model is established in the Cartesian coordinate system, and the solving domain is limited to finite extents by using the truncated region eigenfunction expansion method. Based on the second order vector potential, expressions for the electromagnetic field as well as coil impedance related to the displacement can be expressed in closed-form. Theoretical results are then confirmed by experiments, which prove the suitability and effectiveness of the analytical modeling approach.

  8. Job displacement and stress-related health outcomes

    DEFF Research Database (Denmark)

    Browning, Martin; Danø, Anne Møller; Heinesen, Eskil


    We investigate whether job loss as the result of displacement causes hospitalization for stress-related diseases which are widely thought to be associated with unemployment. In doing this, we use much better data than any previous investigators. Our data are a random 10% sample of the male...... population of Denmark for the years 1981-1999 with full records on demographics, health and work status for each person, and with a link from every working person to a plant. We use the method of matching on observables to estimate the counter-factual of what would have happened to the health of a particular...... group of displaced workers if they had not in fact been displaced. Our results indicate unequivocally that being displaced in Denmark does not cause hospitalization for stress-related disease. An analysis of the power of our test suggests that even though we are looking for a relatively rare outcome...

  9. Vertical Crustal Displacements Due to Surface Fluid Changes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Shiyu; ZHONG Min


    Using the model data for surface mass changes of the atmosphere, ocean, soil moisture and snow depth, the vertical crustal displacements of 25 ficual stations in China were calculated according to the loading theory. From the spectral analysis of the results, we can see that the periods of displacements are 12 months and the semi-periods are 6 months. The results also show that the maximum seasonal displacements can reach 20 mm and even larger. The covariance analyses and significance tests show that the coefficients of 96 percent of the stations are significant at the 0.1 significance level. The results show that one of the reasons of the vertical crustal displacements is the changing surface fluid loads.

  10. Brake Pedal Displacement Measuring System based on Machine Vision

    Directory of Open Access Journals (Sweden)

    Chang Wang


    Full Text Available Displacement of brake pedal was an important characteristic of driving behavior. This paper proposed a displacement measure algorithm based on machine vision. Image of brake pedal was captured by camera from left side, and images were processed in industry computer. Firstly, average smooth algorithm and wavelet transform algorithm were used to smooth the original image consecutively. Then, edge extracting method which combined Roberts’s operator with wavelet analysis was used to identify the edge of brake pedal. At last, least square method was adopted to recognize the characteristic line of brake pedal’s displacement. The experimental results demonstrated that the proposed method takes the advantages of Roberts’s operator and wavelet transform, it can obtain better measurement result as well as linear displacement sensors

  11. Peace in Colombia and solutions for its displaced people

    Directory of Open Access Journals (Sweden)

    Martin Gottwald


    Full Text Available With the prospect of peace comes the need to find solutions for those displaced during 50 years of fighting. Solutions will not come without comprehensive attention to the factors affecting IDPs and refugees.

  12. Displacement of Building Cluster Using Field Analysis Method

    Institute of Scientific and Technical Information of China (English)

    Al Tinghua


    This paper presents a field based method to deal with the displacement of building cluster,which is driven by the street widening. The compress of street boundary results in the force to push the building moving inside and the force propagation is a decay process. To describe the phenomenon above, the field theory is introduced with the representation model of isoline. On the basis of the skeleton of Delaunay triangulation,the displacement field is built in which the propagation force is related to the adjacency degree with respect to the street boundary. The study offers the computation of displacement direction and offset distance for the building displacement. The vector operation is performed on the basis of grade and other field concepts.

  13. Health outcomes of crisis driven urban displacement: A conceptual framework (United States)

    Deola, Claudio; Patel, Ronak B


    With urbanisation, cities are increasingly home to greater proportions of the world's population. As this transition has significant implications on human health, the epidemiology of diseases among relatively stable urban populations is growing. As humanitarian crises increasingly drive people to urban centers rather than traditional refugee camps, however, rapid and massive urban displacements will increase in frequency. This paper explores the idea that such urban displacements combine epidemiological features of forced migration, slum conditions and humanitarian disaster contexts. This paper highlights the lack of primary data and the consequent paucity of solid epidemiological literature in the aftermath of rapid massive urban displacements. A framework of health outcomes in urban displacement drawing from the above 3 phenomenon is presented and avenues for improved epidemiologic work described. PMID:28229003

  14. Analysis of variance of an underdetermined geodetic displacement problem

    Energy Technology Data Exchange (ETDEWEB)

    Darby, D.


    It has been suggested recently that point displacements in a free geodetic network traversing a strike-slip fault may be estimated from repeated surveys by minimizing only those displacement components normal to the strike. It is desirable to justify this procedure. We construct, from estimable quantities, a deformation parameter which is an F-statistic of the type occurring in the analysis of variance of linear models not of full rank. A test of its significance provides the criterion to justify the displacement solution. It is also interesting to study its behaviour as one varies the supposed strike of the fault. Justification of a displacement solution using data from a strike-slip fault is found, but not for data from a rift valley. The technique can be generalized to more complex patterns of deformation such as those expected near the end-zone of a fault in a dislocation model.

  15. Studies on the chemical behavior of 3-(nitroacetyl)-1-ethyl-4-hydroxyquinoline-2(1H)-one towards some electrophilic and nucleophilic reagents

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, Magdy A.; Hassanin, Hany M.; Gabr, Yassin A.; Alnamer, Youssef A., E-mail: [Department of Chemistry, Faculty of Education, Ain Shams University, Cairo (Egypt)


    A variety of heterocyclic systems linked to 1-ethylquinolin-2(1H)-one was prepared from reaction of 3-(nitroacetyl)-1-ethyl-4-hydroxyquinoline-2(1H)-one with some electrophilic and nucleophilic reagents. Besides its cyclization to 5-ethyl-2-(hydroxyimino)-2,3,4,5- tetrahydrofuro[3,2-c]quinoline-3,4-dione, the 3-(nitroacetyl)-1-ethyl-4-hydroxyquinoline-2(1H)- one has been brominated, chlorinated, formylated, acetylated, and condensed with chromone-3- carbonitrile and 2-amino-3-formylchromone. Some new pyrazolo[4,3-c]quinoline, pyrimido[5,4-c] quinoline and quinolino[4,3-b][1,5]benzodiazepine derivatives were also synthesized. (author)

  16. Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant. (United States)

    Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K


    A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1).

  17. A novel approach to modeling unstable EOR displacements. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Peters, E.J.


    Most enhanced oil recovery schemes involve the displacement of a more dense and more viscous oil by a less dense and less viscous fluid in a heterogeneous porous medium. The interaction of heterogeneity with the several competing forces, namely, viscous, capillary, gravitational, and dispersive forces, can conspire to make the displacements unstable and difficult to model and to predict. The objective of this research was to develop a systematic methodology for modeling unstable fluid displacements in heterogeneous media. Flow visualization experiments were conducted using X-ray computed tomography imaging and a video imaging workstation to gain insights into the dynamics of unstable displacements, acquire detailed quantitative experimental image data for calibrating numerical models of unstable displacements, and image and characterize heterogeneities in laboratory cores geostatistically. High-resolution numerical models modified for use on vector-architecture supercomputers were used to replicate the image data. Geostatistical models of reservoir heterogeneity were incorporated in order to study the interaction of hydrodynamic instability and heterogeneity in reservoir displacements. Finally, a systematic methodology for matching the experimental data with the numerical models and scaling the laboratory results to other systems were developed. The result is a new method for predicting the performance of unstable EOR displacements in the field based on small-scale displacements in the laboratory. The methodology is general and can be applied to forecast the performance of most processes that involve fluid flow and transport in porous media. Therefore, this research should be of interest to those involved in forecasting the performance of enhanced oil recovery processes and the spreading of contaminants in heterogeneous aquifers.

  18. Neural processing-type displacement sensor employing multimode waveguide (United States)

    Aisawa, Shigeki; Noguchi, Kazuhiro; Matsumoto, Takao


    A novel neural processing-type displacement sensor, consisting of a multimode waveguide and a neural network, is demonstrated. This sensor detects displacement using changes in the interference output image of the waveguide. The interference image is directly processed by a three-layer perceptron neural network. Environmental change, such as the intensity fluctuation, and change of the temperature can be followed by training the neural network. Experimental results show that the sensor has a resolution of 1 micron.

  19. Urban revitalization and displacement: types, causes, and public policy

    Energy Technology Data Exchange (ETDEWEB)

    Feagin, J.R.


    The policy research report reviews the scholarly and print media literatures on urban revitalization. The extent of revitalization; the incumbent or occupant upgrading; gentrification (displacement of low- and moderate-income households by better-off households); gentrification and displacement from all causes; and the role of powerful actors in revitalization are discussed. Public policy dealing with land use and development in urban areas is discussed. Future research needs are indicated.

  20. Semen Displacement as a Sperm Competition Strategy in Humans

    Directory of Open Access Journals (Sweden)

    Gordon G. Gallup


    Full Text Available We examine some of the implications of the possibility that the human penis may have evolved to compete with sperm from other males by displacing rival semen from the cervical end of the vagina prior to ejaculation. The semen displacement hypothesis integrates considerable information about genital morphology and human reproductive behavior, and can be used to generate a number of interesting predictions.

  1. Measurement of axial injection displacement with trim coil current unbalance (United States)

    Covo, Michel Kireeff


    The Dee probe used for measuring internal radial beam intensity shows large losses inside the radius of 20 cm of the 88 in. cyclotron. The current of the top and bottom innermost trim coil 1 is unbalanced to study effects of the axial injection displacement. A beam profile monitor images the ion beam bunches, turn by turn. The experimental bunch center of mass position is compared with calculations of the magnetic mirror effect displacement and shows good agreement.

  2. MRI anatomy of anteriorly displaced anus: what obstructs defecation?

    Energy Technology Data Exchange (ETDEWEB)

    AbouZeid, Amr Abdelhamid [Ain-Shams University, Department of Pediatric Surgery, Cairo (Egypt); Mohammad, Shaimaa Abdelsattar; Khairy, Khaled Talaat [Ain-Shams University, Department of Radiodiagnosis, Cairo (Egypt)


    Anteriorly displaced anus is an anomaly that is debated with regard to its nomenclature, diagnosis and management. To describe MRI anatomy of the anal canal in children with anteriorly displaced anus and its impact on the process of defecation. We prospectively examined ten children (7 girls, 3 boys; age range 7 months to 8 years, mean 3 years) with anteriorly displaced anus between August 2009 and April 2012. Noncontrast MRI examinations were performed on a 1.5-T magnet. T1- and T2-weighted turbo spin-echo images were acquired in axial, sagittal and coronal planes of the pelvis. The anorectal angle and the relative hiatal distance were measured in mid-sagittal images, and compared with those of a control group using the Mann-Whitney test. In children with anteriorly displaced anus, no anatomical abnormality was depicted at the level of the proximal anal canal. However, the distal anal canal was displaced anteriorly, running out its external muscle cuff, which remained un-displaced at the usual site of the anus. This changes the orientation of the central axis of the anal canal by passing across instead of along the fibers of the longitudinal muscle coat. Children with anteriorly displaced anus had a more obtuse anorectal angle (mean 112.1 ), which was significantly greater than that of the control group (mean 86.2 ). MRI is a valuable tool in studying the anatomy of the anal canal in children with anteriorly displaced anus. The abnormal orientation of the longitudinal muscle across the anal canal can explain the obstructed defecation in these children. Based on this study, it might be of interest to use MRI in studying equivocal cases and children with unexplained constipation. (orig.)

  3. Comprehensive theoretical studies on the gas phase SN2 reactions of anionic nucleophiles toward chloroamine and N-chlorodimethylamine with inversion and retention mechanisms. (United States)

    Ren, Yi; Geng, Song; Wei, Xi-Guang; Wong, Ning-Bew; Li, Wai-Kee


    The anionic S(N)2 reactions at neutral nitrogen, Nu(-) + NR(2)Cl → NR(2)Nu + Cl(-) (R = H, Me; Nu = F, Cl, Br, OH, SH, SeH, NH(2), PH(2), AsH(2)) have been systematically studied computationally at the modified G2(+) level. Two reaction mechanisms, inversion and retention of configuration, have been investigated. The main purposes of this work are to explore the reactivity trend of anions toward NR(2)Cl (R = H, Me), the steric effect on the potential energy surfaces, and the leaving ability of the anion in S(N)2@N reactions. Our calculations indicate that the complexation energies are determined by the gas basicity (GB) of the nucleophile and the electronegativity (EN) of the attacking atom, and the overall reaction barrier in the inversion pathway is basically controlled by the GB value of the nucleophile. The retention pathway in the reactions of NR(2)Cl with Nu(-) (Nu = F, Cl, Br, OH, SH, SeH) is energetically unfavorable due to the barriers being larger than those in the inversion pathway by more than 120 kJ mol(-1). Activation strain model analyses show that a higher deformation energy and a weaker interaction between deformed reactants lead to higher overall barriers in the reactions of NMe(2)Cl than those in the reactions of NH(2)Cl. Our studies on the reverse process of the title reactions suggest that the leaving ability of the anion in the gas phase anionic S(N)2@N reactions is mainly determined by the strength of the N-LG bond, which is related to the negative hyperconjugation inherent in NR(2)Nu (R = H, Me; Nu = HO, HS, HSe, NH(2), PH(2), AsH(2)).

  4. New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+ as a Green Solid Catalyst

    Directory of Open Access Journals (Sweden)

    Lahouaria Medjdoub


    Full Text Available Nucleophilic substitution on hexachlorocyclotriphosphazene (HCCTP with allylamine in order to give hexa(allylaminocyclotriphosphazene (HACTP  is performed for the first time under mild conditions by using diethylether as solvent to replace benzene which is very toxic. The reaction time is reduced to half and also performed at room temperature but especially in the presence of an eco-catalyst called Maghnite-H+. This catalyst has a significant role in the industrial scale. In fact, the use of Maghnite is preferred for its many advantages: a very low purchase price compared to other catalysts, the easy removal of the reaction mixture. Then, Maghnite-H+ is became an excellent catalyst for many chemical reactions. The structure of HACTP synthesized in the presence of Maghnite-H+ to 5% by weight is confirmed by 1H-NMR, 13C-NMR, 31P-NMR (Nuclear magnetic resonance and FTIR (Fourier Transform Infrared spectroscopy. MALDI-TOF (Matrix-Assisted Laser Desorption/Ionisation-time-of-flight mass spectrometry is used to establish the molecular weight of HACTP which is 471 g/mol. DSC (Differential Scanning Calorimetery and TGA (Thermogravimetric Analysis show that HACTP is a crystalline product with a melting point of 88 °C. It is reactive after melting but is degraded from 230 °C. Copyright © 2016 BCREC GROUP. All rights reserved Received: 28th September 2015; Revised: 5th December 2015; Accepted: 4th January 2016 How to Cite: Medjdoub, L., Mohammed, B. (2016. New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+ as a Green Solid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 151-160 (doi:10.9767/bcrec.11.2.541.151-160 Permalink/DOI:

  5. Products Distribution of Meta-Oriented Aromatic Polyamide Needs Improvement

    Institute of Scientific and Technical Information of China (English)

    Sun Maojian


    @@ Capacity holding the second place in the world Metaoriented aromatic polya-mide fiber was first developed by DuPont of the United States. Commercial production began in the late 1960s.Today the world's capacity to produce meta-oriented aromatic polyamide fiber is 28 150t/a, and DuPont holds a 78% market share.

  6. Anaerobic catabolism of aromatic compounds: a genetic and genomic view. (United States)

    Carmona, Manuel; Zamarro, María Teresa; Blázquez, Blas; Durante-Rodríguez, Gonzalo; Juárez, Javier F; Valderrama, J Andrés; Barragán, María J L; García, José Luis; Díaz, Eduardo


    Aromatic compounds belong to one of the most widely distributed classes of organic compounds in nature, and a significant number of xenobiotics belong to this family of compounds. Since many habitats containing large amounts of aromatic compounds are often anoxic, the anaerobic catabolism of aromatic compounds by microorganisms becomes crucial in biogeochemical cycles and in the sustainable development of the biosphere. The mineralization of aromatic compounds by facultative or obligate anaerobic bacteria can be coupled to anaerobic respiration with a variety of electron acceptors as well as to fermentation and anoxygenic photosynthesis. Since the redox potential of the electron-accepting system dictates the degradative strategy, there is wide biochemical diversity among anaerobic aromatic degraders. However, the genetic determinants of all these processes and the mechanisms involved in their regulation are much less studied. This review focuses on the recent findings that standard molecular biology approaches together with new high-throughput technologies (e.g., genome sequencing, transcriptomics, proteomics, and metagenomics) have provided regarding the genetics, regulation, ecophysiology, and evolution of anaerobic aromatic degradation pathways. These studies revealed that the anaerobic catabolism of aromatic compounds is more diverse and widespread than previously thought, and the complex metabolic and stress programs associated with the use of aromatic compounds under anaerobic conditions are starting to be unraveled. Anaerobic biotransformation processes based on unprecedented enzymes and pathways with novel metabolic capabilities, as well as the design of novel regulatory circuits and catabolic networks of great biotechnological potential in synthetic biology, are now feasible to approach.

  7. High atmosphere–ocean exchange of semivolatile aromatic hydrocarbons

    KAUST Repository

    González-Gaya, Belén


    Polycyclic aromatic hydrocarbons, and other semivolatile aromatic-like compounds, are an important and ubiquitous fraction of organic matter in the environment. The occurrence of semivolatile aromatic hydrocarbons is due to anthropogenic sources such as incomplete combustion of fossil fuels or oil spills, and other biogenic sources. However, their global transport, fate and relevance for the carbon cycle have been poorly assessed, especially in terms of fluxes. Here we report a global assessment of the occurrence and atmosphere-ocean fluxes of 64 polycyclic aromatic hydrocarbons analysed in paired atmospheric and seawater samples from the tropical and subtropical Atlantic, Pacific and Indian oceans. The global atmospheric input of polycyclic aromatic hydrocarbons to the global ocean is estimated at 0.09 Tg per month, four times greater than the input from the Deepwater Horizon spill. Moreover, the environmental concentrations of total semivolatile aromatic-like compounds were 10 2 -10 3 times higher than those of the targeted polycyclic aromatic hydrocarbons, with a relevant contribution of an aromatic unresolved complex mixture. These concentrations drive a large global deposition of carbon, estimated at 400 Tg C yr -1, around 15% of the oceanic CO2 uptake. © 2016 Macmillan Publishers Limited.

  8. Bis-perfluoroalkylation of aromatic compounds with sodium perfluoroalkanesulfinates

    Institute of Scientific and Technical Information of China (English)

    LIU, Jin-Tao(刘金涛); LU, He-Jun(吕贺军)


    Bis-perfluoroalkylation of aromatic compounds such as dimethoxybenzenes (2,4,6), anisole (8), pyridine (10) and quinoline (13) was accomplished by reaction with excess sodium perfluoroalkanesulfinates, RFSO2Na (1), in the presence of Mn(OAc)3·2H2O under mild conditions. The reaction provides a facile method for the synthesis of bis-perfluoroalkylated aromatic compounds.

  9. C-Nucleosides Derived from Simple Aromatic Hydrocarbons. (United States)

    Chaudhuri, Narayan C; Ren, Rex X-F; Kool, Eric T


    We describe the synthesis, structure and DNA incorporation of a class of novel aromatic C-deoxynucleosides in which benzenes and larger polycyclic aromatics serve as DNA base analogs. Novel approaches have been developed for glycosidic bond formation and for epimenzation of the anomeric substitutents to β-configuration, and we describe some of the properties of such compounds in DNA.

  10. High atmosphere-ocean exchange of semivolatile aromatic hydrocarbons (United States)

    González-Gaya, Belén; Fernández-Pinos, María-Carmen; Morales, Laura; Méjanelle, Laurence; Abad, Esteban; Piña, Benjamin; Duarte, Carlos M.; Jiménez, Begoña; Dachs, Jordi


    Polycyclic aromatic hydrocarbons, and other semivolatile aromatic-like compounds, are an important and ubiquitous fraction of organic matter in the environment. The occurrence of semivolatile aromatic hydrocarbons is due to anthropogenic sources such as incomplete combustion of fossil fuels or oil spills, and other biogenic sources. However, their global transport, fate and relevance for the carbon cycle have been poorly assessed, especially in terms of fluxes. Here we report a global assessment of the occurrence and atmosphere-ocean fluxes of 64 polycyclic aromatic hydrocarbons analysed in paired atmospheric and seawater samples from the tropical and subtropical Atlantic, Pacific and Indian oceans. The global atmospheric input of polycyclic aromatic hydrocarbons to the global ocean is estimated at 0.09 Tg per month, four times greater than the input from the Deepwater Horizon spill. Moreover, the environmental concentrations of total semivolatile aromatic-like compounds were 102-103 times higher than those of the targeted polycyclic aromatic hydrocarbons, with a relevant contribution of an aromatic unresolved complex mixture. These concentrations drive a large global deposition of carbon, estimated at 400 Tg C yr-1, around 15% of the oceanic CO2 uptake.

  11. Wettability controls slow immiscible displacement through local interfacial instabilities (United States)

    Jung, Michael; Brinkmann, Martin; Seemann, Ralf; Hiller, Thomas; Sanchez de La Lama, Marta; Herminghaus, Stephan


    Immiscible fluid displacement with average front velocities in the capillary-dominated regime is studied in a transparent Hele-Shaw cell with cylindrical posts. Employing various combinations of fluids and wall materials allows us to cover a range of advancing contact angles 46∘≤θa≤180∘ of the invading fluid in our experiments. In parallel, we study the displacement process in particle-based simulations that account for wall wettability. Considering the same arrangement of posts in experiments and simulation, we find a consistent crossover between stable interfacial displacement at θa≲80∘ and capillary fingering at high contact angles θa≳120∘ . The position of the crossover is quantified through the evolution of the interface length and the final saturation of the displaced fluid. A statistical analysis of the local displacement processes demonstrates that the shape evolution of the fluid front is governed by local instabilities as proposed by Cieplak and Robbins for a quasistatic interfacial displacement [Cieplak and Robbins, Phys. Rev. Lett. 60, 2042 (1988), 10.1103/PhysRevLett.60.2042]. The regime of stable front advances coincides with a corresponding region of contact angles where cooperative interfacial instabilities prevail. Capillary fingering, however, is observed only for large θa, where noncooperative instabilities dominate the invasion process.

  12. Dual-frequency laser displacement and angle interferometer (United States)

    Zhao, Shijie; Wei, Haoyun; Li, Yan


    Traditional laser angular interferometers based on a Michelson Interferometer or its modifications have the same principle: changing the angle displacement to an optical path difference. However, measuring the angular error of stage travels is a dynamic process. The main trouble is lack of displacement information and need to be solved urgently. A obvious method is using two dual-frequency interferometers to get the displacement and angular. In this paper, a new kind of displacement and angle interferometer (DIAI) is introduced. In this DIAI, displacement and angular are measured simultaneously by special optical path. The DIAI consists of a stabilized orthogonal polarization dualfrequency laser, a monolithic prism and additional optical and electronic components. The dual-frequency laser is divided into reference light and measurement light by a beam-splitting prism. The measurement light spatially separated into horizontal polarized light and vertical polarized light by the polarization splitting prism. Changing by a fixed 45°- tilted reflector, the vertical polarized light is parallel to the horizontal polarized light. These parallel lights reflected by two corner cube retroreflectors at a moving target. Compared with the reference light, the displacement and angular are measured. Different from the traditional method, there is only one reference corner cube retroreflector in this system. Thus, the angular measurement accuracy is better. The accuracy of the DIAI is better than +/-0.25 arcsec in comparison with an autocollimator.

  13. Technique for Determining Bridge Displacement Response Using MEMS Accelerometers. (United States)

    Sekiya, Hidehiko; Kimura, Kentaro; Miki, Chitoshi


    In bridge maintenance, particularly with regard to fatigue damage in steel bridges, it is important to determine the displacement response of the entire bridge under a live load as well as that of each member. Knowing the displacement response enables the identification of dynamic deformations that can cause stresses and ultimately lead to damage and thus also allows the undertaking of appropriate countermeasures. In theory, the displacement response can be calculated from the double integration of the measured acceleration. However, data measured by an accelerometer include measurement errors caused by the limitations of the analog-to-digital conversion process and sensor noise. These errors distort the double integration results. Furthermore, as bridges in service are constantly vibrating because of passing vehicles, estimating the boundary conditions for the numerical integration is difficult. To address these problems, this paper proposes a method for determining the displacement of a bridge in service from its acceleration based on its free vibration. To verify the effectiveness of the proposed method, field measurements were conducted using nine different accelerometers. Based on the results of these measurements, the proposed method was found to be highly accurate in comparison with the reference displacement obtained using a contact displacement gauge.

  14. Technique for Determining Bridge Displacement Response Using MEMS Accelerometers

    Directory of Open Access Journals (Sweden)

    Hidehiko Sekiya


    Full Text Available In bridge maintenance, particularly with regard to fatigue damage in steel bridges, it is important to determine the displacement response of the entire bridge under a live load as well as that of each member. Knowing the displacement response enables the identification of dynamic deformations that can cause stresses and ultimately lead to damage and thus also allows the undertaking of appropriate countermeasures. In theory, the displacement response can be calculated from the double integration of the measured acceleration. However, data measured by an accelerometer include measurement errors caused by the limitations of the analog-to-digital conversion process and sensor noise. These errors distort the double integration results. Furthermore, as bridges in service are constantly vibrating because of passing vehicles, estimating the boundary conditions for the numerical integration is difficult. To address these problems, this paper proposes a method for determining the displacement of a bridge in service from its acceleration based on its free vibration. To verify the effectiveness of the proposed method, field measurements were conducted using nine different accelerometers. Based on the results of these measurements, the proposed method was found to be highly accurate in comparison with the reference displacement obtained using a contact displacement gauge.

  15. A Wireless Laser Displacement Sensor Node for Structural Health Monitoring

    Directory of Open Access Journals (Sweden)

    Se Woon Choi


    Full Text Available This study describes a wireless laser displacement sensor node that measures displacement as a representative damage index for structural health monitoring (SHM. The proposed measurement system consists of a laser displacement sensor (LDS and a customized wireless sensor node. Wireless communication is enabled by a sensor node that consists of a sensor module, a code division multiple access (CDMA communication module, a processor, and a power module. An LDS with a long measurement distance is chosen to increase field applicability. For a wireless sensor node driven by a battery, we use a power control module with a low-power processor, which facilitates switching between the sleep and active modes, thus maximizing the power consumption efficiency during non-measurement and non-transfer periods. The CDMA mode is also used to overcome the limitation of communication distance, which is a challenge for wireless sensor networks and wireless communication. To evaluate the reliability and field applicability of the proposed wireless displacement measurement system, the system is tested onsite to obtain the required vertical displacement measurements during the construction of mega-trusses and an edge truss, which are the primary structural members in a large-scale irregular building currently under construction. The measurement values confirm the validity of the proposed wireless displacement measurement system and its potential for use in safety evaluations of structural elements.

  16. A wireless laser displacement sensor node for structural health monitoring. (United States)

    Park, Hyo Seon; Kim, Jong Moon; Choi, Se Woon; Kim, Yousok


    This study describes a wireless laser displacement sensor node that measures displacement as a representative damage index for structural health monitoring (SHM). The proposed measurement system consists of a laser displacement sensor (LDS) and a customized wireless sensor node. Wireless communication is enabled by a sensor node that consists of a sensor module, a code division multiple access (CDMA) communication module, a processor, and a power module. An LDS with a long measurement distance is chosen to increase field applicability. For a wireless sensor node driven by a battery, we use a power control module with a low-power processor, which facilitates switching between the sleep and active modes, thus maximizing the power consumption efficiency during non-measurement and non-transfer periods. The CDMA mode is also used to overcome the limitation of communication distance, which is a challenge for wireless sensor networks and wireless communication. To evaluate the reliability and field applicability of the proposed wireless displacement measurement system, the system is tested onsite to obtain the required vertical displacement measurements during the construction of mega-trusses and an edge truss, which are the primary structural members in a large-scale irregular building currently under construction. The measurement values confirm the validity of the proposed wireless displacement measurement system and its potential for use in safety evaluations of structural elements.

  17. Nucleophilic addition to an achiral dehydroalanine Schiff base Ni(II) complex as a route to amino acids. A case of stereodetermining asymmetric protonation in the presence of TADDOL

    NARCIS (Netherlands)

    Belokon, Yuri N.; Harutyunyan, Syuzanna; Vorontsov, Evgeni V.; Peregudov, Alexander S.; Chrustalev, Viktor N.; Kochetkov, Konstantin A.; Pripadchev, Dmitriy; Sagyan, Ashot S.; Beck, Albert K.; Seebach, Dieter


    We describe herein the elaboration of a new type of a substrate based on the Ni(II) complex of a Schiff base of dehydroalanine, 1, and Michael addition of nucleophiles to it, leading to the synthesis of racemic α-amino acids. We have also developed a catalytic method for the asymmetric 1,4 conjugate

  18. Neutral Diboron Analogues of Archetypal Aromatic Species by Spontaneous Cycloaddition. (United States)

    Arrowsmith, Merle; Böhnke, Julian; Braunschweig, Holger; Celik, Mehmet Ali; Claes, Christina; Ewing, William C; Krummenacher, Ivo; Lubitz, Katharina; Schneider, Christoph


    Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition-metal-catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron-boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π-aromatic diborabenzene compound, a 2 π-aromatic triplet biradical 1,3-diborete, and a phosphine-stabilized 2 π-homoaromatic 1,3-dihydro-1,3-diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6 H6 and C4 H4 (2+) , and homoaromatic C4 H5 (+) .

  19. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals

    KAUST Repository

    Zeng, Zebing


    © 2015 The Royal Society of Chemistry. Aromaticity is an important concept to understand the stability and physical properties of π-conjugated molecules. Recent studies on pro-aromatic and anti-aromatic molecules revealed their irresistible tendency to become diradicals in the ground state. Diradical character thus becomes another very important concept and it is fundamentally correlated to the physical (optical, electronic and magnetic) properties and chemical reactivity of most of the organic optoelectronic materials. Molecules with distinctive diradical character show unique properties which are very different from those of traditional closed-shell π-conjugated systems, and thus they have many potential applications in organic electronics, spintronics, non-linear optics and energy storage. This critical review first introduces the fundamental electronic structure of Kekulé diradicals within the concepts of anti-aromaticity and pro-aromaticity in the context of Hückel aromaticity and diradical character. Then recent research studies on various stable/persistent diradicaloids based on pro-aromatic and anti-aromatic compounds are summarized and discussed with regard to their synthetic chemistry, physical properties, structure-property relationships and potential material applications. A summary and personal perspective is given at the end.

  20. Synchronized aromaticity as an enthalpic driving force for the aromatic Cope rearrangement. (United States)

    Babinski, David J; Bao, Xiaoguang; El Arba, Marie; Chen, Bo; Hrovat, David A; Borden, Weston Thatcher; Frantz, Doug E


    We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

  1. Polyenamines from aromatic diacetylenic diketones and diamines (United States)

    Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor); Sinsky, Mark S. (Inventor); Connell, John W. (Inventor)


    The synthesis and characterization of several polyenamine ketones are discussed wherein conjugated diacetylenic diketones and aromatic diamines are used as a route to the formation of high molecular weight polyenamine ketones which exhibit good mechanical properties and can be cast into creasible films. Typical polymerization conditions involved the reaction of stoichiometric amounts of 1,4- or 1,3-PPPO and a diamine at 60 to 130 C in m-cresol at (w/w) solids content of 8 to 26% for a specified period of time under a nitrogen atmosphere. Novel polyenamine ketones were prepared with inherent viscosities as high as 1.99 dl/g and tough, clear amber films with tensile strengths of 12,400 psi and tensile moduli of 397,000 psi were cast from solutions of the polymers in chloroform. In most cases, the elemental analyses for the polyenamine ketones agree within + or - 0.3% of the theoretical values.

  2. Structural Evolution of Interstellar Polycyclic Aromatic Hydrocarbons (United States)

    Hammonds, Mark; Candian, Alessandra; Mori, Tamami; Usui, Fumihiko; Onaka, Takashi


    Polycyclic Aromatic Hydrocarbons (PAHs) are an important reservoir for molecular carbon in the interstellar medium (ISM), and investigations into their chemistry and behaviour may be important to the understanding of how carbon is processed from simple forms into complex prebiotic molecules such as those detected in chondritic meteorites. In this study, infrared astronomical data from AKARI and other observatories are used together with laboratory and theoretical data to study variations in the structure of emitting PAHs in interstellar environments using spectroscopic decomposition techniques and bands arising from carbon-hydrogen bond vibrations at wavelengths from 3 - 14 microns. Results and inferences are discussed in terms of the processing of large carbonaceous molecules in astrophysical environments.

  3. The biodegradation vs. biotransformation of fluorosubstituted aromatics. (United States)

    Kiel, Martina; Engesser, Karl-Heinrich


    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.

  4. Photochemically induced oscillations of aromatic pentazadienes

    Energy Technology Data Exchange (ETDEWEB)

    Kunz, T.; Hahn, C.; Wokaun, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    Aromatic pentazadienes are used to enhance the laser induced ablation of standard polymers with low absorption in the UV. Therefore the photochemistry of substituted 1,5-diaryl-3-alkyl-1,4-pentazadiene monomers was studied with a pulsed excimer laser as irradiation source. The net photochemical reaction proceeds in an overall one-step pathway A{yields}B. Quantum yields for the laser decomposition were determined to be up to 10%. An oscillating behaviour of the absorption was found during the dark period following the irradiation. The temperature dependence of this dark reaction has been studied. An attempt to model this behaviour in terms of a non-linear coupling between heat released, heat transfer, and reaction kinetics will be described. (author) 4 figs., 4 refs.

  5. Environmental Remediation: Removal of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nkansah, Marian Asantewah


    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous persistent semi-volatile organic compounds. They are contaminants that are resistant to degradation and can remain in the environment for long periods due to their high degree of conjugation, and aromaticity. PAHs are present in industrial effluents as products of incomplete combustion processes of organic compounds. Petroleum, coal and shale oil contain extremely complex mixtures of these PAHs, and their transport and refining process can also result in the release of PAHs. It is therefore prudent that such effluents are treated before discharge into the environment. In this project, different approaches to the treatment of PAHs have been investigated. Hydrous pyrolysis has been explored as a potential technique for degrading PAHs in water using anthracene as a model compound. The experiments were performed under different conditions of temperature, substrate, redox systems and durations. The conditions include oxidising systems comprising pure water, hydrogen peroxide and Nafion-SiO2 solid catalyst in water; and reducing systems of formic acid and formic acid / Nafion-SiO2 / Pd-C catalysts to assess a range of reactivities. Products observed in GCMS analysis of the extract from the water phase include anthrone, anthraquinone, xanthone and multiple hydro-anthracene derivatives (Paper I). In addition a modified version of the Nafion-SiO2 solid catalyst in water oxidising system was tested; and reducing systems of formic acid and formic acid / Nafion-SiO2 / Pd-C catalysts were adopted for the conversion of a mixture of anthracene, fluorene and fluoranthene. The rate of conversion in the mixture was high as compared to that of only anthracene (Paper II). Also the use of LECA (Lightweight expanded clay aggregates) as an adsorbent (Paper III) for PAHs (phenanthrene, fluoranthene and pyrene) removal from water has been.(Author)

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

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


    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.

  7. Exploring aromatic chemical space with NEAT: novel and electronically equivalent aromatic template. (United States)

    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


    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.

  8. The future role of aromatics in refining and petrochemistry. Proceedings of the DGMK-Conference (Authors' manuscripts)

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G.; Rupp, M.; Weitkamp, J. [eds.


    Topic of this conference has been the furure role of aromatics in the refinign industry. The articles deal with the following topics: Refining; legal aspects in the aromatics market; transportation fuels; dearomatization; catalytic reforming and aromatics; separation processes for aromatics; oxidation and ammoxidation of aromatics; electrophilic substitution of aromatics; hydrogenation of benzene; zeolites. (orig./sr)

  9. Characteristics of children with hip displacement in cerebral palsy

    Directory of Open Access Journals (Sweden)

    Wagner Philippe


    Full Text Available Abstract Background Hip dislocation in children with cerebral palsy (CP is a common and severe problem. The dislocation can be avoided, by screening and preventive treatment of children with hips at risk. The aim of this study was to analyse the characteristics of children with CP who develop hip displacement, in order to optimise a hip surveillance programme. Methods In a total population of children with CP a standardised clinical and radiological follow-up of the hips was carried out as a part of a hip prevention programme. The present study is based on 212 children followed until 9–16 years of age. Results Of the 212 children, 38 (18% developed displacement with Migration Percentage (MP >40% and further 19 (9% MP between 33 and 39%. Mean age at first registration of hip displacement was 4 years, but some hips showed MP > 40% already at two years of age. The passive range of hip motion at the time of first registration of hip displacement did not differ significantly from the findings in hips without displacement. The risk of hip displacement varied according to CP-subtype, from 0% in children with pure ataxia to 79% in children with spastic tetraplegia. The risk of displacement (MP > 40% was directly related to the level of gross motor function, classified according to the gross motor function classification system, GMFCS, from 0% in children in GMFCS level I to 64% in GMFCS level V. Conclusion Hip displacement in CP often occurs already at 2–3 years of age. Range of motion is a poor indicator of hips at risk. Thus early identification and early radiographic examination of children at risk is of great importance. The risk of hip displacement varies according to both CP-subtype and GMFCS. It is sometimes not possible to determine subtype before 4 years of age, and at present several definitions and classification systems are used. GMFCS is valid and reliable from 2 years of age, and it is internationally accepted. We recommend a hip

  10. Rotation and Displacement Predict Adverse Events in Pediatric Supracondylar Fractures. (United States)

    Flierl, Michael A; Carry, Patrick M; Scott, Frank; Georgopoulos, Gaia; Hadley-Miller, Nancy


    The goal of this study was to identify supracondylar fracture patterns that were predictive of adverse events and poor outcomes. The study consisted of a retrospective review of patients admitted for surgical treatment of a supracondylar humerus fracture between June 2008 and August 2010. Preoperative radiographs were assessed based on appearance (simple vs oblique vs comminuted), coronal plane displacement (angulated, posterior, posteromedial vs posterolateral), and rotation (rotation vs no rotation). Logistic regression models were used to examine the relationship between fracture pattern and clinical outcome parameters in 373 patients who were followed for 4 weeks or more postoperatively. Outcome parameters included postoperative complications (infection, delayed healing, pin migration, revision surgery), need for physical or occupational therapy, need for postoperative intravenous narcotics, and preoperative nerve injury. Rotation and coronal displacement patterns of the fracture segments were significantly associated with postoperative complications, postoperative need for physical or occupational therapy as a result of residual stiffness, and nerve injury (P<.05). Compared with posteriorly displaced fractures, posterolaterally displaced fractures were associated with significantly greater odds of complications (P=.045), need for physical or occupational therapy (P<.001), and nerve injury (P<.001). Additionally, fractures with rotation were associated with significantly greater odds of complications (P<.001), need for physical or occupational therapy (P<.001), and nerve injury (P<.001) compared with fractures without rotation. Rotation and coronal plane displacement were predictive of complications, need for physical or occupational therapy, and nerve injury, and thus should be considered as potential prognostic variables when evaluating the initial injury pattern.

  11. Overhead Transmission Lines Deicing under Different Incentive Displacement

    Directory of Open Access Journals (Sweden)

    Qing He


    Full Text Available Overhead transmission line icing is one of the main factors affecting safety and reliability of power grid. This paper proposed an excitation deicing method of iced wire and theoretically revealed the ice removal mechanism under displacement excitation conditions, by taking the LGJ-70/10 glaze icing wire as the 3D model and analyzing and studying its dynamic response under the effect of displacement excitation. The simulation results show that the stress of wire icing area is enlarged with the increase of excitation displacement and frequency. Through the comparison of the compression strength experimental results on a series of different iced wires in low temperature environment, the authors found out that the stress generated from the wire icing area is greater than the crushing strength of the ice within the scope of the calculation parameters, which proved the validity and the feasibility of the method, and finally the suitable excitation displacement is determined. Following studies show that, as far as possible, it is necessary to reduce the incentive displacement and also to select the appropriate constraint length in order to avoid the line jumping that may be caused by large span ice shedding.

  12. Evaluating the displacement amplification factors of concentrically braced steel frames (United States)

    Mahmoudi, Mussa; Zaree, Mahdi


    According to seismic design codes, nonlinear performance of structures is considered during strong earthquakes. Seismic design provisions estimate the maximum roof and story drifts occurring during major earthquakes by amplifying the drifts computed from elastic analysis at the prescribed seismic force level with a displacement amplification factor. The present study tries to evaluate the displacement amplification factors of conventional concentric braced frames (CBFs) and buckling restrained braced frames (BRBFs). As such, static nonlinear (pushover) analysis and nonlinear dynamic time history analysis have been performed on the model buildings with single and double bracing bays, and different stories and brace configurations (chevron V, invert V, and X bracing). It is observed that the displacement amplification factors for BRBFs are higher than that of CBFs. Also, the number of bracing bays and height of buildings have a profound effect on the displacement amplification factors. The evaluated ratios between displacement amplification factors and response modification factors are from 1 to 1.12 for CBFs and from 1 to 1.4 for BRBFs.

  13. Structure-Activity Relationships in Nitro-Aromatic Compounds (United States)

    Vogt, R. A.; Rahman, S.; Crespo-Hernández, C. E.

    Many nitro-aromatic compounds show mutagenic and carcinogenic properties, posing a potential human health risk. Despite this potential health hazard, nitro-aromatic compounds continue to be emitted into ambient air from municipal incinerators, motor vehicles, and industrial power plants. As a result, understanding the structural and electronic factors that influence mutagenicity in nitro-aromatic compounds has been a long standing objective. Progress toward this goal has accelerated over the years, in large part due to the synergistic efforts among toxicology, computational chemistry, and statistical modeling of toxicological data. The concerted influence of several structural and electronic factors in nitro-aromatic compounds makes the development of structure-activity relationships (SARs) a paramount challenge. Mathematical models that include a regression analysis show promise in predicting the mutagenic activity of nitro-aromatic compounds as well as in prioritizing compounds for which experimental data should be pursued. A major challenge of the structure-activity models developed thus far is their failure to apply beyond a subset of nitro-aromatic compounds. Most quantitative structure-activity relationship papers point to statistics as the most important confirmation of the validity of a model. However, the experimental evidence shows the importance of the chemical knowledge in the process of generating models with reasonable applicability. This chapter will concisely summarize the structural and electronic factors that influence the mutagenicity in nitro-aromatic compounds and the recent efforts to use quantitative structure-activity relationships to predict those physicochemical properties.


    Directory of Open Access Journals (Sweden)

    Yonghong Deng,


    Full Text Available Sodium lignosulfonate (SL fractions with narrow molecular weight distribution and known salt content were used to investigate – stacking of the aromatic groups in SL. Results show that the charge-free aromatic groups of SL tend to form oriented – stacking with the spectroscopic characteristics of J–aggregates. The formation of J–aggregates in SL are recognized by a significant spectral red shift in fluorescent excitation spectra. The other effects that may cause spectral shift, such as the SL species, solvent effect, and the impurities, are investigated to confirm that the formation of J-aggregates is the only viable explanation for the significant spectral redshift of SL. Salt causes molecular shrinkage of SL polyelectrolytes, but has no influence on J–aggregates of the aromatic groups as detected by lack of spectral shift, indicating that the aromatic groups are charge-free. This suggests that not all the aromatic groups but only the charge-free aromatic groups can form – stacking. This work demonstrates the presence of J–aggregation in aqueous SL solutions for the first time, which gives an insight in understanding the preferred orientation of the aromatic groups in lignin-based biopolymers.

  15. How non-conventional feedstocks will affect aromatics technologies

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, E. [Clariant Produkte (Deutschland) GmbH, Muenchen (Germany)


    The abundance of non-conventional feedstocks such as coal and shale gas has begun to affect the availability of traditional base chemicals such as propylene and BTX aromatics. Although this trend is primarily fueled by the fast growing shale gas economy in the US and the abundance of coal in China, it will cause the global supply and demand situation to equilibrate across the regions. Lower demand for gasoline and consequently less aromatics rich reformate from refineries will further tighten the aromatics markets that are expected to grow at healthy rates, however. Refiners can benefit from this trend by abandoning their traditional fuel-oriented business model and becoming producers of petrochemical intermediates, with special focus on paraxylene (PX). Cheap gas from coal (via gasification) or shale reserves is an advantaged feedstock that offers a great platform to make aromatics in a cost-competitive manner, especially in regions where naphtha is in short supply. Gas condensates (LPG and naphtha) are good feedstocks for paraffin aromatization, and methanol from coal or (shale) gas can be directly converted to BTX aromatics (MTA) or alkylated with benzene or toluene to make paraxylene. Most of today's technologies for the production and upgrading of BTX aromatics and their derivatives make use of the unique properties of zeolites. (orig.)

  16. Epoxy Coenzyme A Thioester pathways for degradation of aromatic compounds. (United States)

    Ismail, Wael; Gescher, Johannes


    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.

  17. Theoretical study of aromaticity in inorganic tetramer clusters

    Indian Academy of Sciences (India)

    Sandeep Nigam; Chiranjib Majumder; S K Kulshreshtha


    Ground state geometry and electronic structure of M$^{2-}_{4}$ cluster (M = B, Al, Ga) have been investigated to evaluate their aromatic properties. The calculations are performed by employing the Density Functional Theory (DFT) method. It is found that all these three clusters adopt square planar configuration. Results reveal that square planar M$^{2-}_{4}$ dianion exhibits characteristics of multifold aromaticity with two delocalised -electrons. In spite of the unstable nature of these dianionic clusters in the gas phase, their interaction with the sodium atoms forms very stable dipyramidal M4Na2 complexes while maintaining their square planar structure and aromaticity.

  18. Aromatic oligoamides with a rare ortho-connectivity

    DEFF Research Database (Denmark)

    Hjelmgaard, T.; Nielsen, John


    Even though aromatic oligoamides composed of aromatic amino acids in a "one-way sequence" attract ever increasing research interest, backbones connected through ortho-linked aromatics remain rare. Herein, we present the first synthesis and study of N-alkylated ortho-aminomethyl- benzamides termed...... studies indicated a more restricted rotation about the amide bonds in ortho-arylopeptoids, presumably due to a more congested backbone structure resulting from the ortho-connectivity pattern. Intriguingly, tert-butyl and phenyl side chains offer complete control over the amide conformations; whereas...

  19. Straightening the Density-Displacement Relation with a Logarithmic Transform

    CERN Document Server

    Falck, Bridget L; Aragon-Calvo, Miguel A; Lavaux, Guilhem; Szalay, Alexander S


    We investigate the use of a logarithmic density variable in estimating the Lagrangian displacement field, motivated by the success of a logarithmic transformation in restoring information to the matter power spectrum. The logarithmic relation is an extension of the linear relation, motivated by the continuity equation, in which the density field is assumed to be proportional to the divergence of the displacement field; we compare the linear and logarithmic relations by measuring both of these fields directly in a cosmological N-body simulation. The relative success of the logarithmic and linear relations depends on the scale at which the density field is smoothed. Thus we explore several ways of measuring the density field, including Cloud-In-Cell smoothing, adaptive smoothing, and the (scale-independent) Delaunay tessellation, and we use both a Fourier space and a geometrical tessellation approach to measuring the divergence. We find that the relation between the divergence of the displacement field and the ...

  20. Geometric interpretation of density displacements and charge sensitivities

    Indian Academy of Sciences (India)

    Roman F Nalewajski


    The ``geometric” interpretation of the electronic density displacements in the Hilbert space is given and the associated projection-operator partitioning of the hardness and softness operators (kernels) is developed. The eigenvectors |á 〉 = \\{| 〉 \\} of the hardness operator define the complete (identity) projector $\\hat{P}$ = | 〉 〈 = 1 for general density displacements, including the charge-transfer (CT) component, while the eigenvectors | i 〉 = { | 〉} of the linear response operator determine the polarizational -projector, $\\hat{P}$ = | 〉 〈 |. Their difference thus defines the complementary CT-projector: $\\hat{P}$ = 1 - $\\hat{P}$. The complete vector space for density displacements can be also spanned by supplementing the -modes with the homogeneous CT-mode. These subspaces separate the integral (normalization) and local aspects of density shifts in molecular systems.