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Sample records for 1-pentanol 2-pentanol 3-pentanol

  1. Gaseous 3-pentanol primes plant immunity against a bacterial speck pathogen, Pseudomonas syringae pv. tomato via salicylic acid and jasmonic acid-dependent signaling pathways in Arabidopsis

    PubMed Central

    Song, Geun C.; Choi, Hye K.; Ryu, Choong-Min

    2015-01-01

    3-Pentanol is an active organic compound produced by plants and is a component of emitted insect sex pheromones. A previous study reported that drench application of 3-pentanol elicited plant immunity against microbial pathogens and an insect pest in crop plants. Here, we evaluated whether 3-pentanol and the derivatives 1-pentanol and 2-pentanol induced plant systemic resistance using the in vitro I-plate system. Exposure of Arabidopsis seedlings to 10 μM and 100 nM 3-pentanol evaporate elicited an immune response to Pseudomonas syringae pv. tomato DC3000. We performed quantitative real-time PCR to investigate the 3-pentanol-mediated Arabidopsis immune responses by determining Pathogenesis-Related (PR) gene expression levels associated with defense signaling through salicylic acid (SA), jasmonic acid (JA), and ethylene signaling pathways. The results show that exposure to 3-pentanol and subsequent pathogen challenge upregulated PDF1.2 and PR1 expression. Selected Arabidopsis mutants confirmed that the 3-pentanol-mediated immune response involved SA and JA signaling pathways and the NPR1 gene. Taken together, this study indicates that gaseous 3-pentanol triggers induced resistance in Arabidopsis by priming SA and JA signaling pathways. To our knowledge, this is the first report that a volatile compound of an insect sex pheromone triggers plant systemic resistance against a bacterial pathogen. PMID:26500665

  2. Gaseous 3-pentanol primes plant immunity against a bacterial speck pathogen, Pseudomonas syringae pv. tomato via salicylic acid and jasmonic acid-dependent signaling pathways in Arabidopsis.

    PubMed

    Song, Geun C; Choi, Hye K; Ryu, Choong-Min

    2015-01-01

    3-Pentanol is an active organic compound produced by plants and is a component of emitted insect sex pheromones. A previous study reported that drench application of 3-pentanol elicited plant immunity against microbial pathogens and an insect pest in crop plants. Here, we evaluated whether 3-pentanol and the derivatives 1-pentanol and 2-pentanol induced plant systemic resistance using the in vitro I-plate system. Exposure of Arabidopsis seedlings to 10 μM and 100 nM 3-pentanol evaporate elicited an immune response to Pseudomonas syringae pv. tomato DC3000. We performed quantitative real-time PCR to investigate the 3-pentanol-mediated Arabidopsis immune responses by determining Pathogenesis-Related (PR) gene expression levels associated with defense signaling through salicylic acid (SA), jasmonic acid (JA), and ethylene signaling pathways. The results show that exposure to 3-pentanol and subsequent pathogen challenge upregulated PDF1.2 and PR1 expression. Selected Arabidopsis mutants confirmed that the 3-pentanol-mediated immune response involved SA and JA signaling pathways and the NPR1 gene. Taken together, this study indicates that gaseous 3-pentanol triggers induced resistance in Arabidopsis by priming SA and JA signaling pathways. To our knowledge, this is the first report that a volatile compound of an insect sex pheromone triggers plant systemic resistance against a bacterial pathogen.

  3. Molecular interactions in binary mixtures of methyl formate with 1-butanol, 1-pentanol, and 1-hexanol by using ultrasonic data at 303 K

    NASA Astrophysics Data System (ADS)

    Elangovan, S.; Mullainathan, S.

    2016-05-01

    Density (ρ), viscosity (η), and ultrasonic velocity ( U) have been measured for binary mixtures of methyl formate with 1-butanol, 1-pentanol and 1-hexanol at 303 K. From the experimental results, adiabatic compressibility (β), acoustic impedance ( Z), viscous relaxation time (τ), free length ( L f), free volume ( V f), internal pressure (πi), and Gibbs free energy (Δ G) have been determined. Excess values of various parameters have also been calculated and interoperated in terms of molecular interactions. The deviations in the parameters show that strength of intermolecular interactions between methyl formate with selected 1-alcohols have been observed in the order of 1-butanol < 1-pentanol < 1-hexanol.

  4. Viscosities and densities for heptane + 1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-decanol, and + 1-dodecanol at 298.15 K and 308.15 K

    SciTech Connect

    Sastry, N.V.; Valand, M.K.

    1996-11-01

    Densities and viscosities for heptane + 1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-decanol, and + 1-dodecanol are reported at (298.15 K and 308.15) K. The viscosity deviations were calculated. The mixture viscosity data were fitted to the semiempirical equations of Grunberg-Nissan, Heric, McAllister, and Auslander.

  5. Excess parameters for binary mixtures of ethyl benzoate with 1-propanol, 1-butanol and 1-pentanol at T=303, 308, 313, 318, and 323 K

    NASA Astrophysics Data System (ADS)

    Sreehari Sastry, S.; Babu, Shaik; Vishwam, T.; Parvateesam, K.; Sie Tiong, Ha.

    2013-07-01

    Various thermo-acoustic parameters, such as excess isentropic compressibility (KsE), excess molar volume (VE), excess free length (LfE), excess Gibb's free energy (ΔG*E), and excess Enthalpy (HE), have been calculated from the experimentally determined data of density, viscosity and speed of sound for the binary mixtures of ethyl benzoate+1-propanol, or +1-butanol, or +1-pentanol over the entire range of composition at different temperatures (303, 308, 313, 318 and 323 K). The excess functions have been fitted to the Redlich-Kister type polynomial equation. The deviations for excess thermo-acoustic parameters have been explained on the basis of the intermolecular interactions present in these binary mixtures.

  6. Dilution method study on the interfacial composition, thermodynamic properties and structural parameters of W/O microemulsions stabilized by 1-pentanol and surfactants in absence and presence of sodium chloride.

    PubMed

    Paul, Bidyut K; Nandy, Debdurlav

    2007-12-15

    The phase behaviors, interfacial composition, thermodynamic properties and structural characteristics of water-in-oil microemulsions under varied molar ratio of water to surfactant (omega) at 303 K and also by varying temperatures at a fixed omega(=40) by mixing with 1-pentanol and decane or dodecane in absence and presence of sodium chloride have been studied by the method of dilution. The surfactants used were cetyl pyridinium chloride (CPC), sodium dodecyl sulfate (SDS) and polyoxyethylene (23) lauryl ether (Brij-35). The compositions of 1-pentanol and the surfactant at the interfacial region, the distribution of 1-pentanol between the interfacial region and the continuous oil phase, and the effective packing parameter (P(eff)) at the threshold level of stability have been estimated. The thermodynamics of transfer of 1-pentanol from the continuous oil phase to the interface have been evaluated. The structural parameters viz. radii of the droplet (R(e)) and the waterpool (R(w)), effective thickness of the interfacial layer (d(I)), average aggregation numbers of surfactants (N (s)) and the cosurfactant (1-pentanol) (N (a)) and the number of droplets (N(d)) have also been estimated. The prospect of using these w/o microemulsions for the synthesis of nanoparticles with small size, have been discussed in the light of the radii of the droplet, and waterpool, the extent of variation of effective thickness of the droplet under varied molar ratio of water to surfactant and temperature. An attempt has been made to rationalize the results in a comprehensive manner.

  7. Preparation of zeolite supported TiO2, ZnO and ZrO2 and the study on their catalytic activity in NOx reduction and 1-pentanol dehydration

    NASA Astrophysics Data System (ADS)

    Fatimah, Is

    2016-03-01

    Preparation of zeolite supported TiO2, ZnO and ZrO2 and their catalytic activity was studied. Activated natural zeolite from Indonesia was utilized for the preparation and catalytic activity test on NOx reduction by NH3 and also 1-pentanol dehydration were examined. Physicochemical characterization of materials was studied by x-ray diffraction (XRD) measurement, scanning electron microscope, solid acidity determination and also gas sorption analysis. The results confirmed that the preparation gives some improvements on physicochemical characters suitable for catalysis mechanism in those reactions. Solid acidity and specific surface area contributed significantly to the activity.

  8. Composition and Process for Retarding the Premature Aging of PMR Monomer Solutions and PMR Prepegs

    NASA Technical Reports Server (NTRS)

    Alston, William B. (Inventor); Gahn, Gloria S. (Inventor)

    2000-01-01

    Polyimides are derived from solutions of at least one low-boiling organic solvent, e.g. isopropanol containing a mixture of polyimide-forming monomers. The monomeric solutions have an extended shelf life at ambient (room) temperatures as high as 80 C, and consist essentially of a mixture of monoalkyl ester-acids, alkyl diester-diacids and aromatic polyamines wherein the alkyl radicals of the esteracids are derived from lower molecular weight aliphatic secondary alcohols having 3 to 5 carbon atoms per molecule such as isopropanol, secondary butanol, 2-methyl-3-butanol, 2 pentanol or 3-pentanol. The solutions of the polyimide-forming monomers have a substantially improved shelf-life and are particularly useful in the aerospace and aeronautical industry for the preparation of polyimide reinforced fiber composites such as the polyimide cured carbon composites used in jet engines, missiles, and for other high temperature applications.

  9. Matrix effects on the photocatalytic oxidation of alcohols by [nBu4N]4W10O32 incorporated into sol-gel silica.

    PubMed

    Molinari, Alessandra; Bratovcic, Amra; Magnacca, Giuliana; Maldotti, Andrea

    2010-09-07

    Two heterogeneous photocatalysts have been prepared by entrapment of [nBu(4)N](4)W(10)O(32) in a silica matrix, through a sol-gel procedure: SiO(2)/W30% and SiO(2)/W10% with 30% and 10% of decatungstate, respectively. They are characterized by the presence of micropores of about 7 A and 15 A and mesopores of about 25 A. Due to different preparation procedures, SiO(2)/W10% presents a more remarkable porous network than SiO(2)/W30%. The morphological features of SiO(2)/W30% and SiO(2)/W10% differ from those of their parent material SiO(2)/W0%, indicating that incorporation of the decatungstate induces a significant modification of the porous texture of the siliceous material. These photocatalysts demonstrate good stability in the oxygen-assisted photooxidation of 1-pentanol and 3-pentanol, which have been chosen as models of primary and secondary aliphatic alcohols. In particular, photoexcitation (lambda > 290 nm, 25 degrees C, 760 torr of O(2)) leads to conversion of these two substrates to pentanal or 3-pentanone, with a mass balance of about 90%. There is a strong effect of the solid support on the reactivity of the two alcoholic substrates. In particular, oxidation of 1-pentanol with SiO(2)/W10% is about four times faster than with [nBu(4)N](4)W(10)O(32) in homogeneous solution. Preferential adsorption phenomena, due to the hydrophilic character of silica explain the photocatalytic properties of the two heterogeneous systems, because adsorption favours the contact between the photoexcited decatungstate and the primary OH group of 1-pentanol. Moreover, some kind of shape selectivity, due to the microporous structure of the investigated materials, likely contributes to control the conversion yields.

  10. Effect of Surfactant Supplying with Refrigerant Vapor on Absorption Enhancement

    NASA Astrophysics Data System (ADS)

    Gao, Hongtao; Matsuzaki, Tetsuya; Wang, Jianfeng; Hihara, Eiji

    For the absorption of water vapor into the aqueous lithium bromide solution, eight-carbon alcohol additives such as 2-ethyl-1-hexanolhave been commonly used to improve the absorption process. However, as additives six-carbon and seven-carbon alcohols were not been tested experimentally very much. In present study, absorption of water vapor into the 62 wt% LiBr solution with several six-carbon and seven carbon alcohol additives such as 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-hexanol, 2 , 4-dimethyl-3-pentanol, 4-heptanol, 2-heptanol and 1-heptanol were investigated by using a simple stagnant pool absorber. Besides using the conventional method which mixing additive into LiBr solution, vapor phase adding method was experimented. Surface tensions of aqueous LiBr solution with different surfactant also were measured by Welhelmy plate method. Absorption of water vapor into the LiBr solution with 2-ethyl-1-hexanol and 1-heptanol were also experimented in falling film absorber by vapor phase adding method. The result showed that the lower the surface tension of LiBr aqueous solution with an additive, the better the effect of absorption enhancement by the corresponding additive, and vapor phase adding method is effective for the absorption of water vapor into the LiBr aqueous solution.

  11. An investigation of bubble coalescence and post-rupture oscillation in non-ionic surfactant solutions using high-speed cinematography.

    PubMed

    Bournival, G; Ata, S; Karakashev, S I; Jameson, G J

    2014-01-15

    Most processes involving bubbling in a liquid require small bubbles to maximise mass/energy transfer. A common method to prevent bubbles from coalescing is by the addition of surfactants. In order to get an insight into the coalescence process, capillary bubbles were observed using a high speed cinematography. Experiments were performed in solutions of 1-pentanol, 4-methyl-2-pentanol, tri(propylene glycol) methyl ether, and poly(propylene glycol) for which information such as the coalescence time and the deformation of the resultant bubble upon coalescence was extracted. It is shown in this study that the coalescence time increases with surfactant concentration until the appearance of a plateau. The increase in coalescence time with surfactant concentration could not be attributed only to surface elasticity. The oscillation of the resultant bubble was characterised by the damping of the oscillation. The results suggested that a minimum elasticity is required to achieve an increased damping and considerable diffusion has a detrimental effect on the dynamic response of the bubble, thereby reducing the damping.

  12. Comparative study of boson peak in normal and secondary alcohols with terahertz time-domain spectroscopy

    NASA Astrophysics Data System (ADS)

    Yomogida, Yoshiki; Sato, Yuki; Nozaki, Ryusuke; Mishina, Tomobumi; Nakahara, Jun'ichiro

    2010-05-01

    Using terahertz (THz) time-domain spectroscopy, we measured the complex permittivity of some normal (1-propanol, 1-butanol, and 1-pentanol) and secondary alcohols (2-propanol, 2-butanol, and 2-pentanol) in the frequency ranges from 0.2 to 2.5 THz at temperatures from 253 to 323 K. For all the samples, the complex permittivity in the THz region includes the following three components: (i) a high frequency side of dielectric relaxation processes, (ii) a broad mode around 1 THz, and (iii) a low frequency side of an intermolecular vibration mode located above 2.5 THz. The mode around 1 THz is recognized as a boson peak which is related to the local structure of disordered materials. The intensity of the boson peak in secondary alcohols is higher than that in normal alcohols. On the other hand, the number of carbon atoms slightly affects the appearance of the boson peak. These observations indicate that the position of an OH group in a molecule has a profound effect on the local structures in monohydric alcohols.

  13. [Metabolism and toxicity of n-pentane and isopentane].

    PubMed

    Chiba, S; Oshida, S

    1991-04-01

    n-Pentane and isopentane have a wide range of use, for example, for cleaning precision machinery, extracting essence and oil, and as liquid fuel for now very popular disposable lighters. They are contained in liquefied petroleum gas and natural gas as trace constituents. In our present experiments, we studied the metabolism and toxicity of these n-pentane and isopentane metabolites. Male mice of ICR strain were exposed to about 5% n-pentane for one hour while the oxygen in the environmental air was maintained at about 20%. Then their blood and liver tissue were collected and analyzed by means of GC and GC-MS. The metabolites thus obtained were 2-pentanol, 3-pentanol and 2-pentanone. The same procedure was repeated with isopentane; 3-methyl-2-butanol, 2-methyl-2-butanol and 3-methyl-2-butanone were detected as the resultant metabolites. In the presence of the NADPH-generating system liver microsomes were made to react to the substrate of saturated n-pentane or isopentane aqueous solution at 37 degrees C for one hour. As a result, the same metabolites were produced as obtained in the exposure experiment. It was therefore suggested that n-pentane and isopentane were metabolized chiefly by liver microsomes. Male mice of ICR strain were fed with 80 mg/kg b.w. of phenobarbital for consecutive four days and exposed to n-pentane or isopentane for one hour. This resulted in an increase in the amount of 2-pentanol and 2-pentanone in the n-pentane inhalation and 2-methyl-2-butanol in the isopentane inhalation experiment. The toxicity of each metabolite was studied on cultured cells. The metabolites were individually mixed with HeLa S3 cell suspension, incubated for three days, and their concentration which inhibited the growth of cells by 50% (IGC 50) were compared. It was demonstrated as a result that the IGC 50 for any of the metabolites was lower than that for methanol, ethanol or acetone used as control.

  14. Liquid chromatographic analysis of coal surface properties. Final report, September 1991--February 1995

    SciTech Connect

    Kwon, K.C.

    1996-03-01

    Experiments on equilibrium adsorption loadings of various probe compounds on 60-200 mesh Illinois {number_sign}6 coal (PSOC-1539), Adaville {number_sign}1 coal (PSOC-1544), Wyodak coal (PSOC-1545) and Pittsburgh {number_sign}8 coal (PSOC-1549) were performed. the probe compounds include m-cresol, p-cresol, o-cresol, phenol, n-octanol, n-heptanol, n-propanol, isopropanol n-butanol, s-butanol, 2-butanol, t-butanol, 2-naphthol, cyclohexanol, 2-methyl-1-pentanol (2M1P), 4-methyl-2-pentanol (4M2P), benzene and toluene. Equilibrium adsorption of various probe compounds on the coals were measured with the inverse liquid chromatography method. Experiments on flotation of various 60-200 mesh treated coals such as Illinois {number_sign}6 coal (PSOC-1539), Adaville {number_sign}1 coal (PSOC-1544), Wyodak coal (PSOC-1545) and Pittsburgh {number_sign}8 coal (PSOC-1549) were performed. The chosen coals were treated with steam, nitrogen and air at 1 atm and 125-225{degrees}C for 24 hours. The coals were treated with water as well as 20-1000 ppm aqueous alcohol solutions for 3-24 hours at 150-225{degrees}C. The coals also were treated with 20-ppm alcohol aqueous solutions for 1-24 hours at the 0.002-g/min mass flow rate of alcohol aqueous solutions and at 225{degrees}C. Flotation experiments were conducted with a 500-cm{sup 3} batch-type micro flotation apparatus, introducing nitrogen at the bottom of the apparatus. This final report was prepared with the experimental data obtained during the period of September 1991-March 1994.

  15. Preparation of 2-Bromopentane.

    ERIC Educational Resources Information Center

    Howell, B. A.; Kohrman, R. E.

    1984-01-01

    Suggests that the preparation of 2-bromopentane from 2-pentanol might represent an instructive addition to a published description of pheromone synthesis in that it is economical, extends the synthetic nature of the problem, and amplifies the mechanistic vagaries of the substitution reaction. Theory, procedures used, and safety considerations are…

  16. Federal and State Water Quality Standards/Guidelines for Selected Parameters.

    DTIC Science & Technology

    1979-02-01

    Arsenic, total Barium Benzaldehyde Benzanthrone Biochemical Oxygen Demand 1-(2-Butoxyethoxy) ethanol Cadmium Calcium 4 SUBSTANCE LIST FOR SIX STATES... styphnate Magnes i um Mercury Mercury fulminate Mercury, total Methylcyclohexane Methylene chloride Methyl isopropyl ketone 2-Methyl-2-pentanol Nemagon...dye (1-Methylaminoanthraquinone) Silver Sodium Sodium styphnate Strontium nitrate Strontium oxalate Strontium peroxide Sulfate Tetrachlorobenzene

  17. Investigations of aroma volatile biosynthesis under anoxic conditions and in different tissues of "Redchief Delicious" apple fruit (Malus domestica Borkh.).

    PubMed

    Rudell, D R; Mattinson, D S; Mattheis, J P; Wyllie, S G; Fellman, J K

    2002-04-24

    Disks from different tissues were obtained from "Redchief Delicious" apple fruit (Malus domestica Borkh.) and analyzed for the ability to metabolize 1-pentanol as well as synthesize constitutive esters and alcohols under anoxic and aerobic conditions. The skin tissue displayed a greater capacity to synthesize pentanal, pentyl acetate, pentyl propionate, pentyl butyrate, and pentyl hexanoate than the hypanthial and carpellary tissues during incubation with 1-pentanol. With the exception of pentyl acetate and pentyl propionate biosynthesis, the hypanthial tissue synthesized these compounds at a higher rate than the carpellary tissue. Anoxia inhibited both constituent and 1-pentanol-derived ester biosynthesis. While anoxia inhibited ester biosynthesis, ethanol biosynthesis increased at a greater rate in tissue disks held under these conditions. Biosynthesis of 1-butanol, 2-methyl-1-butanol, and 1-hexanol was greater in tissue disks held in air during the first part of the measurement period and dropped off more rapidly than those transpiring in tissue disks held under anoxic conditions. The biosynthetic rates of all esters, both constituent and 1-pentanol-derived, increased as a result of air exposure. While hypoxic or anoxic conditions may promote ethanol synthesis, these conditions also appear to inhibit the formation of the ethanol-derived esters partially responsible for the off-flavor in apples attributed to ultralow O(2) controlled atmosphere storage.

  18. New methodology for simultaneous volumetric and calorimetric measurements: Direct determination of {alpha}{sub p} and C{sub p} for liquids under pressure

    SciTech Connect

    Casas, L. M.

    2009-12-15

    A new batch cell has been developed to measure simultaneously both isobaric thermal expansion and isobaric heat capacity from calorimetric measurements. The isobaric thermal expansion is directly proportional to the linear displacement of an inner flexible below and the heat capacity is calculated from the calorimetric signal. The apparatus used was a commercial Setaram C-80 calorimeter and together with this type of vessels can be operated up to 20 MPa and in the temperature range of 303.15-523.15 K, In this work, calibration was carried out using 1-hexanol and subsequently both thermophysical properties were determined for 3-pentanol, 3-ethyl-3-pentanol, and 1-octanol at atmospheric pressure, 5 and 10 MPa, and from 303.15 to 423.15 K in temperature. Finally experimental values were compared with the literature in order to validate this new methodology, which allows a very accurate determination of isobaric thermal expansion and isobaric heat capacity.

  19. Neurotoxic metabolites of ''commercial hexane'' in the urine of shoe factory workers

    SciTech Connect

    Perbellini, L.; Brugnone, F.; Gaffuri, E.

    1981-12-01

    Urinary metabolites were tested in 41 shoe-factory workers exposed to a mixture of 10 solvents among which ''commercial hexane'' was the prevailing component. Cyclohexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, and trichloroethanol were determined in connection with exposure to cyclohexane, 2-methylpentane, 3-methylpentane, and trichloroethylene, respectively. 2-Hexanol, 2,5-hexanedione, 2,5-dimethylfuran, and gamma-valerolactone were all determined in connection with n-hexane exposure only. 2,5-Hexanedione was the principal n-hexane metabolite found in the workers' urine. This finding of the experimentally proven neurotoxin 2,5-hexanedione in the urine of shoe-factory workers exposed to ''commercial hexane'' is consistent with the idea that this compound is responsible for the development of neuropathy in this group of individuals.

  20. A rhodamine-deoxylactam based sensor for chromo-fluorogenic detection of nerve agent simulant.

    PubMed

    Wu, Zhisheng; Wu, Xuanjun; Yang, Yuhui; Wen, Ting-bin; Han, Shoufa

    2012-10-15

    N-(rhodamine B)-deoxylactam-5-amino-1-pentanol (dRB-APOH) was designed and prepared as the chromo-fluorogenic sensor for detection of a nerve agent simulant via analyte triggered tandem phosphorylation and opening of the intramolecular deoxylactam. The successful detection of diethyl chlorophosphate suggests the utility of rhodamine-deoxylactams as the chromo-fluorogenic signal reporting platform for design of sensors targeting reactive chemical species via various chemistries.

  1. Do the interfacial fluidities of cationic reverse micelles enhance with an increase in the water content?

    NASA Astrophysics Data System (ADS)

    Mali, K. S.; Dutt, G. B.

    2009-11-01

    The role of cosurfactant and water on the interfacial fluidities of reverse micelles formed with the cationic surfactant, cetyltrimethylammonium bromide (CTAB) has been examined by measuring the fluorescence anisotropies of two structurally similar ionic solutes, rhodamine 110 and fluorescein. For this purpose, reverse micellar systems with (CTAB/1-pentanol/cyclohexane/water) and without a cosurfactant (CTAB/chloroform-isooctane/water) have been chosen. In this study, the mole ratio of water to surfactant W has been varied in the region of 4-25. Experimental results indicate that the average reorientation time of the probe, which is a measure of the fluidity near the interfacial region, decreases by a factor of 1.5 and 1.4 for rhodamine 110 and fluorescein, respectively, as W goes up from 5 to 25 in CTAB/1-pentanol/cyclohexane/water reverse micellar system. In contrast, the average reorientation time, remains invariant for both the probe molecules in CTAB/chloroform-isooctane/water reverse micellar system despite an increase in W from 4 to 24. In case of CTAB/1-pentanol/cyclohexane/water reverse micellar system, the added water binds to bromide counter ions and also the hydroxyl groups of the cosurfactant, 1-pentanol, which results in an increase in the effective head group area. Such an increase in the effective head group area leads to a decrease in the packing parameter, and hence an increase in the interfacial fluidity. On the other hand, in CTAB/chloroform-isooctane/water system, the added water merely hydrates the bromide ions, thereby leaving the effective head group area unchanged. Thus, the interfacial fluidities remain invariant upon the addition of water in the absence of a cosurfactant.

  2. Enhancement of critical heat flux in subcooled flow boiling of water by use of a volatile additive

    SciTech Connect

    Pabisz, R.A. Jr.; Bergles, A.E.

    1996-12-31

    The present investigation considers the effect of a 1-pentanol additive in water on the critical heat flux (CHF) and pressure drop in forced subcooled boiling. A small quantity of 1-pentanol was added to distilled water with the objective of getting an approximate 2% by weight mixture, which had been found to give superior performance in previous studies of pool and flow boiling. Experiments were performed using stainless steel tubes with internal diameters of 4.4 and 6.1 mm. Tests were conducted with mass fluxes of 4,400 kg/m{sup 2}s, exit pressures of 9 bar, length-to-diameter ratios of 25, and exit subcoolings from 65 to 90 C. Test sections were heated directly by DC power, and critical heat flux data were inferred from test-section burnout. The alcohol concentration was periodically checked by draining off a sample and performing a Proton Nuclear Magnetic Resonance scan on the mixture. At high subcoolings, the mixture exhibited an increase in the critical heat flux over that of pure water. However at low subcoolings there is a decrease in the critical heat flux. The increases in critical heat flux noted with the 1-pentanol mixture in this experiment were not as large as would be expected from saturated pool boiling results published by Van Stralen (1959). Pressure drop data for both the mixture and the pure water also were recorded. The 1-pentanol mixture, in general, exhibited larger pressure drops for the same conditions. Subcooled flow boiling has a wide array of commercial cooling applications, including blades in gas turbines, high power laser optics, plasma-facing components in fusion reactors, supercomputers, etc.

  3. Mechanistic studies of the pathways leading to ethers via coupling of alcohols

    SciTech Connect

    Sun, Qun; Lietti, L.; Herman, R.G.; Klier, K.

    1995-12-31

    The reaction mechanisms for the solid acid-catalyzed dehydrative coupling of methanol and ethanol with isobutanol and 2-pentanol to form ethers were examined by using isotope labelling and chiral inversion experiments. When the reactions were carried out it 110{degrees}C and 1 MPa with {sup 18}O-ethanol and {sup 16}O-isobutanol over the Amberlyst-35 resin catalyst, 95% of the major product ethyl isobutyl ether (EIBE) contained {sup 16}O, while 96% of the minor product ethyl tertiarybutyl ether (ETBE) contained {sup 18}O. Similar results were obtained with methanol and isobutanol over Nafion-H and Amberlyst-35 catalysts, with methyl isobutyl ether (MIBE) and methyl tertiarybutyl ether (MTBE) as the products. These results indicate that EIBE (MIBE) was produced by a surface-catalyzed S{sub N}2 reaction, while the ETBE (MTBE) product arose via a carbenium intermediate. The analogous reaction carried out over Nafion-H and HZSM-5 catalysts with chiral 2-pentanol verified the surface-mediated S{sub N}2 reaction, wherein chiral inversion of the product ether was observed relative to the S- and R-2-pentanol reactants.

  4. Mechanistic studies of the pathways leading to ethers via coupling of alcohols

    SciTech Connect

    Sun, Qun; Lietti, L.; Herman, R.G.

    1995-12-01

    The reaction mechanisms for the solid acid-catalyzed dehydrative coupling of methanol and ethanol with isobutanol and 2-pentanol to form ethers were examined by using isotope labelling and chiral inversion experiments. When the reactions were carried out at 110{degrees}C and 1 MPa with Et{sup 18}OH and {sup 16}O-isobutanol over Amberlyst-35, 95% of the major product ethyl isobutyl ether (EIBE) contained {sup 16}O, while 96% of the minor product ethyl tertiarybutyl ether (ETBE) contained {sup 18}O. Similar results were obtained with methanol and isobutanol over Nafion-H and Amberlyst-35 catalysts, with MIBE and MTBE as the products. These results indicate that EIBE (MIBE) was produced by a surface-catalyzed S{sub N}2 reaction, while the ETBE (MTBE) product arose via a carbenium intermediate. The analogous reactions carried out over Nafion-H and H-ZSM-5 catalysts with chiral 2-pentanol verified the surface-mediated S{sub N}2 reaction, where in chiral inversion of the product ether was observed relative to the S- and R-2-pentanol reactants. In addition, a remarkable shape selectivity with chiral inversion was observed over the H-ZSM-5 zeolite to selectively form 2-ethoxypentane but not 3-ethoxypentane.

  5. Behavioral and electrophysiological responses of Aedes albopictus to certain acids and alcohols present in human skin emanations.

    PubMed

    Guha, Lopamudra; Seenivasagan, T; Iqbal, S Thanvir; Agrawal, O P; Parashar, B D

    2014-10-01

    Human skin emanations attract hungry female mosquitoes toward their host for blood feeding. In this study, we report the flight orientation and electroantennogram response of Aedes albopictus females to certain unsaturated acids and alcohols found in human skin. In the Y-tube olfactometer, odors of lactic acid and 2-methyl-3-pentanol attracted 54-65% of Ae. albopictus females at all doses in a dose-dependent manner. However, at the highest dose (10(-2) g), the acids repelled 40-45% females. Attractancy (ca. 62-68%) at lower doses and repellency (ca. 30-45%) at higher doses were recorded for 3-methyl-3-pentanol and 1-octen-3-ol, while 5-hexen-1-ol, cis-2-hexen-1-ol, and trans 2-hexen-1-ol odor repelled ca. 55-65% of Ae. albopictus females at all doses. Antenna of female Ae. albopictus exhibited a dose-dependent EAG response up to 10(-3) g of L-lactic acid, trans-2-methyl-2-pentenoic acid, 2-octenoic acid, trans-2-hexen-1-ol and 1-octen-3-ol stimulations; however, the highest dose (10(-2) g) caused a little decline in the EAG response. EAG response of 9-10-fold was elicited by lactic acid, 2-octenoic acid, trans-2-hexenoic acid, and 3-methyl-3-pentanol, while cis-2-hexen-1-ol and trans-2-methyl pentenoic acid elicited 1-5-fold responses compared to solvent control. A blend of attractive compounds could be utilized in odor-baited trap for surveillance and repellent molecules with suitable formulation could be used to reduce the biting menace of mosquitoes.

  6. The substrate binding cavity of particulate methane monooxygenase from Methylosinus trichosporium OB3b expresses high enantioselectivity for n-butane and n-pentane oxidation to 2-alcohol.

    PubMed

    Miyaji, Akimitsu; Miyoshi, Teppei; Motokura, Ken; Baba, Toshihide

    2011-11-01

    The particulate methane monooxygenase (pMMO) of Methylosinus trichosporium OB3b oxidized n-butane and n-pentane and mainly produced (R)-2-butanol and (R)-2-pentanol that comprised 78 and 89% of the product, respectively, indicating that the pro-R hydrogen of the 2-position carbon of n-butane and n-pentane is oriented toward a catalytic site within the substrate binding site of pMMO. The protein cavity adjacent to the catalytic center for pMMO has optimum volume for recognizing n-butane and n-pentane for enantioselective hydroxylation.

  7. Synergic effects in the extraction of paracetamol from aqueous NaCl solution by the binary mixtures of diethyl ether and low molecular weight primary alcohols

    NASA Astrophysics Data System (ADS)

    Nikolić, G. M.; Živković, J. V.; Atanasković, D. S.; Nikolić, M. G.

    2013-12-01

    Liquid-liquid extraction of paracetamol from aqueous NaCl solutions was performed with diethyl ether, 1-propanol, 1-butanol, isobutanol, 1-pentanol, and binary mixtures diethyl ether/1-propanol, diethyl ether/1-butanol, and diethyl ether/isobutanol. Among the pure solvents investigated in this study best extraction efficacy was obtained with 1-butanol. Synergic effects in the extraction with binary mixtures was investigated and compared with some other systems used for the extraction of poorly extractable compounds. Results obtained in this study may be of both fundamental and practical importance.

  8. Influence of urea additives on micellar morphology/protein conformation.

    PubMed

    Gull, Nuzhat; Kumar, Sanjeev; Ahmad, Basir; Khan, Rizwan Hassan; Kabir-ud-Din

    2006-08-01

    The present study highlights the fact that the effect of additives (urea, monomethylurea, thiourea) on the supramolecular assemblies and proteins is strikingly similar. To investigate the effect, a viscometeric study on sphere-to-rod transition (s-->r) was undertaken in a system (3.5% tetradecyltrimethylammonium bromide+0.05 M NaBr + 1-pentanol [P.M. Lindemuth, G.L. Bertand, J. Phys. Chem. 97 (1993) 7769]) in the presence and absence of the said additives. [1-pentanol] needed for s-->r (i.e. [1-pentanol]s-->r) was determined from the relative viscosity versus [1-pentanol] profiles. It was observed that the additives preponed as well as postponed s-->r depending upon their nature and concentrations. These effects are explained in terms of increased polarity of the medium and the adsorption ability of urea/monomethylurea on the charged surfactant monomers of the micelle. In case of thiourea, postponement of s-->r was observed throughout which is attributed to its structure. To derive an analogy between micelles and proteins the additive-induced conformational changes of the protein, bovine serum albumin (BSA) was taken to monitor secondary structural changes and tryptophanyl fluorescence. A marked increase in secondary structure (far-UVCD) and increased tryptophanyl fluorescence with a marked blue shift in lambdamax was observed in presence of low concentrations of urea or alkylurea. This indicates that a more compact environment is created in presence of these additives, if added judiciously. Addition of thiourea to BSA caused a marked quenching without any significant change in lambdamax. The large decrease in tryptophanyl emission in presence of low thiourea concentrations seems to be specific and related to thiourea structure as no corresponding changes were observed in urea/alkylurea. All these effects pertaining to protein behavior fall in line with that of morphological observations on the present as well as surfactant systems studied earlier [S. Kumar, N

  9. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    SciTech Connect

    Koch, Daniel J.; Arnold, Frances H.

    2013-01-29

    Cytochrome P450 CYP153A6 from Myobacterium sp. strain HXN1500 was engineered using in-vivo directed evolution to hydroxylate small-chain alkanes regioselectively. Mutant CYP153A6-BMO1 selectively hydroxylates butane and pentane at the terminal carbon to form 1-butanol and 1-pentanol, respectively, at rates greater than wild-type CYP153A6 enzymes. This biocatalyst is highly active for small-chain alkane substrates and the regioselectivity is retained in whole-cell biotransformations.

  10. Effect of specific wavelengths on light-induced quality changes in Havarti cheese.

    PubMed

    Mortensen, Grith; Sørensen, John; Danielsen, Bente; Stapelfeldt, Henrik

    2003-11-01

    The effects of exposure of slices of Havarti cheeses to monochromatic light of wavelengths 366 nm, 405 nm, and 436 nm, respectively, were studied by tristimulus colorimetry, solid-phase microextraction gas chromatographic analysis of volatiles, and open-end fluorescence spectroscopy. Having determined the photon fluxes of the three wavelengths by ferrioxalate actinometry, it was possible to quantify the effects of light exposure in an absolute manner. For all analyses, the most severe effects were caused by visible light, leading to colour bleaching, change in hue, riboflavin degradation, and formation of the secondary oxidation products hexanal, 1-pentanol, and 1-hexanol. Apparent quantum yields for formation of hexanal and 1-pentanol were found to be insignificantly different for 405 nm and 436 nm exposures, having values of (3-5) x 10(-5) mol x einstein(-1) and (9-13) x 10(-5) mol x einstein(-1), respectively. These compounds were not formed when exposed to 366 nm light. In contrast, 1-hexanol was formed when exposing cheese to all three wavelengths, resulting in apparent quantum yields of (2-6) x 10(-5) mol x einstein(-1). The results obtained are discussed in relation to the interplay between inherent product colorants, light sources, and transmission characteristics of the packaging materials.

  11. Enhancement of nitrate-induced bioremediation in marine sediments contaminated with petroleum hydrocarbons by using microemulsions.

    PubMed

    Zhang, Zhen; Zheng, Guanyu; Lo, Irene M C

    2015-06-01

    The effect of microemulsion on the biodegradation of total petroleum hydrocarbons (TPH) in nitrate-induced bioremediation of marine sediment was investigated in this study. It was shown that the microemulsion formed with non-ionic surfactant polyoxyethylene sorbitan monooleate (Tween 80), 1-pentanol, linseed oil, and either deionized water or seawater was stable when subjected to dilution by seawater. Desorption tests revealed that microemulsion was more effective than the Tween 80 solution or the solution containing Tween 80 and 1-pentanol to desorb TPH from marine sediment. In 3 weeks of bioremediation treatment, the injection of microemulsion and NO3 (-) seems to have delayed the autotrophic denitrification between NO3 (-) and acid volatile sulfide (AVS) in sediment compared to the control with NO3 (-) injection alone. However, after 6 weeks of treatment, the delaying effect of microemulsion on the autotrophic denitrification process was no longer observed. In the meantime, the four injections of microemulsion and NO3 (-) resulted in as high as 29.73 % of TPH degradation efficiency, higher than that of two injections of microemulsion and NO3 (-) or that of four or two injections of NO3 (-) alone. These results suggest that microemulsion can be potentially applied to enhance TPH degradation in the nitrate-induced bioremediation of marine sediment.

  12. Analysis of volatile compounds from various types of barley cultivars.

    PubMed

    Cramer, Anne-Chrystelle J; Mattinson, D Scott; Fellman, John K; Baik, Byung-Kee

    2005-09-21

    We identified volatile compounds of barley flour and determined the variation in volatile compound profiles among different types and varieties of barley. Volatile compounds of 12 barley and two wheat cultivars were analyzed using solid phase microextraction (SPME) and gas chromatography. Twenty-six volatiles comprising aldehydes, ketones, alcohols, and a furan were identified in barley. 1-Octen-3-ol, 3-methylbutanal, 2-methylbutanal, hexanal, 2-hexenal, 2-heptenal, 2-nonenal, and decanal were identified as key odorants in barley as their concentration exceeded their odor detection threshold in water. Hexanal (46-1269 microg/L) and 1-pentanol (798-1811 microg/L) were the major volatile compounds in barley cultivars. In wheat, 1-pentanol (723-748 microg/L) was a major volatile. Hulled barley had higher total volatile, aldehyde, ketone, alcohol, and furan contents than hulless barley, highlighting the importance of the husk in barley grain aroma. The proanthocyanidin-free varieties generally showed higher total volatile and aldehyde contents than wild-type varieties, potentially due to decreased antioxidant activity by the absence of proanthocyanidins.

  13. Copper(II) benzoate dimers coordinated by different linear alcohols - A systematic study of crystal structures

    NASA Astrophysics Data System (ADS)

    Katzsch, Felix; Münch, Alexander S.; Mertens, Florian O. R. L.; Weber, Edwin

    2014-05-01

    Three new copper(II) benzoates coordinated by 1-propanol, [Cu2(PhCOO)4(1-PrOH)2] [Cu2(PhCOO)4(H2O)2] (3), 1-butanol, [Cu2(PhCOO)4(1-BuOH)2] (4) and 1-pentanol, [Cu2(PhCOO)4(1-PentOH)2] (5) at the available metal coordination sites, have been prepared and investigated with reference to their X-ray crystal structures. In all cases, dimeric paddle-wheel complexes where two copper(II) ions are held together by four benzoates were found. Moreover, the complexes show 1-propanol and water (3), 1-butanol (4) and 1-pentanol (5) coordinated to the free coordination sites of the Cu(II) ions. The dimeric complex units are connected with each other by strong Osbnd H⋯O hydrogen bonds to form strands linked together via weaker Csbnd H⋯O and Csbnd H⋯π interactions. Comparative discussion including the redetermined crystal structures obtained from copper(II) benzoate in the presence of methanol (1) or ethanol (2) allows to draw argumentation regarding the coordination of linear alcohols in corresponding crystals of paddle-wheel complexes.

  14. Ultrasonic studies of mixtures of ethyl formate and n-alcohols in carbon tetrachloride

    NASA Astrophysics Data System (ADS)

    Elangovan, S.; Mullainathan, S.

    2013-04-01

    Density ( ρ), viscosity ( η) and ultrasonic velocity ( U) have been measured for the ternary mixtures of ethyl formate with 1-butanol, 1-pentanol and 1-hexanol in carbon tetrachloride at 303 K. From the experimental data, several acoustic parameters such as adiabatic compressibility ( β), acoustic impedance( Z), viscous relaxation time( τ), free length ( L f ), free volume ( V f ), internal pressure ( π i ) and Gibb's free energy (Δ G) have been determined. The excess values of the above parameters ( β E , Z E , τ E , L f E , V f E , π i E and Δ G E ) were also determined and interpreted in terms of molecular association such as hydrogen bonding formed between the liquid mixtures. The results show that hetero-association and homo-association of molecules decrease with the increase in chain length of carbon atoms in alcohols. It is observed that the molecular interaction of alcohols with ethyl formate is in the order of 1-butanol < 1-pentanol < 1-hexanol.

  15. Solubility of simvastatin: A theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Aceves-Hernández, Juan M.; Hinojosa-Torres, Jaime; Nicolás-Vázquez, Inés; Ruvalcaba, Rene Miranda; García, Rosa María Lima

    2011-05-01

    Solubility experimental data from Simvastatin in a family of alcohols were obtained at different temperatures. Simvastatin was characterized by using thermal analysis and X-ray diffraction. From the experimental solubility data an anomalous behavior was observed, since an increase the number of alcohol carbon atoms shows an increase in solubility only for the three first alcohols, ethanol, 1-propanol and 1-butanol. A decrease in solubility was obtained for 1-pentanol, 1-hexanol and 1-octanol. Van't·Hoff equation was used to obtain the theoretical solubility value and the ideal activity coefficient. Experimental error was very low and does not affect the plots and equations used. No polymorphic phenomenon was found from the Simvastatin characterization. Theoretical calculations were carried out in order to corroborate the experimental solubility data. Trends and results are similar in both cases. The geometry optimizations of Simvastatin was carried out using density functional theory with Becke's three parameter hybrid method and correlation functional of Lee, Yang and Parr (B3LYP) with 6-311++G∗∗ basis set. The solvent effect was treated using a continuum model as modeled in water, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol and 1-octanol. Moreover, dielectric constant, dipolar moment and solubility in the solvents were obtained for explaining the former behavior.

  16. Yields and decay kinetics of the solvated electron in pulse radiolysis of 1-alkanols

    NASA Astrophysics Data System (ADS)

    Kalachandra, S.; Farhataziz; Foyt, David C.

    The products of the yields of the solvated electron in 1-alkanols, G(e alk-, and the extinction coefficient of e alk- at its absorption maximum, ɛ(e alk-) max, relative to the same product for the hydrated electron, G(e aq-)ɛ(e aq-) max, for a 60 nsec irradiation at room temperature are given in parentheses after the name of each 1-alkanol: methanol (0.38), ethanol (0.42), 1-propanol (0.33), 1-butanol (0.30), 1-pentanol (0.28), 1-hexanol (0.31), 1-heptanol (0.27), 1-octanol (0.29), 1-nonanol (0.26), and 1-decanol (0.24). The decay kinetics of e alk- after 60 or 400 nsec of pulse irradiation of 1-alkanols, C 1-C 10, fit competitive pseudo-first order and second order (initial concentrations of both reactants the same) processes. Except for 1-propanol to 1-pentanol, the observed second order specific rates are a function of the dose per pulse. A mechanism is proposed for the above given decay kinetics of e alk- in C 1C 10 1-alkanols.

  17. Electron spin resonance and electron spin echo modulation studies of N,N,N',N'-tetramethylbenzidine photoionization in sodium dodecyl sulfate micelles: structural effects of alcohol addition

    SciTech Connect

    Baglioni, P.; Kevan, L.

    1987-04-09

    Electron spin echo modulation (ESEM) and electron spin resonance (ESR) spectra of the photogenerated N,N,N',N'-tetramethylbenzidine cation radical (TMB/sup +/) in frozen micellar solutions of sodium dodecyl sulfate containing 2-propanol, 1-propanol, 1-pentanol, 1-octanol, 2-propanol-d/sub 7/, and 1-octanol-d/sub 17/ in H/sub 2/O and D/sub 2/O have been studied as a function of the alcohol concentration from 0 to 200 mM. Modulation effects due to the TMB/sup +/ interactions with deuteriums in D/sub 2/O and in 2-propanol-d/sub 7/ or 1-octanol-d/sub 17/ give direct evidence that 2-propanol is mainly located at the micellar interface whereas the alkyl chain of 1-octanol is located deeper into the micelle. Alcohol addition leads to an increase of water penetration into the micellar interface in the order 1-propanol < 2-propanol approx.= 1-pentanol < 1-octanol. The initial efficiency of charge separation upon potoionization of TMB as a function of alcohol concentration correlates with the degree of water penetration into the micelle, but the maximum photoionization efficiency seems more related to the degree of water organization at the micellar surface due to specific perturbing effects on the micellar structure dependent on the alcohol structure.

  18. Adsorption of sodium dodecyl sulfate on kaolin from different alcohol-water mixtures

    SciTech Connect

    Blokhus, A.M.; Hoeiland, H.; Gjerde, M.I.; Ersland, E.K.

    1996-05-10

    The adsorption of surfactants on solid/liquid interfaces is a subject of great interest especially for enhanced oil recovery processes. The adsorption of sodium dodecyl sulfate (SDS) onto kaolin from different alcohol-water mixtures has been studied. The alcohols used were 1-propanol, 1-butanol, 1-pentanol, and 1-decanol containing 3.5 or 7 wt% water. In all cases the adsorption isotherms show a rather steep rise at low surfactant concentrations. Thereafter, there is a more or less continuous leveling off. The plateau adsorption of SDS on kaolin is found to increase with increasing chain length of the alcohol in the alcohol-water solvent. The adsorption properties are discussed in relation to the dielectric constant of the solvents; the aggregation properties of the surfactant in the bulk phase and the molecular packing of the surfactant in the adsorbed state are also considered.

  19. Characterization of a new mobility separation tool: HRIMS as differential mobility analyzer.

    PubMed

    Bouza, Marcos; López-Vidal, Silvia; Pisonero, Jorge; Bordel, Nerea; Pereiro, Rosario; Sanz-Medel, Alfredo

    2014-12-01

    High resolution ion mobility spectrometer (HRIMS) is a new instrument that uses parallel plate Differential Mobility Analysis as principle of separation. Gas phase analysis of volatile organic compounds (VOCs) has been performed for the characterization of this new mobility system using an UV-lamp for ionization. Studies of the effect of temperature and the presence of a desiccant are detailed. Identification of the different peaks obtained with an electrometer was successfully carried out for a group of alcohols, aromatic compounds and ketones (ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-heptanol, acetone, 2-butanone, 2-pentanone, 2-octanone, benzene, toluene, xylene and bromobenzene) following a modified Millikan equation. Moreover, the investigation of the discrimination capabilities within the different VOCs families as well as the mobility dependence with molecular mass was successfully achieved.

  20. Polymer/Solvent and Polymer/Polymer Interaction Studies

    DTIC Science & Technology

    1980-09-01

    pentane Hl Methanol B3 2-Methyl hexane H2 Ethanol B4 i-Octane H3 l-Propanol H4 2-Propanol Cl Ethylene H5 1-Butanol C2 Allene H6 2-Butanol 03 2-Hexene H7...i-Butanol C4 2-Heptene H8 1-Pentanol C5 1- Octene H9 1-Hexanol C6 2- Octene HIO Cyclohexanol C7 2,6-Dimethyl-3-heptene HII Allyl alcohol H12 Benzyl...E2 Toluene 16 m-Methoxyl phenol E3 m-Xylene 17 Propylene glycol E4 Ethyl benzene 18 Resorcinol monoacetate 19 Ethylene glycol Fl Furan I10 1,5

  1. Quantum-chemical modeling of energy parameters and vibrational spectra of chain and cyclic clusters of monohydric alcohols

    NASA Astrophysics Data System (ADS)

    Golub, P.; Doroshenko, I.; Pogorelov, V.

    2014-05-01

    The specific peculiarities of alcohols such as heightened viscosity, boiling temperature and surface tension can be explained by the capability of their molecules to form relatively stable associates named clusters due to hydrogen bonding. In present work the stability of different chain-like and cyclic clusters of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol was investigated by means of quantum-chemical simulation and particular by recently developed DFT exchange-correlation functional M06-2X. The relative stability of the cluster structure was evaluated by the total energy per molecule at low temperatures (where all alcohols exist in solid state) and by the changing of the free Gibbs energy upon cluster formation at the room temperature. For the verification of revealed results the conformity of calculated IR spectra of the most stable cluster structures with the experimental IR spectra at different temperatures was analyzed.

  2. Synthesis of Ag and AgI quantum dots in AOT-stabilized water-in-CO2 microemulsions.

    PubMed

    Liu, Juncheng; Raveendran, Poovathinthodiyil; Shervani, Zameer; Ikushima, Yutaka; Hakuta, Yukiya

    2005-03-04

    Silver and silver iodide nanocrystals have been synthesized in the water-in-CO(2) reverse microemulsions formed by the commonly used surfactant, sodium bis(2-ethylhexyl)sulfosuccinate (AOT), in the presence of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol as cosurfactant. The nanometer-sized aqueous domains in the microemulsion cores not only act as nanoreactors, but the surfactant interfacial monolayer also helps the stabilization of the metal and semiconductor nanoparticles. The transmission electron microscopy results show that silver and silver iodide nanocrystals with average diameters of 6.0 nm (standard deviation, SD=1.3 nm) and 5.7 nm (SD=1.4 nm), respectively, were formed. The results indicate that the method can be utilized as a general and economically viable approach for the synthesis of metal and semiconductor quantum dots in environmentally benign supercritical carbon dioxide.

  3. Optical constants of alcohols in the infrared

    NASA Technical Reports Server (NTRS)

    Sethna, P. P.; Williams, D.

    1979-01-01

    The spectral reflectances at near-normal incidence for methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol are reported for the spectral range 6700-350 kaysers. The real and imaginary parts of the complex index of refraction of these liquids are obtained in the range 4000-400 kaysers by use of Kramers-Kronig phase-shift analysis. For all of the alcohols studied, the strength for the OH-stretch bands is directly proportional to the number of OH groups per unit volume; similar relations are established for CH- and CO-stretch bands. Absorption cross sections for stretch vibrations of the three groups are considered, and the role of characteristic group intensities in intensity spectroscopy is discussed.

  4. Modification of the murakami retention model in reversed-phase high-performance liquid chromatography for micellar chromatographic separations

    NASA Astrophysics Data System (ADS)

    Loginova, L. P.; Boichenko, A. P.; Kulikov, A. Yu.

    2008-09-01

    A retention model for micellar liquid chromatography was tested based on the data of separation of three benzodiazepins and six β-blockers. The model was obtained by analyzing changes in the microenvironment of a sorbate in transferring from the mobile to stationary phase. It can be used to describe the retention of benzodiazepins, which are neutral under the separation conditions, and the positively charged β-blockers. The calculated model coefficients are indicative of an increase in the number of 1-pentanol molecules and sodium dodecyl sulfate monomers in the microenvironment of the sorbates in transferring from the mobile to stationary phase. The solvation of the positive β-blockers by anionic surfactant monomers was higher than that of neutral benzodiazepins.

  5. Real-time feedback control using online attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy for continuous flow optimization and process knowledge.

    PubMed

    Skilton, Ryan A; Parrott, Andrew J; George, Michael W; Poliakoff, Martyn; Bourne, Richard A

    2013-10-01

    The use of automated continuous flow reactors is described, with real-time online Fourier transform infrared spectroscopy (FT-IR) analysis to enable rapid optimization of reaction yield using a self-optimizing feedback algorithm. This technique has been applied to the solvent-free methylation of 1-pentanol with dimethyl carbonate using a γ-alumina catalyst. Calibration of the FT-IR signal was performed using gas chromatography to enable quantification of yield over a wide variety of flow rates and temperatures. The use of FT-IR as a real-time analytical technique resulted in an order of magnitude reduction in the time and materials required compared to previous studies. This permitted a wide exploration of the parameter space to provide process understanding and validation of the optimization algorithms.

  6. Urinary excretion of 2,5-hexanedione and peripheral polyneuropathies in workers exposed to hexane

    SciTech Connect

    Governa, M.; Calisti, R.; Coppa, G.; Tagliavento, G.; Colombi, A.; Troni, W.

    1987-01-01

    Forty shoe factory workers who were exposed to hexane were investigated to see if there was a correlation between electroneuromyographic changes indicative of neuropathy and urinary excretion of 2,5-hexanedione. Urinary samples were analyzed for the presence of the metabolic products of n-hexane and its isomers. Electrodiagnostic examination was carried out following the urinary sampling. A rating scale was used to obtain a cumulative numeric index of electrodiagnostic findings. 2,5-Hexanedione and ..gamma..-valerolactone were discovered in all cases, while 2-hexanol was found in 11 cases. 2,5-Hexanedione was the main metabolite in most cases (39 of 40). Only in 1 case was a low level of 2-methyl-2-pentanol detected; 3-methyl-2-pentanol was never detected. Metabolic products of cyclohexane were present in about one-fifth of the cases, while trichloroethanol, a metabolic product of trichloroethylene, was nearly always present, all at very low concentrations. Electromyographic abnormalities significant for early detection of toxic polyneuropathy were found in 14 cases. A statistically significant correlation of the electroneuromyographic scoring on the urinary concentrations of measured metabolites was observed only with 2,5-hexanedione and ..gamma..-valerolactone, both derived from n-hexane. Since ..gamma..-valerolactone is probably not a true metabolite of n-hexane, the authors results support the hypothesis that polyneuropathies in shoemakers are due to 2,5-hexanedione. For practical purposes the urinary concentration of 2,5-hexanedione can serve as a predictive measurement for early detection of neurotoxic lesions at preclinical states.

  7. Enhanced solubilization and desorption of organochlorine pesticides (OCPs) from soil by oil-swollen micelles formed with a nonionic surfactant.

    PubMed

    Zheng, Guanyu; Selvam, Ammaiyappan; Wong, Jonathan W C

    2012-11-06

    The effect of oil-swollen micelles formed with nonionic surfactant polyoxyethylene sorbitan monooleate (Tween 80), cosurfactant 1-pentanol, and linseed oil on the solubilization and desorption of organochlorine pesticides (OCPs) including DDT and γ-HCH from both loam soil and clay soil were investigated. Results showed that the solubilizing capacities of oil-swollen micelles were dependent on the critical micelle concentration (CMC) of Tween 80. Once the concentrations of oil-swollen micelles exceeded the CMC of Tween 80, the oil-swollen micelles exhibited much higher solubilizing capacity than empty Tween 80 micelles for the two OCPs. Desorption tests revealed that oil-swollen micelles could successfully enhance desorption of OCPs from both loam soil and clay soil. However, compared with the efficiencies achieved by empty Tween 80 micelles, oil-swollen micelles exhibited their superiority to desorb OCPs only in loam soil-water system while was less effective in clay soil-water system. Distribution of Tween 80, 1-pentanol and linseed oil in soil-water system revealed that the difference in the sorption behavior of linseed oil onto the two soils is responsible for the different effects of oil-swollen micelles on the desorption of OCPs in loam soil and clay soil systems. Therefore, oil-swollen micelles formed with nonionic surfactant Tween 80 are better candidates over empty micelle counterparts to desorb OCPs from soil with relatively lower sorption capacity for oil fraction, which may consequently enhance the availability of OCPs in soil environment during remediation processes of contaminated soil.

  8. Development and evaluation of novel sensing materials for detecting food contamination

    NASA Astrophysics Data System (ADS)

    Sankaran, Sindhuja

    Rapid detection of food-borne volatile organic compounds (VOCs) such as organic acids and alcohols released by bacterial pathogens is being used as an indicator for detecting bacterial contamination in food by our research group. One of our current research thrusts is to develop novel sensors that will be sensitive to specific compounds (at low operating temperature) associated with food safety. This study evaluates two approaches employed to develop sensors for detecting acid and alcohols at low concentrations. Chemoresistive and piezoelectric sensors were developed based on metal oxides and olfactory system based biomaterials, respectively to detect acetic acid, butanol, 3-methyl-1-butanol, 1-pentanol, and 1-hexanol. The metal oxide based sensors were developed by the sol-gel method. A zinc oxide (ZnO) sensor was found to be sensitive to acetic acid with lower detection limit ranging from 13-40 ppm. The three-layered dip-coated gold electrode based ZnO sensors had a LDL of 18 ppm for acetic acid detection. The ZnO-iron oxide (Fe2O3) based nanocomposite sensors were developed to detect butanol operating at 100°C. The 5% Fe/Zn mole ratio based ZnO-Fe2O3 nanocomposite sensors had high correlation coefficients (>0.90) of calibration curves, low butanol LDLs (26 +/- 7 ppm), and lower variation among the sensor responses. The ZnO and ZnO-Fe2O3 nanocomposite sensors showed potential to detect acetic acid and butanol at low concentrations, respectively at 100°C. QCM based olfactory sensors were developed from olfactory receptor and odorant binding protein based sequences to detect low concentrations of acetic acid and alcohols (3-methyl-1-butanol and 1-hexanol), respectively. The average LDLs for acetic acid as well as alcohols detection of the QCM sensors were < 5 ppm. The linear calibration curve based correlation coefficients of the QCM sensors were > 0.80. Finally, a computational simulation based peptide sequences was designed from olfactory receptors and

  9. Electrophysiological and Behavioral Responses of Male Fall Webworm Moths (Hyphantria cunea) to Herbivory-Induced Mulberry (Morus alba) Leaf Volatiles

    PubMed Central

    Tang, Rui; Zhang, Jin Ping; Zhang, Zhong Ning

    2012-01-01

    Volatile organic compounds (VOCs) were collected from damaged and intact mulberry leaves (Morus alba L., Moraceae) and from Hyphantria cunea larvae by headspace absorption with Super Q columns. We identified their constituents using gas chromatography-mass spectrometry, and evaluated the responses of male H. cunea antennae to the compounds using gas chromatography-flame ionization detection coupled with electroantennographic detection. Eleven VOC constituents were found to stimulate antennae of male H. cunea moths: β-ocimene, hexanal, cis-3-hexenal, limonene, trans-2-hexenal, cyclohexanone, cis-2-penten-1-ol, 6-methyl-5-hepten-2-one, 4-hydroxy-4-methyl-2-pentanone, trans-3-hexen-1-ol, and 2,4-dimethyl-3-pentanol. Nine of these chemicals were released by intact, mechanically-damaged, and herbivore-damaged leaves, while cis-2-penten-1-ol was released only by intact and mechanically-damaged leaves and β-ocimene was released only by herbivore-damaged leaves. Results from wind tunnel experiments conducted with volatile components indicated that male moths were significantly more attracted to herbivory-induced volatiles than the solvent control. Furthermore, male moths' attraction to a sex pheromone lure was increased by herbivory-induced compounds and β-ocimene, but reduced by cis-2-penten-1-ol. A proof long-range field trapping experiment showed that the efficiency of sex pheromone lures in trapping male moths was increased by β-ocimene and reduced by cis-2-penten-1-ol. PMID:23166622

  10. Degradation mechanisms of geosmin and 2-MIB during UV photolysis and UV/chlorine reactions.

    PubMed

    Kim, Tae-Kyoung; Moon, Bo-Ram; Kim, Taeyeon; Kim, Moon-Kyung; Zoh, Kyung-Duk

    2016-11-01

    We conducted chlorination, UV photolysis, and UV/chlorin reactions to investigate the intermediate formation and degradation mechanisms of geosmin and 2-methylisoborneol (2-MIB) in water. Chlorination hardly removed geosmin and 2-MIB, while the UV/chlorine reaction at 254 nm completely removed geosmin and 2-MIB within 40 min and 1 h, respectively, with lesser removals of both compounds during UV photolysis. The kinetics during both UV photolysis and UV/chlorine reactions followed a pseudo first-order reaction. Chloroform was found as a chlorinated intermediate during the UV/chlorine reaction of both geosmin and 2-MIB. The pH affected both the degradation and chloroform production during the UV/chlorine reaction. The open ring and dehydration intermediates identified during UV/chlorine reactions were 1,4-dimethyl-adamantane, and 1,3-dimethyl-adamantane from geosmin, 2-methylenebornane, and 2-methyl-2-bornene from 2-MIB, respectively. Additionally, 2-methyl-3-pentanol, 2,4-dimethyl-1-heptene, 4-methyl-2-heptanone, and 1,1-dichloro-2,4-dimethyl-1-heptane were newly identified intermediates from UV/chlorine reactions of both geosmin and 2-MIB. These intermediates were degraded as the reaction progressed. We proposed possible degradation pathways during the UV photolysis and UV/chlorine reactions of both compounds using the identified intermediates.

  11. Electrophysiological and behavioral responses of male fall webworm moths (Hyphantria cunea) to Herbivory-induced mulberry (Morus alba) leaf volatiles.

    PubMed

    Tang, Rui; Zhang, Jin Ping; Zhang, Zhong Ning

    2012-01-01

    Volatile organic compounds (VOCs) were collected from damaged and intact mulberry leaves (Morus alba L., Moraceae) and from Hyphantria cunea larvae by headspace absorption with Super Q columns. We identified their constituents using gas chromatography-mass spectrometry, and evaluated the responses of male H. cunea antennae to the compounds using gas chromatography-flame ionization detection coupled with electroantennographic detection. Eleven VOC constituents were found to stimulate antennae of male H. cunea moths: β-ocimene, hexanal, cis-3-hexenal, limonene, trans-2-hexenal, cyclohexanone, cis-2-penten-1-ol, 6-methyl-5-hepten-2-one, 4-hydroxy-4-methyl-2-pentanone, trans-3-hexen-1-ol, and 2,4-dimethyl-3-pentanol. Nine of these chemicals were released by intact, mechanically-damaged, and herbivore-damaged leaves, while cis-2-penten-1-ol was released only by intact and mechanically-damaged leaves and β-ocimene was released only by herbivore-damaged leaves. Results from wind tunnel experiments conducted with volatile components indicated that male moths were significantly more attracted to herbivory-induced volatiles than the solvent control. Furthermore, male moths' attraction to a sex pheromone lure was increased by herbivory-induced compounds and β-ocimene, but reduced by cis-2-penten-1-ol. A proof long-range field trapping experiment showed that the efficiency of sex pheromone lures in trapping male moths was increased by β-ocimene and reduced by cis-2-penten-1-ol.

  12. Two Volatile Organic Compounds Trigger Plant Self-Defense against a Bacterial Pathogen and a Sucking Insect in Cucumber under Open Field Conditions

    PubMed Central

    Song, Geun Cheol; Ryu, Choong-Min

    2013-01-01

    Systemic acquired resistance (SAR) is a plant self-defense mechanism against a broad-range of pathogens and insect pests. Among chemical SAR triggers, plant and bacterial volatiles are promising candidates for use in pest management, as these volatiles are highly effective, inexpensive, and can be employed at relatively low concentrations compared with agrochemicals. However, such volatiles have some drawbacks, including the high evaporation rate of these compounds after application in the open field, their negative effects on plant growth, and their inconsistent levels of effectiveness. Here, we demonstrate the effectiveness of volatile organic compound (VOC)-mediated induced resistance against both the bacterial angular leaf spot pathogen, Pseudononas syringae pv. lachrymans, and the sucking insect aphid, Myzus persicae, in the open field. Using the VOCs 3-pentanol and 2-butanone where fruit yields increased gave unexpectedly, a significant increase in the number of ladybird beetles, Coccinella septempunctata, a natural enemy of aphids. The defense-related gene CsLOX was induced by VOC treatment, indicating that triggering the oxylipin pathway in response to the emission of green leaf volatiles can recruit the natural enemy of aphids. These results demonstrate that VOCs may help prevent plant disease and insect damage by eliciting induced resistance, even in open fields. PMID:23698768

  13. Dislodgement effect of natural semiochemicals released by disturbed triatomines: a possible alternative monitoring tool.

    PubMed

    Minoli, Sebastián; Palottini, Florencia; Crespo, Jose Guillermo; Manrique, Gabriel

    2013-12-01

    The quick detection of domestic and peridomestic triatomines in their environments becomes difficult without the use of dislodgement substances that flush them out from their shelters. At present, tetramethrin 0.2% is being widely used in control programs. Although it is an efficient dislodging agent, its toxicity might affect the health of captured triatomines, of other insects and, to a lesser extent, of other animals, including humans. Here, we tested if semiochemicals released by disturbed adults of Triatoma infestans and/or Rhodnius prolixus can make larvae of the same species exit from their refuges. In a walking olfactometer we found that: 1) larvae of T. infestans were repelled by the odors released by disturbed adults of their own species and of R. prolixus, 2) larvae of R. prolixus did not change their behavior in the presence of odors released by adults of both species, and 3) activity levels were not modulated by these odors in any of both species. Besides, in pseudo-natural conditions we found an increased flushing-out activity of larvae of T. infestans when their shelters were sprayed with isobutyric acid or 3-pentanol, and of larvae of R. prolixus when sprayed with 3-methyl-1-butanol. We succeeded in this work to dislodge larvae of triatomines from artificial shelters using natural volatile compounds, allowing the capture of live bugs for further investigations (e.g., xenodiagnosis or genetic studies) and favoring ecological aspects (e.g., minimizing environmental insecticide-contamination and non-targeted mortality).

  14. A Long-Chain Secondary Alcohol Dehydrogenase from Rhodococcus erythropolis ATCC 4277

    PubMed Central

    Ludwig, B.; Akundi, A.; Kendall, K.

    1995-01-01

    A NAD-dependent secondary alcohol dehydrogenase has been purified from the alkane-degrading bacterium, Rhodococcus erythropolis ATCC 4277. The enzyme was found to be active against a broad range of substrates, particularly long-chain secondary aliphatic alcohols. Although optimal activity was observed with linear 2-alcohols containing between 6 and 11 carbon atoms, secondary alcohols as long as 2-tetradecanol were oxidized at 25% of the rate seen with mid-range alcohols. The purified enzyme was specific for the S-(+) stereoisomer of 2-octanol and had a specific activity for 2-octanol of over 200 (mu)mol/min/mg of protein at pH 9 and 37(deg)C, 25-fold higher than that of any previously reported S-(+) secondary alcohol dehydrogenase. Linear primary alcohols containing between 3 and 13 carbon atoms were utilized 20- to 40-fold less efficiently than the corresponding secondary alcohols. The apparent K(infm) value for NAD(sup+) with 2-octanol as the substrate was 260 (mu)M, whereas the apparent K(infm) values for the 2-alcohols ranged from over 5 mM for 2-pentanol to less than 2 (mu)M for 2-tetradecanol. The enzyme showed moderate thermostability (half-life of 4 h at 60(deg)C) and could potentially be useful for the synthesis of optically pure stereoisomers of secondary alcohols. PMID:16535152

  15. Homogeneous catalysis on the gas-phase dehydration reaction of tertiary alcohols by hydrogen bromide. Density functional theory calculation

    NASA Astrophysics Data System (ADS)

    Maldonado, Alexis; Rosas, Felix; Mora, Jose R.; Brusco, Yannely; Córdova-Sintjago, Tania C.; Chuchani, Gabriel

    2015-02-01

    The gas-phase thermal dehydration mechanism of tert-butanol, 2-methyl-2-butanol, 2-methyl-2-pentanol and 2,3-dimethyl-2-butanol by homogeneous catalysis of hydrogen bromide was examined by density functional theory calculations with the hybrid functionals: M062X, CAMB3LYP and WB97XD. Reasonable agreements were found between theoretical and experimental enthalpy values at the WB97XD/6-311++G(d,p) level. The dehydration mechanism of tert-butanol with and without catalysis was evaluated in order to examine the catalyst effect on the mechanism. The elimination reaction without catalysis involves a four-membered transition state (TS), while the reaction with catalysis involves a six-membered TS. The mechanism without catalysis has enthalpy activation over 150 kJ mol-1 greater than the catalysed reaction. In all these reactions, the elongation of the C-O bond is significant in the TS. The un-catalysed reaction is controlled by breaking of C-O bond, and it was found to be more synchronous (Sy ≈ 0.91) than the hydrogen bromide catalysed reactions (Sy ≈ 0.75-0.78); the latter reactions are dominated by the three reaction coordinates associated with water formation. No significant effect on the enthalpies of activation was observed when the size of the alkyl chain was increased.

  16. Interplay of Metalloligand and Organic Ligand to Tune Micropores within Isostructural Mixed-Metal Organic Frameworks (M MOFs) for Their Highly Selective Separation of Chiral and Achiral Small Molecules

    SciTech Connect

    Madhab, Das; He, Yabing; Kim, Jaheon; Guo, Qunsheng; Zhao, Cong-Gui; Hong, Kunlun; Xiang, Sheng-Chang; Zhang, Zhangjing; Thomas, K Mark; Krishna, Rajamani; Chen, Banglin

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M'MOFs) have been synthesized and structurally characterized. The pores within these M'MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selective separation of chiral alcohols 1-phenylethanol (PEA), 2-butanol (BUT), and 2-pentanol (2-PEN) with the highest ee up to 82.4% but also to lead highly selective separation of achiral C{sub 2}H{sub 2}/C{sub 2}H{sub 4} separation. The potential application of these M'MOFs for the fixed bed pressure swing adsorption (PSA) separation of C{sub 2}H{sub 2}/C{sub 2}H{sub 4} has been further examined and compared by the transient breakthrough simulations in which the purity requirement of 40 ppm in the outlet gas can be readily fulfilled by the fixed bed M'MOF-4a adsorber at ambient conditions.

  17. Studies on the interaction between ethanol and two industrial solvents (methyl isobutyl ketone) in mice

    SciTech Connect

    Granvil, C.P.; Sharkawi, M.; Plaa, G.L. )

    1991-03-11

    Methyl n-butyl ketone (MnBK) and methyl isobutyl ketone (MiBK) prolong the duration of ethanol-induced loss of righting reflex (EILRR) in mice. MnBK was almost twice as potent in this regard. To explain this difference, the metabolism of both ketones was studied in male CD-1 mice using GC. MiBK was converted to 4-methyl-2-pentanol (4MPOL) and 4-hydroxy methyl isobutyl ketone (HMP). MnBK metabolites were 2-hexanol (2HOL) and 2,5-hexanedione (2,5HD). The effects of both ketones and metabolites on EILRR and ethanol (E) elimination were studied in mice. The ketones and their metabolites were dissolved in corn oil and injected intraperitoneally 30 min before E 4g/kg for EILRR and 2g/kg for E elimination. In the following doses: MnBK, 5; MiBK, 5; 2HOL, 2.5; 4MPOL, 2.5; and HMP 2.5, significantly prolonged EILRR. Concentrations of E in blood and brain upon return of the righting reflex were similar in solvent-treated and control animals. The mean elimination rate of E was slower in groups given MnBK or 2HOL than in control animals. No change in E elimination was observed with MiBK, HMP, 4MPOL, or 2, 5HD.

  18. Headspace solid phase microextraction and gas chromatography-olfactometry dilution analysis of young and aged Chinese "Yanghe Daqu" liquors.

    PubMed

    Fan, Wenlai; Qian, Michael C

    2005-10-05

    The aroma compounds of young and aged Chinese "Yanghe Daqu" liquor samples were extracted by solid phase microextraction (SPME) and analyzed by gas chromatography (GC)-olfactometry dilution analysis. The original liquor samples were diluted with deionized water to give a final alcohol content of 14% (v/v). The samples were stepwise diluted (1:1) with 14% (by volume) ethanol-water solution and then extracted by headspace SPME. The samples were preequilibrated at 50 degrees C for 15 min and extracted with stirring at the same temperature for 30 min prior to injection into GC. The aroma compounds were identified by both GC-MS and GC-olfactometry using DB-Wax and DB-5 columns. The results suggested that esters were the major contributors to Yanghe Daqu liquor aroma. Ethyl hexanoate, ethyl butanoate, and ethyl pentanoate had very high flavor dilution values in both young and aged liquors (FD > 8192). Methyl hexanoate, ethyl heptanoate, ethyl benzoate, and butyl hexanoate could also be very important because of their high flavor dilution values (FD > or = 256). Moreover, two acetals, 1,1-diethoxyethane and 1,1-diethoxy-3-methylbutane, also were shown high flavor dilution values in Yanghe Daqu liquors (FD > or = 256). Other aroma compounds having moderate flavor dilution values included acetaldehyde, 3-methylbutanol, and 2-pentanol (FD > or = 32). Comparing young and aged liquors, the aroma profiles were similar, but the aroma compounds in the aged sample had higher flavor dilution values than in the young ones.

  19. The effect of oxygen on chemical dechlorination of dieldrin using iron sulphides.

    PubMed

    Hara, Junko

    2011-02-01

    The degradation of dieldrin by ferric sulphide (FeS(2)) in aqueous solution was investigated when shielded against sunlight. An oxidative dechlorination process was observed under aerobic and anaerobic conditions; oxygen volume changed the degradation rate of dieldrin and the generation rate of reaction products. The dechlorination rate under microaerophilic conditions was fastest among the anaerobic to air oxygen concentrations. For this experiment, over 99% of the dieldrin was degraded, and 90% of the released chloride was detected after 30 d under 10 μ mol oxygen. The major reaction products were different depending on the dose of oxygen. In the case of aerobic conditions, low molecular weight organic acids, such as formic acid, lactic acid, and oxalic acid, were generated as major reaction products. However, under anaerobic conditions, C(16)H(22)O(4) (dibutyl phthalate) and C(6)H(13)ClO (3-chloro-4-methyl-2-pentanol) were detected as reaction intermediates, and small amounts of succinic acid, malonic acid, and formic acid were also generated. These reactions proceed by FeS(2) interface reactions with H(2)O under anaerobic condition, or O(2) under aerobic condition.

  20. Development and validation of a method to determine thiabendazole and o-phenylphenol in wastewater using micellar liquid chromatography-fluorescence detection.

    PubMed

    Peris-Vicente, Juan; Roca-Genovés, Pasqual; Tayeb-Cherif, Khaled; Esteve-Romero, Josep

    2016-10-01

    A micellar liquid chromatographic method to determine thiabendazole (TBZ) and o-phenylphenol in wastewater is described here. The sample was directly injected without any additional treatment other filtration. The pesticides were resolved in <11 min, using a mobile phase of 0.10 M SDS-6% 1-pentanol buffered at pH 3 running through a C18 column at 1 mL/min. The detection was performed by fluorescence at 305/360 and 245/345 nm excitation/emission wavelengths for TBZ and o-phenylphenol, respectively. The method was validated following the directives of the Validation and Peer Review of U.S. Environmental Protection Agency Chemical Methods of Analysis guidelines in terms of selectivity, quantitation range (0.01-0.02 to 2 mg/L), detection limit (0.005-0.008 mg/L), trueness (92.1-104.2%), precision (<13.9%), robustness (<6.6%), and stability under storage conditions. The procedure was applied to the screening of TBZ and o-phenylphenol in wastewater samples from citrus packing plants, agricultural gutters, urban sewage, as well as in influent and effluent wastewater treatment plants.

  1. Alcohol-tolerant mutants of cyanobacterium Synechococcus elongatus PCC 7942 obtained by single-cell mutant screening system.

    PubMed

    Arai, Sayuri; Hayashihara, Kayoko; Kanamoto, Yuki; Shimizu, Kazunori; Hirokawa, Yasutaka; Hanai, Taizo; Murakami, Akio; Honda, Hiroyuki

    2017-04-12

    Enhancement of alcohol tolerance in microorganisms is an important strategy for improving bioalcohol productivity. Although cyanobacteria can be used as a promising biocatalyst to produce various alcohols directly from CO2 , low productivity and low tolerance against alcohols are the main issues to be resolved. Nevertheless, to date, a mutant with increasing alcohol tolerance has rarely been reported.n this study, we attempted to select isopropanol (IPA)-tolerant mutants of Synechococcus elongatus PCC 7942 using UV-C-induced random mutagenesis, followed by enrichment of the tolerant candidates in medium containing 10 g/L IPA and screening of the cells with a high growth rate in the single cell culture system in liquid medium containing 10 g/L IPA. We successfully acquired the most tolerant strain, SY1043, which maintains the ability to grow in medium containing 30 g/L IPA. The photosynthetic oxygen-evolving activities of SY1043 were almost same in cells after 72-h incubation under light with or without 10 g/L IPA, while the activity of the wild-type was remarkably decreased after the incubation with IPA. SY1043 also showed higher tolerance to ethanol, 1-butanol, isobutanol, and 1-pentanol than the wild type. These results suggest that SY1043 would be a promising candidate to improve alcohol production using cyanobacteria. This article is protected by copyright. All rights reserved.

  2. Volatile compounds originating from mixed microbial cultures on building materials under various humidity conditions.

    PubMed

    Korpi, A; Pasanen, A L; Pasanen, P

    1998-08-01

    We examined growth of mixed microbial cultures (13 fungal species and one actinomycete species) and production of volatile compounds (VOCs) in typical building materials in outside walls, separating walls, and bathroom floors at various relative humidities (RHs) of air. Air samples from incubation chambers were adsorbed on Tenax TA and dinitrophenylhydrazine cartridges and were analyzed by thermal desorption-gas chromatography and high-performance liquid chromatography, respectively. Metabolic activity was measured by determining CO2 production, and microbial concentrations were determined by a dilution plate method. At 80 to 82% RH, CO2 production did not indicate that microbial activity occurred, and only 10% of the spores germinated, while slight increases in the concentrations of some VOCs were detected. All of the parameters showed that microbial activity occurred at 90 to 99% RH. The microbiological analyses revealed weak microbial growth even under drying conditions (32 to 33% RH). The main VOCs produced on the building materials studied were 3-methyl-1-butanol, 1-pentanol, 1-hexanol, and 1-octen-3-ol. In some cases fungal growth decreased aldehyde emissions. We found that various VOCs accompany microbial activity but that no single VOC is a reliable indicator of biocontamination in building materials.

  3. Rapid ester biosynthesis screening reveals a high activity alcohol-O-acyltransferase (AATase) from tomato fruit.

    PubMed

    Lin, Jyun-Liang; Zhu, Jie; Wheeldon, Ian

    2016-05-01

    Ethyl and acetate esters are naturally produced in various yeasts, plants, and bacteria. The biosynthetic pathways that produce these esters share a common reaction step, the condensation of acetyl/acyl-CoA with an alcohol by alcohol-O-acetyl/acyltransferase (AATase). Recent metabolic engineering efforts exploit AATase activity to produce fatty acid ethyl esters as potential diesel fuel replacements as well as short- and medium-chain volatile esters as fragrance and flavor compounds. These efforts have been limited by the lack of a rapid screen to quantify ester biosynthesis. Enzyme engineering efforts have also been limited by the lack of a high throughput screen for AATase activity. Here, we developed a high throughput assay for AATase activity and used this assay to discover a high activity AATase from tomato fruit, Solanum lycopersicum (Atf-S.l). Atf1-S.l exhibited broad specificity towards acyl-CoAs with chain length from C4 to C10 and was specific towards 1-pentanol. The AATase screen also revealed new acyl-CoA substrate specificities for Atf1, Atf2, Eht1, and Eeb1 from Saccharomyces cerevisiae, and Atf-C.m from melon fruit, Cucumis melo, thus increasing the pool of characterized AATases that can be used in ester biosynthesis of ester-based fragrance and flavor compounds as well as fatty acid ethyl ester biofuels.

  4. Use of micellar liquid chromatography for rapid monitoring of fungicides post harvest applied to citrus wastewater.

    PubMed

    Peris-Vicente, Juan; Marzo-Mas, Ana; Roca-Genovés, Pasqual; Carda-Broch, Samuel; Esteve-Romero, Josep

    2016-04-01

    A method based on micellar liquid chromatography has been developed to simultaneously monitor four pesticides largely post-harvest applied to citrus: thiabendazole, pyrimethanil, o-phenylphenol and imazalil. Water samples were filtered and directly injected without other treatment, thus avoiding extraction steps. The composition of the mobile phase was optimized using a chemometrical approach to achieve and excellent resolution to 0.07 mol/L SDS/5%, V/V 1-pentanol buffered at pH3. Mobile phase run through a C18 column at 1 mL/min at room temperature. The detection was performing by UV-Visible absorbance using a wavelength program: 0-10 min, 305 nm (for thiabendazole); 10-12; 265 nm (for pyrimethanil) and 12-18, 220 nm (o-phenylphenol and imazalil). The developed method was validated following the guidelines of the US Environmental Protection Agency in terms of: quantitation range, (0.5-4 to 15 μg/mL), linearity (r(2)>0.9995), sensitivity (LOD, 0.18-1.4 μg/mL), precision (<9.2%), trueness (93.9%-103.7%), and ruggedness (<9.9%). It was found that the fungicides remain up to eight days in surface water at outdoor conditions. The method was used to screen the presence of the analytes in several waste water samples, and was proved to be useful in routine analysis.

  5. Analysis of volatile compounds and triglycerides of seed oils extracted from different poppy varieties (Papaver somniferum L.).

    PubMed

    Krist, Sabine; Stuebiger, Gerald; Unterweger, Heidrun; Bandion, Franz; Buchbauer, Gerhard

    2005-10-19

    Poppy seed oil (Oleum Papaveris Seminis) is used for culinary and pharmaceutical purposes, as well as for making soaps, paints, and varnishes. Astonishingly, hardly anything was yet known about the volatile compounds of this promising comestible. Likewise, there are no current published data about the triglyceride (TAG) composition of poppy seed oils available. In this investigation solid-phase microextraction (SPME) with DVB/Carboxen/PDMS Stable-Flex fiber was applied to the study of volatile compounds of several seed oil samples from Papaver somniferum L. (Papaveraceae). 1-Pentanol (3.3-4.9%), 1-hexanal (10.9-30.9%), 1-hexanol (5.3-33.7%), 2-pentylfuran (7.2-10.0%), and caproic acid (2.9-11.5%) could be identified as the main volatile compounds in all examined poppy seed oil samples. Furthermore, the TAG composition of these oils was analyzed by MALDI-ReTOF- and ESI-IT-MS/MS. The predominant TAG components were found to be composed of linoleic, oleic, and palmitic acid, comprising approximately 70% of the oils. TAG patterns of the different poppy varieties were found to be very homogeneous, showing also no significant differences in terms of the applied pressing method of the plant seeds.

  6. Surface Tension Characteristics of Aqueous Lithium Bromide Solution with Alcoholic Surfactant

    NASA Astrophysics Data System (ADS)

    Sasaki, Naoe; Ogawa, Kiyoshi

    At present, the combination of aqueous lithium bromide (LiBr) solution as an absorbent and water as a refrigerant have widely been used as the working fluid for absorption refrigerating machines. In order to obtain absorption enhancement of water vapor into the LiBr solution by Marangoni convection, an alcoholic surfactant is being added in the LiBr solution. In that case, the surface tension of the LiBr solution with the surfactant plays an important role for the vapor absorption. In this study, the surface tensions of the LiBr solution with several alcoholic surfactants such as 1-butanol, 1-hexanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol and 2-ethyl-1-hexanol were measured by Wilhelmy plate method. As a result, the surface tensions of 50 wt% LiBr solution with several surfactants were obtained over the LiBr solution temperature range from 298 K to 318 K and the surfactant concentration range from 0 to 104 ppm by mass. The measured surface tension has decreased with the increasing number of carbons included in the surfactant at constant concentration, and the surface tension has increased with the increasing temperature of 50 wt% LiBr solution. The surface tension increase of 1-octanol became greater than any other surfactant used in this work. The effective carbon number of the surfactant for the absorption enhancement was in the range from 7 to 8.

  7. Nucleation of ethanol, propanol, butanol, and pentanol: A systematic experimental study along the homologous series

    NASA Astrophysics Data System (ADS)

    Manka, Alexandra A.; Wedekind, Jan; Ghosh, David; Höhler, Kristina; Wölk, Judith; Strey, Reinhard

    2012-08-01

    We present homogeneous vapor-liquid nucleation rates of the 1-alcohols (CnH2n+1OH, n = 2-4) measured in the well-established two-valve nucleation pulse chamber as well as in a novel one-piston nucleation pulse chamber at temperatures between 235 and 265 K. The nucleation rates and critical cluster sizes show a very systematic behavior with respect to the hydrocarbon chain length of the alcohol, just as their thermo-physical parameters such as surface tension, vapor pressure, and density would suggest. For all alcohols, except ethanol, predictions of classical nucleation theory lie several orders of magnitude below the experimental results and show a strong temperature-dependence typically found in nucleation experiments. The more recent Reguera-Reiss theory [J. Phys. Chem. B 108(51), 19831 (2004)] achieves reasonably good predictions for 1-propanol, 1-butanol, and 1-pentanol, and independent of the temperature. Ethanol, however, clearly shows the influence of strong association between molecules even in the vapor phase. We also scaled all experimental results with classic nucleation theory to compare our data with other data from the literature. We find the same overall temperature trend for all measurement series together but inverted and inconsistent temperature trends for individual 1-propanol and 1-butanol measurements in other devices. Overall, our data establishe a comprehensive and reliable data set that forms an ideal basis for comparison with nucleation theory.

  8. Molecular Interaction Study of N-Benzylformamide with 1-ALCOHOLS Using X-Band Microwave

    NASA Astrophysics Data System (ADS)

    Manjunath, M. S.; Sannappa, J.

    The secondary amide unit is a subject of particular interest, because of its occurrence in peptides and proteins. Molecular interaction between N-benzylformamide (NBF) with 1-alcohols (1-propanol, 1-butanol, 1-pentanol) has been studied in carbon tetrachloride by using X-band microwave bench at 936 GHz. Dielectric constant (ɛ') and dielectric loss (ɛ″) of alcohol and NBF and their binary mixture for different mole fractions of NBF have been determined. Dielectric relaxation time (τ) of the binary system is obtained by both Higasi's method and the Gopalakrishna single-frequency concentration variational method. The results show that the most likely interaction between alcohols and NBF is 1:1 complex for binary mixture through the free hydroxyl group of the alcohol and the carbonyl group of NBF. The alkyl chain-length of both alcohol and amide plays an important role in the determination of the strength of hydrogen bond (O-H: C=O) formed. The variation of relaxation time of NBF+1-alcohol mixtures in CCl4 indicates a weak solute-solvent type of molecular association. The result shows that as the relaxation time of the proton acceptor increases, the donating ability of the solute environment increase.

  9. Improved conversion efficiencies for n-fatty acid reduction to primary alcohols by the solventogenic acetogen "Clostridium ragsdalei".

    PubMed

    Isom, Catherine E; Nanny, Mark A; Tanner, Ralph S

    2015-01-01

    "Clostridium ragsdalei" is an acetogen that ferments synthesis gas (syngas, predominantly H2:CO2:CO) to ethanol, acetate, and cell mass. Previous research showed that C. ragsdalei could also convert propionic acid to 1-propanol and butyric acid to 1-butanol at conversion efficiencies of 72.3 and 21.0 percent, respectively. Our research showed that C. ragsdalei can also reduce pentanoic and hexanoic acid to the corresponding primary alcohols. This reduction occurred independently of growth in an optimized medium with headspace gas exchange (vented and gassed with CO) every 48 h. Under these conditions, conversion efficiencies increased to 97 and 100 % for propionic and butyric acid, respectively. The conversion efficiencies for pentanoic and hexanoic acid to 1-pentanol and 1-hexanol, respectively, were 82 and 62 %. C. ragsdalei also reduced acetone to 2-propanol at a conversion efficiency of 100 %. Further, we showed that C. ragsdalei uses an aldehyde oxidoreductase-like enzyme to reduce n-fatty acids to the aldehyde intermediates in a reaction that requires ferredoxin and exogenous CO.

  10. Experimental and computational study of the effect of alcohols on the solution and adsorption properties of a nonionic symmetric triblock copolymer.

    PubMed

    Liu, Xiaomeng; He, Feng; Salas, Carlos; Pasquinelli, Melissa A; Genzer, Jan; Rojas, Orlando J

    2012-02-02

    This study investigates the effect of alcohols on the solution and adsorption properties of symmetric triblock nonionic copolymers comprising blocks of ethylene oxide (EO) and propylene oxide (PO) (EO(37)PO(56)EO(37)). The cloud point, surface tension, critical micelle concentration (CMC), and maximum packing at the air-water interface are determined, and the latter is compared to the amount of polymer that adsorbs from solution onto polypropylene (PP) and cellulose surfaces. The interaction energy and radius of micelles are calculated by using molecular dynamics (MD) simulations. Equivalent MD bead parameters were used in dynamic density functional theory (DDFT) simulations to study the influence of alcohols on the phase behavior of EO(37)PO(56)EO(37) and its adsorption on PP from aqueous solutions. The simulation results agree qualitatively with the experimental observations. Ethanol acts as a good cosolvent for EO(37)PO(56)EO(37) and reduces the amount of EO(37)PO(56)EO(37) that adsorbs on PP surfaces; however, little or no influence is observed on the adsorption on cellulose. Interestingly, longer chain alcohols, such as 1-pentanol, produce the opposite effect. Overall, the solution and adsorption properties of nonionic symmetric triblock copolymers in the presence of alcohols are rationalized by changes in solvency and the hydrophobic effect.

  11. Improvement of the Dimensional Stability of Powder Injection Molded Compacts by Adding Swelling Inhibitor into the Debinding Solvent

    NASA Astrophysics Data System (ADS)

    Fan, Yang-Liang; Hwang, Kuen-Shyang; Su, Shao-Chin

    2008-02-01

    Defects are frequently found in powder injection molded (PIM) compacts during solvent debinding due to the swelling of the binders. This problem can be alleviated by adjusting the composition of the debinding solvent. In this study, 10 vol pct swelling inhibitors were added into heptane, and the in-situ amounts of swelling and sagging of the specimen in the solvent were recorded using a noncontacting laser dilatometer. The results show that the addition of ethanol, 2-propanol, 1-butanol, and 1-pentanol reduced the amounts of swelling by 31, 21, 17, and 11 pct, respectively. This was because the small molecule alcohols, which do not dissolve paraffin wax (PW) or stearic acid (SA) in the binder system, could diffuse easily into the specimen and increased the portion of the swelling inhibitor inside. The amount of the extracted PW and SA also decreased, but only by 8.3, 6.1, 4.3, and 2.4 pct, respectively. The solubility parameters of 1-bromopropane (n-PB) and ethyl acetate (EA) are between those of heptane and alcohols, and they also yielded a slight reduction in the amounts of swelling by 6 and 11 pct, respectively. These results suggest that to reduce defects caused by binder swelling during solvent debinding, alcohols with high solubility parameters can be added into heptane without sacrificing significantly on the debinding rate.

  12. Fractionation and identification of minor and aroma-active constituents in Kangra orthodox black tea.

    PubMed

    Joshi, Robin; Gulati, Ashu

    2015-01-15

    The aroma constituents of Kangra orthodox black tea were isolated by simultaneous distillation extraction (SDE), supercritical fluid extraction and beverage method. The aroma-active compounds were identified using gas chromatography-olfactometry-mass spectrometry. Geraniol, linalool, (Z/E)-linalool oxides, (E)-2-hexenal, phytol, β-ionone, hotrienol, methylpyrazine and methyl salicylate were major volatile constituents in all the extracts. Minor volatile compounds in all the extracts were 2-ethyl-5-methylpyrazine, ethylpyrazine, 2-6,10,14-trimethyl-2-pentadecanone, acetylfuran, hexanoic acid, dihydroactinidiolide and (E/Z)-2,6-nonadienal. The concentrated SDE extract was fractionated into acidic, basic, water-soluble and neutral fractions. The neutral fraction was further chromatographed on a packed silica gel column eluted with pentane and diethyl ether to separate minor compounds. The aroma-active compounds identified using gas chromatography-olfactometry-mass spectrometry were 2-amylfuran, (E/Z)-2,6-nonadienal, 1-pentanol, epoxylinalool, (Z)-jasmone, 2-acetylpyrrole, farnesyl acetone, geranyl acetone, cadinol, cubenol and dihydroactinidiolide. AEDA studies showed 2-hexenal, 3-hexenol, ethylpyrazine, (Z/E)-linalool oxides, linalool, (E/Z)-2,6-nonadienal, geraniol, phenylethanol, β-ionone, hotrienol and dihydroactinidiolide to be odour active components.

  13. Dielectric barrier discharge carbon atomic emission spectrometer: universal GC detector for volatile carbon-containing compounds.

    PubMed

    Han, Bingjun; Jiang, Xiaoming; Hou, Xiandeng; Zheng, Chengbin

    2014-01-07

    It was found that carbon atomic emission can be excited in low temperature dielectric barrier discharge (DBD), and an atmospheric pressure, low power consumption, and compact microplasma carbon atomic emission spectrometer (AES) was constructed and used as a universal and sensitive gas chromatographic (GC) detector for detection of volatile carbon-containing compounds. A concentric DBD device was housed in a heating box to increase the plasma operation temperature to 300 °C to intensify carbon atomic emission at 193.0 nm. Carbon-containing compounds directly injected or eluted from GC can be decomposed, atomized, and excited in this heated DBD for carbon atomic emission. The performance of this new optical detector was first evaluated by determination of a series of volatile carbon-containing compounds including formaldehyde, ethyl acetate, methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol, and absolute limits of detection (LODs) were found at a range of 0.12-0.28 ng under the optimized conditions. Preliminary experimental results showed that it provided slightly higher LODs than those obtained by GC with a flame ionization detector (FID). Furthermore, it is a new universal GC detector for volatile carbon-containing compounds that even includes those compounds which are difficult to detect by FID, such as HCHO, CO, and CO2. Meanwhile, hydrogen gas used in conventional techniques was eliminated; and molecular optical emission detection can also be performed with this GC detector for multichannel analysis to improve resolution of overlapped chromatographic peaks of complex mixtures.

  14. Removal of acrylic coatings from works of art by means of nanofluids: understanding the mechanism at the nanoscale

    NASA Astrophysics Data System (ADS)

    Baglioni, Michele; Rengstl, Doris; Berti, Debora; Bonini, Massimo; Giorgi, Rodorico; Baglioni, Piero

    2010-09-01

    Conservation of works of art often involves the inappropriate application of synthetic polymers. We have proposed the use of alternative methodologies for conservation and formulated innovative cleaning nanostructured systems to remove previously applied polymer films and grime from painted surfaces. In particular, a novel ``micellar system'' composed of water, SDS, 1-pentanol, ethyl acetate and propylene carbonate was recently formulated and successfully used to remove acrylic and vinyl/acrylic copolymers from Mesoamerican wall paintings in the archeological site of Cholula, Mexico. This contribution reports on the mechanism of the interaction process that takes place between the nanostructured fluid and the polymer coating at the nanoscale. The structural properties of the ``micellar solution'' and of the polymer film are investigated before, during and after the interaction process using several surface and solution techniques. Rather than a classical detergency mechanism, we demonstrate that micelles act as solvent containers and interact with the polymer film leading to its swelling and detachment from the surface and to its segregation in a liquid droplet, which phase-separates from the aqueous bulk. After the removal process the micelles become smaller in size and undergo a structural re-arrangement due to the depletion of the organic solvents. These findings can be framed in an interaction mechanism which describes the removal process, opening up new perspectives in the design and formulation of new cleaning systems specifically tailored for intervention on particular conservation issues.

  15. Removal of acrylic coatings from works of art by means of nanofluids: understanding the mechanism at the nanoscale.

    PubMed

    Baglioni, Michele; Rengstl, Doris; Berti, Debora; Bonini, Massimo; Giorgi, Rodorico; Baglioni, Piero

    2010-09-01

    Conservation of works of art often involves the inappropriate application of synthetic polymers. We have proposed the use of alternative methodologies for conservation and formulated innovative cleaning nanostructured systems to remove previously applied polymer films and grime from painted surfaces. In particular, a novel "micellar system" composed of water, SDS, 1-pentanol, ethyl acetate and propylene carbonate was recently formulated and successfully used to remove acrylic and vinyl/acrylic copolymers from Mesoamerican wall paintings in the archeological site of Cholula, Mexico. This contribution reports on the mechanism of the interaction process that takes place between the nanostructured fluid and the polymer coating at the nanoscale. The structural properties of the "micellar solution" and of the polymer film are investigated before, during and after the interaction process using several surface and solution techniques. Rather than a classical detergency mechanism, we demonstrate that micelles act as solvent containers and interact with the polymer film leading to its swelling and detachment from the surface and to its segregation in a liquid droplet, which phase-separates from the aqueous bulk. After the removal process the micelles become smaller in size and undergo a structural re-arrangement due to the depletion of the organic solvents. These findings can be framed in an interaction mechanism which describes the removal process, opening up new perspectives in the design and formulation of new cleaning systems specifically tailored for intervention on particular conservation issues.

  16. Preparation of hydrophilic polyhydroxyalkyl glutamine crosslinked films and its biodegradability.

    PubMed

    Pan, Shi-Rong; Wang, Qin-Mei; Yi, Wu

    2007-09-01

    Polybenzyl glutamate (PBLG) or polymethyl glutamate (PMLG) films have been aminolyzed with amino alcohol and crosslinked with aliphatic diamine at 60 degrees C for 48 h simultaneously which led to the formation of crosslinked films of polyhydroxyalkyl glutamine (PHAG). ATR-IR indicates that for the aminolysis of PBLG with 2-amino-1-ethanol or 3-amino-1-propanol, benzyl glutamate almost completely turned to hydroxyalkyl glutamine, however for the aminolysis of PMLG with 5-amino-1-pentanol, methyl glutamate partially turned to hydroxypentanyl glutamine. The water-swelling test shows that water-swelling ratio Q of PHAG films from amino alcohol with longer carbon chain was smaller, the PHAG films crosslinked by 1,2-diamino ethane have the higher water-swelling ratio Q, but the PHAG films crosslinked by 1,8-diamino octane have the lower water swelling ratio Q; and PHAG films with a greater amount of crosslinking agents have high crosslinking density or the low water swelling-ratio Q for same amino alcohol and diamine. It is obvious from in vitro enzymatic hydrolysis test that specimens with smaller swelling ratio Q displayed larger T(1/2), time for half weight digestion of PHAG film, that is, less biodegradability. Therefore, biodegradability of the crosslinked PHAG films can be controlled by changing amino alcohol and diamine.

  17. Heat capacity contributions to the formation of inclusion complexes.

    PubMed

    Olvera, Angeles; Pérez-Casas, Silvia; Costas, Miguel

    2007-10-04

    An analysis scheme for the formation of the inclusion complexes in water is presented. It is exemplified for the case where the host is alpha-cyclodextrin and the guest is a linear alcohol (1-propanol to 1-octanol) or the isomers of 1-pentanol. Eight transfer isobaric heat capacities, DeltatCp, involving different initial and final states are evaluated at infinite dilution of the guest using both data determined in this work and from the literature. Apart from the usual definition for the inclusion heat capacity change, three inclusion transfers are used. The sign of each DeltatCp indicates if the transfer is an order-formation or an order-destruction process. From the DeltatCp data, the main contributions to the heat capacity of cyclodextrin complexation, namely, those due to dehydration of the hydrophobic section of the guest molecule, H-bond formation, formation of hydrophobic interactions, and release of water molecules from the cyclodextrin cavity, are estimated. The relative weight of each of these contributions to the DeltatCp values is discussed, providing a better characterization of the molecular recognition process involved in the inclusion phenomena.

  18. Oil-in-water microemulsions enhance the biodegradation of DDT by Phanerochaete chrysosporium.

    PubMed

    Zheng, Guanyu; Selvam, Ammaiyappan; Wong, Jonathan W C

    2012-12-01

    A novel approach was developed using oil-in-water (O/W) microemulsions formed with non-ionic surfactant, cosurfactant (1-pentanol) and linseed oil, at the cosurfactant to surfactant ratio (C/S ratio, w/w) of 1:3 and oil to surfactant ratio (O/S ratio, w/w) of 1:10, to enhance the biodegradation of DDT by the white rot fungus Phanerochaete chrysosporium. Results showed that microemulsions formed with Tween 80 effectively enhanced the biodegradation of DDT by P. chrysosporium and the enhancement was about two times that of Tween 80 solution, while microemulsion formed with Triton X-100 exhibited negative effect. Further studies revealed that microemulsion formed with Tween 80 enhanced the biodegradation of DDT through transporting DDT from crystalline phase to mycelium as well as their positive effect on the growth of P. chrysosporium; of these, the former is likely the most important and pre-requisite for the biodegradation of DDT by P. chrysosporium.

  19. Fine Control over Site and Substrate Selectivity in Hydrogen Atom Transfer-Based Functionalization of Aliphatic C-H Bonds.

    PubMed

    Salamone, Michela; Carboni, Giulia; Bietti, Massimo

    2016-10-07

    The selective functionalization of unactivated aliphatic C-H bonds over intrinsically more reactive ones represents an ongoing challenge of synthetic chemistry. Here we show that in hydrogen atom transfer (HAT) from the aliphatic C-H bonds of alkane, ether, alcohol, amide, and amine substrates to the cumyloxyl radical (CumO(•)) fine control over site and substrate selectivity is achieved by means of acid-base interactions. Protonation of the amines and metal ion binding to amines and amides strongly deactivates the C-H bonds of these substrates toward HAT to CumO(•), providing a powerful method for selective functionalization of unactivated or intrinsically less reactive C-H bonds. With 5-amino-1-pentanol, site-selectivity has been drastically changed through protonation of the strongly activating NH2 group, with HAT that shifts to the C-H bonds that are adjacent to the OH group. In the intermolecular selectivity studies, trifluoroacetic acid, Mg(ClO4)2, and LiClO4 have been employed in a orthogonal fashion for selective functionalization of alkane, ether, alcohol, and amide (or amine) substrates in the presence of an amine (or amide) one. Ca(ClO4)2, that promotes deactivation of amines and amides by Ca(2+) binding, offers, moreover, the opportunity to selectively functionalize the C-H bonds of alkane, ether, and alcohol substrates in the presence of both amines and amides.

  20. Trace level determination of molybdenum in environmental and biological samples using surfactant-mediated liquid-liquid extraction.

    PubMed

    Shrivas, Kamlesh; Agrawal, Kavita; Harmukh, Neetu

    2009-01-15

    A novel and sensitive spectrophotometric method for the determination of molybdenum at trace levels in environmental and biological samples is proposed. The method is based on the reaction of Mo (V) with thiocyanate (SCN(-)) and methyltrioctyl ammonium chloride (MTOAC) in acidic medium. The red colored complex of molybdenum is extracted with N-phenylbenzimidoyl thiourea (PBITU) in 1-pentanol for its determination by spectrophotometry. The sensitivity of the present method is higher than other conventional thiocyanate method, due to the use of MTOAC in liquid-liquid extraction. The value of molar absorptivity of the complex with respect to molybdenum is 7.6x10(4)Lmol(-1)cm(-1) at 470nm. The limit of detection of the metal is 5ngmL(-1). The system obeys Beer's law between 20 and 1000ngmL(-1) with slope, intercept and correlation coefficient values of 0.81, 2.5x10(-3) and +0.999, respectively. Most of the metal ions tested did not interfere in the determination of molybdenum. The proposed method has been successfully applied for the determination of the molybdenum in environmental and biological samples.

  1. Olfactory discrimination of structurally similar alcohols by cockroaches.

    PubMed

    Sakura, M; Okada, R; Mizunami, M

    2002-11-01

    The capability of the cockroach Periplaneta americana to discriminate odors of structurally similar aliphatic alcohols was studied by using an operant conditioning paradigm. Cockroaches were trained to discriminate three odors: one odor associated with sucrose solution (reward) and two odors associated with NaCl solution (non-reward). After training, their odor preferences were tested by counting the number of visits to each odor source. We tested the capability of cockroaches to discriminate (1) three normal aliphatic alcohols with different numbers of carbon (1-pentanol, 1-hexanol and 1-octanol), (2) three C6 aliphatic alcohols (1-hexanol, 2-hexanol and trans-2-hexen-1-ol), (3) binary mixtures of two of these three alcohols and their components, and (4) 1-hexanol solution of three different concentrations (1, 10 and 100 micro g micro l(-1)). Cockroaches exhibited higher preferences for the odors associated with reward in these tests, and we therefore conclude that cockroaches can discriminate these odors. However, discrimination of 1-hexanol and trans-2-hexen-1-ol and their binary mixture was imperfect, in that some statistical tests suggested significant level of discrimination but other tests did not. In addition, the cockroaches learned to associate a 1-hexanol solution of the highest or lowest concentration with sucrose reward but failed to learn to associate 1-hexanol of an intermediate concentration with reward.

  2. Management of postharvest grape withering to optimise the aroma of the final wine: A case study on Amarone.

    PubMed

    Bellincontro, A; Matarese, F; D'Onofrio, C; Accordini, D; Tosi, E; Mencarelli, F

    2016-12-15

    Amarone wine is different from regular dry wine due to the postharvest withering of Corvina, Corvinone and Rondinella grapes. Grapes were withered in a commercial facility with variability in terms of temperature and relative humidity (R.H.). Sugar content reached 230-240gL(-1) and 280gL(-1) at 20% and 30% mass loss, respectively. Most of VOCs (volatile organic compounds) decreased during withering but few VOCs increased during withering and we considered as markers; in Corvinone they were methylhexanoate, dimethylsuccinate, nerol, nonanoic acid, and benzyl alcohol; in Corvina, benzyl alcohol, isoamyl alcohol, 1-hexanol, p-cymen-8-ol, 2,3 pinanediol, 3-oxo-ionol and 3-methyl-1-pentanol, coumaran and damascenone; in Rondinella, hexanol, nonanoic acid, methyl vanillate, damascenone, 3-oxo-ionol, eugenol, p-cymen-8-ol, 2,3 pinanediol, coumaran and raspberry keton. Olfactive descriptors of the wines and the potential aroma of the combination of Corvina wine with the wines of the other two varieties at different percentages of mass loss are reported.

  3. On the Investigation of Coarse-Grained Models for Water: Balancing Computational Efficiency and the Retention of Structural Properties

    PubMed Central

    Hadley, Kevin R.; McCabe, Clare

    2010-01-01

    Developing accurate models of water for use in computer simulations is important for the study of many chemical and biological systems, including lipid bilayer self-assembly. The large temporal and spatial scales needed to study such self-assembly have led to the development and application of coarse-grained models for the lipid-lipid, lipid-solvent and solvent-solvent interactions. Unfortunately, popular center-of-mass-based coarse-graining techniques are limited to modeling water with one-water per bead. In this work, we have utilized the K-means algorithm to determine the optimal clustering of waters to allow the mapping of multiple waters to single coarse-grained beads. Through the study of a simple mixture between water and an amphiphilic solute (1-pentanol), we find a 4-water bead model has the optimal balance between computational efficiency and accurate solvation and structural properties when compared to water models ranging from 1 to 9 waters per bead. The 4-water model was subsequently utilized in studies of the solvation of hexadecanoic acid and the structure, as measured via radial distribution functions, for the hydrophobic tails and the bulk water phase were found to agree well with experimental data and their atomistic targets. PMID:20230012

  4. Synthesis and chemical modifications of in-situ grown anatase TiO2 microspheres with isotropically exposed {0 0 1} facets for superhydrophobic and self-cleaning properties

    NASA Astrophysics Data System (ADS)

    Hu, Wanbiao; Yu, Yuanlie; Chen, Hua; Lau, Kenny; Craig, Vincent; Brink, Frank; Withers, Ray L.; Liu, Yun

    2015-12-01

    Excellent and robust hydrophobic materials generally benefit from specifically exposed surfaces i.e. always the low-energy surfaces, and well-defined micro/nano-structures that are achieved through advanced facilities and complicated process with a high cost. We hereof demonstrate that the superhydrophobicity and further self-cleaning properties are also attainable based on high-energy crystalline facets by an appropriate chemical modification. Specifically, anatase TiO2 microspheres were large-scale synthesized to exhibit isotropically exposed high-energy {0 0 1} facets through optimizing the HF/H2O2/H2O ratio during hydrothermal processes. The formation of the microspheres was uncovered to be an in-situ "growth-cum-assembly" grown mechanism. Such high-energy {0 0 1} facets facilitate the strong coupling between the resultant TiO2 microspheres and the modifier (2,2,3,3,4,4,5,5-octafluoro-1-pentanol) because the {0 0 1} facets offer abundant active sites for chemical bonding, showing great merits for superhydrophobicity (with water contact angle of 154 ± 2°, 6 μl droplets), and further stably surface self-cleaning i.e. easily removing surface contamination (e.g. Al2O3 powders). This integrated strategy represents a milestone in design and fabrication of delicate composites with high-energy surfaces for specific functions and properties.

  5. A ground level interpretation of the dielectric behavior of diluted alcohol-in-carbon tetrachloride mixtures

    NASA Astrophysics Data System (ADS)

    Pieruccini, M.; Saija, F.; Ponterio, R.; Vasi, C.

    2003-11-01

    The dielectric behavior at room temperature of alcohol/carbon tetrachloride binary mixtures over the whole composition range is analyzed in the low frequency domain (100 kHz). Methanol, ethanol, 1-, 2-propanol, and 1-pentanol are considered. The results are compared with the ideal case as described in the framework of Onsager theory [J. Am. Chem. Soc. 58, 1486 (1936)]. We find that the observed negative deviation from the ideal dielectric constant at high alcohol dilution is almost independent of the alcohol species. This behavior is interpreted as an effect of the presence of closed chainlike alcohol clusters. Good quantitative agreement is found with a simple lattice model describing the equilibrium distribution of alcohol clusters in the framework of the semigrand canonical ensemble. The observed dielectric behavior is then compared with the results of the calorimetric investigations carried out by Otterstedt and Missen [Trans. Faraday Soc. 57, 879 (1962)]. It is concluded that the dielectric and the calorimetric behaviors of these mixtures at high dilutions can be both interpreted consistently as effects of homogeneous association of the alcohol.

  6. Size and Fiber Density Controlled Synthesis of Fibrous Nanosilica Spheres (KCC-1)

    PubMed Central

    Bayal, Nisha; Singh, Baljeet; Singh, Rustam; Polshettiwar, Vivek

    2016-01-01

    We report a facile protocol for the synthesis of fibrous nano-silica (KCC-1) with controllable size and fiber density. In this work, we have shown that the particle size, fiber density, surface area and pore volume of KCC-1 can be effectively controlled and tuned by changing various reaction parameters, such as the concentrations of urea, CTAB, 1-pentanol, reaction time, temperature, solvent ratio, and even outside stirring time. For the first time, we were able to control the particle size ranging from as small as 170 nm to as large as 1120 nm. We were also able to control the fiber density from low to medium to very dense, which consequently allowed the tuning of the pore volume. We were able to achieve a pore volume of 2.18 cm3/g, which is the highest reported for such a fibrous material. Notably we were even able to increase the surface area up to 1244 m2/g, nearly double the previously reported surface area of KCC-1. Thus, one can now synthesize KCC-1 with various degrees of size, surface area, pore volume, and fiber density. PMID:27118152

  7. Parametric analysis of the growth of colloidal ZnO nanoparticles synthesized in alcoholic medium

    NASA Astrophysics Data System (ADS)

    Fonseca, A. S.; Figueira, P. A.; Pereira, A. S.; Santos, R. J.; Trindade, T.; Nunes, M. I.

    2017-02-01

    The growth kinetics of nanosized ZnO was studied considering the influence of different parameters (mixing degree, temperature, alcohol chain length, reactant concentration and Zn/OH ratios) on the synthesis reaction and modelling the outputs using typical kinetic growth models, which were then evaluated by means of a sensitivity analysis. The Zn/OH ratio, the temperature and the alcohol chain length were found to be essential parameters to control the growth of ZnO nanoparticles, whereas zinc acetate concentration (for Zn/OH = 0.625) and the stirring during the ageing stage were shown to not have significant influence on the particle size growth. This last operational parameter was for the first time investigated for nanoparticles synthesized in 1-pentanol, and it is of outmost importance for the implementation of continuous industrial processes for mass production of nanosized ZnO and energy savings in the process. Concerning the nanoparticle growth modelling, the results show a different pattern from the more commonly accepted diffusion-limited Ostwald ripening process, i.e. the Lifshitz-Slyozov-Wagner (LSW) model. Indeed, this study shows that oriented attachment occurs during the early stages whereas for the later stages the particle growth is well represented by the LSW model. This conclusion contributes to clarify some controversy found in the literature regarding the kinetic model which better represents the ZnO NPs' growth in alcoholic medium.

  8. An endophyte of Picrorhiza kurroa Royle ex. Benth, producing menthol, phenylethyl alcohol and 3-hydroxypropionic acid, and other volatile organic compounds.

    PubMed

    Qadri, Masroor; Deshidi, Ramesh; Shah, Bhawal Ali; Bindu, Kushal; Vishwakarma, Ram A; Riyaz-Ul-Hassan, Syed

    2015-10-01

    An endophytic fungus, PR4 was found in nature associated with the rhizome of Picrorhiza kurroa, a high altitude medicinal plant of Kashmir Himalayas. The fungus was found to inhibit the growth of several phyto-pathogens by virtue of its volatile organic compounds (VOCs). Molecular phylogeny, based on its ITS1-5.8S-ITS2 ribosomal gene sequence, revealed the identity of the fungus as Phomopsis/Diaporthe sp. This endophyte was found to produce a unique array of VOCs, particularly, menthol, phenylethyl alcohol, (+)-isomenthol, β-phellandrene, β-bisabolene, limonene, 3-pentanone and 1-pentanol. The purification of compounds from the culture broth of PR4 led to the isolation of 3-hydroxypropionic acid (3-HPA) as a major metabolite. This is the first report of a fungal culture producing a combination of biologically and industrially important metabolites—menthol, phenylethyl alcohol, and 3-HPA. The investigation into the monoterpene biosynthetic pathway of PR4 led to the partial characterization of isopiperitenone reductase (ipr) gene, which seems to be significantly distinct from the plant homologue. The biosynthesis of plant-like-metabolites, such as menthol, is of significant academic and industrial significance. This study indicates that PR4 is a potential candidate for upscaling of menthol, phenylethyl alcohol, and 3-HPA, as well as for understanding the menthol/monoterpene biosynthetic pathway in fungi.

  9. Use of micellar liquid chromatography to analyze darunavir, ritonavir, emtricitabine, and tenofovir in plasma.

    PubMed

    Peris-Vicente, Juan; Villarreal-Traver, Mónica; Casas-Breva, Inmaculada; Carda-Broch, Samuel; Esteve-Romero, Josep

    2014-10-01

    Danuravir, ritonavir, emtricitabine, and tenofovir are together prescribed against AIDS as a highly active antiretroviral therapy regimen. Micellar liquid chromatography has been applied to determine these four antiretroviral drugs in plasma. The sample preparation is shortened to the dilution of the sample in a micellar solution, filtration, and injection. Clean-up steps are avoided, due to the solubilization of plasma matrix in micellar media. The drugs were analyzed in <20 min using a mobile phase of 0.06 M sodium dodecyl sulfate/2.5% 1-pentanol (pH 7) running under isocratic mode through a C18 column at 1 mL/min at room temperature. Absorbance wavelength detection was set at 214 nm. The method was successfully validated following the ICH Harmonized Tripartite Guideline in terms of selectivity, limit of detection (0.080-0.110 μg/mL), limit of quantification (0.240-0.270 μg/mL), linearity between 0.25 and 25 μg/mL (r(2) > 0.995), accuracy (89.3-103.2%), precision (<8.2%) and robustness (<7.5%). Real plasma sample from patients taking this therapy were analyzed. This is the first paper showing the simultaneous detection of this four drugs. Therefore, the methodology was proven useful for the routine analysis of these samples in a hospital laboratory for clinical purposes.

  10. Biosynthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and characterisation of its blend with oil palm empty fruit bunch fibers.

    PubMed

    Salim, Yoga Sugama; Abdullah, Amirul Al-Ashraf; Nasri, Coswald Stephen Sipaut Mohd; Ibrahim, Mohamad Nasir Mohamad

    2011-02-01

    Poly(3-hydroxybutyrate-co-38 mol%-3-hydroxyvalerate) [P(3HB-co-38mol%-3HV)] was produced by Cupriavidus sp. USMAA2-4 in the presence of oleic acid and 1-pentanol. Due to enormous production of empty fruit bunch (EFB) in the oil palm plantation and high production cost of P(3HB-co-3HV), oil palm EFB fibers were used for biocomposites preparation. In this study, maleic anhydride (MA) and benzoyl peroxide (DBPO) were used to improve the miscibility between P(3HB-co-3HV) and EFB fibers. Introduction of MA into P(3HB-co-3HV) backbone reduced the molecular weight and improved the thermal stability of P(3HB-co-3HV). Thermal stability of P(3HB-co-3HV)/EFB composites was shown to be comparable to that of commercial packaging product. Composites with 35% EFB fibers content have the highest tensile strength compared to 30% and 40%. P(3HB-co-3HV)/EFB blends showed less chemicals leached compared to commercial packaging.

  11. Monitoring of HAART regime antiretrovirals in serum of acquired immunodeficiency syndrome patients by micellar liquid chromatography.

    PubMed

    Casas-Breva, I; Peris-Vicente, J; Rambla-Alegre, M; Carda-Broch, S; Esteve-Romero, J

    2012-09-21

    A methodology based on micellar liquid chromatography to monitor five antiretroviral drugs (lamivudine, stavudine, tenofovir, zidovudine and efavirenz) was proposed. Antiretrovirals were studied in sets of three, corresponding to each highly active antiretroviral therapy (HAART) regime, prescribed to acquired immunodeficiency syndrome (AIDS)-infected patients. Four aqueous micellar mobile phases buffered at pH 7 were optimized to separate these compounds, using sodium dodecyl sulfate as the tensioactive, and 1-propanol or 1-pentanol as the organic modifier. The composition of each mobile phase was optimized for each antiretroviral. The common separation conditions were: C18 apolar column (125 × 4.6 mm, 5 μm particle size), UV detection set at 214 nm, and mobile phase running at 1 mL min(-1) without controlling the temperature. The finally suggested method was validated for five analysed antiretroviral drugs following the US Food and Drug Administration guidelines in terms of: linearity between 0.5 and 50 ppm (r(2) > 0.9995), sensitivity (LOD lower than 0.25 ppm), intra- and inter-day precision (<7.1 and <5.2%, respectively) and accuracy (recovery 88.5-105.3% and 93.5-101.3%, respectively), as well as robustness (<6.5%). The proposed method was used to monitor the level of antiretrovirals in the serum of AIDS patients. The suggested methodology was found to be useful in the routine analysis of antiretrovirals in serum samples.

  12. Shape-tunable hollow silica nanomaterials based on a soft-templating method and their application as a drug carrier.

    PubMed

    Chen, Jiao; Wu, Xu; Hou, Xiaodong; Su, Xingguang; Chu, Qianli; Fahruddin, Nenny; Zhao, Julia Xiaojun

    2014-12-24

    A one-step soft-templating method for synthesizing shape-tunable hollow silica nanomaterials was developed in a reliable and highly reproducible way. For the first time, both nonspherical and spherical shapes with hollow interiors, including nanowire, nanospheres, and nanotadpole, were successfully obtained by simply changing the solvent. Poly(vinylpyrrolidone) (PVP)-water droplets were used as soft templates for the formation of hollow structures, while three different solvents, including 1-propanol, 1-pentanol, and ethanol, led to the designed shapes. It was found that the solvent, the formation of PVP-water droplets, the amount of ammonia, and the reaction time had great effects on the morphology of synthesized hollow nanomaterials. The effect of various factors on the morphology was systematically studied to propose a growth mechanism. The obtained hollow silica nanomaterials showed excellent reproducibility and great potential for a large-scale synthesis. Finally, the application of the developed hollow silica nanomaterials was demonstrated using the hollow spherical silica nanoparticles. Its drug-carrying ability was studied. The results could be extended for doping various target molecules into the hollow structures for a broad range of applications.

  13. Poly(vinyl alcohol)-borate hydro/cosolvent gels: viscoelastic properties, solubilizing power, and application to art conservation.

    PubMed

    Carretti, Emiliano; Grassi, Scilla; Cossalter, Manuela; Natali, Irene; Caminati, Gabriella; Weiss, Richard G; Baglioni, Piero; Dei, Luigi

    2009-08-04

    We report the development of a new type of hydrogel in which a cosolvent has been added to the water component. The gel networks are based on the well-known poly(vinyl alcohol)-borate systems (PVA-borate). However, it is shown that the rheological and solubilizing properties of the hydrogels can be modified drastically by the addition of a cosolvent. The studies have focused on 1-propanol as the added liquid, although it is shown that others (propylene carbonate, 1-pentanol, cyclohexanone, and 2-butanol) are amenable to making modified hydrogels as well. In addition to the rheological measurements, the gels have been investigated by differential scanning calorimetry (free water index) and determination of their solubilizing power. Finally, the gels have been applied to clean and oxidized varnish (patina) from the surface of a XVI-XVII century oil-on-wood painting by Ludovico Cardi detto il Cigoli. The mode of cleaning by and removal of the PVA-borate water/1-propanol gel from the painted surface demonstrate several advantages over other gels used in art conservation.

  14. Can volatile organic metabolites be used to simultaneously assess microbial and mite contamination level in cereal grains and coffee beans?

    PubMed

    Salvador, Angelo C; Baptista, Inês; Barros, António S; Gomes, Newton C M; Cunha, Angela; Almeida, Adelaide; Rocha, Silvia M

    2013-01-01

    A novel approach based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToFMS) was developed for the simultaneous screening of microbial and mite contamination level in cereals and coffee beans. The proposed approach emerges as a powerful tool for the rapid assessment of the microbial contamination level (ca. 70 min versus ca. 72 to 120 h for bacteria and fungi, respectively, using conventional plate counts), and mite contamination (ca. 70 min versus ca. 24 h). A full-factorial design was performed for optimization of the SPME experimental parameters. The methodology was applied to three types of rice (rough, brown, and white rice), oat, wheat, and green and roasted coffee beans. Simultaneously, microbiological analysis of the samples (total aerobic microorganisms, moulds, and yeasts) was performed by conventional plate counts. A set of 54 volatile markers was selected among all the compounds detected by GC×GC-ToFMS. Principal Component Analysis (PCA) was applied in order to establish a relationship between potential volatile markers and the level of microbial contamination. Methylbenzene, 3-octanone, 2-nonanone, 2-methyl-3-pentanol, 1-octen-3-ol, and 2-hexanone were associated to samples with higher microbial contamination level, especially in rough rice. Moreover, oat exhibited a high GC peak area of 2-hydroxy-6-methylbenzaldehyde, a sexual and alarm pheromone for adult mites, which in the other matrices appeared as a trace component. The number of mites detected in oat grains was correlated to the GC peak area of the pheromone. The HS-SPME/GC×GC-ToFMS methodology can be regarded as the basis for the development of a rapid and versatile method that can be applied in industry to the simultaneous assessment the level of microbiological contamination and for detection of mites in cereals grains and coffee beans.

  15. Bacterial Degradation of tert-Amyl Alcohol Proceeds via Hemiterpene 2-Methyl-3-Buten-2-ol by Employing the Tertiary Alcohol Desaturase Function of the Rieske Nonheme Mononuclear Iron Oxygenase MdpJ

    PubMed Central

    Schuster, Judith; Schäfer, Franziska; Hübler, Nora; Brandt, Anne; Rosell, Mònica; Härtig, Claus; Harms, Hauke; Müller, Roland H.

    2012-01-01

    Tertiary alcohols, such as tert-butyl alcohol (TBA) and tert-amyl alcohol (TAA) and higher homologues, are only slowly degraded microbially. The conversion of TBA seems to proceed via hydroxylation to 2-methylpropan-1,2-diol, which is further oxidized to 2-hydroxyisobutyric acid. By analogy, a branched pathway is expected for the degradation of TAA, as this molecule possesses several potential hydroxylation sites. In Aquincola tertiaricarbonis L108 and Methylibium petroleiphilum PM1, a likely candidate catalyst for hydroxylations is the putative tertiary alcohol monooxygenase MdpJ. However, by comparing metabolite accumulations in wild-type strains of L108 and PM1 and in two mdpJ knockout mutants of strain L108, we could clearly show that MdpJ is not hydroxylating TAA to diols but functions as a desaturase, resulting in the formation of the hemiterpene 2-methyl-3-buten-2-ol. The latter is further processed via the hemiterpenes prenol, prenal, and 3-methylcrotonic acid. Likewise, 3-methyl-3-pentanol is degraded via 3-methyl-1-penten-3-ol. Wild-type strain L108 and mdpJ knockout mutants formed isoamylene and isoprene from TAA and 2-methyl-3-buten-2-ol, respectively. It is likely that this dehydratase activity is catalyzed by a not-yet-characterized enzyme postulated for the isomerization of 2-methyl-3-buten-2-ol and prenol. The vitamin requirements of strain L108 growing on TAA and the occurrence of 3-methylcrotonic acid as a metabolite indicate that TAA and hemiterpene degradation are linked with the catabolic route of the amino acid leucine, including an involvement of the biotin-dependent 3-methylcrotonyl coenzyme A (3-methylcrotonyl-CoA) carboxylase LiuBD. Evolutionary aspects of favored desaturase versus hydroxylation pathways for TAA conversion and the possible role of MdpJ in the degradation of higher tertiary alcohols are discussed. PMID:22194447

  16. Can Volatile Organic Metabolites Be Used to Simultaneously Assess Microbial and Mite Contamination Level in Cereal Grains and Coffee Beans?

    PubMed Central

    Salvador, Ângelo C.; Baptista, Inês; Barros, António S.; Gomes, Newton C. M.; Cunha, Ângela; Almeida, Adelaide; Rocha, Silvia M.

    2013-01-01

    A novel approach based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC×GC–ToFMS) was developed for the simultaneous screening of microbial and mite contamination level in cereals and coffee beans. The proposed approach emerges as a powerful tool for the rapid assessment of the microbial contamination level (ca. 70 min versus ca. 72 to 120 h for bacteria and fungi, respectively, using conventional plate counts), and mite contamination (ca. 70 min versus ca. 24 h). A full-factorial design was performed for optimization of the SPME experimental parameters. The methodology was applied to three types of rice (rough, brown, and white rice), oat, wheat, and green and roasted coffee beans. Simultaneously, microbiological analysis of the samples (total aerobic microorganisms, moulds, and yeasts) was performed by conventional plate counts. A set of 54 volatile markers was selected among all the compounds detected by GC×GC–ToFMS. Principal Component Analysis (PCA) was applied in order to establish a relationship between potential volatile markers and the level of microbial contamination. Methylbenzene, 3-octanone, 2-nonanone, 2-methyl-3-pentanol, 1-octen-3-ol, and 2-hexanone were associated to samples with higher microbial contamination level, especially in rough rice. Moreover, oat exhibited a high GC peak area of 2-hydroxy-6-methylbenzaldehyde, a sexual and alarm pheromone for adult mites, which in the other matrices appeared as a trace component. The number of mites detected in oat grains was correlated to the GC peak area of the pheromone. The HS-SPME/GC×GC–ToFMS methodology can be regarded as the basis for the development of a rapid and versatile method that can be applied in industry to the simultaneous assessment the level of microbiological contamination and for detection of mites in cereals grains and coffee beans. PMID:23613710

  17. STIMULATION OF TARSAL RECEPTORS OF THE BLOWFLY BY ALIPHATIC ALDEHYDES AND KETONES

    PubMed Central

    Chadwick, L. E.; Dethier, V. G.

    1949-01-01

    Rejection of eight aldehydes, eight ketones, five secondary alcohols, and 3-pentanol has been studied in the blowfly Phormia regina Meigen. The data agree with results previously reported for normal alcohols and several series of glycols in showing a logarithmic increase in stimulating effect with increasing chain length. The order of increasing effectiveness among the different species of compounds thus far investigated is the following: polyglycols, diols, secondary alcohols, iso-alcohols, normal alcohols, ketones, iso-aldehydes, normal aldehydes. Curves relating the logarithms of threshold concentration to the logarithms of chain length for diols, alcohols, aldehydes, and ketones show inflections in the 3 to 6 carbon range. Above and below the region of inflection the curves are nearly rectilinear. The slopes for the upper limbs (smaller molecules) are of the order of –2; for the lower limbs, about –10. Comparisons of the threshold data with numerical values for molecular weights, molecular areas and volumes, oil-water distribution coefficients, activity coefficients, standard free energies, vapor pressures, boiling points, melting points, dipole moments, dielectric constants, and degree of association are discussed briefly, and it is concluded that none of the comparisons serves to bring the data from the several series and from the two portions of each series into a single homogeneous system. A qualitative comparison with water solubilities shows fewer discrepancies. It is suggested that the existence of a combination of aqueous and lipoid phases at the receptor surface would fit best with what is presently known about the relationship between chemical structure and stimulating effect in contact chemoreception. In this hypothesis the smaller and more highly water-soluble compounds are envisaged as gaining access to the receptors partly through the aqueous phase, the larger molecules predominantly through the lipoid phase. PMID:18114559

  18. Contribution of liver alcohol dehydrogenase to metabolism of alcohols in rats.

    PubMed

    Plapp, Bryce V; Leidal, Kevin G; Murch, Bruce P; Green, David W

    2015-06-05

    The kinetics of oxidation of various alcohols by purified rat liver alcohol dehydrogenase (ADH) were compared with the kinetics of elimination of the alcohols in rats in order to investigate the roles of ADH and other factors that contribute to the rates of metabolism of alcohols. Primary alcohols (ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol) and diols (1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol) were eliminated in rats with zero-order kinetics at doses of 5-20 mmol/kg. Ethanol was eliminated most rapidly, at 7.9 mmol/kgh. Secondary alcohols (2-propanol-d7, 2-propanol, 2-butanol, 3-pentanol, cyclopentanol, cyclohexanol) were eliminated with first order kinetics at doses of 5-10 mmol/kg, and the corresponding ketones were formed and slowly eliminated with zero or first order kinetics. The rates of elimination of various alcohols were inhibited on average 73% (55% for 2-propanol to 90% for ethanol) by 1 mmol/kg of 4-methylpyrazole, a good inhibitor of ADH, indicating a major role for ADH in the metabolism of the alcohols. The Michaelis kinetic constants from in vitro studies (pH 7.3, 37 °C) with isolated rat liver enzyme were used to calculate the expected relative rates of metabolism in rats. The rates of elimination generally increased with increased activity of ADH, but a maximum rate of 6±1 mmol/kg h was observed for the best substrates, suggesting that ADH activity is not solely rate-limiting. Because secondary alcohols only require one NAD(+) for the conversion to ketones whereas primary alcohols require two equivalents of NAD(+) for oxidation to the carboxylic acids, it appears that the rate of oxidation of NADH to NAD(+) is not a major limiting factor for metabolism of these alcohols, but the rate-limiting factors are yet to be identified.

  19. Chemical communication in Chagas disease vectors. Source, identity, and potential function of volatiles released by the metasternal and Brindley's glands of Triatoma infestans adults.

    PubMed

    Manrique, Gabriel; Vitta, Ana C R; Ferreira, Raquel A; Zani, Carlos L; Unelius, C Rikard; Lazzari, Claudio R; Diotaiuti, Lileia; Lorenzo, Marcelo G

    2006-09-01

    Compounds from the metasternal and Brindley's glands of the blood-sucking bug, Triatoma infestans, were identified by solid phase microextraction (SPME) and gas chromatography-mass spectrometry. Volatile compounds released by adult bugs during copulation or after mechanical disturbance were also characterized. Six compounds were identified and found consistently in all samples from metasternal glands. The most abundant were 3-pentanone, 2-methylbutanol, 3-pentanol, and an unidentified compound. The metasternal gland blends did not differ qualitatively between sexes. Compounds found in Brindley's glands were short chain acids, alcohols, esters, and a ketone with no qualitative differences between sexes. Isobutyric acid was the main component of this blend, and two new confirmed compounds were described as products of these glands: 2-butanone and 2-methylbutyric acid. 3-Pentanone was collected from the headspace over 33% of the copulating pairs of T. infestans. Volatiles found in the headspace of disturbed T. infestans adults included short-chain fatty acids, alcohols, esters, and ketones, with no qualitative differences between sexes. Both types of glands apparently discharge their contents after disturbance. However, most of the volatiles released by bugs after disturbance came from Brindley's glands. The locomotor activity of fourth instars increased significantly after stimulation with the odors emitted by disturbed adults, as compared with larvae stimulated by the odor of undisturbed adults or by clean air. We also studied the directional behavioral response of fifth instars to the disturbance scent in a locomotion compensator. Larvae exposed to volatiles released by disturbed adults walked away from the direction of the odor. The results suggest that this blend or part of it functions as an alarm pheromone for T. infestans. We suggest that the metasternal glands of this species are involved both in the sexual and the alarm contexts, and that the Brindley

  20. Comparative study of aromatic compounds in fruit wines from raspberry, strawberry, and mulberry in central Shaanxi area

    PubMed Central

    Feng, Yiming; Liu, Min; Ouyang, Yanan; Zhao, Xianfang; Ju, Yanlun; Fang, Yulin

    2015-01-01

    Background Although grape wines have firmly dominated the production and consumption markets of fruit wines, raspberry, strawberry, and mulberry have been utilized to make wines because of their joyful aroma and high contents of polyphenolic phytochemicals and essential fatty acids. However, little is known about aromatic compounds of the wines produced from these three fruits. Methods The aromatic composition of fruit wines produced from raspberry, strawberry, mulberry, and red grape was analyzed by GC-MS. Odor activity values (OAVs) and relative odor contributions (ROCs) were used to estimate the sensory contribution of the aromatic compounds to the overall flavor of the wines. Results In strawberry, raspberry, and mulberry wines, 27, 30, and 31 odorants were detected, respectively. Alcohols formed the most abundant group, followed by esters and acids. The grape wine contained a wider variety (16 types) of alcohols, and 4-methyl-2-pentanol and 2,3-butanediol were not present in the three fruit wines. The quantity of esters in raspberry (1.54%) and mulberry wines (2.08%) were higher than those of strawberry wine (0.78%), and mulberry wine contained more types of esters. There were no significant differences of acids between the three fruit wines and the control wine. In addition, 2-heptanone, 2-octanone, 2-nonanone, and 2-undecanone were unique to raspberry wine, and nonanal was present only in mulberry wine. The indistinguishable aroma of the three fruit wines was attributed to the dominance of fruity and floral odor components derived from ethyl esters of fatty acids and their contributions to the global aroma of the three fruit wines. Conclusion The present study demonstrated that there were significant differences in the volatile components of fruit wines made from raspberry, strawberry, and mulberry. The aroma compounds were more abundant in the raspberry and mulberry wines than in the strawberry wine, but the quality of strawberry wine was superior to

  1. Topical delivery of hexamidine.

    PubMed

    Parisi, Nicola; Paz-Alvarez, Miguel; Matts, Paul J; Lever, Rebecca; Hadgraft, Jonathan; Lane, Majella E

    2016-06-15

    Hexamidine diisethionate (HEX D) has been used for its biocidal actions in topical preparations since the 1950s. Recent data also suggest that it plays a beneficial role in skin homeostasis. To date, the extent to which this compound penetrates the epidermis has not been reported nor how its topical delivery may be modulated. In the present work we set out to characterise the interaction of HEX D with the skin and to develop a range of simple formulations for topical targeting of the active. A further objective was to compare the skin penetration of HEX D with its corresponding dihydrochloride salt (HEX H) as the latter has more favourable physicochemical properties for skin uptake. Candidate vehicles were evaluated by in vitro Franz cell permeation studies using porcine skin. Initially, neat solvents were investigated and subsequently binary systems were examined. The solvents and chemical penetration enhancers investigated included glycerol, dimethyl isosorbide (DMI), isopropyl alcohol (IPA), 1,2-pentanol (1,2-PENT), polyethylene glycol (PEG) 200, propylene glycol (PG), propylene glycol monolaurate (PGML) and Transcutol(®)P (TC). Of a total of 30 binary solvent systems evaluated only 10 delivered higher amounts of active into the skin compared with the neat solvents. In terms of topical efficacy, formulations containing PGML far surpassed all other solvents or binary combinations. More than 70% of HEX H was extracted from the skin following application in PG:PGML (50:50). Interestingly, the same vehicle effectively promoted skin penetration of HEX D but demonstrated significantly lower uptake into and through the skin (30%). The findings confirm the unpredictable nature of excipients on delivery of actives with reference to skin even where there are minor differences in molecular structures. We also believe that they underline the ongoing necessity for fundamental studies on the interaction of topical excipients with the skin.

  2. Analysis of thiabendazole, 4-tert-octylphenol and chlorpyrifos in waste and sewage water by direct injection – micellar liquid chromatography.

    PubMed

    Romero-Cano, Ricard; Kassuha, Diego; Peris-Vicente, Juan; Roca-Genovés, Pasqual; Carda-Broch, Samuel; Esteve-Romero, Josep

    2015-03-07

    A micellar liquid chromatographic method has been developed for the simultaneous quantification of the pesticides thiabendazole and chlorpyrifos, as well as an alkylphenol, which is included in pesticide formulations, i.e., 4-tert-octylphenol, in water. A sample was filtered and directly injected, avoiding large extraction steps using toxic solvents, thus expediting the experimental procedure. The contaminants were eluted without interferences in <17 min, using a mobile phase of 0.15 M sodium dodecyl sulfate – 6% 1-pentanol buffered at pH 3, running through a C18 column at 1 mL min(-1) under the isocratic mode. This optimal mobile phase was selected using a statistical approach, which considers the retention factor, efficiency and peak shape of the analytes measured in only a few mobile phases. The detection was carried out by measuring absorbance at 220 nm. The method was successfully validated in terms of specificity, calibration range (0.5-10 mg L(-1)), linearity (r(2) > 0.994), limit of detection and quantification (0.2-0.3; and 0.5-0.8 mg L(-1), respectively), intra- and interday accuracy (95.2-102.9%), precision (<8.3%), and ruggedness (<9.3%). The stability in storage conditions (at least 14 days) was studied. The method was safe, inexpensive, produced little pollutant and has a short analysis time, thus it is useful for the routine analysis of samples. Finally, the method was applied to analyse wastewater from the fruit-processing industry, wastewater treatment plants, and in sewage water belonging to the Castelló area (Spain). The results were similar to those obtained by an already reliable method.

  3. The effects of electrolysis on operational solutions in electromembrane extraction: The role of acceptor solution.

    PubMed

    Kubáň, Pavel; Boček, Petr

    2015-06-12

    Fundamental operational principle and instrumental set-up of electromembrane extraction (EME) suggest that electrolysis may play an important role in this recently developed micro-extraction technique. In the present study, the effect of electrolysis in EME is described comprehensively for the first time and it is demonstrated that electrolysis considerably influences EME performance. Micro-electromembrane extraction (μ-EME) across free liquid membrane formed by 1-pentanol was utilized for real-time monitoring of the electrolytically induced changes in composition of μ-EME solutions. These changes were visualized with a set of acid-base indicators. Changes in colours of their aqueous solutions revealed serious variations in their pH values, which occurred within seconds to minutes of the μ-EME process. Variations of up to eight pH units were observed for indicator solutions initially prepared in 1, 5 and 10mM hydrochloric acid. No or only negligible pH changes (less than 0.15 pH unit) were observed for indicator solutions prepared in 50 and 100mM acetic acid demonstrating that initial composition of the aqueous solutions was the crucial parameter. These results were also confirmed by theoretical calculations of maximum pH variations in the solutions, which were based on total electric charge transfers measured in the μ-EME systems, and by exact measurements of their pH values after μ-EMEs. Acceptor solutions that, in the current practice, consist predominantly of low concentrations of strong mineral acids or alkali hydroxides may thus not always ensure adequate EME performance, which was manifested by decrease in extraction recoveries of a basic drug papaverine. A suitable remedy to the observed effects is the application of acceptor solutions containing high concentrations of weak acids or bases. These solutions not only eliminate the decrease in recoveries but also serve well as matrices of extracted samples for subsequent analysis by capillary

  4. Determination of volatile compounds in wine by gas chromatography-flame ionization detection: comparison between the U.S. Environmental Protection Agency 3sigma approach and Hubaux-Vos calculation of detection limits using ordinary and bivariate least squares.

    PubMed

    Caruso, Rosario; Scordino, Monica; Traulo, Pasqualino; Gagliano, Giacomo

    2012-01-01

    A capillary GC-flame ionization detection (FID) method to determine volatile compounds (ethyl acetate, 1,1-diethoxyethane, methyl alcohol, 1-propanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-butanol, and 2-butanol) in wine was investigated in terms of calculation of detection limits and calibration method. The main objectives were: (1) calculation of regression coefficient parameters by ordinary least-squares (OLS) and bivariate least-squares (BLS) regression models, taking into account errors in both axes; (2) estimation of linear dynamic range (LDR) according to International Conference on Harmonization recommendations; (3) performance evaluation of a method by using three different internal standards (ISs) such as acetonitrile, acetone, and 1-pentanol; (4) evaluation of LODs according to the U.S. Environmental Protection Agency (EPA) 3sigma approach and the Hubaux-Vos (H-V) method; (5) application of H-V theory to a gas chromatographic analytical method and to a food matrix; and (6) accuracy assessment of the method relative to methyl alcohol content through a Unione Italiana Vini (UIV) interlaboratory proficiency test. Calibration curves calculated via BLS and OLS show similar slopes, while intercepts are closer to zero in the first case, independent of the chosen IS. The studied ISs show a substantially equivalent behavior, even though the IS closer to the analyte retention time seems to be more appropriate in terms of LDR and LOD. Results indicate an underestimation of LODs using the EPA 3sigma approach instead of the more realistic H-V method, both with OLS and BLS regression models. Methanol contents compared with UIV average values indicate recovery between 90 and 110%.

  5. Phase Behavior of Liquid Crystals Formed in [C12mim]CI/H2O and [C12mim]CI/Alcohols Systems

    NASA Astrophysics Data System (ADS)

    Pei, Mei-shan; Wu, Zhi-yan; Wang, Lu-yan; Wu, Xin-zhou; Tao, Xu-tang

    2009-10-01

    Phase behaviors of different binary systems involving 1-dodecyl-3-methylimidazolium chloride ([C12mim]Cl) and H2O, [C12mim]Cl and different alcohols (1-butanol, 1-pentanol, 1-hexanol and 1-octanol) are investigated at 25 °C. Hexagonal liquid crystal phase (H1) is identified in [C12mim]Cl/H2O system, and lamellar liquid-crystalline (Lα) phase is found in [C12mim]Cl/alcohols systems by using polarized optical microscopy and small-angle X-ray scattering techniques. The formation of such phases is considered as a synergetic result of the solvatophobic force and the hydrogen-bonded network comprising an imidazolium ring, chloride ion and water (or alcohols), which can be confirmed by Fourier transform infrared spectra. It is noticeable that in [C12mim]Cl/1-octanol system, the lattice spacings of lamellar phase increase with increasing C12mimCl concentration, which is opposite to the results of [C12mim]Cl/H2O system. This may result mainly from stronger static repulsion among hydrophilic headgroups of imidazolium salts arranged in the bilayers of lamellar structures. Further measurements by differential scanning calorimetry indicate that the lamellar phase is stable within a wide temperature range above room temperature. However, the lattice spacings decrease with the increase of temperature, which may be due to the softening of the hydrocarbon chain of [C12mim]Cl molecules. In different alcohols systems, it is found that the lamellar lyotropic liquid crystal structure is easier to be formed when the carbon chain length becomes longer.

  6. In Vitro Evaluation of Antimicrobial Efficacy of Extracts Obtained from Raw and Fermented Wild Macrofungus, Lenzites quercina

    PubMed Central

    Ogidi, Olusola Clement; Oyetayo, Victor Olusegun; Akinyele, Bamidele Juliet

    2015-01-01

    In recent time, there is a major concern about antibiotic resistance displayed by some pathogenic microorganisms and this had involved a continuous search for natural antimicrobial products. The phytochemistry as well as antimicrobial activity of extracts obtained from Lenzites quercina was investigated. The extracts and purified fractions were, respectively, tested against indicator organisms using agar well diffusion and disc diffusion methods. The quantity of phytochemicals found in the extracts of L. quercina ranged from 14.4 to 20.7 mg/g for alkaloids, 6.1 to 12.8 mg/g for steroids, 4.5 to 10.6 mg/g for saponins, 2.8 to 17.2 mg/g for terpenoids, and 0.41 to 17.1 mg/g for flavonoids. The gas chromatography mass spectrophotometry (GCMS) analysis of the extract reveals the presence of caprylic acid, stearic acid, tetradecanoic acid, methyl-11-octadecenoate, oleic acid, and 4-methyl-2-propyl-1-pentanol. Extracts of L. quercina and its purified fractions exhibited wider range of inhibition (4 mm to 26 mm) on Staphylococcus aureus (ATCC 29213), Pseudomonas aeruginosa (ATCC 27853), Escherichia coli (ATCC 35218), Methicillin Resistant Staphylococcus aureus (MRSA), Salmonella typhi, Bacillus cereus, Enterococcus faecalis, Candida albicans, and Aspergillus niger. The antimicrobial effects of L. quercina extracts indicate that this wild macrofungus contains significant amount of pharmacological agents, which could be extracted to curb the menace of antibiotic resistances by pathogenic organisms. PMID:26604928

  7. Physicochemical studies of mixed surfactant microemulsions with isopropyl myristate as oil.

    PubMed

    Bardhan, Soumik; Kundu, Kaushik; Saha, Swapan K; Paul, Bidyut K

    2013-07-15

    The present study is focused on evaluation of interfacial compositions and thermodynamic properties of w/o mixed surfactant [(sodium dodecylsulfate, SDS/polyoxyethylene (23) lauryl ether, Brij-35)/1-pentanol (Pn)/isopropyl myristate (IPM)] microemulsions under various physicochemical conditions by the dilution method. The number of moles of Pn at the interface (n(a)(i)) and bulk oil (n(a)(o)), and various thermodynamic parameters [viz. standard Gibbs free energy (ΔG(o→i)(0)), standard enthalpy (ΔH(o→i)(0)), and standard entropy (ΔS(o→i)(0)) of the transfer of Pn from bulk oil to the interface] have been found to be dependent on the molar ratio of water to surfactant (ω), concentration of Brij-35 (X(Brij-35)), and temperature. Temperature-insensitive microemulsions with zero specific heat capacity (ΔC(p)(0))(o→i) have been formed at specific compositions. The intrinsic enthalpy change of the transfer process (ΔH(0))(o→i)* has been evaluated from linear correlation between ΔH(o→i)(0) and ΔS(o→i)(0) at different experimental temperatures. The present report also aims at a precise characterization on the basis of molecular interactions between the constituents and provides insight into the nature of the oil/water interfaces of these systems by conductivity and dynamic light scattering studies as a function of ω and X(Brij-35). Conductivity studies reveal that incorporation of Brij-35 in non-percolating water/SDS/Pn/IPM systems makes them favorable for ω-induced percolation behavior up to X(Brij-35) ≤ 0.5. But further addition of Brij-35 causes a decrease in conductivity with increasing ω. Furthermore, the hydrodynamic diameters of the microemulsion droplets increase with increase in both X(Brij-35) and ω. Correlations of the results in terms of the evaluated physicochemical parameters have been attempted.

  8. Manipulating volatile emission in tobacco leaves by expressing Aspergillus nigerbeta-glucosidase in different subcellular compartments.

    PubMed

    Wei, Shu; Marton, Ira; Dekel, Mara; Shalitin, Dror; Lewinsohn, Efraim; Bravdo, Ben-Ami; Shoseyov, Oded

    2004-07-01

    Expression of the Aspergillus nigerbeta-glucosidase gene, BGL1, in Nicotiana tabacum plants (cv. Xanthi) had a profound effect on the volatile emissions of intact and crushed leaves. BGL1 was expressed under the control of the cauliflower mosaic virus (CaMV) 35S promoter and targeted to the cytoplasm, cell wall, lytic vacuole (LV), chloroplast or endoplasmic reticulum (ER). Subcellular localization was confirmed by gold immunolabelling, followed by transmission electron microscopy (TEM). Significant beta-glucosidase activity was observed in transgenic plants expressing BGL1 in the cell wall, LV and ER. Compared with controls, all intact transgenic leaves were found to emit increased levels of 2-ethylhexanol, as determined by gas chromatography-mass spectrometry (GC-MS) analysis of the headspace volatiles. Plants expressing BGL1 in the cell wall (Tcw) emitted more trans-caryophyllene than did non-transgenic controls, whereas plants expressing BGL1 in the ER (Ter) and LV (Tvc) emitted more cembrene than did non-transgenic controls. Volatiles released from crushed transgenic leaves and collected with solid-phase microextraction (SPME) polydimethylsiloxane fibre were distinctly enhanced. Significant increases in linalool, nerol, furanoid cis-linalool oxide, 4-methyl-1-pentanol, 6-methyl-hept-5-en-2-ol and 2-ethylhexanol were detected in transgenic plants when compared with wild-type controls. 3-Hydroxyl-beta-ionone levels were increased in crushed Tcw and Ter leaves, but were undetectable in Tvc leaves. The addition of glucoimidazole, a beta-glucosidase inhibitor, abolished the increased emission of these volatiles. These results indicate that the expression of a fungal beta-glucosidase gene in different subcellular compartments has the potential to affect the emission of plant volatiles, and thereby to modify plant-environment communication and aroma of agricultural products.

  9. The toxic and metabolic effects of 23 aliphatic alcohols in the isolated perfused rat liver.

    PubMed

    Strubelt, O; Deters, M; Pentz, R; Siegers, C P; Younes, M

    1999-05-01

    We investigated the acute toxic and metabolic effects of 23-aliphatic alcohols (16 saturated and 7 unsaturated) in the isolated perfused rat liver at a concentration of 65.1 mmol/l (approximately 0.3% ethanol). The capacity of the straight chain primary alcohols (methanol, ethanol, 1-propanol, 1-butanol and 1-pentanol) to release the enzymes glutamate-pyruvate transaminase (GPT), lactate dehydrogenase (LDH) and glutamate dehydrogenase (GLDH) into the perfusate was strongly correlated with their carbon chain length. The secondary alcohols were less active in this respect whereas branching of the carbon chain did not consistently change alcohol toxicity. Unsaturation in the straight chain but not in the branched chain alcohols was accompanied by an increase in toxicity. An increased enzyme release was in general accompanied by, and correlated to, reductions in oxygen consumption, bile secretion, and perfusion flow of the isolated livers. Statistically significant correlations exist between parameters of alcohol-induced hepatotoxicity and the membrane/buffer partition coefficents of the alcohols. With the exception of methanol, all alcohols tested increased the lactate/pyruvate ratio of the perfusate, although this effect was not correlated to the degree of hepatic injury. Hepatic ATP concentrations decreased in most cases in line with hepatic injury and were particularly correlated with changes in oxygen consumption. Hepatic concentrations of reduced glutathione (GSH) were only diminished by the unsaturated alcohols, whereas an increase in hepatic oxidized glutathione (GSSG) occurred only with some of the saturated alcohols. Hepatic concentrations of malondialdehyde (MDA) increased after two saturated and three unsaturated alcohols but did not correlate with other parameters of hepatotoxicity. In conclusion, alcohol-induced hepatotoxicity is primarily due to membrane damage induced by the direct solvent properties of the alcohols. The consequences and relative

  10. Binding of higher alcohols onto Mn(12) single-molecule magnets (SMMs): access to the highest barrier Mn(12) SMM.

    PubMed

    Lampropoulos, Christos; Redler, Gage; Data, Saiti; Abboud, Khalil A; Hill, Stephen; Christou, George

    2010-02-15

    Two new members of the Mn(12) family of single-molecule magnets (SMMs), [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(Bu(t)OH)(H(2)O)(3)].2Bu(t)OH (3.2Bu(t)OH) and [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(C(5)H(11)OH)(4)] (4) (C(5)H(11)OH is 1-pentanol), are reported. They were synthesized from [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)].2MeCO(2)H.4H(2)O (1) by carboxylate substitution and crystallization from the appropriate alcohol-containing solvent. Complexes 3 and 4 are new members of the recently established [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(solv)(4)] (solv = H(2)O, alcohols) family of SMMs. Only one bulky Bu(t)OH can be accommodated into 3, and even this causes significant distortion of the [Mn(12)O(12)] core. Variable-temperature, solid-state alternating current (AC) magnetization studies were carried out on complexes 3 and 4, and they established that both possess an S = 10 ground state spin and are SMMs. However, the magnetic behavior of the two compounds was found to be significantly different, with 4 showing out-of-phase AC peaks at higher temperatures than 3. High-frequency electron paramagnetic resonance (HFEPR) studies were carried out on single crystals of 3.2Bu(t)OH and 4, and these revealed that the axial zero-field splitting constant, D, is very different for the two compounds. Furthermore, it was established that 4 is the Mn(12) SMM with the highest kinetic barrier (U(eff)) to date. The results reveal alcohol substitution as an additional and convenient means to affect the magnetization relaxation barrier of the Mn(12) SMMs without major change to the ligation or oxidation state.

  11. Development of a standard gas generating vial comprised of a silicon oil-polystyrene/divinylbenzene composite sorbent.

    PubMed

    Grandy, Jonathan J; Gómez-Ríos, German A; Pawliszyn, Janusz

    2015-09-04

    In this work, a highly reproducible standard gas generating vial is proposed. The vial is comprised of a silicon diffusion pump oil spiked with an appropriate calibration compound, such as modified McReynolds probes (benzene, 2-pentanone, pyridine, 1-nitropropane, 1-pentanol, and n-octane), and then mixed with polystyrene/divinylbenzene (PS/DVB) particles. The concentrations of these compounds in gaseous headspace were found to substantially decrease in comparison to previously developed hydrocarbon pump oil based vials; hence, the amount of standard loaded onto SPME fibers was at most, half that of the previous vial design. Depletion for all compounds after 208 successive extractions was shown to be less than 3.5%. Smaller quantities of standards being used resulted in a vial that depleted slower while remaining statistically repeatable over a wider number of runs. Indeed, it was found that depletion could be largely predicted by using a mass balance theoretical model. This behavior allowed a further increase in the number of loadings that could be performed repeatedly. At a 95% level of confidence, the ANOVA test demonstrated that the prepared vials were statistically identical, with no significant intra- or inter-batch differences. In addition, it was found that vials stored under different conditions (e.g. under light exposure, room temperature, and within a refrigerator) were stable over 10 weeks. Silicon based vials proved to be ideal for performing instrument quality control and loading of internal standards onto fibers, both of which are of great importance when performing on-site analysis using portable GC-MS instrumentation and high throughput determinations in laboratory.

  12. Gas-Phase Reactivity of Protonated 2-, 3- and 4-Dehydropyridine Radicals Toward Organic Reagents

    PubMed Central

    Adeuya, Anthony; Price, Jason M.; Jankiewicz, Bartłomiej J.; Nash, John J.; Kenttämaa, Hilkka I.

    2009-01-01

    In order to explore the effects of the electronic nature of charged phenyl radicals on their reactivity, reactions of the three distonic isomers of ndehydropyridinium cation (n = 2, 3 or 4) have been investigated in the gas phase by using Fourier-transform ion cyclotron resonance mass spectrometry. All three isomers react with cyclohexane, methanol, ethanol and 1-pentanol exclusively via hydrogen atom abstraction, and with allyl iodide mainly via iodine atom abstraction, with a reaction efficiency ordering: 2 > 3 > 4. The observed reactivity ordering correlates well with the calculated vertical electron affinities of the charged radicals (i.e., the higher the vertical electron affinity, the faster the reaction). Charged radicals 2 and 3 also react with tetrahydrofuran exclusively via hydrogen atom abstraction, but the reaction of 4 with tetrahydrofuran yields products arising from nonradical reactivity. The unusual reactivity of 4 is likely to result from the contribution of an ionized carbene-type resonance structure that facilitates nucleophilic addition to the most electrophilic carbon atom (C-4) in this charged radical. The influence of such a resonance structure on the reactivity of 2 is not obvious, and this may be due to stabilizing hydrogen-bonding interactions in the transition states for this molecule. Charged radicals 2 and 3 abstract a hydrogen atom from the substituent in both phenol and toluene, but 4 abstracts a hydrogen atom from the phenyl ring – a reaction that is unprecedented for phenyl radicals. Charged radical 4 reacts with tert-butyl isocyanide mainly by hydrogen cyanide (HCN) abstraction while CN abstraction is the principal reaction for 2 and 3. The different reactivity observed for 4 (compared to 2 and 3) is likely to result from different charge and spin distributions of the reaction intermediates for these charged radicals. PMID:19902945

  13. Determination of diuron, terbuthylazine, and terbutryn in wastewater and soil by micellar liquid chromatography.

    PubMed

    Pitarch-Andrés, Susana; Roca-Genovés, Pasqual; Peris-Vicente, Juan; Esteve-Romero, Josep

    2017-03-01

    An analytical method for the quantification of the herbicides and algaecides diuron, terbuthylazine, and terbutryn in wastewater and soil by micellar liquid chromatography was developed. The sample preparation was expedited to reduce the number of intermediate steps and the use of chemicals. The analytes in soils were recovered by ultrasonication in the mobile phase. The obtained supernatant and the water samples were directly injected, thus avoiding intermediate steps. The chromatographic behavior of the analytes, depending on the surfactant and alcohol was studied, in order to optimize the chromatographic run, by a chemometrical approach. The herbicides were resolved in <16 min using a C18 column and a mobile phase of 0.07 M sodium dodecyl sulfate/6% 1-pentanol phosphate buffered at pH 3, running under isocratic mode at 1 mL/min. The detection absorbance wavelength was set to 240 nm. The method was successfully validated in terms of selectivity, detection limit (0.06 mg/L in water and 0.3 mg/kg in soil), quantitation range (0.2-2 mg/L in water and 1-10 mg/kg in soil), trueness (-6.1 to +5.0%), precision (<9.4%), and ruggedness (<8.3%). The procedure was reliable, practical, easy-to-handle, available, short-time and ecofriendly and useful for routine analysis. Its applicability to real samples was evaluated by analyzing several wastewater, decorative reservoir, and soil samples from agricultural and urban sources.

  14. Sensory and physicochemical evolution of tropical cooked peeled shrimp inoculated by Brochothrix thermosphacta and Lactococcus piscium CNCM I-4031 during storage at 8°C.

    PubMed

    Fall, Papa Abdoulaye; Pilet, Marie France; Leduc, François; Cardinal, Mireille; Duflos, Guillaume; Guérin, Camille; Joffraud, Jean-Jacques; Leroi, Françoise

    2012-01-16

    This study investigated the sensory quality and physicochemical evolution (pH, glucose, l-lactic acid, biogenic amine, free amino-acids and volatile compounds) during storage at 8°C of cooked peeled shrimp inoculated with the specific spoilage bacteria Brochothrix thermosphacta alone or mixed with the protective strain Lactococcus piscium CNCM I-4031. Growth of both bacteria was monitored at regular intervals during storage by microbial counts and the thermal temperature gradient gel electrophoresis (TTGE) technique. Bacterial counts showed that L. piscium and B. thermosphacta inoculated at 7 log CFU/g and 3 log CFU/g were well adapted to shrimp, reaching a maximum level of 9 log CFU/g after 4days and 10days respectively. In mixed culture, the growth of B. thermosphacta was reduced by 3.2±0.1 log CFU/g. The TTGE technique allowed monitoring the colonisation of the strains on the shrimp matrix and confirming the dominance of L. piscium in mixed culture throughout the experiment. Sensory analysis confirmed that B. thermosphacta spoiled the product after 11days, when its cell number attained 8 log CFU/g with the emission of strong butter/caramel off-odours. This sensory profile could be linked to the production of 2,3 butanedione, cyclopentanol, 3-methylbutanol, 3-methylbutanal, 2-methylbutanal, 4-methyl-3-chloro-3-pentanol and ethanol, which were produced in more significant quantities in the B. thermosphacta batch than in the batches in which the protective strain was present. On the contrary, TVBN and TMA were not suitable as quality indicators for B. thermosphacta spoilage activity. In the products where the protective L. piscium strain was present, no adverse effect on sensory quality was noted by the sensory panels. Moreover, biogenic amine assessment did not show any histamine or tyramine production by this strain, underlining its safety profile. Both strains produced lactic acid (1850mg/kg in L. piscium and B. thermosphacta batch on days 3 and 10

  15. Contribution of Liver Alcohol Dehydrogenase to Metabolism of Alcohols in Rats

    PubMed Central

    Plapp, Bryce V.; Leidal, Kevin G.; Murch, Bruce P.; Green, David W.

    2015-01-01

    The kinetics of oxidation of various alcohols by purified rat liver alcohol dehydrogenase (ADH) were compared with the kinetics of elimination of the alcohols in rats in order to investigate the roles of ADH and other factors that contribute to the rates of metabolism of alcohols. Primary alcohols (ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol) and diols (1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol) were eliminated in rats with zero-order kinetics at doses of 5–20 mmole/kg. Ethanol was eliminated most rapidly, at 7.9 mmole/kg•h. Secondary alcohols (2-propanol-d7, 2-propanol, 2-butanol, 3-pentanol, cyclopentanol, cyclohexanol) were eliminated with first order kinetics at doses of 5–10 mmole/kg, and the corresponding ketones were formed and slowly eliminated with zero or first order kinetics. The rates of elimination of various alcohols were inhibited on average 73% (55% for 2-propanol to 90% for ethanol) by 1 mmole/kg of 4-methylpyrazole, a good inhibitor of ADH, indicating a major role for ADH in the metabolism of the alcohols. The Michaelis kinetic constants from in vitro studies (pH 7.3, 37 °C) with isolated rat liver enzyme were used to calculate the expected relative rates of metabolism in rats. The rates of elimination generally increased with increased activity of ADH, but a maximum rate of 6 ± 1 mmole/kg•h was observed for the best substrates, suggesting that ADH activity is not solely rate-limiting. Because secondary alcohols only require one NAD+ for the conversion to ketones whereas primary alcohols require two equivalents of NAD+ for oxidation to the carboxylic acids, it appears that the rate of oxidation of NADH to NAD+ is not a major limiting factor for metabolism of these alcohols, but the rate-limiting factors are yet to be identified. PMID:25641189

  16. Purification and characterization of alcohol dehydrogenase reducing N-benzyl-3-pyrrolidinone from Geotrichum capitatum.

    PubMed

    Yamada-Onodera, Keiko; Fukui, Masato; Tani, Yoshiki

    2007-02-01

    (S)-N-Benzyl-3-pyrrolidinol is widely used in the synthesis of pharmaceuticals as a chiral building block. We produced 30 mM (S)-N-benzyl-3-pyrrolidinol (enantiometric excess > 99.9%) from the corresponding ketone N-benzyl-3-pyrrolidinone with more than 99.9% yield in 28 h of the resting-cell reaction of Geotrichum capitatum JCM 3908. NAD(+)-dependent alcohol dehydrogenase reducing N-benzyl-3-pyrrolidinone from G. capitatum JCM 3908 was purified to homogeneity by ammonium sulfate fractionation and a series of DEAE-Toyopearl, Butyl-Toyopearl, Superdex 200, and Hydroxyapatite column chromatographies. The results of SDS-PAGE and HPLC showed the enzyme to be a dimer with a molecular mass of 78 kDa. The purified enzyme produced (S)-N-benzyl-3-pyrrolidinol (e.e.>99.9%) from N-benzyl-3-pyrrolidinone. The enzyme reduced 2,3-butanedione, 2-hexanone, cyclohexanone, propionaldehyde, n-butylaldehyde, n-hexylaldehyde, n-octylaldehyde, n-valeraldehyde, and benzylacetone more effectively than it did N-benzyl-3-pyrrolidinone. No activity was detected towards N-benzyl-2-pyrrolidinone or 2-pyrrolidinone. The activity towards (R)-N-benzyl-3-pyrrolidinol was not detected under the assay conditions employed. The oxidizing activity of the enzyme was higher towards 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 3-hexanol, and 1-phenyl-2-propanol than towards (S)-N-benzyl-3-pyrrolidinol. The K(m) values for N-benzyl-3-pyrrolidinone reduction and (S)-N-benzyl-3-pyrrolidinol oxidation were 0.13 and 8.47 mM, respectively. To our knowledge, this is the first time that an N-benzyl-3-pyrrolidinol/N-benzyl-3-pyrrolidinone oxidoreductase was purified from a eukaryote; moreover, this is the first report of (S)-N-benzyl-3-pyrrolidinol dehydrogenase activity in microorganisms. This enzyme showed features different from those of known prokaryotic N-benzyl-3-pyrrolidinone reductases. This enzyme will be very useful for the production of chiral compounds.

  17. Aliphatic β-Nitroalcohols for Therapeutic Corneoscleral Cross-linking: Chemical Mechanisms and Higher Order Nitroalcohols

    PubMed Central

    Solomon, Marissa R.; Wen, Quan; Turro, Nicholas J.; Trokel, Stephen L.

    2010-01-01

    Purpose. The recent tissue cross-linking studies indicate that aliphatic β-nitroalcohols (BNAs) may be useful as pharmacologic corneoscleral cross-linking agents. The present study was performed to identify the specific chemistry involved under physiologic conditions, with the intent of identifying more effective agents. Methods. The mechanism of chemical cross-linking at pH 7.4 and 37°C was studied using three techniques. The colorimetric Griess assay was used to follow the release of nitrite from three mono-nitroalcohols (2-nitroethanol [2ne], 2-nitro-1-propanol [2nprop]), and 3-nitro-2-pentanol [3n2pent]). Second, the evolution of 2nprop in 0.2 M NaH2PO4/Na2HPO4/D2O was studied using 1H-NMR. Third, thermal shrinkage temperature analysis (Ts), a measure of tissue cross-linking, was used to support information from 1the H-NMR studies. Results. A time-dependent release of nitrite was observed for all three mono-nitroalcohols studied. The maximum levels were comparable using either 2ne or 2nprop (∼30%). However, much less (∼10%) was observed from 3n2pent. Using 1H-NMR, 2nprop evolved into a unique splitting pattern. No match was observed with reference spectra from three possible products of denitration. In contrast, 2-methyl-2-nitro-1,3-propanediol (MNPD), a nitro-diol, was identified, implying the formation of formaldehyde from a retro-nitroaldol (i.e., reverse Henry) reaction. In support of this mechanism, Ts shifts induced by the nitro-triol 2-hydroxymethyl-2-nitro-1,3-propanediol (HNPD) were superior to the nitro-diol MNPD which were superior to the mono nitroalcohol 2nprop. Conclusions. BNAs function as both formaldehyde and nitrite donors under physiologic conditions to cross-link collagenous tissue. Higher order BNAs are more effective than mono nitroalcohols, raising the possibility of using these agents for therapeutic corneoscleral cross-linking. PMID:19797229

  18. Organic compound composition in soil and sediments collected in Jackson, Mississippi.

    PubMed

    Gołębiowski, Marek; Stepnowski, Piotr; Hemmingway, Tometrick; Leszczyńska, Danuta

    2016-01-01

    The aim of our study was to identify organic pollutants found in soil and sediment samples collected within the Jackson, MS metropolitan area. The chemical characterization of the organic compound fractions in soil and sediment samples was carried out by separating the organic fraction using column chromatography (CC) and quantitatively analyzing the polycyclic aromatic hydrocarbons (PAHs), n-alkanes and other organic compounds using gas chromatography-electron impact mass spectrometry (GC-MS). Fifty-six compounds were identified and quantified in the soil samples and 33 compounds were identified and quantified in the sediment samples. The PAHs, n-alkanes and other organic compound profiles in the soil and sediment samples were compared. The percentage contents of the organic compounds in the soil samples were very diverse (from traces to 12.44 ± 1.47%). The compounds present in the highest concentrations were n-alkanes: n-C31 (12.44 ± 1.47%), n-C29 (11.64 ± 1.21%), and n-C33 (8.95 ± 1.08%). The components occurring in smaller quantities (from 1% to 5%) were 2 PAHs (fluoranthene 1.28 ± 0.25%, pyrene 1.16 ± 0.20%), 10 n-alkanes from n-C21 (1.25 ± 0.29%) to n-C32 (2.67 ± 0.52%) and 11 other compounds (e.g., 2-pentanol, 4-methyl (3.33 ± 0.44%), benzyl butyl phthalate (4.25 ± 0.59%), benzenedicarboxylic acid (1.14 ± 0.08%), ethane, 1,1-diethoxy (3.15 ± 0.41) and hexadecanoic acid (2.52 ± 0.34). The soil samples also contained 30 compounds present in concentrations <1% (e.g., anthracene (0.13 ± 0.04%), n-C20 (0.84 ± 0.21%) and acetic acid (0.12 ± 0.04%). The compounds present in the highest concentrations in the sediment samples were PAHs: pyrene (7.73 ± 1.15%) and fluoranthene (6.23 ± 1.07%) and n-alkanes: n-C31 (6.74 ± 1.21%), n-C29 (6.65 ± 0.98%) and n-C27 (6.13 ± 1.09%). The remaining organic compounds were present in smaller quantities (< 5%).

  19. The effect of cavitating ultrasound on the aqueous phase hydrogenation of cis-2-buten-1-ol and cis-2-penten-1-ol on Pd-black

    SciTech Connect

    Disselkamp, Robert S.; Denslow, Kayte M.; Hart, Todd R.; White, James F.; Peden, Charles HF.

    2005-07-15

    We have studied the effect of cavitating ultrasound on the heterogeneous aqueous hydrogenation of cis-2-buten-1-ol (C4 olefin) and cis-2-penten-1-ol (C5 olefin) on Pd-black to form the trans-olefins (trans-2-buten-1-ol and trans-2-penten-1-ol) and saturated alcohols (1-butanol and 1-pentanol, respectively). Silent (and magnetically stirred) experiments served as control experiments. As described in an earlier publication by our group, we have added an inert dopant, 1-propanol, in the reaction mixture to ensure the rapid onset of cavitation in the ultrasound-assisted reactions that can lead to altered selectivity compared to silent reaction systems [R.S. Disselkamp, Ya-Huei Chin, C.H.F. Peden, J. Catal. 227 (2004) 552]. The motivation for this study is to examine whether cavitating ultrasound can reduce the [trans-olefin/saturated alcohol] molar ratio during the course of the reaction. This could have practical application in that it may offer an alternative processing methodology of synthesizing healthier edible seed oils by reducing trans-fat content.We have observed that cavitating ultrasound results in a [(trans-olefin/saturated alcohol)ultrasound/(trans-olefin/saturated alcohol)silent] ratio quantity less than 0.5 at the reaction mid-point for both the C4 and C5 olefin systems. This indicates that ultrasound reduces trans-olefin production compared to the silent control experiment. Furthermore, there is an added 30% reduction for the C5 versus C4 olefin compounds again at reaction mid-point. We attribute differences in the ratio quantity as a moment of inertia effect. In principle, the C4 versus C5 olefins has a {approx}52% increase in moment of inertia about C2 C3 double bond slowing isomerization. Since seed oils are C18 multiple cis-olefins and have a moment of inertia even greater than our C5 olefin here, our study suggests that even a greater reduction in trans-olefin content may occur for partial hydrogenation of C18 seed oils.

  20. The Effect of Cavitating Ultrasound on the Aqueous Phase Hydrogenation of Cis-2-buten-1-ol and Cis-2-penten-1-ol on Pd-black

    SciTech Connect

    Disselkamp, Robert S.; Denslow, Kayte M.; Hart, Todd R.; White, James F.; Peden, Charles HF.

    2005-07-15

    We have studied the effect of cavitating ultrasound on the heterogeneous aqueous hydrogenation of cis-2-buten-1-ol (C4 olefin) and cis-2-penten-1-ol (C5 olefin) on Pd-black to form the trans-olefins (trans-2-buten-1-ol and trans-2-penten-1-ol) and saturated alcohols (1-butanol and 1-pentanol, respectively). Silent (and magnetically stirred) experiments served as control experiments. As described in an earlier publication by our group, we have added an inert dopant, 1-propanol, in the reaction mixture to ensure the rapid onset of cavitation in the ultrasound-assisted reactions that can lead to altered selectivity compared to silent reaction systems [Disselkamp et al., J. Catal., 227 (2004) 552]. The motivation for this study is to examine whether cavitating ultrasound can reduce the [trans-olefin/saturated alcohol] molar ratio during the course of the reaction. This could have practical application in that it may offer an alternative processing methodology of synthesizing healthier edible seed oils by reducing trans-fat content. We have observed that cavitating ultrasound results in a [(trans-olefin/saturated alcohol)ultrasound/(trans-olefin/saturated alcohol)silent] ratio quantity less than 0.5 at the reaction mid-point for both the C4 and C5 olefin systems. This indicates that ultrasound reduces trans-olefin production compared to the silent control experiment. Furthermore, there is an added 30% reduction for the C5 versus C4 olefin compounds again at reaction mid-point. We attribute differences in the ratio quantity as a moment of inertia effect. In principle, the C4 versus C5 olefins has a {approx}52% increase in moment of inertia about C2=C3 double bond slowing isomerization. Since seed oils are C18 multiple cis olefins and have an moment of inertia even greater than our C5 olefin here, our study suggests that even a greater reduction in trans-olefin content may occur for partial hydrogenation of C18 seed oils.

  1. Chemoenzymatic synthesis of artificial glycopolypeptides containing multivalent sialyloligosaccharides with a gamma-polyglutamic acid backbone and their effect on inhibition of infection by influenza viruses.

    PubMed

    Ogata, Makoto; Murata, Takeomi; Murakami, Kouki; Suzuki, Takashi; Hidari, Kazuya I P J; Suzuki, Yasuo; Usui, Taichi

    2007-02-01

    Highly water-soluble, artificial glycopolypeptides with a gamma-polyglutamic acid (gamma-PGA) backbone derived from Bacillus subtilis sp. and multivalent sialyloligosaccharide units have been chemoenzymatically synthesized as potential polymeric inhibitors of infection by bird and human influenza viruses. 5-Trifluoroacetamidopentyl beta-N-acetyllactosaminide and 5-trifluoroacetamidopentyl beta-lactoside were enzymatically synthesized from LacNAc and lactose, respectively, by cellulase-mediated condensation with 5-trifluoroacetamido-1-pentanol. After deacetylation, the resulting 5-aminopentyl beta-LacNAc and beta-lactoside glycosides were coupled to the alpha-carboxyl groups of the gamma-PGA side chains. The artificial glycopolypeptides carrying LacNAc and lactose were further converted to Neu5Acalpha2-(3/6)Galbeta1-4Glcbeta and Neu5Acalpha2-(3/6)Galbeta1-4GlcNAcbeta sialyloligosaccharide units by alpha2,3- and alpha2,6-sialyltransferase, respectively. The interaction of these glycopolypeptides with various influenza virus strains has been investigated by three different methods. Glycopolypeptides carrying Neu5Acalpha2,6LacNAc inhibited hemagglutination mediated by influenza A and B viruses, and their relative binding affinities for hemagglutinin were 10(2)- to 10(4)-fold higher than that of the naturally occurring fetuin control. A glycopolypeptide carrying Neu5Acalpha2,6LacNAc inhibited infection by A/Memphis/1/71 (H3N2) 93 times more strongly than fetuin, as assessed by cytopathic effects on virus-infected MDCK cells. The avian virus [A/duck/Hong kong/4/78 (H5N3)] bound strongly to Neu5Acalpha2,3LacNAc/Lac-carrying glycopolypeptides, whereas the human virus [A/Memphis/1/71 (H3N2)] bound to Neu5Acalpha2,6LacNAc in preference to Neu5Acalpha2,6Lac. Taken together, these results indicate that the binding of viruses to terminal sialic acids is markedly affected by the structure of the asialo portion, in this case either LacNAc or lactose, in the sugar chain of

  2. Comparison of the olfactory sensitivity of two sympatric steppe grasshopper species (Orthoptera: Acrididae) to plant volatile compounds.

    PubMed

    Chen, Huhai; Zhao, Yunxian; Kang, Le

    2004-04-01

    Electroantennogram (EAG) responses of male and female Oedipodinae grasshoppers, Oedaleus decorus asiaticus B.-Bienko and Angaracris barabensis Pall to 37 plant volatile compounds were recorded. The two species have sympatric distribution and synchronous seasonal activity in Inner Mongolia Grasslands. They have different host plant preference with Oedaleus decorus asiaticus graminivorous and A. barabensis forbivorous. The EAG response profiles to 37 compounds of the two species and their both sexes were similar. Most of the green leaf volatiles elicited higher EAG responses in both species and sexes than terpenic compounds and some aromatic compounds. Strong EAG responses were elicited by 6-carbon alcohols (1-hexanol, Z-hexen-2-ol-1, E-2-hexen-1-ol, E-hexen-3-ol-1), aldehyde (E-2-hexen-1-al), ester (Z-hexen-3-yl acetate), and 7-carbon alcohols (1-heptanol) in both species and sexes. Monoterpenes with functional groups of alcohols and aldehydes were more stimulating than other monoterpenes tested. The sesquiterpenes tested elicited relatively low responses. Benzaldehyde elicited the highest responses for both species among aromatic components. Oedaleus decorus asiaticus showed higher EAG responses than A. barabensis to the green leaf volatiles, 1-decanol, 1-nonanol, 1-pentanol, hexanal, Z-hexen-3-yl acetate and to the sesquiterpenes (-)-trans-caryophyllene. Males have higher responses than females in Oedaleus decorus asiaticus. No sexual difference was observed in A. barabensis. Dose-dependent responses to six selected chemicals were observed from females. In both species, all the chemicals tested elicit EAG responses at concentration between 10(-3) mol/L and 10(-2) mol/L, except that the responses of A. barabensis to terpineol had a threshold concentration of 10(-2) mol/L benzaldehyde and 1-hexanol had the highest slopes in dose curves, while 1-octen-3-ol showed the smallest slope in responses to the six chemicals tested. Comparative studies on the responses of two

  3. Experimental study of the effect of test-well arrangement for partitioning interwell tracer test on the estimation of NAPL saturation

    NASA Astrophysics Data System (ADS)

    Kim, B.; Kim, Y.; Yeo, I.; Yongcheol Kim, In Wook Yeo

    2011-12-01

    Partitioning interwell tracer test (PITT) is a method to quantify and qualify a contaminated site with NAPLs through a degree of retardation of partitioning tracers compared to a conservative one. Although PITT is known to be a more effective method to measure the saturation of spatially-distributed NAPL contaminant than the point investigation method, the saturation estimation from PITT is reported to be underestimated due to various factors including heterogeneity of the media, adsorption, source zone NAPL architecture, and long tailing in breakthrough curves of partitioning tracers. Analytical description of PITT assumes that the injection-pumping well pair is on the line of ambient groundwater flow direction, but the test-well pair could easily be off the line in the field site, which could be another erroneous factor in analyzing PITT data. The purpose of this work is to study the influence of the angle of the test-well pair to ambient groundwater flow direction based on the result from PITT. The experiments were conducted in a small-scale 3D sandbox with dimensions of 0.5 m × 0.4 m × 0.15 m (LWH) of stainless steel. The surface is covered and sealed with a plexiglass plate to make the physical model a confined aquifer. Eight full-screened wells of Teflon material were installed along the perimeter of a 50 mm circle with 45 degree intervals in the middle of the physical model. Both ends of the sand box are connected to constant head reservoirs. The physical model was wet-packed with sieved and washed sand. Trichloroethylene (TCE) and bromide were used as the contaminant and the conservative tracer, respectively. Hexanol, 2,4-dimethyl-3-pentanol and 6-methyl-2-heptanol were used as partitioning tracers. Before the injection of TCE, a PITT was conducted to measure adsorption coefficient of partitioning tracers to the sand material. TCE of 4.5 mL, dyed with Sudan IV, was injected into the inner part of the circle of the wells. PITTs using the test-well pair

  4. Safety assessment of MIBK (methyl isobutyl ketone).

    PubMed

    Johnson, Wilbur

    2004-01-01

    MIBK (Methyl Isobutyl Ketone) is an aliphatic ketone that functions as both a denaturant and solvent in cosmetic products. Current use in cosmetic products is very limited, but MIBK is reported to be used in one nail correction pen (volume = 3 ml) at a concentration of 21%. The maximum percutaneous absorption rate in guinea pigs is 1.1 micromol/min/cm2 at 10 to 45 min. Metabolites include 4-hydroxy-4-methyl-2-pentanone (oxidation product) and 4-methyl-2-pentanol (4-MPOL) (reduction product). Values for the serum half-life and total clearance time of MIBK in animals were 66 min and 6 h, respectively. In clinical tests, most of the absorbed MIBK had been eliminated from the body 90 min post exposure. MIBK was not toxic via the oral or dermal route of exposure in acute, short-term, or subchronic animal studies, except that nephrotoxicity was observed in rats dosed with 1 g/kg in a short-term study. MIBK was an ocular and skin irritant in animal tests. Ocular irritation was noted in 12 volunteers exposed to 200 ppm MIBK for 15 min in a clinical test. A depression of the vestibulo-oculomotor reflex was seen with intravenous infusion of MIBK (in an emulsion) at 30 microM/kg/min in female rats. The no-observed-effect level in rats exposed orally to MIBK was 50 mg/kg. Both gross and microscopic evidence of lung damage were reported in acute inhalation toxicity studies in animals. Short-term and subchronic inhalation exposures (as low as 100 ppm) produced effects in the kidney and liver that were species and sex dependent. Dermal doses of 300 or 600 mg/kg for 4 months in rats produced reduced mitotic activity in hair follicles, increased thickness of horny and granular cell layers of the epidermis, a decrease in the number of reactive centers in follicles (spleen), an increase in the number of iron-containing pigments in the area of the red pulp (spleen), and a reduction in the lipid content of the cortical layer of the adrenal glands. Neuropathological changes in the most

  5. Kinetics of n-butoxy and 2-pentoxy isomerization and detection of primary products by infrared cavity ringdown spectroscopy.

    PubMed

    Sprague, Matthew K; Garland, Eva R; Mollner, Andrew K; Bloss, Claire; Bean, Brian D; Weichman, Marissa L; Mertens, Laura A; Okumura, Mitchio; Sander, Stanley P

    2012-06-21

    The primary products of n-butoxy and 2-pentoxy isomerization in the presence and absence of O(2) have been detected using pulsed laser photolysis-cavity ringdown spectroscopy (PLP-CRDS). Alkoxy radicals n-butoxy and 2-pentoxy were generated by photolysis of alkyl nitrite precursors (n-butyl nitrite or 2-pentyl nitrite, respectively), and the isomerization products with and without O(2) were detected by infrared cavity ringdown spectroscopy 20 μs after the photolysis. We report the mid-IR OH stretch (ν(1)) absorption spectra for δ-HO-1-C(4)H(8)•, δ-HO-1-C(4)H(8)OO•, δ-HO-1-C(5)H(10)•, and δ-HO-1-C(5)H(10)OO•. The observed ν(1) bands are similar in position and shape to the related alcohols (n-butanol and 2-pentanol), although the HOROO• absorption is slightly stronger than the HOR• absorption. We determined the rate of isomerization relative to reaction with O(2) for the n-butoxy and 2-pentoxy radicals by measuring the relative ν(1) absorbance of HOROO• as a function of [O(2)]. At 295 K and 670 Torr of N(2) or N(2)/O(2), we found rate constant ratios of k(isom)/k(O(2)) = 1.7 (±0.1) × 10(19) cm(-3) for n-butoxy and k(isom)/k(O(2)) = 3.4(±0.4) × 10(19) cm(-3) for 2-pentoxy (2σ uncertainty). Using currently known rate constants k(O(2)), we estimate isomerization rates of k(isom) = 2.4 (±1.2) × 10(5) s(-1) and k(isom) ≈ 3 × 10(5) s(-1) for n-butoxy and 2-pentoxy radicals, respectively, where the uncertainties are primarily due to uncertainties in k(O(2)). Because isomerization is predicted to be in the high pressure limit at 670 Torr, these relative rates are expected to be the same at atmospheric pressure. Our results include corrections for prompt isomerization of hot nascent alkoxy radicals as well as reaction with background NO and unimolecular alkoxy decomposition. We estimate prompt isomerization yields under our conditions of 4 ± 2% and 5 ± 2% for n-butoxy and 2-pentoxy formed from photolysis of the alkyl nitrites at 351 nm. Our

  6. A Unique Equation to Estimate Flash Points of Selected Pure Liquids Application to the Correction of Probably Erroneous Flash Point Values

    NASA Astrophysics Data System (ADS)

    Catoire, Laurent; Naudet, Valérie

    2004-12-01

    several flash points have been reported erroneously, whatever the reason, in one or several reference compilations. In the following lists, the currently accepted flash points for bold compounds err, or probably err, on the hazardous side by at least 10 °C and for the nonbolded compounds, the currently accepted flash points err, or probably err, on the nonhazardous side by at least 10 °C: bicyclohexyl, sec-butylamine, tert-butylamine, 2-cyclohexen-1-one, ethanethiol, 1,3-cyclohexadiene, 1,4-pentadiene, methyl formate, acetonitrile, cinnamaldehyde, 1-pentanol, diethylene glycol, diethyl fumarate, diethyl phthalate, trimethylamine, dimethylamine, 1,6-hexanediol, propylamine, methanethiol, ethylamine, bromoethane, 1-bromopropane, tert-butylbenzene, 1-chloro-2-methylpropane, diacetone alcohol, diethanolamine, 2-ethylbutanal, and formic acid. For some other compounds, no other data than the currently accepted flash points are available. Therefore, it cannot be assessed that these flash point data are erroneous but it can be stated that they are probably erroneous. At least, they need experimental re-examination. They are probably erroneous by at least 15 °C: 1,3-cyclopentadiene, di-tert-butyl sulfide, dimethyl ether, dipropyl ether, 4-heptanone, bis(2-chloroethyl)ether, 1-decanol, 1-phenyl-1-butanone, furan, ethylcyclopentane, 1-heptanethiol, 2,5-hexanediol, 3-hexanone, hexanoic acid methyl ester, 4-methyl-1,3-pentadiene, propanoyl chloride, tetramethylsilane, thiacyclopentane, 1-chloro-2-methyl-1-propene, trans-1,3-pentadiene, 2,3-dimethylheptane, triethylenetetramine, methylal, N-ethylisopropylamine, 3-methyl-2-pentene, and 2,3-dimethyl-1-butene.

  7. Influence of Mass Transfer Kinetics on Interpretation of Push-Pull Partitioning Tracer Tests

    NASA Astrophysics Data System (ADS)

    Ervin, R. E.; Boroumand, A.; Abriola, L. M.; Ramsburg, C. A.

    2012-12-01

    There is now considerable interest in predicting plume response to various levels of treatment applied within a DNAPL source zone. An important component to the development of this predictive capability is the ability to characterize the distribution of DNAPL within the source zone. Metrics developed for description of source zone architecture are frequently based upon some combination of downgradient contaminant concentrations and in source testing. One option for in source testing is the use of partition tracers in either interwell or push-pull test configurations. Push-pull tracer tests are advantageous for obtaining more localized information that can be integrated with other observations to reduce the uncertainty related the links between the architecture of a source and its associated plume. Here we examined push-pull tracer tests in a series of aquifer cell experiments to evaluate the potential of this type of test to quantify metrics of the DNAPL distribution at the local-scale (i.e., 1 m flow path). Three DNAPL architectures were characterized by conducting push-pull tracer tests using a solution which comprised three partitioning tracers (1-pentanol, 1-hexanol, and 2-octanol) and one non-partitioning tracer (bromide). Each architecture was characterized using three flow regimes that employed combinations of fast (~30 cm/hr) and slow (~2 cm/hr) velocities. Production curves (i.e., tracer concentrations during the pull phase of the test) for the partitioning tracers were found to be asymmetric. This asymmetry severely degraded the ability of an analytical solution employing the local equilibrium assumption to predict the overall saturations. Saturation estimates from the analytical solution were found to be improved when the application of the model was restricted to later time data (Vext/Vinj >1). This observation suggests it is important to better understand the factors influencing the early time data. Experiments were also simulated using a numerical