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Sample records for 1-propanol

  1. 40 CFR 721.8175 - 1-Propanol, 3-mercapto-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8175 1-Propanol, 3-mercapto-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-propanol, 3-mercapto (PMN P-85-433; CAS No....

  2. 40 CFR 721.8175 - 1-Propanol, 3-mercapto-.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8175 1-Propanol, 3-mercapto-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-propanol, 3-mercapto (PMN P-85-433; CAS No....

  3. 40 CFR 721.8175 - 1-Propanol, 3-mercapto-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8175 1-Propanol, 3-mercapto-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-propanol, 3-mercapto (PMN P-85-433; CAS No....

  4. 40 CFR 721.8175 - 1-Propanol, 3-mercapto-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8175 1-Propanol, 3-mercapto-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-propanol, 3-mercapto (PMN P-85-433; CAS No....

  5. 40 CFR 721.8175 - 1-Propanol, 3-mercapto-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8175 1-Propanol, 3-mercapto-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-propanol, 3-mercapto (PMN P-85-433; CAS No....

  6. Synthesis of polypropylene from 1-propanol using AlCl3 Ziegler-Natta catalyst

    NASA Astrophysics Data System (ADS)

    Salmahaminati, Jumina

    2016-11-01

    Synthesis of polypropylene from 1-propanol had been done. Polypropylene was synthesized via dehydration of 1-propanol using sulfuric acid catalyst followed with polymerization using AlCl3 catalyst to produce polypropylene. Structural characterization of products was done by means of IR spectrometer and the molecular weight of polypropylene was measured by viscometri Ubbelohde. Polymerization reaction by dehydration of 1-propanol using sulfuric acid catalyst produced propylene and followed with polymerization gave polypropylene in the molecular weight of 3900 g/mol with repetitive units of 93.

  7. Photocatalytic degradation of gaseous 1-propanol using an annular reactor: kinetic modelling and pathways.

    PubMed

    Vincent, G; Marquaire, P M; Zahraa, O

    2009-01-30

    Photocatalytic oxidation of airborne contaminants appears to be a promising process for remediation of air polluted by Volatile Organic Compounds (VOCs). In the present work, the photocatalytic oxidation of gaseous 1-propanol has been investigated by using an annular photoreactor. The annular photocatalytic reactor was modelled by a cascade of heightened elementary continuously stirred tank reactors. The influence of several kinetic parameters such as pollutant concentration, incident light irradiance, contact time and humidity content has been studied. The photocatalytic degradation by-products of 1-propanol has been identified in the gas-phase by GC/MS. Propionaldehyde and acetaldehyde were found to be the main gaseous intermediates. Propionaldehyde and acetaldehyde have been taken into account in a "two-site model" to evaluate the possible competition of adsorption between 1-propanol and its by-products of degradation. A mechanistic pathway is then proposed for the photocatalytic degradation of 1-propanol.

  8. Dehydration pathways of 1-propanol on HZSM-5 in the presence and absence of water

    SciTech Connect

    Zhi, Yuchun; Shi, Hui; Mu, Linyu; Liu, Yue; Mei, Donghai; Camaioni, Donald M.; Lercher, Johannes A.

    2015-12-23

    The Brønsted acid-catalyzed gas-phase dehydration of 1-propanol (0.075-4 kPa) was studied on zeolite H-MFI (Si/Al = 26, containing minimal amounts of extraframework Al moieties) in the absence and presence of co-fed water (0-2.5 kPa) at 413-443 K. It is shown that propene can be formed from monomeric and dimeric adsorbed 1-propanol. The stronger adsorption of 1-propanol relative to water indicates that the reduced dehydration rates in the presence of water are not a consequence of the competitive adsorption between 1-propanol and water. Instead, the deleterious effect is related to the different extents of stabilization of adsorbed intermediates and the relevant elimination/substitution transition states by water. Water stabilizes the adsorbed 1-propanol monomer significantly more than the elimination transition state, leading to a higher activation barrier and a greater entropy gain for the rate-limiting step, which eventually leads to propene. In a similar manner, an excess of 1-propanol stabilizes the adsorbed state of 1-propanol more than the elimination transition state. In comparison with the monomer-mediated pathway, adsorbed dimer and the relevant transition states for propene and ether formation are similarly, while less effectively, stabilized by intrazeolite water molecules. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and was performed in part using the Molecular Sciences Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a DOE national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located and the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE.

  9. Solubilities of carbon dioxide in aqueous mixtures of diethanolamine and 2-amino-2-methyl-1-propanol

    SciTech Connect

    Seo, D.J.; Hong, W.H.

    1996-03-01

    The gas solubility of CO{sub 2} has been measured in aqueous mixtures of diethanolamine and 2-amino-2-methyl-1-propanol at (40, 60, and 80) C and in the pressure range (10 to 300) kPa. The concentrations of the amine mixtures were 6 mass % diethanolamine (DEA) + 24 mass % 2-amino-2-methyl-1-propanol (AMP), 12 mass % DEA + 18 mass % AMP, and 18 mass % DEA + 12 mass % AMP. The solubilities show a systematic change as the composition of the aqueous mixtures varies.

  10. Liquid 1-propanol studied by neutron scattering, near-infrared, and dielectric spectroscopy.

    PubMed

    Sillrén, P; Matic, A; Karlsson, M; Koza, M; Maccarini, M; Fouquet, P; Götz, M; Bauer, Th; Gulich, R; Lunkenheimer, P; Loidl, A; Mattsson, J; Gainaru, C; Vynokur, E; Schildmann, S; Bauer, S; Böhmer, R

    2014-03-28

    Liquid monohydroxy alcohols exhibit unusual dynamics related to their hydrogen bonding induced structures. The connection between structure and dynamics is studied for liquid 1-propanol using quasi-elastic neutron scattering, combining time-of-flight and neutron spin-echo techniques, with a focus on the dynamics at length scales corresponding to the main peak and the pre-peak of the structure factor. At the main peak, the structural relaxation times are probed. These correspond well to mechanical relaxation times calculated from literature data. At the pre-peak, corresponding to length scales related to H-bonded structures, the relaxation times are almost an order of magnitude longer. According to previous work [C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E. Rössler, and R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)] this time scale difference is connected to the average size of H-bonded clusters. The relation between the relaxation times from neutron scattering and those determined from dielectric spectroscopy is discussed on the basis of broad-band permittivity data of 1-propanol. Moreover, in 1-propanol the dielectric relaxation strength as well as the near-infrared absorbance reveal anomalous behavior below ambient temperature. A corresponding feature could not be found in the polyalcohols propylene glycol and glycerol.

  11. Optimization of lipase-catalyzed enantioselective production of 1-phenyl 1-propanol using response surface methodology.

    PubMed

    Soyer, Asli; Bayraktar, Emine; Mehmetoglu, Ulku

    2010-01-01

    Optically active 1-phenyl 1-propanol is used as a chiral building block and synthetic intermediate in the pharmaceutical industries. In this study, the enantioselective production of 1-phenyl 1-propanol was investigated systematically using response surface methodology (RSM). Before RSM was applied, the effects of the enzyme source, the type of acyl donor, and the type of solvent on the kinetic resolution of 1-phenyl 1-propanol were studied. The best results were obtained with Candida antartica lipase (commercially available as Novozym 435), vinyl laurate as the acyl donor, and isooctane as the solvent. In the RSM, substrate concentration, molar ratio of acyl donor to the substrate, amount of enzyme, temperature, and stirring rate were chosen as independent variables. The predicted optimum conditions for a higher enantiomeric excess (ee) were as follows: substrate concentration, 233 mM; molar ratio of acyl donor to substrate, 1.5; enzyme amount, 116 mg; temperature, 47 °C; and stirring rate, 161 rpm. A verification experiment conducted at these optimized conditions for maximum ee yielded 91% for 3 hr, which is higher than the predicted value of 83%. The effect of microwave on the ee was also investigated and ee reached 87% at only 5 min.

  12. Liquid 1-propanol studied by neutron scattering, near-infrared, and dielectric spectroscopy

    SciTech Connect

    Sillrén, P.; Matic, A.; Karlsson, M.; Koza, M.; Maccarini, M.; Fouquet, P.; Götz, M.; Bauer, Th.; Gulich, R.; Lunkenheimer, P.; Loidl, A.; Mattsson, J.; Gainaru, C.; Vynokur, E.; Schildmann, S.; Bauer, S.; Böhmer, R.

    2014-03-28

    Liquid monohydroxy alcohols exhibit unusual dynamics related to their hydrogen bonding induced structures. The connection between structure and dynamics is studied for liquid 1-propanol using quasi-elastic neutron scattering, combining time-of-flight and neutron spin-echo techniques, with a focus on the dynamics at length scales corresponding to the main peak and the pre-peak of the structure factor. At the main peak, the structural relaxation times are probed. These correspond well to mechanical relaxation times calculated from literature data. At the pre-peak, corresponding to length scales related to H-bonded structures, the relaxation times are almost an order of magnitude longer. According to previous work [C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E. Rössler, and R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)] this time scale difference is connected to the average size of H-bonded clusters. The relation between the relaxation times from neutron scattering and those determined from dielectric spectroscopy is discussed on the basis of broad-band permittivity data of 1-propanol. Moreover, in 1-propanol the dielectric relaxation strength as well as the near-infrared absorbance reveal anomalous behavior below ambient temperature. A corresponding feature could not be found in the polyalcohols propylene glycol and glycerol.

  13. Liquid 1-propanol studied by neutron scattering, near-infrared, and dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Sillrén, P.; Matic, A.; Karlsson, M.; Koza, M.; Maccarini, M.; Fouquet, P.; Götz, M.; Bauer, Th.; Gulich, R.; Lunkenheimer, P.; Loidl, A.; Mattsson, J.; Gainaru, C.; Vynokur, E.; Schildmann, S.; Bauer, S.; Böhmer, R.

    2014-03-01

    Liquid monohydroxy alcohols exhibit unusual dynamics related to their hydrogen bonding induced structures. The connection between structure and dynamics is studied for liquid 1-propanol using quasi-elastic neutron scattering, combining time-of-flight and neutron spin-echo techniques, with a focus on the dynamics at length scales corresponding to the main peak and the pre-peak of the structure factor. At the main peak, the structural relaxation times are probed. These correspond well to mechanical relaxation times calculated from literature data. At the pre-peak, corresponding to length scales related to H-bonded structures, the relaxation times are almost an order of magnitude longer. According to previous work [C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E. Rössler, and R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)] this time scale difference is connected to the average size of H-bonded clusters. The relation between the relaxation times from neutron scattering and those determined from dielectric spectroscopy is discussed on the basis of broad-band permittivity data of 1-propanol. Moreover, in 1-propanol the dielectric relaxation strength as well as the near-infrared absorbance reveal anomalous behavior below ambient temperature. A corresponding feature could not be found in the polyalcohols propylene glycol and glycerol.

  14. Systematically engineering Escherichia coli for enhanced production of 1,2-propanediol and 1-propanol.

    PubMed

    Jain, Rachit; Sun, Xinxiao; Yuan, Qipeng; Yan, Yajun

    2015-06-19

    The biological production of high value commodity 1,2-propanediol has been established by engineering the glycolysis pathway. However, the simultaneous achievement of high titer and high yield has not been reported yet, as all efforts in increasing the titer have resulted in low yields. In this work, we overcome this limitation by employing an optimal minimal set of enzymes, channeling the carbon flux into the 1,2-propanediol pathway, increasing NADH availability, and improving the anaerobic growth of the engineered Escherichia coli strain by developing a cell adaptation method. These efforts lead to 1,2-propanediol production at a titer of 5.13 g/L with a yield of 0.48 g/g glucose in 20 mL shake flask studies. On this basis, we pursue the enhancement of 1-propanol production from the 1,2-propanediol platform. By constructing a fusion diol dehydratase and developing a dual strain process, we achieve a 1-propanol titer of 2.91 g/L in 20 mL shake flask studies. To summarize, we report the production of 1,2-propanediol at enhanced titer and enhanced yield simultaneously in E. coli for the first time. Furthermore, we establish an efficient system for the production of biofuel 1-propanol biologically.

  15. Solubility of anthracene in binary alcohol + 2-methyl-1-propanol and alcohol + 3-methyl-1-butanol solvent mixtures

    SciTech Connect

    Zvaigzne, A.I.; Acree, W.E. Jr.

    1995-07-01

    Solid-liquid equilibrium data of organic nonelectrolyte systems are becoming increasingly important in the petroleum industry, particularly in light of present rends toward heavier feedstocks and known carcinogenicity/mutagenicity of many of the larger polycyclic aromatic compounds. Experimental solubilities are reported for anthracene dissolved in binary 2-propanol + 3-methyl-1-butanol, 2-propanol + 2-methyl-1-propanol, 1-propanol + 2-methyl-1-propanol, 1-octanol + 2-methyl-1-propanol, 1-butanol + 3-methyl-1-butanol, 2-butanol + 3-methyl-1-butanol, 2-butanol + 2-methyl-1-propanol, 1-octanol + 3-methyl-1-butanol, and 2-methyl-1-propanol + 3-methyl-1-butanol solvent mixtures at 25 C. Results of these measurements are used to test two mathematical representations based upon the combined nearly ideal binary solvent (NIBS)/Redlich-Kister equation and modified Wilson model. For the systems studied, the combined NIBS/Redlich-Kister and modified Wilson equations were found to provide very reasonable mathematical representations, with most deviations between experimental and back-calculated values being on the order of {+-} 1.0% or less.

  16. Dissociative ionization of the 1-propanol dimer in a supersonic expansion under tunable synchrotron VUV radiation.

    PubMed

    Tao, Yanmin; Hu, Yongjun; Xiao, Weizhan; Guan, Jiwen; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

    2016-05-11

    Photoionization and dissociation of the 1-propanol dimer and subsequent fragmentations have been investigated by synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry and theoretical calculations. Besides the protonated monomer cation (C3H7OH)·H(+) (m/z = 61) and Cα-Cβ bond cleavage fragment CH2O·(C3H7OH)H(+) (m/z = 91), the measured mass spectrum at an incident photon energy of 13 eV suggests a new dissociation channel resulting in the formation of the (C3H7OH)·H(+)·(C2H5OH) (m/z = 107) fragment. The appearance energies of the fragments (C3H7OH)·H(+), CH2O·(C3H7OH)H(+) and (C3H7OH)·H(+)·(C2H5OH) are measured at 10.05 ± 0.05 eV, 9.48 ± 0.05 eV, and 12.8 ± 0.1 eV, respectively, by scanning photoionization efficiency (PIE) spectra. The 1-propanol ion fragments as a function of VUV photon energy were interpreted with the aid of theoretical calculations. In addition to O-H and Cα-Cβ bond cleavage, a new dissociation channel related to Cβ-Cγ bond cleavage opens. In this channel, molecular rearrangement (proton transfer and hydrogen transfer after surmounting an energy barrier) gives rise to the generated complex, which then dissociates to produce the mixed propanol/ethanol proton bound cation (C3H7OH)·H(+)·(C2H5OH). This new dissociation channel has not been reported in previous studies of ethanol and acetic acid dimers. The photoionization and dissociation processes of the 1-propanol dimer are described in the photon energy range of 9-15 eV.

  17. Density and viscosity for monoethanolamine + 1-propanol, + 1-hexanol, and + 1-octanol

    SciTech Connect

    Lee, M.J.; Lin, T.K.; Pai, Y.H.; Lin, K.S.

    1997-09-01

    Monoethanolamine (MEA) is a feasible agent for removing carbon dioxide and hydrogen sulfide from sour gases. Densities and viscosities were measured for monoethanolamine (MEA) + 1-propanol, MEA + 1-hexanol, and MEA + 1-octanol at 303.15 K, 313.15 K, and 323.15 K. The excess volumes and viscosity deviations from the mole fraction average were calculated and correlated by a Redlich-Kister type equation. McAllister`s three-body interaction model was also applied to correlate the kinematic viscosities.

  18. Kinetic resolution of racemic 1-phenyl 1-propanol by lipase catalyzed enantioselective esterification reaction.

    PubMed

    Karadeniz, Fatma; Bayraktar, Emine; Mehmetoglu, Ulkü

    2010-10-01

    In this study, resolution of (R,S)-1-phenyl 1-propanol by lipase-catalyzed enantioselective esterification was achieved. To investigate the effect of lipase type on enantiomeric excess, three different lipases were used. Novozym 435 exhibited the highest enantioselectivity for resolution of (R,S)-1-phenyl 1-propanol. The effects of carbon length of fatty acids from C12 to C16, which were used as acyl donor, organic solvents with Log P values from 0.5 to 4.5, acyl donor/alcohol molar ratio (1:1, 3:2, 2:1, 3:1), amount of added molecular sieves (0-133.2 kg/m(3)), and temperature (10-60° C) on the enantioselectivity were investigated. The best reaction conditions were comprised of using toluene (Log P= 2.5) as solvent, lauric acid (12C) as acyl donor, 133.2 kg/m(3) molecular sieves at 50° C and acyl donor/alcohol molar ratio as 1:1. Under these conditions, the enantiomeric excess of S enantiomer ee (S) was obtained as 95% for a reaction time of 2.5 hours.

  19. Homogeneous nucleation rate measurements of 1-propanol in helium: the effect of carrier gas pressure.

    PubMed

    Brus, David; Zdímal, Vladimír; Stratmann, Frank

    2006-04-28

    Kinetics of homogeneous nucleation in supersaturated vapor of 1-propanol was studied using an upward thermal diffusion cloud chamber. Helium was used as a noncondensable carrier gas and the influence of its pressure on observed nucleation rates was investigated. The isothermal nucleation rates were determined by a photographic method that is independent on any nucleation theory. In this method, the trajectories of growing droplets are recorded using a charge coupled device camera and the distribution of local nucleation rates is determined by image analysis. The nucleation rate measurements of 1-propanol were carried out at four isotherms 260, 270, 280, and 290 K. In addition, the pressure dependence was investigated on the isotherms 290 K (50, 120, and 180 kPa) and 280 K (50 and 120 kPa). The isotherm 270 K was measured at 25 kPa and the isotherm 260 K at 20 kPa. The experiments confirm the earlier observations from several thermal diffusion chamber investigations that the homogeneous nucleation rate of 1-propanol tends to increase with decreasing total pressure in the chamber. In order to reduce the possibility that the observed phenomenon is an experimental artifact, connected with the generally used one-dimensional description of transfer processes in the chamber, a recently developed two-dimensional model of coupled heat, mass, and momentum transfer inside the chamber was used and results of both models were compared. It can be concluded that the implementation of the two-dimensional model does not explain the observed effect. Furthermore the obtained results were compared both to the predictions of the classical theory and to the results of other investigators using different experimental devices. Plotting the experimental data on the so-called Hale plot shows that our data seem to be consistent both internally and also with the data of others. Using the nucleation theorem the critical cluster sizes were obtained from the slopes of the individual isotherms

  20. Metabolic engineering of Escherichia coli for 1-butanol and 1-propanol production via the keto-acid pathways.

    PubMed

    Shen, C R; Liao, J C

    2008-11-01

    Production of higher alcohols via the keto-acid intermediates found in microorganism's native amino-acid pathways has recently shown promising results. In this work, an Escherichia coli strain that produces 1-butanol and 1-propanol from glucose was constructed. The strain first converts glucose to 2-ketobutyrate, a common keto-acid intermediate for isoleucine biosynthesis. Then, 2-ketobutyrate is converted to 1-propanol through reactions catalyzed by the heterologous decarboxylase and dehydrogenase, or to 1-butanol via the chemistry involved in the synthesis of the unnatural amino acid norvaline. We systematically improved the synthesis of 1-propanol and 1-butanol through deregulation of amino-acid biosynthesis and elimination of competing pathways. The final strain demonstrated a production titer of 2 g/L with nearly 1:1 ratio of butanol and propanol.

  1. Thermochemistry of radicals formed by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal.

    PubMed

    Papajak, Ewa; Seal, Prasenjit; Xu, Xuefei; Truhlar, Donald G

    2012-09-14

    We calculate the standard state entropy, heat capacity, enthalpy, and Gibbs free energy for 13 radicals important for the combustion chemistry of biofuels. These thermochemical quantities are calculated from recently proposed methods for calculating partition functions of complex molecules by taking into account their multiple conformational structures and torsional anharmonicity. The radicals considered in this study are those obtained by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal. Electronic structure calculations for all conformers of the radicals were carried out using both density functional theory and explicitly correlated coupled cluster theory with quasipertubative inclusion of connected triple excitations. The heat capacity and entropy results are compared with sparsely available group additivity data, and trends in enthalpy and free energy as a function of radical center are discussed for the isomeric radicals.

  2. Thermochemistry of radicals formed by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal

    NASA Astrophysics Data System (ADS)

    Papajak, Ewa; Seal, Prasenjit; Xu, Xuefei; Truhlar, Donald G.

    2012-09-01

    We calculate the standard state entropy, heat capacity, enthalpy, and Gibbs free energy for 13 radicals important for the combustion chemistry of biofuels. These thermochemical quantities are calculated from recently proposed methods for calculating partition functions of complex molecules by taking into account their multiple conformational structures and torsional anharmonicity. The radicals considered in this study are those obtained by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal. Electronic structure calculations for all conformers of the radicals were carried out using both density functional theory and explicitly correlated coupled cluster theory with quasipertubative inclusion of connected triple excitations. The heat capacity and entropy results are compared with sparsely available group additivity data, and trends in enthalpy and free energy as a function of radical center are discussed for the isomeric radicals.

  3. Ab initio Study on Ionization Energies of 3-Amino-1-propanol

    NASA Astrophysics Data System (ADS)

    Wang, Ke-dong; Jia, Ying-bin; Lai, Zhen-jiang; Liu, Yu-fang

    2011-06-01

    Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311++G** level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the intramolecular OH···N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molecular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of photoelectron spectra is interpreted.

  4. Application of the Extended Langmuir Model for the Determination of Lyophobicity of 1-Propanol in Acetonitrile

    NASA Astrophysics Data System (ADS)

    Tsierkezos, Nikos G.

    2009-06-01

    Surface tensions ( σ) of binary liquid mixtures of acetonitrile (ACN) with 1-propanol (PrOH) were measured over the entire composition range at eight different temperatures, 278.15 K, 283.15 K, 288.15 K, 293.15 K, 298.15 K, 303.15 K, 308.15 K, and 313.15 K. The lyophobicities ( β) of the surfactant PrOH relative to that of ACN as well as the surface mole fractions ({x^S2}) of PrOH at various temperatures were derived using the extended Langmuir model (Langmuir 17, 4261, 2001). The β values indicate the greater affinity of PrOH for the surface, and this trend slightly increases with rising temperature. The determined {x^S_{2 }} values indicate that the surface concentration of PrOH is always higher than its bulk concentration and consequently confirm that the surface is enriched with PrOH.

  5. Synergy as design principle for metabolic engineering of 1-propanol production in Escherichia coli.

    PubMed

    Shen, Claire R; Liao, James C

    2013-05-01

    Synthesis of a desired product can often be achieved via more than one metabolic pathway. Whether naturally evolved or synthetically engineered, these pathways often exhibit specific properties that are suitable for production under distinct conditions and host organisms. Synergy between pathways arises when the underlying pathway characteristics, such as reducing equivalent demand, ATP requirement, intermediate utilization, and cofactor preferences, are complementary to each other. Utilization of such pathways in combination leads to an increased metabolite productivity and/or yield compared to using each pathway alone. This work illustrates the principle of synergy between two different pathways for 1-propanol production in Escherichia coli. A model-guided design based on maximum theoretical yield calculations identified synergy of the native threonine pathway and the heterologous citramalate pathway in terms of production yield across all flux ratios between the two pathways. Characterization of the individual pathways by host gene deletions demonstrates their distinct metabolic characteristics: the necessity of TCA cycle for threonine pathway and the independence of TCA cycle for the citramalate pathway. The two pathways are also complementary in driving force demands. Production experiments verified the synergistic effects predicted by the yield model, in which the platform with dual pathway for 2-ketobutyrate synthesis achieved higher yield (0.15g/g of glucose) and productivity (0.12g/L/h) of 1-propanol than individual ones alone: the threonine pathway (0.09g/g; 0.04g/L/h) or the citramalate pathway (0.11g/g; 0.04g/L/h). Thus, incorporation of synergy into the design principle of metabolic engineering may improve the production yield and rate of the desired compound.

  6. Directed evolution of Methanococcus jannaschii citramalate synthase for biosynthesis of 1-propanol and 1-butanol by Escherichia coli.

    PubMed

    Atsumi, Shota; Liao, James C

    2008-12-01

    Biofuels synthesized from renewable resources are of increasing interest because of global energy and environmental problems. We have previously demonstrated production of higher alcohols from Escherichia coli using a 2-keto acid-based pathway. Here, we took advantage of the growth phenotype associated with 2-keto acid deficiency to construct a hyperproducer of 1-propanol and 1-butanol by evolving citramalate synthase (CimA) from Methanococcus jannaschii. This new pathway, which directly converts pyruvate to 2-ketobutyrate, bypasses threonine biosynthesis and represents the shortest keto acid-mediated pathway for producing 1-propanol and 1-butanol from glucose. Directed evolution of CimA enhanced the specific activity over a wide temperature range (30 to 70 degrees C). The best CimA variant was found to be insensitive to feedback inhibition by isoleucine in addition to the improved activity. This CimA variant enabled 9- and 22-fold higher production levels of 1-propanol and 1-butanol, respectively, compared to the strain expressing the wild-type CimA. This work demonstrates (i) the first production of 1-propanol and 1-butanol using the citramalate pathway and (ii) the benefit of the 2-keto acid pathway that enables a growth-based evolutionary strategy to improve the production of non-growth-related products.

  7. Statistical thermodynamics of 1-butanol, 2-methyl-1-propanol, and butanal.

    PubMed

    Seal, Prasenjit; Papajak, Ewa; Yu, Tao; Truhlar, Donald G

    2012-01-21

    The purpose of the present investigation is to calculate partition functions and thermodynamic quantities, viz., entropy, enthalpy, heat capacity, and Gibbs free energies, for 1-butanol, 2-methyl-1-propanol, and butanal in the vapor phase. We employed the multi-structural (MS) anharmonicity method and electronic structure calculations including both explicitly correlated coupled cluster theory and density functional theory. The calculations are performed using all structures for each molecule and employing both the local harmonic approximation (MS-LH) and the inclusion of torsional anharmonicity (MS-T). The results obtained from the MS-T calculations are in excellent agreement with experimental data taken from the Thermodynamics Research Center data series and the CRC Handbook of Chemistry and Physics, where available. They are also compared with Benson's empirical group additivity values, where available; in most cases, the present results are more accurate than the group additivity values. In other cases, where experimental data (but not group additivity values) are available, we also obtain good agreement with experiment. This validates the accuracy of the electronic structure calculations when combined with the MS-T method for estimating the thermodynamic properties of systems with multiple torsions, and it increases our confidence in the predictions made with this method for molecules and temperatures where experimental or empirical data are not available.

  8. Statistical thermodynamics of 1-butanol, 2-methyl-1-propanol, and butanal

    NASA Astrophysics Data System (ADS)

    Seal, Prasenjit; Papajak, Ewa; Yu, Tao; Truhlar, Donald G.

    2012-01-01

    The purpose of the present investigation is to calculate partition functions and thermodynamic quantities, viz., entropy, enthalpy, heat capacity, and Gibbs free energies, for 1-butanol, 2-methyl-1-propanol, and butanal in the vapor phase. We employed the multi-structural (MS) anharmonicity method and electronic structure calculations including both explicitly correlated coupled cluster theory and density functional theory. The calculations are performed using all structures for each molecule and employing both the local harmonic approximation (MS-LH) and the inclusion of torsional anharmonicity (MS-T). The results obtained from the MS-T calculations are in excellent agreement with experimental data taken from the Thermodynamics Research Center data series and the CRC Handbook of Chemistry and Physics, where available. They are also compared with Benson's empirical group additivity values, where available; in most cases, the present results are more accurate than the group additivity values. In other cases, where experimental data (but not group additivity values) are available, we also obtain good agreement with experiment. This validates the accuracy of the electronic structure calculations when combined with the MS-T method for estimating the thermodynamic properties of systems with multiple torsions, and it increases our confidence in the predictions made with this method for molecules and temperatures where experimental or empirical data are not available.

  9. Ab initio calculations of cooperativity effects on clusters of methanol, ethanol, 1-propanol, and methanethiol

    SciTech Connect

    Sum, A.K.; Sandler, S.I.

    2000-02-17

    The results of ab initio calculations for cyclic clusters of methanol, ethanol, 1-propanol, and methanethiol are presented. Dimer, trimer, and tetramer clusters of all four compounds are studied, as are pentamer and hexamer clusters of methanol. From optimized clusters at HG/6--31G**, total energies and binding energies were calculated with both the HF and MP2 theories using the aug-cc-pVDZ basis set. Accurate binding energies were also calculated for the dimer and trimer of methanol using symmetry-adapted perturbation theory with the same basis set. Intermolecular and intramolecular distances, charge distribution of binding sites, binding energies, and equilibrium constants were computed to determine the hydrogen bond cooperativity effect for each species. The cooperativity effect, exclusive to hydrogen bonding systems, results form specific forces among the molecules, in particular charge-transfer processes and the greater importance of interactions between molecules not directly hydrogen bonded because of the longer range of the interactions. The ratios of equilibrium constants for forming multimer hydrogen bonds to that for dimer hydrogen bond formation increase rapidly with the cluster size, in contrast to the constant value commonly used in thermodynamic models for hydrogen bonding liquids.

  10. Vibrational spectra and assignments of 3-phenylprop-2-en-1-ol (cinnamyl alcohol) and 3-phenyl-1-propanol

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.; Förner, Wolfgang

    2011-09-01

    The complex conformational behavior of 3-phenylprop-2-en-1-ol (cinnamyl alcohol) and its saturated analogue 3-phenyl-1-propanol were investigated at the DFT-B3LYP/6-311G **, MP2 and MP4(SDQ) levels of theory. The unsaturated 3-phenylprop-2-en-1-ol was predicted to exist in Cg and Gg1 conformational mixture as a result of competitive conjugation and hyperconjugation interactions in the molecule. The saturated 3-phenyl-1-propanol was predicted to exist predominantly in a Ggg structure as a result of predominant steric hindrances in the alcohol. Only the one predominant form was identified in the infrared and Raman spectra of both alcohols. The excellent agreement between the calculated wavenumbers and the observed ones in the infrared and Raman spectra supports the conclusion that each of the two alcohols is present in one predominant form in the condensed phases. The vibrational frequencies of 3-phenylprop-2-en-1-ol and 3-phenyl-1-propanol in their lowest energy forms were computed at the B3LYP level and tentative vibrational assignments were provided on the basis of combined calculated and experimental data.

  11. Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)

    DOE PAGES

    Lepore, Andrew W.; Li, Zhenglong; Davison, Brian H.; ...

    2017-04-03

    Here, the impetus to explore biomass derived chemicals arises from a desire to enable renewable and sustainable commodity chemicals. To this end, we report catalytic production of propene, a building-block molecule, from 1-propanol. We found that zeolite catalysts are quite versatile and can produce propene at or below 230 C with high selectivity. Increasing the reaction temperature above 230 C shifted product selectivity towards C4+ hydrocarbons. Cu-ZSM-5 was found to exhibit a broader temperature window for high propene selectivity and could function at higher 1-propanol space velocities than H-ZSM-5. A series of experiments with 1-propan(ol-D) showed deuterium incorporation in themore » hydrocarbon product stream including propene suggesting that hydrocarbon pool type pathway might be operational concurrent with dehydration to produce C4+ hydrocarbons. Diffuse reflectance infra-red spectroscopy of 1-propanol and 1-propan(ol-D) over Cu-ZSM-5 in combination with deuterium labeling experiments suggest that deuterium incorporation occurs in two steps. Incorporation of deuterium occurs post dehydration via exchange with the partially deuterated catalyst surface.« less

  12. Interactions of methanol, ethanol, and 1-propanol with polar and nonpolar species in water at cryogenic temperatures.

    PubMed

    Souda, Ryutaro

    2017-01-18

    Methanol is known as a strong inhibitor of hydrate formation, but clathrate hydrates of ethanol and 1-propanol can be formed in the presence of help gases. To elucidate the hydrophilic and hydrophobic effects of alcohols, their interactions with simple solute species are investigated in glassy, liquid, and crystalline water using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. Nonpolar solute species embedded underneath amorphous solid water films are released during crystallization, but they tend to withstand water crystallization under the coexistence of methanol additives. The CO2 additives are released after crystallization along with methanol desorption. These results suggest strongly that nonpolar species that are hydrated (i.e., caged) associatively with methanol can withstand water crystallization. In contrast, ethanol and 1-propanol additives weakly affect the dehydration of nonpolar species during water crystallization, suggesting that the former tend to be caged separately from the latter. The hydrophilic vs. hydrophobic behavior of alcohols, which differs according to the aliphatic group length, also manifests itself in the different abilities of surface segregation of alcohols and their effects on the water crystallization kinetics.

  13. A study of the conformational stability and the vibrational spectra of 2,3-dichloro-1-propanol

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.; Ali, Shaikh A.

    2010-02-01

    The conformational stability and the three rotor internal rotations in 2,3-dichloro-1-propanol were investigated at DFT-B3LYP/6-311 + G**, MP2/6-311 + G** and MP4(SDQ) levels of theory. From the calculated potential energy surface, ten distinct minima were located all of which were predicted to have real frequencies at the B3LYP level of theory. The calculated lowest energy minima in the potential curves of the molecule were predicted to correspond to the Ggg and Gtg1 structures. The observed broad and very intense infrared band centered at about 3370 cm -1 supports the existence of the strong intermolecular H-bonding in 2,3-dichloro-1-propanol. The equilibrium constants for the conformational interconversion in the molecule were estimated from the calculated Gibb's energies at the B3LYP/6-311 + G** level of calculation and found to correspond to an equilibrium mixture of about 49% Ggg, 27 % Gtg1, 5% Ggt and 5% Tgg conformations at 298.15 K.

  14. Communication: Single crystal x-ray diffraction observation of hydrogen bonding between 1-propanol and water in a structure II clathrate hydrate.

    PubMed

    Udachin, Konstantin; Alavi, Saman; Ripmeester, John A

    2011-03-28

    Single crystal x-ray crystallography is used to detect guest-host hydrogen bonding in structure II (sII) binary clathrate hydrate of 1-propanol and methane. X-ray structural analysis shows that the 1-propanol oxygen atom is at a distance of 2.749 and 2.788 Å from the closest clathrate hydrate water oxygen atoms from a hexagonal face of the large sII cage. The 1-propanol hydroxyl hydrogen atom is disordered and at distances of 1.956 and 2.035 Å from the closest cage water oxygen atoms. These distances are compatible with guest-water hydrogen bonding. The C-C-C-O torsional angle in 1-propanol in the cage is 91.47° which corresponds to a staggered conformation for the guest. Molecular dynamics studies of this system demonstrated guest-water hydrogen bonding in this hydrate. The molecular dynamics simulations predict most probable distances for the 1-propanol-water oxygen atoms to be 2.725 Å, and the average C-C-C-O torsional angle to be ~59° consistent with a gauche conformation. The individual cage distortions resulting from guest-host hydrogen bonding from the simulations are rather large, but due to the random nature of the hydrogen bonding of the guest with the 24 water molecules making up the hexagonal faces of the large sII cages, these distortions are not observed in the x-ray structure.

  15. Prebiotic Polymerization: Oxidative Polymerization of 2,3 Dimercapto-1- Propanol on the Surface of Iron(III) Hydroxide Oxide

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    1995-01-01

    The oxidation of 2,3-dimercapto-1-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers. This polymerization occurred readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron(III) hydroxide oxide (20 mg, 160 micromole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the FE(OH)O phase. Reactions carried out at the same ratio of dithiol to FE(OH)O but at higher dithiol concentrations gave higher yields of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis is discussed.

  16. Prebiotic polymerization: Oxidative polymerization of 2, 3-dimercapto-1-propanol on the surface of iron(III) hydroxide oxide

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    1995-01-01

    The oxidation of 2, 3-dimercapto-1-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers. This polymerization occurred readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron(III) hydroxide oxide (20 mg, 160 micromole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the Fe(OH)O phase. Reactions carried out at the same ratio of dithiol to Fe(OH)O but at higher dithiol concentrations gave higher yields of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis is discussed.

  17. Molecular probe dynamics and free volume in organic glass-formers and their relationships to structural relaxation: 1-propanol

    NASA Astrophysics Data System (ADS)

    Bartoš, J.; Švajdlenková, H.; Šauša, O.; Lukešová, M.; Ehlers, D.; Michl, M.; Lunkenheimer, P.; Loidl, A.

    2016-01-01

    A joint study of the rotational dynamics and free volume in amorphous 1-propanol (1-PrOH) as a prototypical monohydroxy alcohol by electron spin resonance (ESR) or positron annihilation lifetime spectroscopy (PALS), respectively, is reported. The dynamic parameters of the molecular spin probe 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and the annihilation ones of the atomic ortho-positronium (o-Ps) probe as a function of temperature are compared. A number of coincidences between various effects in the ESR and PALS responses at the corresponding characteristic ESR and PALS temperatures were found suggesting a common origin of the underlying dynamic processes that were identified using viscosity (VISC) in terms of the two-order parameter (TOP) model and broadband dielectric spectroscopy (BDS) data.

  18. Thermodynamic and mass transfer modeling of carbon dioxide absorption into aqueous 2-amino-2-methyl-1-propanol

    SciTech Connect

    Sherman, Brent J.; Rochelle, Gary T.

    2016-12-16

    Explanations for the mass transfer behavior of 2-amino-2-methyl-1-propanol (AMP) are conflicting, despite extensive study of the amine for CO2 capture. At equilibrium, aqueous AMP reacts with CO2 to give bicarbonate in a 1:1 ratio. While this is the same stoichiometry as a tertiary amine, the reaction rate of AMP is 100 times faster. This work aims to explain the mass transfer behavior of AMP, specifically the stoichiometry and kinetics. An eNRTL thermodynamic model was used to regress wetted-wall column mass transfer data with two activity-based reactions: formation of carbamate and formation of bicarbonate. Data spanned 40–100 C and 0.15–0.60 mol CO2/mol alk). The fitted carbamate rate constant is three orders of magnitude greater than the bicarbonate rate constant. Rapid carbamate formation explains the kinetics, while the stoichiometry is explained by the carbamate reverting in the bulk liquid to allow CO2 to form bicarbonate. Understanding the role of carbamate formation and diffusion in hindered amines enables optimizing solvent amine concentration by balancing viscosity and free amine concentration. Furthermore, this improves absorber design for CO2 capture.

  19. Thermodynamic and mass transfer modeling of carbon dioxide absorption into aqueous 2-amino-2-methyl-1-propanol

    DOE PAGES

    Sherman, Brent J.; Rochelle, Gary T.

    2016-12-16

    Explanations for the mass transfer behavior of 2-amino-2-methyl-1-propanol (AMP) are conflicting, despite extensive study of the amine for CO2 capture. At equilibrium, aqueous AMP reacts with CO2 to give bicarbonate in a 1:1 ratio. While this is the same stoichiometry as a tertiary amine, the reaction rate of AMP is 100 times faster. This work aims to explain the mass transfer behavior of AMP, specifically the stoichiometry and kinetics. An eNRTL thermodynamic model was used to regress wetted-wall column mass transfer data with two activity-based reactions: formation of carbamate and formation of bicarbonate. Data spanned 40–100 C and 0.15–0.60 molmore » CO2/mol alk). The fitted carbamate rate constant is three orders of magnitude greater than the bicarbonate rate constant. Rapid carbamate formation explains the kinetics, while the stoichiometry is explained by the carbamate reverting in the bulk liquid to allow CO2 to form bicarbonate. Understanding the role of carbamate formation and diffusion in hindered amines enables optimizing solvent amine concentration by balancing viscosity and free amine concentration. Furthermore, this improves absorber design for CO2 capture.« less

  20. NBO, conformational, NLO, HOMO-LUMO, NMR and electronic spectral study on 1-phenyl-1-propanol by quantum computational methods

    NASA Astrophysics Data System (ADS)

    Xavier, S.; Periandy, S.; Ramalingam, S.

    2015-02-01

    In this study, FT-IR, FT-Raman, NMR and UV spectra of 1-phenyl-1-propanol, an intermediate of anti-depressant drug fluoxetine, has been investigated. The theoretical vibrational frequencies and optimized geometric parameters have been calculated by using HF and density functional theory with the hybrid methods B3LYP, B3PW91 and 6-311+G(d,p)/6-311++G(d,p) basis sets. The theoretical vibrational frequencies have been found in good agreement with the corresponding experimental data. 1H and 13C NMR spectra were recorded and chemical shifts of the molecule were compared to TMS by using the Gauge-Independent Atomic Orbital (GIAO) method. A study on the electronic and optical properties, absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies are performed using HF and DFT methods. The thermodynamic properties (heat capacity, entropy and enthalpy) at different temperatures are also calculated. NBO analysis is carried out to picture the charge transfer between the localized bonds and lone pairs. The local reactivity of the molecule has been studied using the Fukui function. NLO properties related to polarizability and hyperpolarizability are also discussed.

  1. Solubilities of mixtures of carbon dioxide and hydrogen sulfide in water + diethanolamine + 2-amino-2-methyl-1-propanol

    SciTech Connect

    Jane, I.S.; Li, M.H.

    1997-01-01

    The removal of acidic gases such as CO{sub 2}, H{sub 2}S, and COS from gas streams is an important operation in the natural gas and synthetic ammonia industries, oil refineries, and petrochemical chemical plants. The solubilities of mixtures of carbon dioxide and hydrogen sulfide in water + diethanolamine (DEA) + 2-amino-2-methyl-1-propanol (AMP) have been measured at 40 C and 80 C and at partial pressures of acid gases ranging from 1.0 to 200 kPa. The ternary mixtures studied were 30 mass % AMP, 6 mass % DEA + 24 mass % AMP, 12 mass % DEA + 18 mass % AMP, 18 mass % DEA + 12 mass % AMP, 24 mass % DEA + 6 mass % AMP, and 30 mass % DEA aqueous solutions. The model of Deshmukh and Mather (1981) has been used to represent the solubility of mixtures of CO{sub 2} and H{sub 2}S in the ternary solutions. The model reasonably reproduces the equilibrium partial pressures of CO{sub 2} and H{sub 2}S above the ternary solutions for the systems tested.

  2. 1-Propanol probing methodology: two-dimensional characterization of the effect of solute on H2O.

    PubMed

    Koga, Yoshikata

    2013-09-21

    The wording "hydrophobicity/hydrophilicity" has been used in a loose manner based on human experiences. We have devised a more quantitative way to redefine "hydrophobes" and "hydrophiles" in terms of the mole fraction dependence pattern of one of the third derivative quantities, the enthalpic interaction between solute molecules. We then devised a thermodynamic methodology to characterize the effect of a solute on H2O in terms of its hydrophobicity and/or hydrophilicity. We use a thermodynamic signature, the enthalpic interaction of 1-propanol, H, to monitor how the test solute modifies H2O. By this method, characterization is facilitated by two indices; one pertaining to its hydrophobicity and the other its hydrophilicity. Hence differences among amphiphiles are quantified in a two-dimensional manner. Furthermore, an individual ion can be characterized independent of a counter ion. By using this methodology, we have studied the effects on H2O of a number of solutes, and gained some important new insights. For example, such commonly used examples of hydrophobes in the literature as tetramethyl urea, trimethylamine-N-oxide, and tetramethylammonium salts are in fact surprisingly hydrophilic. Hence the conclusions about "hydrophobes" using these samples ought to be interpreted with caution. The effects of anions on H2O found by this methodology are in the same sequence of the Hofmeister ranking, which will no doubt aid a further investigation into this enigma in biochemistry. Thus, it is likely that this methodology could play an important role in the characterization of the effects of solutes in H2O, and a perspective view may be useful. Here, we describe the basis on which the methodology is developed and the methodology itself in m.ore detail than given in individual papers. We then summarize the results in two dimensional hydrophobicity/hydrophilicity maps.

  3. Analysis of vibrational spectra of 3-halo-1-propanols CH 2XCH 2CH 2OH (X is Cl and Br)

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.; Förner, Wolfgang

    2008-12-01

    The conformational stability and the three rotor internal rotations in 3-chloro- and 3-bromo-1-propanols were investigated by DFT-B3LYP/6-311 + G** and ab initio MP2/6-311 + G**, MP3/6-311 + G** and MP4(SDTQ)//MP3/6-311 + G** levels of theory. On the calculated potential energy surface twelve distinct minima were located all of which were not predicted to have imaginary frequencies at the B3LYP level of theory. The calculated lowest energy minimum in the potential curves of both molecules was predicted to correspond to the Gauche- gauche- trans ( Ggt) conformer in excellent agreement with earlier microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the two 3-halo-1-propanols were calculated at the B3LYP/6-311 + G** level of calculation and found to correspond to an equilibrium mixture of about 32% Ggt, 18% Ggg1, 13% Tgt, 8% Tgg and 8% Gtt conformations for 3-chloro-1-propanol and 34% Ggt, 15% Tgt, 13% Ggg1, 9% Tgg and 7% Gtt conformations for 3-bromo-1-propanol at 298.15 K. The nature of the high energy conformations was verified by carrying out solvent experiments using formamide ( ɛ = 109.5) and MP3 and MP4//MP3 calculations. The vibrational frequencies of each molecule in its three most stable forms were computed at the B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecules.

  4. Toxicity and carcinogenicity of 2,3-dibromo-1-propanol in F344/N rats and B6C3F1 mice.

    PubMed

    Eustis, S L; Haseman, J K; Mackenzie, W F; Abdo, K M

    1995-06-01

    2,3-Dibromo-1-propanol is a metabolite of the flame retardant tris(2,3-dibromopropyl) phosphate, previously shown to be a mutagen and carcinogen in experimental animals. Toxicology and carcinogenesis studies of 2,3-dibromo-1-propanol were conducted by applying the chemical in 95% ethanol to the interscapular skin of male and female F344/N rats and B6C3F1 mice 5 days a week for 13 weeks in the prechronic study and 48-55 weeks (rats) or 36-42 weeks (mice) in the carcinogenicity study. In the 13-week study, 10 rats and 10 mice of each sex received doses of 0, 44, 88, 177, 375, or 750 mg/kg. Deaths associated with chemical application occurred only in the high-dose (750 mg/kg) male mice. Chemical-related lesions were seen in the kidney of male rats, liver of female rats, and liver and lung of both sexes of mice. Based on the toxicity observed in the 13-week study, 50 rats of each sex received doses of 0, 188, or 375 mg/kg and 50 mice of each sex received 0, 88, or 177 mg/kg in the carcinogenicity study. The planned 2-year study was terminated early because of reduced survival of rats related to chemical-induced neoplasia and because of the appearance of antibodies to lymphocytic choriomeningitis virus in sentinel mice. Nearly all dosed rats had malignant neoplasms at one or more sites, while only one control male and one control female had malignant neoplasms. In rats, neoplasms induced by 2,3-dibromo-1-propanol occurred in the skin, nasal mucosa, Zymbal's gland, oral mucosa, esophagus, forestomach, intestines, liver, kidney, mammary gland (females), clitoral gland (females), spleen (males), and mesothelium (males). In mice, chemical-induced neoplasms occurred in the skin, forestomach, liver (males), and lung (males).

  5. Vapor-liquid equilibrium measurements at 101. 32 kPa for binary mixtures of methyl acetate + ethanol or 1-propanol

    SciTech Connect

    Ortega, J.: Susial, P.; de Alfonso, C. )

    1990-07-01

    This paper reports on isobaric vapor-liquid equilibrium data at 101.32 {plus minus} 0.02 kPa for methyl acetate (1) + ethane (2) or + 1-propanol (2). The results are compared with those predicted by the UNIFAC and ASOG methods. The methyl acetate (1) + ethanol (2) system forms an azeotrope at 329.8 K and a molar concentration of x{sub 1} = 0.958. Both methods predict the vapor-phase compositions equally well, with overall mean errors of less than 5%.

  6. Three rotor potential energy scans, conformational equilibrium constants and vibrational analysis of 3-fluoro-1-propanol CH(2)FCH(2)CH(2)OH.

    PubMed

    Badawi, Hassan M; Förner, Wolfgang; Ali, Shaikh A

    2008-01-01

    The conformational stability and the three rotor internal rotations in 3-fluoro-1-propanol were investigated by the DFT-B3LYP/6-311+G** and the ab initio MP2/6-311+G** levels of theory. The calculated potential energy curves of the molecule at both levels of theory were consistent with complex conformational equilibria of about 12 minima, all of which were predicted to have real frequencies at both the B3LYP and the MP2 levels. The lowest energy minimum in the potential curves of 3-fluoro-1-propanol was predicted to correspond to the Gauche-gauche-trans (Ggt) conformer in excellent agreement with microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the molecule were calculated and found to correspond to an equilibrium mixture of about 33% Ggt, 14% Ggg1 and 13% Gg1g and about 43% Ggt, 12% Ggg1 and 10% Gg1g distribution by the B3LYP/6-311+G** and the MP2/6-311+G** calculations, respectively, at 298.15K. The vibrational frequencies of each molecule in its three stable forms were computed at B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecule.

  7. 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.

  8. Vapor pressures of binary mixtures of hexane + 1-butanol, + 2-butanol, + 2-methyl-1-propanol, or + 2-methyl-2-propanol at 298. 15 K

    SciTech Connect

    Rodriguez, V.; Pardo, J.; Lopez, M.C.; Royo, F.M.; Urieta, J.S. . Dept. de Quimica Organica-Quimica Fisica)

    1993-07-01

    Previous papers from this laboratory reported measurements of excess enthalpies, excess volumes, vapor pressures, and dipole moments for mixtures containing an alkanol. The authors have now begun a systematic study of the properties of mixtures containing isomeric butanols. While many studies of the thermodynamic properties of 1-butanol have been published, only a few systematic investigations have been carried out for mixtures containing isomeric butanols. The total vapor pressures of binary mixtures of hexane + 1-butanol, + 2-butanol, + 2-methyl-1-propanol, or + 2-methyl-2-propanol were measured by a static method at 298.15 K. Vapor-phase compositions, activity coefficients, and excess molar Gibbs energies were calculated by Barker's method.

  9. Toxicology, occurrence and risk characterisation of the chloropropanols in food: 2-monochloro-1,3-propanediol, 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol.

    PubMed

    Andres, Susanne; Appel, Klaus E; Lampen, Alfonso

    2013-08-01

    Great attention has been paid to chloropropanols like 3-monochloro-1,2-propanediol and the related substance glycidol due to their presence in food and concerns about their toxic potential as carcinogens. The other chloropropanols 2-monochloro-1,3-propanediol, 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol have been found in certain foods, but occurrence data are generally limited for these compounds. 1,3-dichloro-2-propanol has the most toxicological relevance showing clear carcinogenic effects in rats possibly via a genotoxic mechanism. The dietary exposure to 1,3-dichloro-2-propanol is quite low. Calculated "Margins of Exposure" values are above 10,000. It is concluded that the 1,3-dichloro-2-propanol exposure is of low concern for human health. The toxicology of 2,3-dichloro-1-propanol has not been adequately investigated. Its toxicological potential regarding hepatotoxic effects seems to be lower than that of 1,3-dichloro-2-propanol. Limited data show that 2,3-dichloro-1-propanol occurs only in trace amounts in food, indicating that exposure to 2,3-dichloro-1-propanol seems to be also of low concern for human health. The dietary 2-monochloro-1,3-propanediol burden appears to be lower than that of 3-monochloro-1,2-propanediol. An adequate risk assessment for 2-monochloro-1,3-propanediol cannot be performed due to limited data on the toxicology and occurrence in food. This article reviews the relevant information about the toxicology, occurrence and dietary exposure to the chloropropanols 2-monochloro-1,3-propanediol, 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol.

  10. A comparative study of the mass and heat transfer dynamics of evaporating ethanol/water, methanol/water, and 1-propanol/water aerosol droplets.

    PubMed

    Hopkins, Rebecca J; Reid, Jonathan P

    2006-02-23

    The mass and heat transfer dynamics of evaporating multicomponent alcohol/water droplets have been probed experimentally by examining changes in the near surface droplet composition and average droplet temperature using cavity-enhanced Raman scattering (CERS) and laser-induced fluorescence (LIF). The CERS technique provides a sensitive measure of the concentration of the volatile alcohol component in the outer shell of the droplet, due to the exponential relationship between CERS intensity and species concentration. Such volatile droplets, which are probed on a millisecond time scale, evaporate nonisothermally, resulting in both temperature and concentration gradients, as confirmed by comparisons between experimental measurements and quasi-steady state model calculations. An excellent agreement between the experimental evaporation trends and quasi-steady state model predictions is observed. An unexpectedly slow evaporation rate is observed for the evaporation of 1-propanol from a multicomponent droplet when compared to the model; possible explanations for this observation are discussed. In addition, the propagation depth of the CERS signal, and, therefore, the region of the droplet from which compositional measurements are made, can be estimated. Such measurements, when considered in conjunction with quasi-steady state theory, can allow droplet temperature gradients to be measured and vapor pressures and activity coefficients of components within the droplet to be determined.

  11. Acceleration of the effect of solute on the entropy-volume cross fluctuation density in aqueous 2-butoxyethanol, 1-propanol, and glycerol: the fourth derivative of Gibbs energy.

    PubMed

    Yoshida, Koh; Baluja, Shipra; Inaba, Akira; Koga, Yoshikata

    2011-06-07

    Using a differential pressure perturbation calorimetry developed by us recently [K. Yoshida, S. Baluja, A. Inaba, K. Tozaki, and Y. Koga, "Experimental determination of third derivative of G (III): Differential pressure perturbation calorimetry (II)," J. Solution Chem. (in press)], we experimentally determined the partial molar S-V cross fluctuation density of solute B, (SV)δ(B) , in binary aqueous solutions for B = 1-propanol (1P) and glycerol (Gly). This third derivative of G provides information about the effect of solute B on the S-V cross fluctuation density, (SV)δ, in aqueous solution as the concentration of B varies. Having determined (SV)δ(B) by better than 1% uncertainty, we evaluated for the first time the fourth derivative quantity (SV)δ(B-B) = N(∂(SV)δ(B) ∕∂n(B)) for B = 1P and Gly graphically without resorting to any fitting functions within several percent. This model-free quantity gives information about the acceleration of the effect of solute B on (SV)δ. By comparing fourth derivative quantities, (SV)δ(B-B) , among B = 1P, Gly, and 2-butoxyethanol obtained previously, the distinction of the effect of solute on H(2)O becomes clearer than before when only the third derivative quantities were available.

  12. Acceleration of the effect of solute on the entropy-volume cross fluctuation density in aqueous 2-butoxyethanol, 1-propanol, and glycerol: The fourth derivative of Gibbs energy

    NASA Astrophysics Data System (ADS)

    Yoshida, Koh; Baluja, Shipra; Inaba, Akira; Koga, Yoshikata

    2011-06-01

    Using a differential pressure perturbation calorimetry developed by us recently [K. Yoshida, S. Baluja, A. Inaba, K. Tozaki, and Y. Koga, "Experimental determination of third derivative of G (III): Differential pressure perturbation calorimetry (II)," J. Solution Chem. (in press)], we experimentally determined the partial molar S-V cross fluctuation density of solute B, SVδB, in binary aqueous solutions for B = 1-propanol (1P) and glycerol (Gly). This third derivative of G provides information about the effect of solute B on the S-V cross fluctuation density, SVδ, in aqueous solution as the concentration of B varies. Having determined SVδB by better than 1% uncertainty, we evaluated for the first time the fourth derivative quantity SVδB-B = N(∂SVδB /∂nB) for B = 1P and Gly graphically without resorting to any fitting functions within several percent. This model-free quantity gives information about the acceleration of the effect of solute B on SVδ. By comparing fourth derivative quantities, SVδB-B, among B = 1P, Gly, and 2-butoxyethanol obtained previously, the distinction of the effect of solute on H2O becomes clearer than before when only the third derivative quantities were available.

  13. Thermal chemistry of 2-halo-1-propanols on Ni(1 1 1) and Cu(1 1 1) surfaces: A UBI-QEP energetic modeling

    NASA Astrophysics Data System (ADS)

    Mirzanejad, Amir

    2015-12-01

    The effect of β-halogen substitutions on the thermal chemistry of 1-propanol over Ni(1 1 1) and Cu(1 1 1) single-crystal surfaces was investigated using the method of unity bond index-quadratic exponential potential (UBI-QEP). This method was employed to investigate the energetics of the catalytic conversion routes of the ad-molecule mainly at the zero-coverage limit by calculating activation barriers and enthalpy changes for surface reactions. The alcohol molecule can be oxidized partially and totally over the Ni surface, however, the molecule is rather inactive on Cu. The β-halogen substitution makes extensive conversion of the alcohol possible on the Cu surface and changes conversion pathways on the Ni surface. It was found that halogen substitution as well as hydrogen bonding can affect the reactivity and conversion routes of the molecules on Ni and Cu surfaces. On account of energetic criteria, the predicted routes for decompositions and the TPD patterns for the surface species are in accord with the available experimental observations.

  14. Monte Carlo simulation and SAFT modeling study of the solvation thermodynamics of dimethylformamide, dimethylsulfoxide, ethanol and 1-propanol in the ionic liquid trimethylbutylammonium bis(trifluoromethylsulfonyl)imide.

    PubMed

    Vahid, A; Maginn, E J

    2015-03-21

    Understanding fundamental solvation phenomena and mixture thermodynamic properties for organic molecules in ionic liquids is essential to the development of ionic liquids in many application areas. In the present work, molecular simulations were used to compute a wide range of properties for the pure ionic liquid trimethylbutylammonium bis(trifluoromethylsulfonyl)imide as well as mixtures of this ionic liquid with ethanol, 1-propanol, dimethylformamide, and dimethylsulfoxide. A new force field for the ionic liquid was developed and validated by computing ionic liquid surface tension and density as a function of temperature. Force fields for ethanol and propanol were taken from the literature, while new force fields were developed for dimethylformamide and dimethylsulfoxide. These force fields were shown to yield vapor-liquid coexistence curves, vapor pressure curves and critical points in excellent agreement with experimental data. Absorption isotherms, enthalpies of mixing and mixture volumes were then computed and shown to agree well with available literature. The simulations help rationalize the observed trends in solubility and enthalpy of mixing in terms of the relative strength of hydrogen bonding between the solutes and the ionic liquid. It was found that the entropy of absorption plays a very important role in the solvation process. The PCIP-SAFT equation of state was able to fit the experimental data (or simulation results when experiments were unavailable) very accurately with only small adjustable binary interaction parameters.

  15. Comparison of nitroethane, 2-nitro-1-propanol, lauric acid, Lauricidin® and the Hawaiian marine algae, Chaetoceros, for potential broad-spectrum control of anaerobically grown lactic acid bacteria.

    PubMed

    Božic, Aleksandar K; Anderson, Robin C; Ricke, Steven C; Crandall, Philip G; O'Bryan, Corliss A

    2012-01-01

    The gastrointestinal tract of bovines often contains bacteria that contribute to disorders of the rumen, and may also contain foodborne or opportunistic human pathogens as well as bacteria capable of causing mastitis in cows. Thus there is a need to develop broad-spectrum therapies that are effective while not leading to unacceptably long antibiotic withdrawal times. The effects of the CH(4)-inhibitors nitroethane (2 mg/mL), 2-nitro-1-propanol (2 mg/mL), lauric acid (5 mg/mL), the commercial product Lauricidin® (5 mg/mL), and a finely ground product of the Hawaiian marine algae, Chaetoceros (10 mg/mL), were compared in pure cultures of Streptococcus agalactia, Enterococcus faecium, Streptococcus bovis, and in a mixed lactic acid rumen bacterial culture. Lauricidin® and lauric acid exhibited the most bactericidal acidity against all bacteria. These results suggest potential animal health benefits from supplementing cattle diets with lauric acid or Lauricidin® to improve the health of the rumen and help prevent shedding of human pathogens.

  16. (3R,4S)-3-[4-(4-fluorophenyl)-4-hydroxypiperidin-1-yl]chroman-4,7-diol: a conformationally restricted analogue of the NR2B subtype-selective NMDA antagonist (1S,2S)-1-(4-hydroxyphenyl)-2-(4-hydroxy-4-phenylpiperidino)- 1-propanol.

    PubMed

    Butler, T W; Blake, J F; Bordner, J; Butler, P; Chenard, B L; Collins, M A; DeCosta, D; Ducat, M J; Eisenhard, M E; Menniti, F S; Pagnozzi, M J; Sands, S B; Segelstein, B E; Volberg, W; White, W F; Zhao, D

    1998-03-26

    (1S,2S)-1-(4-Hydroxyphenyl)-2-(4-hydroxy-4-phenylpiperidino)-1-propanol (CP-101,606, 1) is a recently described antagonist of N-methyl-D-aspartate (NMDA) receptors containing the NR2B subunit. In the present study, the optimal orientation of compounds of this structural type for their receptor was explored. Tethering of the pendent methyl group of 1 to the phenolic aromatic ring via an oxygen atom prevents rotation about the central portion of the molecule. Several of the new chromanol compounds have high affinity for the racemic [3H]CP-101,606 binding site on the NMDA receptor and protect against glutamate toxicity in cultured hippocampal neurons. The new ring caused a change in the stereochemical preference of the receptor-cis (erythro) compounds had better affinity for the receptor than the trans isomers. Computational studies suggest that steric interactions between the pendent methyl group and the phenol ring in the acyclic series determine which structures can best fit the receptor. The chromanol analogue, (3R,4S)-3-[4-(4-fluorophenyl)-4-hydroxypiperidin-1- yl]chroman-4,7-diol (12a, CP-283,097), was found to possess potency and selectivity comparable to CP-101,606. Thus 12a is a new tool to explore the function of the NR2B-containing NMDA receptors.

  17. Hydrogen bond analysis in alcohol (1-Propanol, 2-Propanol and Glycerol)-DMF mixtures based on dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Jia, Guo-Zhu; Jie, Qian; Feng, Wang

    2015-11-01

    Dielectric properties of Propanol-DMF, and Glycerol-DMF mixtures at full concentrations have been obtained by the dielectric relaxation spectroscopy method at frequency from 20 MHz to 20 GHz at room temperature. The mixture behavior is described by the Davidson-Cole model using four parameters that relate to molecular structure. The hydrogen bond (HB) numbers and binding energies between two pairs (solute-solute and solute-solvent pairs) are estimated by Luzar model, also the type of dipolar ordering which depends on the extent of DMF is obtained. The combination of the excess inverse permittivity and the Luzar model gives a satisfactory explanation and valuable insights into the underlying of the relaxation acts. The binding energy of solute-solute (E11) and solute-solvent (E12) both decrease with the increased number of hydroxyl in mixture system.

  18. Laser-Based Measurement of Refractive Index Changes: Kinetics of 2,3-Epoxy-1-propanol Hydrolysis.

    ERIC Educational Resources Information Center

    Spencer, Bert; Zare, Richard N.

    1988-01-01

    Describes an experiment in which a simple laser-based apparatus is used for measuring the change in refractive index during the acid-catalyzed hydrolysis of glycidol into glycerine. Gives a schematic of the experimental setup and discusses the kinetic analysis. (MVL)

  19. PIV Measurement of Transient 3-D (Liquid and Gas Phases) Flow Structures Created by a Spreading Flame over 1-Propanol

    NASA Technical Reports Server (NTRS)

    Hassan, M. I.; Kuwana, K.; Saito, K.

    2001-01-01

    In the past, we measured three-D flow structure in the liquid and gas phases that were created by a spreading flame over liquid fuels. In that effort, we employed several different techniques including our original laser sheet particle tracking (LSPT) technique, which is capable of measuring transient 2-D flow structures. Recently we obtained a state-of-the-art integrated particle image velocimetry (IPIV), whose function is similar to LSPT, but it has an integrated data recording and processing system. To evaluate the accuracy of our IPIV system, we conducted a series of flame spread tests using the same experimental apparatus that we used in our previous flame spread studies and obtained a series of 2-D flow profiles corresponding to our previous LSPT measurements. We confirmed that both LSPT and IPIV techniques produced similar data, but IPIV data contains more detailed flow structures than LSPT data. Here we present some of newly obtained IPIV flow structure data, and discuss the role of gravity in the flame-induced flow structures. Note that the application of IPIV to our flame spread problems is not straightforward, and it required several preliminary tests for its accuracy including this IPIV comparison to LSPT.

  20. Comparison of nitroethane, 2-nitro-1-propanol, lauric acid, Lauricidin and the Hawaiian marine algae, Chaetoceros, for potential broad-spectrum control of anaerobically grown lactic acid bacteria

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The gastrointestinal tract of bovines often contains bacteria that contribute to disorders of the rumen and may also contain foodborne or opportunistic human pathogens as well as bacteria capable of causing mastitis in cows. Thus, there is a need to develop broad-spectrum therapies that are effecti...

  1. Thermodynamic and acoustical properties of mixtures p-anisaldehyde—alkanols (C1-C4)—2-methyl-1-propanol at 303.15 K

    NASA Astrophysics Data System (ADS)

    Saini, Balwinder; Kumar, Ashwani; Rani, Ruby; Bamezai, Rajinder K.

    2016-07-01

    The density, viscosity and speed of sound of pure p-anisaldehyde and some alkanols, for example, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol, and the binary mixtures of p-anisaldehyde with these alkanols were measured over the entire composition range at 303.15 K. From the experimental data, various thermodynamic parameters such as excess molar volume ( V E), excess Gibbs free energy of activation (Δ G*E), and deviation parameters like viscosity (Δη), speed of sound (Δ u), isentropic compressibility (Δκs), are calculated. The excess as well as deviation parameters are fitted to Redlich—Kister equation. Additionally, the viscosity data for the systems has been used to correlate the application of empirical relation given by Grunberg and Nissan, Katti and Chaudhari, and Hind et al. The results are discussed in terms of specific interactions present in the mixtures.

  2. In vitro comparison of nitroethane, 2-nitro-1-propanol, lauric acid, Lauricidin(R), and the Hawaiian marine algae, Chaetoceros, activity against anaerobically grown Staphylococcus aureus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The gastrointestinal tract of bovines often contains bacteria that contribute to disorders of the rumen and may also contain foodborne or opportunistic human pathogens as well as causative agents of mastitis in cows. Thus, there is a need to develop broad-spectrum therapies that are effective while...

  3. In vitro comparison of nitroethane, 2-nitro-1-propanol, lauric acid, Lauricidin(R), and the Hawaiian marine algae, Chaetoceros, activity against anaerobically grown Staphylococcus aureus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mastitis is a common illness of dairy cattle and is very costly, economically, to the dairy farmer. Thus, there is a need to develop broad-spectrum therapies that are effective while not leading to unacceptably long antibiotic withdrawal times. The effects of the CH4-inhibitors nitroethane (2 mg/m...

  4. On the origin of preferred bicarbonate production from carbon dioxide (CO₂) capture in aqueous 2-amino-2-methyl-1-propanol (AMP).

    PubMed

    Stowe, Haley M; Vilčiauskas, Linas; Paek, Eunsu; Hwang, Gyeong S

    2015-11-21

    AMP and its blends are an attractive solvent for CO2 capture, but the underlying reaction mechanisms still remain uncertain. We attempt to elucidate the factors enhancing bicarbonate production in aqueous AMP as compared to MEA which, like most other primary amines, preferentially forms carbamate. According to our predicted reaction energies, AMP and MEA exhibit similar thermodynamic favorability for bicarbonate versus carbamate formation; moreover, the conversion of carbamate to bicarbonate also does not appear more favorable kinetically in aqueous AMP compared to MEA. Ab initio molecular dynamics simulations, however, demonstrate that bicarbonate formation tends to be kinetically more probable in aqueous AMP while carbamate is more likely to form in aqueous MEA. Analysis of the solvation structure and dynamics shows that the enhanced interaction between N and H2O may hinder CO2 accessibility while facilitating the AMP + H2O → AMPH(+) + OH(-) reaction, relative to the MEA case. This study highlights the importance of not only thermodynamic but also kinetic factors in describing CO2 capture by aqueous amines.

  5. Synthesis of propyl gallate by transesterification of tannic acid in aqueous media catalysed by immobilised derivatives of tannase from Lactobacillus plantarum.

    PubMed

    Fernandez-Lorente, Gloria; Bolivar, Juan Manuel; Rocha-Martin, Javier; Curiel, Jose A; Muñoz, Rosario; de Las Rivas, Blanca; Carrascosa, Alfonso V; Guisan, Jose M

    2011-09-01

    Immobilised derivatives of tannase from Lactobacillus plantarum were able to catalyse the transesterification of tannic acid by using moderate concentrations of 1-propanol in aqueous media. Transesterification of tannic acid was very similar to transesterification of methyl gallate. The synthetic yield depended on the pH and concentration of 1-propanol, although it did not vary much when using 30% or 50% 1-propanol. Synthetic yields of 45% were obtained with 30% of 1-propanol at pH 5.0. The product was chromatographically pure, and the reaction by-product was 55% pure gallic acid. On the other hand, immobilised tannase was fairly stable under optimal reaction conditions.

  6. Characterisation of tequila according to their major volatile composition using multilayer perceptron neural networks.

    PubMed

    Ceballos-Magaña, Silvia G; de Pablos, Fernando; Jurado, José Marcos; Martín, María Jesús; Alcázar, Ángela; Muñiz-Valencia, Roberto; Gonzalo-Lumbreras, Raquel; Izquierdo-Hornillos, Roberto

    2013-02-15

    Differentiation of silver, gold, aged and extra-aged tequila using 1-propanol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanol and 2-methyl-1-butanol and furan derivatives like 5-(hydroxymethyl)-2-furaldehyde and 2-furaldehyde has been carried out. The content of 1-propanol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanol and 2-methyl-1-butanol was determined by means of head space solid phase microextraction gas chromatography mass-spectrometry. 5-(Hydroxymethyl)-2-furaldehyde and 2-furaldehyde were determined by high performance liquid chromatography with diode array detection. Kruskal-Wallis test was used to highlight significant differences between types of tequila. Principal component analysis was applied as visualisation technique. Linear discriminant analysis and multilayer perceptron artificial neural networks were used to construct classification models. The best classification performance was obtained when multilayer perceptron model was applied.

  7. High energy chlorine for chlorine substitution involving Walden inversion in gaseous enantiomers

    NASA Astrophysics Data System (ADS)

    To, Kar-Chun; Rack, E. P.; Wolf, A. P.

    1981-01-01

    The reactions of 34mCl- for cl substitution in gaseous 2(S)-(+)- a and 2(R)-(-)-chloro-1-propanol are reported at various system pressures and in the presence of neon moderator and a radical scavenger. (AIP).

  8. Prediction of vapor-liquid equilibria for the alcohol + glycerol systems using UNIFAC and modified UNIFAC (Dortmund)

    NASA Astrophysics Data System (ADS)

    Hartanto, Dhoni; Mustain, Asalil; Nugroho, Febry Dwi

    2017-03-01

    The vapor-liquid equilibria for eight systems of alcohols + glycerol at 101.325 kPa have been predicted in this study using UNIFAC and Modified UNIFAC (Dortmund) group contribution methods. The investigated alcohols were methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol. In order to study the accuracy of both contribution methods, the predicted data obtained from both approaches were compared to the experimental data from the literature. The prediction accuracy using modified UNIFAC (Dortmund) give better results compared to the UNIFAC method for (ethanol, 1-propanol, 2-propanol and 1-butanol) + glycerol but UNIFAC method show better accuracy for methanol + glycerol system. In addition, the influences of carbon chain length on the phase behaviours of alcohol + glycerol systems were also discussed as well.

  9. 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.

  10. Excess volumes of binary mixtures of 1,3-dichloropropane with isomeric butanols at 298. 15 and 313. 15 K

    SciTech Connect

    Lafuente, C.; Pardo, J.; Rodriguez, V.; Royo, F.M.; Urieta, J.S. . Dept. de Quimica Organica-Quimica Fisica)

    1993-10-01

    Excess molar volumes, V[sub m][sup E], for binary mixtures of 1,3-dichloropropane with 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol have been determined from density measurements at 298.15 and 313.15 K by means of an Anton Paar DMA-58 vibrating tube densimeter. V[sub m][sup E] is positive over the whole composition range except for mixtures containing 1-butanol and 2-methyl-1-propanol at 298.15 K in which V[sub m][sup E] shows negative values at low mole fractions of dichloroalkane.

  11. Production of graphene by exfoliation of graphite in a volatile organic solvent.

    PubMed

    Choi, Eun-Young; Choi, Won San; Lee, Young Boo; Noh, Yong-Young

    2011-09-07

    The production of unfunctionalized and nonoxidized graphene by exfoliation of graphite in a volatile solvent, 1-propanol, is reported. A stable homogeneous dispersion of graphene was obtained by mild sonication of graphite powder and subsequent centrifugation. The presence of a graphene monolayer was observed by atomic force microscopy and transmission electron microscopy. The solvent, 1-propanol, from the deposited dispersion was simply and quickly removed by air drying at room temperature, without the help of high temperature annealing or vacuum drying, which shortens production time and does not leave any residue of the solvent in the graphene sheets.

  12. Anti-inflammatory effect of ethanol and other alcohols on rat paw edema and pleurisy.

    PubMed

    Strubelt, O; Zetler, G

    1980-06-01

    The rat paw edema due to carrageenan, yeast, and dextran was dose-dependently antagonized by oral administration of ethanol. Carrageenan-induced paw edema was also inhibited by methanol, 1-propanol, and 1-butanol. The rat carrageenan pleurisy was reduced by oral pretreatment with methanol, ethanol, 1-propanol, 1-butanol, and dimethyl sulfoxide. Central depression, altered adrenal functions, increased osmolality, and hypothermia were no important factors for these actions of solvents. It is concluded that the inhibitory effect of ethanol on inflammatory responses increases the susceptibility of alcoholics to infection.

  13. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  14. Using Nuclear Magnetic Resonance Spectroscopy for Measuring Ternary Phase Diagrams

    ERIC Educational Resources Information Center

    Woodworth, Jennifer K.; Terrance, Jacob C.; Hoffmann, Markus M.

    2006-01-01

    A laboratory experiment is presented for the upper-level undergraduate physical chemistry curriculum in which the ternary phase diagram of water, 1-propanol and n-heptane is measured using proton nuclear magnetic resonance (NMR) spectroscopy. The experiment builds upon basic concepts of NMR spectral analysis, typically taught in the undergraduate…

  15. AGONISTIC SENSORY EFFECTS OF AIRBORNE CHEMICALS IN MIXTURES: ODOR, NASAL PUNGENCY, AND EYE IRRITATION

    EPA Science Inventory

    Threshold responses of odor, nasal pungency (irritation), and eye irritation were measured for single chemicals (1-propanol, 1-hexanol, ethyl acetate, heptyl acetate, 2-pentanone, 2-heptanone, toluene, ethyl benzene, and propyl benzene) and mixtures of them (two three-component m...

  16. Application of Pattern Recognition to Metal Ion Chemical Ionization Mass Spectra.

    DTIC Science & Technology

    1985-10-01

    experiments. ORGANICS FOR RECOGNITION OF SIX CLASSES ALJAJE AL-KE KETONE butane 1 - butene butanone pentane 1 -pentene 2-pentanone hexane 1 -hezene 2... butene cyclopentanone 1 -methyl cyclopentane cyclopentene methyl cyclopropyl k etone cyclobexane cyclohexene 3-methyl cyclopentanone * 1 -methyl...cyclobeiane vinyl cyclohexane cyclohexanone * ALDEH YDE ETHER ALCOHOL propanal ethyl ether ethanol butanal methyl butyl ether 1 -propanol pentanal ethyl

  17. Ruminal fermentation of anti-methanogenic nitrate- and nitro-containing forages in vitro

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrate, 3-nitro-1-propionic acid (NPA), and 3-nitro-1-propanol (NPOH) can accumulate in forages and be poisonous to animals if fed at high enough amounts. These chemicals are also recognized as potent anti-methanogenic compounds, but plants naturally containing these chemicals have been studied li...

  18. 40 CFR Appendix I to Part 192 - Listed Constituents

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Hydrocyanic acid Hydrofluoric acid Hydrogen sulfide (H2 S) Indeno(1,2,3-cd)pyrene Isobutyl alcohol (1-Propanol... dioxide (Selenious acid) Selenium sulfide (SeS2) Selenourea Silver and compounds, N.O.S. Silver cyanide... (Benzene, 1,3,5-trinitro-) Tris(1-aziridinyl)phosphine sulfide (Aziridine,...

  19. 40 CFR Appendix I to Part 192 - Listed Constituents

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Hydrocyanic acid Hydrofluoric acid Hydrogen sulfide (H2 S) Indeno(1,2,3-cd)pyrene Isobutyl alcohol (1-Propanol... dioxide (Selenious acid) Selenium sulfide (SeS2) Selenourea Silver and compounds, N.O.S. Silver cyanide... (Benzene, 1,3,5-trinitro-) Tris(1-aziridinyl)phosphine sulfide (Aziridine,...

  20. Preparation of Novel Hydrolyzing Urethane Modified Thiol-Ene Networks

    DTIC Science & Technology

    2011-10-25

    tetrafluoro-1-propanol (98%), 2,2′-azobisiso butlyronitrile (ABIN 98%), and dibutyltin diaularate (95%) were obtained from Aldrich. Irgacure 651 and...chloroform at 50 wt %. The dibutyltin dilaurate catalyst was added at 0.1 wt % of total solids to the ethylene glycol vinyl ether solution. The

  1. Excimer Formation of a Naphthalene Diisocyanate Based Polyurethane in Solution.

    DTIC Science & Technology

    1987-07-29

    dlylbiscarbamate (1,5-DNB). To a p-dioxane soltuion containing 1-propanol (1.71 g) and dibutyltin dilaurate (Polysciences, 0.2 g) was added 1,5- naphthalene...tetrachloroethane (Baker, distilled and dried) containing polytetramethylene ether glycol (Polysciences, average MW 650, 2.17 g), dibutyltin dilaurate

  2. Mass balance evaluation of alcohol emission from cattle feed

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Silage on dairy farms has been recognized as an important source of volatile organic compounds (VOCs) to the atmosphere, and therefore a contributor to tropospheric ozone. Considering reactivity and likely emission rates, ethanol, 1-propanol, and acetaldehyde probably make the largest contribution t...

  3. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

    Alcohol transformation to transportation fuel range hydrocarbon on HZSM-5 (SiO2 / Al2O3 = 30) catalyst was studied at 360oC and 300psig. Product distributions and catalyst life were compared using methanol, ethanol, 1-propanol or 1-butanol as a feed. The catalyst life for 1-propanol and 1-butanol was more than double compared to that for methanol and ethanol. For all the alcohols studied, the product distributions (classified to paraffin, olefin, napthene, aromatic and naphthalene compounds) varied with time on stream (TOS). At 24 hours TOS, liquid product from 1-propanol and 1-butanol transformation primarily contains higher olefin compounds. The alcohol transformation process to higher hydrocarbon involves a complex set of reaction pathways such as dehydration, oligomerization, dehydrocyclization, and hydrogenation. Compared to ethylene generated from methanol and ethanol, oligomerization of propylene and butylene has a lower activation energy and can readily take place on weaker acidic sites. On the other hand, dehydrocyclization of propylene and butylene to form the cyclic compounds requires the sits with stronger acid strength. Combination of the above mentioned reasons are the primary reasons for olefin rich product generated in the later stage of the time on stream and for the extended catalyst life time for 1 propanol and 1 butanol compared to methanol and ethanol conversion over HZSM-5.

  4. One pot direct synthesis of amides or oxazolines from carboxylic acids using Deoxo-Fluor reagent.

    PubMed

    Kangani, Cyrous O; Kelley, David E

    2005-12-19

    A mild and highly efficient one pot-one step condensation and/or condensation-cyclization of various acids to amides and/or oxazolines using Deoxo-Fluor reagents is described. Parallel syntheses of various free fatty acids with 2-amino-2, 2-dimethyl-1-propanol resulted with excellent yields.

  5. HPLC Preparation of the Chiral Forms of 6-Methoxy-Gossypol and 6,6'-Dimethoxy-Gossypol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A concentrated mixture of gossypol, 6-methoxy-gossypol and 6,6'-dimethoxy-gossypol was extracted with acetone from the root bark of St. Vincent Sea Island cotton. This extract was derivatized with R-(-)-2-amino-1-propanol to form diastereomeric gossypol Schiff’s bases. Analytical-scale reverse-pha...

  6. Solubility of anthracene and pyrene in binary alcohol + alcohol solvent mixtures

    SciTech Connect

    Zvaigzne, A.I.; McHale, M.E.R.; Powell, J.R.; Kauppila, A.S.M.; Acree, W.E. Jr.

    1995-11-01

    Solid-liquid equilibrium data of organic nonelectrolyte systems are becoming increasingly important in the petroleum industry, particularly in light of present trends toward heavier feedstocks and known carcinogenicity/mutagenicity of many of the larger polycyclic aromatic compounds. Experimental solubilities are reported for anthracene dissolved in binary 1-octanol + 2-propanol, 2-butanol + 1-butanol, 1-octanol + 1-butanol, 3-methyl-1-butanol + 1-propanol, and 2-methyl-1-propanol + 1-butanol mixtures at 25 C, and for pyrene dissolved in binary solvent mixtures containing 2-ethyl-1-hexanol with 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-octanol, 2-methyl-1-propanol, and 3-methyl-1-butanol at 26 C. Results of these measurements are used to test two mathematical representations based upon the combined nearly ideal binary solvent (NIBS)/Redlich-Kister equation and modified Wilson model. For the 12 systems studied, the combined NIBS/Redlich-Kister equation was found to provide an accurate mathematical representation of the experimental data, with an overall average absolute deviation between measured and calculated values being on the order of 0.4%. Slightly larger deviations were noted in the case of the modified Wilson equation.

  7. Characterization of bovine ruminal and equine cecal microbial populations enriched for enhanced nitro-toxin metabolizing activity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The phytochemicals 3-nitro-1-propionic acid (NPA) and 3-nitro-1-propanol (NPOH) are produced by a wide variety of leguminous plants, including over 150 different species and varieties of Astragalus. These compounds are toxic to naive grazing animals, but can be safely fed to cattle and sheep that h...

  8. Aversive Olfactory Learning and Associative Long-Term Memory in "Caenorhabditis elegans"

    ERIC Educational Resources Information Center

    Amano, Hisayuki; Maruyama, Ichiro N.

    2011-01-01

    The nematode "Caenorhabditis elegans" ("C. elegans") adult hermaphrodite has 302 invariant neurons and is suited for cellular and molecular studies on complex behaviors including learning and memory. Here, we have developed protocols for classical conditioning of worms with 1-propanol, as a conditioned stimulus (CS), and hydrochloride (HCl) (pH…

  9. Evolution of volatile byproducts during wine fermentations using immobilized cells on grape skins.

    PubMed

    Mallouchos, Athanasios; Komaitis, Michael; Koutinas, Athanasios; Kanellaki, Maria

    2003-04-09

    A biocatalyst was prepared by immobilization of Saccharomyces cerevisiae cells on grape skins. Repeated batch fermentations were conducted using this biocatalyst as well as free cells, at 25, 20, 15, and 10 degrees C. Solid phase microextraction (SPME) was used in monitoring the evolution of volatile byproducts. The effect of immobilization and temperature on evolution patterns of volatiles was obvious. The major part of esters was formed after consumption of 40-50% of the sugars. Similar processes were observed for amyl alcohols and 2-phenylethanol, whereas 1-propanol and 2-methyl-1-propanol were formed during the whole alcoholic fermentation period at an almost constant formation rate. Acetaldehyde and acetoin were synthesized in the early stages of fermentation. Afterward, their amount decreased. In most cases, immobilized cells exhibited higher formation rates of volatiles than free cells. The final concentration of esters was higher in wines produced by immobilized biocatalyst. Their amount increased with temperature decrease. The opposite was observed for higher alcohols.

  10. Synthesis of 1,3,3-trinitroazetidine

    DOEpatents

    Hiskey, M.A.; Coburn, M.D.

    1994-08-09

    A process of preparing 1,3,3-trinitroazetidine includes forming a 5-hydroxymethyl-5-nitro-1-alkyltetrahydro-1,3-oxazine, e.g., reacting a 1,3,5-trialkyl hexahydrotriazine and tris(hydroxymethyl)nitromethane, ring opening said 5-hydroxymethyl-5-nitro-1-alkyltetrahydro-1,3-oxazine to form a 3-alkylamino-2-hydroxymethyl-2-nitro-1-propanol salt, ring closing said 3-alkylamino-2-hydroxymethyl-2-nitro-1-propanol salt to form a 3-hydroxymethyl-3-nitro-1-alkylazetidine salt, nitrating said 3-hydroxymethyl-3-nitro-1-alkylazetidine salt to form a 1-alkyl-3,3-dinitroazetidine, and converting said 1-alkyl-3,3-dinitroazetidine into 1,3,3-trinitroazetidine is disclosed. 1 fig.

  11. Synthesis of 1,3,3-trinitroazetidine

    DOEpatents

    Hiskey, Michael A.; Coburn, Michael D.

    1994-01-01

    A process of preparing 1,3,3-trinitroazetidine including forming a 5-hydroxymethyl-5-nitro-1-alkyltetrahydro-1,3-oxazine, e.g., reacting a 1,3,5-trialkyl hexahydrotriazine and tris(hydroxymethyl)nitromethane, ring opening said 5-hydroxymethyl-5-nitro-1-alkyltetrahydro-1,3-oxazine to form a 3-alkylamino-2-hydroxymethyl-2-nitro-1-propanol salt, ring closing said 3-alkylamino-2-hydroxymethyl-2-nitro-1-propanol salt to form a 3-hydroxymethyl-3-nitro-1-alkylazetidine salt, nitrating said 3-hydroxymethyl-3-nitro-1-alkylazetidine salt to form a 1-alkyl-3,3-dinitroazetidine, and converting said 1-alkyl-3,3-dinitroazetidine into 1,3,3-trinitroazetidine is disclosed.

  12. Biocatalytic synthesis of C3 chiral building blocks by chloroperoxidase-catalyzed enantioselective halo-hydroxylation and epoxidation in the presence of ionic liquids.

    PubMed

    Liu, Yan; Wang, Yali; Jiang, Yucheng; Hu, Mancheng; Li, Shuni; Zhai, Quanguo

    2015-01-01

    The optically active C3 synthetic blocks are remarkably versatile intermediates for the synthesis of numerous pharmaceuticals and agrochemicals. This work provides a simple and efficient enzymatic synthetic route for the environment-friendly synthesis of C3 chiral building blocks. Chloroperoxidase (CPO)-catalyzed enantioselective halo-hydroxylation and epoxidation of chloropropene and allyl alcohol was employed to prepare C3 chiral building blocks in this work, including (R)-2,3-dichloro-1-propanol (DCP*), (R)-2,3-epoxy-1-propanol (GLD*), and (R)-3-chloro-1-2-propanediol (CPD*). The ee values of the formed C3 chiral building blocks DCP*, CPD*, and glycidol were 98.1, 97.5, and 96.7%, respectively. Moreover, the use of small amount of imidazolium ionic liquid enhanced the yield efficiently due to the increase of solubility of hydrophobic organic substrates in aqueous reaction media, as well as the improvement of affinity and selectivity of CPO to substrate.

  13. [Preparation of monolithic polylaurylmethacrylate column and its application in capillary electrochromatographic separation of myoglobin digests].

    PubMed

    Wang, Tingting; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

    2010-03-01

    The monolithic polylaurylmethacrylate column was prepared in a single step using the monomer solution containing lauryl methacrylate (LMA), ethylene dimethacrylate (EDMA), and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), with the ternary porogenic solvent consisting of 1-propanol, 1,4-butanediol and H2O. The effects of AMPS content and the ratio of monomer solution to porogenic solvent were investigated. The optimal mass ratio of monomer solution to porogenic solvent was 35:65, the monomer solution was composed of 59.5% (w/w) LMA, 40% (w/w) EDMA and 0.5% (w/w) AMPS, and the porogenic solution was composed of 60% (w/w) 1-propanol, 30% (w/w) 1,4-butanediol and 10% (w/w) H2O. The prepared monolithic column was successfully applied in the capillary electrochromatographic (CEC) separation of myoglobin digests under the optimized mobile phase.

  14. Selective deoxygenation of aldehydes and alcohols on molybdenum carbide (Mo2C) surfaces

    NASA Astrophysics Data System (ADS)

    Xiong, Ke; Yu, Weiting; Chen, Jingguang G.

    2014-12-01

    The selective deoxygenation of aldehydes and alcohols without cleaving the Csbnd C bond is crucial for upgrading bio-oil and other biomass-derived molecules to useful fuels and chemicals. In this work, propanal, 1-propanol, furfural and furfuryl alcohol were selected as probe molecules to study the deoxygenation of aldehydes and alcohols on molybdenum carbide (Mo2C) prepared over a Mo(1 1 0) surface. The reaction pathways were investigated using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The deoxygenation of propanal and 1-propanol went through a similar intermediate (propoxide or η2(C,O)-propanal) to produce propene. The deoxygenation of furfural and furfuryl alcohol produced a surface intermediate similar to adsorbed 2-methylfuran. The comparison of these results revealed the promising deoxygenation performance of Mo2C, as well as the effect of the furan ring on the selective deoxygenation of the Cdbnd O and Csbnd OH bonds.

  15. Solubility of esomeprazole magnesium trihydrate in alcohols at temperatures from 298.15 to 318.15 K

    NASA Astrophysics Data System (ADS)

    Bhesaniya, K.; Baluja, S.

    2013-12-01

    The solubility of esomeprazole magnesium trihydrate in methanol, ethanol, 1-propanol and 1-butanol was determined at temperatures ranging from 298.15 to 318.15 K at atmospheric pressure using gravimetrical method. The highest solubility is found in 1-butanol and lowest in ethanol. The experimental solubility data are correlated by the modified Apelblat equation. Thermodynamic properties such as dissolution enthalpy, Gibb's energy, and entropy of mixing have been determined from the solubility data.

  16. High octane ethers from synthesis gas-derived alcohols

    SciTech Connect

    Klier, K.; Herman, R.G.; Johansson, M.; Feeley, O.C.

    1992-01-01

    The objective of the proposed research is to synthesize high octane ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from H{sub 2}/CO/CO{sub 2} coal-derived synthesis gas via alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers.

  17. High octane ethers from synthesis gas-derived alcohols. Technical progress report, October--December 1991

    SciTech Connect

    Klier, K.; Herman, R.G.; Johansson, M.; Feeley, O.C.

    1992-01-01

    The objective of the proposed research is to synthesize high octane ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from H{sub 2}/CO/CO{sub 2} coal-derived synthesis gas via alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers.

  18. The Extraction of Caffeine from Tea: An Old Undergraduate Experiment Revisited

    NASA Astrophysics Data System (ADS)

    Murray, Scott D.; Hansen, Peter J.

    1995-09-01

    The extraction of caffeine from tea leaves is a common organic chemistry experiment. A water/1-propanol/sodium chloride ternary system was found to be a suitable replacement for the more traditional water/organochlorine solvent systems. Approximately 80% of the caffeine in the tea leaves can be recovered as crude caffeine. The ternary system employs chemicals which are not only less expensive, but also less toxic.

  19. The bellamy relationship and the nature of the H-bond. 2-Haloethanols

    NASA Astrophysics Data System (ADS)

    Vokin, A. I.; Turchaninov, V. K.

    2015-01-01

    IR-spectroscopy data show that the intramolecular H-bond in alcohols with the general formula XCH2CH2OH (X = F, Cl, Br) in a solution is mainly of a nonspecific nature. Molecules of 2-haloethanol form three-center complexes with an external H-bond acceptor. The intramolecular component of their bifurcated bond causes a stronger spectroscopic effect as compared to the two-center H-bond of ethanol or 1-propanol.

  20. Thermodynamics of the solubility of sulfamethoxydiazine in organic solvents in the range 293.15-323.15 K

    NASA Astrophysics Data System (ADS)

    Zhang, C.-L.; Cui, S.-J.; Wang, Y.

    2017-01-01

    The solubilities of sulfamethoxydiazine in methanol, ethanol, 1-propanol, 2-propanol, acetone, and chloroform have been determined in the range 293.15-323.15 K by a static equilibrium method. The calculated results show that the correlation of the Apelblat equation for measured systems has less deviation than that of the λ h equation. The positive Δsol H and Δsol S for each system revealed that sulfamethoxydiazine being dissolved in each solvent was an entropy-driven process.

  1. Aggregation kinetics of latex microspheres in alcohol-water media.

    PubMed

    Odriozola, G; Schmitt, A; Callejas-Fernández, J; Hidalgo-Alvarez, R

    2007-06-15

    We report zeta potential and aggregation kinetics data on colloidal latex particles immersed in water-alcohol media. Zeta potential values show absolute maxima for volume fractions of alcohol of 0.10 and 0.05 for ethanol and 1-propanol, respectively. For methanol, no maximum of the absolute value of the zeta potential was found. Aggregation kinetics was studied by means of a single-cluster optical sizing equipment and for alcohol volume fractions ranging from 0 to 0.1. The aggregation processes are induced by adding different potassium bromide concentrations to the samples. We expected to find a slowdown of the overall aggregation kinetics for ethanol and 1-propanol, and no significant effect for methanol, as compared with pure water data. That is, we expected the zeta potential to govern the overall aggregation rate. However, we obtained a general enhancement of the aggregation kinetics for methanol and 1-propanol and a general slowdown of the aggregation rate for ethanol. In addition, aggregation data under ethanol show a slower kinetics for large electrolyte concentration than that obtained for intermediate electrolyte concentration. We think that these anomalous behaviors are linked to layering, changes in hydrophobicity of particle surfaces due to alcohol adsorption, complex ion-water-alcohol-surface structuring, and competition between alcohol-surface adsorption and alcohol-alcohol clustering.

  2. Aversive olfactory learning and associative long-term memory in Caenorhabditis elegans

    PubMed Central

    Amano, Hisayuki; Maruyama, Ichiro N.

    2011-01-01

    The nematode Caenorhabditis elegans (C. elegans) adult hermaphrodite has 302 invariant neurons and is suited for cellular and molecular studies on complex behaviors including learning and memory. Here, we have developed protocols for classical conditioning of worms with 1-propanol, as a conditioned stimulus (CS), and hydrochloride (HCl) (pH 4.0), as an unconditioned stimulus (US). Before the conditioning, worms were attracted to 1-propanol and avoided HCl in chemotaxis assay. In contrast, after massed or spaced training, worms were either not attracted at all to or repelled from 1-propanol on the assay plate. The memory after the spaced training was retained for 24 h, while the memory after the massed training was no longer observable within 3 h. Worms pretreated with transcription and translation inhibitors failed to form the memory by the spaced training, whereas the memory after the massed training was not significantly affected by the inhibitors and was sensitive to cold-shock anesthesia. Therefore, the memories after the spaced and massed trainings can be classified as long-term memory (LTM) and short-term/middle-term memory (STM/MTM), respectively. Consistently, like other organisms including Aplysia, Drosophila, and mice, C. elegans mutants defective in nmr-1 encoding an NMDA receptor subunit failed to form both LTM and STM/MTM, while mutations in crh-1 encoding the CREB transcription factor affected only the LTM. PMID:21960709

  3. Escherichia coli mar and acrAB mutants display no tolerance to simple alcohols.

    PubMed

    Ankarloo, Jonas; Wikman, Susanne; Nicholls, Ian A

    2010-03-31

    The inducible Mar phenotype of Escherichia coli is associated with increased tolerance to multiple hydrophobic antibiotics as well as some highly hydrophobic organic solvents such as cyclohexane, mediated mainly through the AcrAB/TolC efflux system. The influence of water miscible alcohols ethanol and 1-propanol on a Mar constitutive mutant and a mar deletion mutant of E. coli K-12, as well as the corresponding strains carrying the additional acrAB deletion, was investigated. In contrast to hydrophobic solvents, all strains were killed in exponential phase by 1-propanol and ethanol at rates comparable to the parent strain. Thus, the Mar phenotype does not protect E. coli from killing by these more polar solvents. Surprisingly, AcrAB does not contribute to an increased alcohol tolerance. In addition, sodium salicylate, at concentrations known to induce the mar operon, was unable to increase 1-propanol or ethanol tolerance. Rather, the toxicity of both solvents was increased in the presence of sodium salicylate. Collectively, the results imply that the resilience of E. coli to water miscible alcohols, in contrast to more hydrophobic solvents, does not depend upon the AcrAB/TolC efflux system, and suggests a lower limit for substrate molecular size and functionality. Implications for the application of microbiological systems in environments containing high contents of water miscible organic solvents, e.g., phage display screening, are discussed.

  4. "Wet" Versus "Dry" Folding of Polyproline

    NASA Astrophysics Data System (ADS)

    Shi, Liuqing; Holliday, Alison E.; Bohrer, Brian C.; Kim, Doyong; Servage, Kelly A.; Russell, David H.; Clemmer, David E.

    2016-06-01

    When the all- cis polyproline-I helix (PPI, favored in 1-propanol) of polyproline-13 is introduced into water, it folds into the all- trans polyproline-II (PPII) helix through at least six intermediates [Shi, L., Holliday, A.E., Shi, H., Zhu, F., Ewing, M.A., Russell, D.H., Clemmer, D.E.: Characterizing intermediates along the transition from PPI to PPII using ion mobility-mass spectrometry. J. Am. Chem. Soc. 136, 12702-12711 (2014)]. Here, we show that the solvent-free intermediates refold into the all- cis PPI helix with high (>90%) efficiency. Moreover, in the absence of solvent, each intermediate appears to utilize the same small set of pathways observed for the solution-phase PPII → PPI transition upon immersion of PPIIaq in 1-propanol. That folding in solution (under conditions where water is displaced by propanol) and folding in vacuo (where energy required for folding is provided by collisional activation) occur along the same pathway is remarkable. Implicit in this statement is that 1-propanol mimics a "dry" environment, similar to the gas phase. We note that intermediates with structures that are similar to PPIIaq can form PPII under the most gentle activation conditions—indicating that some transitions observed in water (i.e. , "we t" folding, are accessible (albeit inefficient) in vacuo. Lastly, these "dry" folding experiments show that PPI (all cis) is favored under "dry" conditions, which underscores the role of water as the major factor promoting preference for trans proline.

  5. Indirectly suspended droplet microextraction of water-miscible organic solvents by salting-out effect for the determination of polycyclic aromatic hydrocarbons.

    PubMed

    Daneshfar, Ali; Khezeli, Tahere

    2014-12-01

    A simple and low-cost method that indirectly suspended droplet microextraction of water-miscible organic solvents (ISDME) by salting-out effect before high-performance liquid chromatography and ultraviolet (HPLC-UV) detection was used for the determination of polycyclic aromatic hydrocarbons (PAHs) in different samples. The ISDME is a combination of salting-out extraction of water-miscible organic solvent and directly suspended droplet microextraction (DSDME). Ninety-five microliters water-miscible organic solvent (1-propanol) was added to a 500-µL sample. A homogeneous solution was formed immediately. To produce a steady vortex at the top of the solution, the sample was agitated at 700 rpm using a magnetic stirrer. By the addition of ammonium sulfate (saturated solution) to the homogeneous solution, 1-propanol was separated and collected at the bottom of the steady vortex. Finally, 20 µL 1-propanol was injected into HPLC-UV. The effects of important parameters such as water-miscible organic solvent (type and volume), type of salt, and extraction time were evaluated. Under optimum conditions, the method has a good linear calibration range (0.1 µg/L-300 µg/L), coefficients of determination (R(2) > 0.998), low limits of detection (between 0.02 µg/L and 0.27 µg/L), and acceptable recovery (>85.0%).

  6. The use of coenzyme Q0 as a template in the development of a molecularly imprinted polymer for the selective recognition of coenzyme Q10.

    PubMed

    Contin, Mario; Flor, Sabrina; Martinefski, Manuela; Lucangioli, Silvia; Tripodi, Valeria

    2014-01-07

    In this work, a novel molecularly imprinted polymer (MIP) for use as a solid phase extraction sorbent was developed for the determination of coenzyme Q10 (CoQ10) in liver extract. CoQ10 is an essential cofactor in mitochondrial oxidative phosphorylation and a powerful antioxidant agent found in low concentrations in biological samples. This fact and its high hydrophobicity make the analysis of CoQ10 technically challenging. Accordingly, a MIP was synthesised using coenzyme Q0 as the template, methacrylic acid as the functional monomer, acetonitrile as the porogen, ethylene glycol dimethacrylate as the crosslinker and benzoyl peroxide as the initiator. Various parameters affecting the polymer preparation and extraction efficiency were evaluated. Morphological characterisation of the MIP and its proper comparison with C18 as a sorbent in solid phase extraction were performed. The optimal conditions for the molecularly imprinted solid phase extraction (MISPE) consisted of 400 μL of sample mixed with 30 mg of MIP and 600 μL of water to reach the optimum solution loading. The loading was followed by a washing step consisting of 1 mL of a 1-propanol solution (1-propanol:water, 30:70,v/v) and elution with 1 mL of 1-propanol. After clean-up, the CoQ10 in the samples was analysed by high performance liquid chromatography. The extraction recoveries were higher than 73.7% with good precision (3.6-8.3%). The limits of detection and quantification were 2.4 and 7.5 μg g(-1), respectively, and a linear range between 7.5 and 150 μg g(-1) of tissue was achieved. The new MISPE procedure provided a successful clean-up for the determination of CoQ10 in a complex matrix.

  7. Lead-induced catalase activity differentially modulates behaviors induced by short-chain alcohols.

    PubMed

    Correa, M; Pascual, M; Sanchis-Segura, C; Guerri, C; Aragon, C M G

    2005-11-01

    Acute lead administration produces a transient increase in brain catalase activity. This effect of lead has been used to assess the involvement of brain ethanol metabolism, and therefore centrally formed acetaldehyde, in the behavioral actions of ethanol. In mice, catalase is involved in ethanol and methanol metabolism, but not in the metabolism of other alcohols such as 1-propanol or tert-butanol. In the present study, we assessed the specificity of the effects of lead acetate on catalase-mediated metabolism of alcohols, and the ability of lead to modulate the locomotion and loss of the righting reflex (LRR) induced by 4 different short-chain alcohols. Animals were pretreated i.p. with lead acetate (100 mg/kg) or saline, and 7 days later were injected i.p. with ethanol (2.5 or 4.5 g/kg), methanol (2.5 or 6.0 g/kg), 1-propanol (0.5 or 2.5 g/kg) or tert-butanol (0.5 or 2.0 g/kg) for locomotion and LRR, respectively. Locomotion induced by ethanol was significantly potentiated in lead-treated mice, while methanol-induced locomotion was reduced by lead treatment. The loss of righting reflex induced by ethanol was shorter in lead-treated mice, and lead produced the opposite effect in methanol-treated mice. There was no effect of lead on 1-propanol or tert-butanol-induced behaviors. Lead treatment was effective in inducing catalase activity and protein both in liver and brain. These results support the hypothesis that the effects of lead treatment on ethanol-induced behaviors are related to changes in catalase activity, rather than some nonspecific effect that generalizes to all alcohols.

  8. Comparison of solvents for removing pesticides from skin using an in vitro porcine model.

    PubMed

    Campbell, J L; Smith, M A; Eiteman, M A; Williams, P L; Boeniger, M F

    2000-01-01

    This study compared four solvents (1-propanol, polyethylene glycol [avg. MW 400], 10% Ivory Liquid and water, and D-TAM) for their ability to remove selected pesticides from an in vitro porcine skin model using a solvent-moistened wipe. Wipes were performed 90 min after pesticide was applied to the skin. The four pesticides selected (glyphosate, alachlor, methyl parathion, and trifluralin) were chosen because of their differences in water solubility. This study also determined whether pretreatment of skin with a solvent prior to pesticide application would either increase or decrease recovery of the pesticide. Recovery efficiencies for all solvents and pesticides were affected by the amount of contaminant on the skin. Although pesticide recoveries from all four solvents were similar (range: 45-57%), on average 1-propanol had significantly higher recoveries, followed by soap and water. There was no significant difference between polyethylene glycol, and D-TAM. When skin was pretreated with any of the four solvents before pesticide application, the recoveries of the more water soluble compounds, glyphosate and alachlor, decreased. When pretreatment with solvent preceded application of trifluralin, the pesticide with the lowest water solubility, recoveries increased. 1-Propanol or soap and water were more effective in removing pesticides from skin than polyethylene glycol or D-TAM, but the amount of pesticide recovered from skin was affected by the chemical characteristics of the pesticide (such as water solubility) and the amount of pesticide originally on the skin. This study provides information useful to the interpretation of skin wipe sample results collected in field studies.

  9. Application of solubility parameters in 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol organogel in binary organic mixtures.

    PubMed

    Shen, Huahua; Niu, Libo; Fan, Kaiqi; Li, Jingjing; Guan, Xidong; Song, Jian

    2014-08-05

    The gelation behavior of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) in binary solvents has been systematically investigated. DMDBS is soluble in DMSO and insoluble in toluene (apolar) or 1-propanol (polar). When DMSO is added to a poor solvent at a certain volume fraction, DMDBS forms an organogel in the mixed solvent. With increasing DMSO content, the minimum gelation concentration increases and the gel-to-sol transition temperature decreases in both systems. However, compared with those in toluene-DMSO mixtures, the gelation ability and thermal stability are better in 1-propanol-DMSO mixtures. Scanning electron microscopy images reveal that the gelators aggregate to form three-dimensional networks. X-ray diffraction shows that the gel has a lamellar structure, which is different from the structure of the precipitate. Fourier transform infrared results reveal H-bonding is the main driving force for self-aggregation and indicate that stronger H-bonding interactions exist between gelators in 1-propanol-DMSO mixtures in contrast with toluene-DMSO mixtures. Attempts have been taken to correlate solvent parameters to gelation behavior in binary solvents. A Teas plot exhibits distinctly different solvent zones in the studied mixed solvents. The polar parameter (δp) indicates a narrow favorable domain for gel formation in the range of 1.64-7.99 MPa(1/2) for some apolar solvent-DMSO mixtures. The hydrogen-bonding parameter (δh) predicts that gelation occurs for values of 14.00-16.50 MPa(1/2) for some polar solvent-DMSO mixtures. The result may have potential applications in predicting the gelation behavior of 1,3:2,4-di-O-benzylidene-d-sorbitol derivatives in mixed solvents.

  10. Enantioselective nano liquid chromatographic separation of racemic pharmaceuticals: a facile one-pot in situ preparation of lipase-based polymer monoliths in capillary format.

    PubMed

    Ahmed, Marwa; Ghanem, Ashraf

    2014-11-01

    New affinity monolithic capillary columns of 150 µm internal diameter were prepared in situ fused glass capillary via either immobilization or encapsulation of Candida antarctica lipase B (CALB) on or within polymer monoliths, respectively. The immobilized lipase-based monoliths were prepared via copolymerization of 19.1% monomers (8.9% MMA and 10.2% GMA), 19.8% EDMA, and 61.1% porogens (54.2% formamide and 6.9% 1-propanol) w/w or 20% GMA, 20% EDMA, and 60% porogens (51.6% cyclohexanol and 8.4% 1-dodecanol) in the presence of AIBN (1%) as a radical initiator. This was followed by pumping a solution of lipase through the capillaries and rinsing with potassium phosphate buffer. On the other hand, the encapsulated lipase-based monoliths were prepared via copolymerization of 20% monomers (GMA), 20% EDMA, and 60% porogens (48% 1-propanol, 6% 1,4-butanediol) or 16.4% monomers (16% BuMA, 0.4% SPMA), 23.6% EDMA, and 60% porogens (36% 1-propanol, 18% 1,4-butanediol along with 6% lipase aqueous solution in potassium phosphate buffer. The prepared capillary columns were investigated for the enantioselective nano liquid chromatographic separation of a set of different classes of racemic pharmaceuticals, namely, α- and β-blockers, antiinflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs, and antiarrhythmic drugs. Run-to-run repeatability was quite satisfactory. The encapsulated lipase-based capillary monolith showed better enantioselective separations of most of the investigated compounds. Baseline separation was achieved for alprenolol, atenolol, bromoglutithimide, carbuterol, chloropheneramine, cizolertine carbinol, 4-hydroxy-3-methoxymandelic acid, desmethylcizolertine, nomifensine, normetanephrine, and sulconazole under reversed phase chromatographic conditions. A speculation about the understanding of the chiral recognition mechanism of

  11. Metabolism of the plant toxins nitropropionic acid and nitropropanol by ruminal microorganisms.

    PubMed

    Anderson, R C; Rasmussen, M A; Allison, M J

    1993-09-01

    The nitro toxins 3-nitro-1-propionic acid (NPA) and 3-nitro-1-propanol (NPOH), which are found in many leguminous plants, are known to be detoxified by ruminal microorganisms. The rates of the detoxification reactions are critical to acquisition of tolerance to the plants by ruminant animals, but further information is needed about factors which influence reaction rates and about the nature of the detoxification reactions. We found that rates of disappearance of NPA and NPOH varied somewhat between samples of ruminal fluid but were usually about 0.4 and 0.1 mumol/ml of ruminal fluid per h, respectively, and that rates with threefold-concentrated cells from rumen fluid were correspondingly higher. We present evidence that ruminal microbes from both cattle and sheep reduce these nitro groups in situ, so that NPA is converted to bet-alanine and NPOH is converted to 3-amino-1-propanol. These products were identified by thin-layer chromatography and, as their dabsyl derivatives, separated by high-performance liquid chromatography. The product beta-alanine was itself metabolized by these mixed suspensions of rumen microbes, so its recovery was always less than what would be estimated from NPA loss, but as much as 87% of the NPOH lost from incubation mixtures was recovered as 3-amino-1-propanol. Addition of sulfide and ferrous ions to suspensions of ruminal microbes increased the rate of NPOH reduction about threefold, but rates of NPA reduction were not similarly increased. When incubations were under hydrogen gas instead of carbon dioxide, the addition of sulfide and ferrous ions led to even greater (five- to eightfold) increases in the rates of NPOH metabolism.(ABSTRACT TRUNCATED AT 250 WORDS)

  12. Determination of trace elements in biodiesel and vegetable oil by inductively coupled plasma optical emission spectrometry following alcohol dilution

    NASA Astrophysics Data System (ADS)

    Chaves, Eduardo S.; de Loos-Vollebregt, Margaretha T. C.; Curtius, Adilson J.; Vanhaecke, Frank

    2011-09-01

    A method for the simultaneous determination of Ca, Cu, Fe, K, Mg, Na, P, S and Zn in biodiesels and vegetable oils by inductively coupled plasma optical emission spectrometry (ICP-OES) has been developed. The method - based on the use of an ICP-OES instrument outfitted with a spectrometer in Paschen-Runge mount, equipped with linear charge coupled device detectors monitoring the entire spectrum from 130 to 770 nm - offers a high sample throughput as sample preparation is limited to dilution with alcohol, while all elements of interest are determined simultaneously. Ethanol is only suitable in the context of biodiesel analysis, whereas dilution with 1-propanol also allows application of the method, without any additional modification, to analysis of vegetable oils. As a result, the dilution with 1-propanol is preferable. Sample introduction was carried out with pneumatic nebulization and spectral interferences from carbon-containing compounds were reduced by cooling the cyclonic spray chamber to - 5 °C. The remaining spectral interferences in the low-UV region were efficiently corrected for by the background correction system offered in the software of the ICP-OES instrument used. Calibration was carried out against inorganic standards diluted in ethanol or 1-propanol, while Y was used as an internal standard, correcting for non-spectral interference and sensitivity drift. The accuracy of the method was verified through the analysis of the NIST SRMs 2772 and 2773 biodiesel reference materials. Additionally, as for most of the target elements only indicative concentration values are available for these reference materials, recovery tests have been performed using inorganic and organic standards. The results obtained were in good agreement with the values found on the certificate for both ethanol and 1-propanol sample dilution, while the recoveries were between 87 and 116% for biodiesel and between 95 and 106% for vegetable oils. The measurement precision expressed

  13. In search of the thermo/halochromism of the ET(30) pyridinium-N-phenolate betaine dye

    NASA Astrophysics Data System (ADS)

    Rezende, Marcos Caroli; Aracena, Andrés

    2012-12-01

    The thermohalochromic behavior of Reichardt's ET(30) betaine - the temperature-dependent variation of its halochromic band in the presence of a cation - was investigated for the first time in NaI solutions of HBD- (methanol, ethanol, 1-propanol, 1-butanol) and non-HBD-solvents (acetonitrile, dimethylformamide) at 15 and 55 °C. The solvent-dependent thermohalochromism of the pyridinium-N-phenolate betaine dye was interpreted in terms of the effect of the temperature on the dye-cation association in solution.

  14. Propylene from renewable resources: catalytic conversion of glycerol into propylene.

    PubMed

    Yu, Lei; Yuan, Jing; Zhang, Qi; Liu, Yong-Mei; He, He-Yong; Fan, Kang-Nian; Cao, Yong

    2014-03-01

    Propylene, one of the most demanded commodity chemicals, is obtained overwhelmingly from fossil resources. In view of the diminishing fossil resources and the ongoing climate change, the identification of new efficient and alternative routes for the large-scale production of propylene from biorenewable resources has become essential. Herein, a new selective route for the synthesis of propylene from bio-derived glycerol is demonstrated. The route consists of the formation of 1-propanol (a versatile bulk chemical) as intermediate through hydrogenolysis of glycerol at a high selectivity. A subsequent dehydration produces propylene.

  15. Formation of middle-phase microemulsions using surfactants derived from a renewable resource: ethoxylated tall oils

    SciTech Connect

    Magid, L.J.

    1982-06-01

    The range of salinities over which a large number of multicomponent systems containing ethoxylated tall oils or tall-oil derivatives form middle-phase microemulsions was determined. n-Octane and n-decane were used as the hydrocarbons; 2 methyl-1-propanol and 2-butanol as the cosurfactants. It is possible, with an appropriate choice of surfactant, to produce systems with optimal salinities from 0 to ca. 17 wt% NaCl. Phase volume diagrams are presented for 24 of the systems investigated; interfacial tension measurements for selected systems show tensions in the millidyn/cm range at the optimal salinities.

  16. Sound absorption and concentration fluctuations in water-propanol mixtures

    NASA Astrophysics Data System (ADS)

    Madigosky, W. M.; Warfield, R. W.

    1987-02-01

    The excess ultrasonic sound absorption in 1-propanol water mixtures has been measured from 45 kHz to 474 MHz and is shown to result from a coupling of the sound wave with the long-wavelength spectrum of the composition fluctuations. The results are shown to be in agreement with the fluctuation theories of Fixman, Romanov and Solovyev, and Kawasaki and the more recent theories of Kroll and Ruhland, and Bhattacharjee and Ferrell. It is further suggested that the large absorption observed in alcohol-water mixtures may be due to the presence of large associated groups, or clusters.

  17. Separation of cis and trans Isomers of Polyproline by FAIMS Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Creese, Andrew J.; Cooper, Helen J.

    2016-12-01

    High field asymmetric waveform ion mobility spectrometry (FAIMS) is well-established as a tool for separating peptide isomers (sequence inversions and post-translationally modified localization variants). Here, we demonstrate the FAIMS is able to differentiate cis and trans isomers of polyproline. Polyproline assumes an all- cis conformation—the PPI helix—in 1-propanol, and an all- trans conformation—the PPII helix—in aqueous solutions. Differentiation of these conformers may be achieved both through use of a cylindrical FAIMS device and a miniaturized ultrahigh field planar FAIMS device.

  18. Initial activity and inactivation of alkaline phosphatase in different lots of buffer.

    PubMed

    Pekelharing, J M; Leijnse, B

    1978-05-02

    Alkaline phosphatase activities were determined in six lots of 2-amino-2-methyl-1-propanol (AMP) and in six lots of diethanolamine (DEA) buffers without preincubation of the sample. There appeared to be differences between the lot numbers in both cases, resulting in a variation in initial activity. When serum samples are preincubated with buffer a loss of activity was observed in 4 out of the 6 AMP buffers. Four human isoenzymes showed varying inactivation during preincubation with AMP buffer. No loss of activity was observed when the preincubation was done with the six DEA buffers. These results indicate that the purity of the commercially-available buffers is quite unsatisfactory.

  19. Tunable PhoXonic Band Gap Materials from Self-Assembly of Block Copolymers and Colloidal Nanocrystals (NBIT Phase II)

    DTIC Science & Technology

    2013-12-12

    collection of information if it does not display a currently valid OMB control number. 1 . REPORT DATE 09 JAN 2014 2. REPORT TYPE Final 3. DATES COVERED...has been no previous report of the Flory-Huggins parameter between P2VP with binary mixtures of water and methanol, ethanol and 1 - propanol at various...gels, the P2VP block in the lamellar PS-P2VP shows significantly lower degrees of swelling in alcohol -water co-solvents due to restrictions imposed

  20. Method for producing high dielectric strength microvalves

    DOEpatents

    Kirby, Brian J.; Reichmuth, David S.; Shepodd, Timothy J.

    2006-04-04

    A microvalve having a cast-in-place and lithographically shaped mobile, polymer monolith for fluid flow control in microfluidic devices and method of manufacture. The microvalve contains a porous fluorinated polymer monolithic element whose pores are filled with an electrically insulating, high dielectric strength fluid, typically a perfluorinated liquid. This combination provides a microvalve that combines high dielectric strength with extremely low electrical conductivity. These microvalves have been shown to have resistivities of at least 100 G.OMEGA. and are compatible with solvents such as water at a pH between 2.7 and 9.0, 1-1 propanol, acetonitrile, and acetone.

  1. Debaryomyces hansenii strains differ in their production of flavor compounds in a cheese-surface model

    PubMed Central

    Gori, Klaus; Sørensen, Louise Marie; Petersen, Mikael Agerlin; Jespersen, Lene; Arneborg, Nils

    2012-01-01

    Flavor production among 12 strains of Debaryomyces hansenii when grown on a simple cheese model mimicking a cheese surface was investigated by dynamic headspace sampling followed by gas chromatography-mass spectrometry. The present study confirmed that D. hansenii possess the ability to produce important cheese flavor compounds, primarily branched-chain aldehydes and alcohols, and thus important for the final cheese flavor. Quantification of representative aldehydes (2-Methylpropanal, 3-Methylbutanal) and alcohols (2-Methyl-1-propanol, 3-Methyl-1-butanol, and 3-Methyl-3-buten-1-ol) showed that the investigated D. hansenii strains varied significantly with respect to production of these flavor compounds. Contrary to the alcohols (2-Methyl-1-propanol, 3-Methyl-1-butanol, and 3-Methyl-3-buten-1-ol), the aldehydes (2-Methylpropanal, 3-Methylbutanal) were produced by the D. hansenii strains in concentrations higher than their sensory threshold values, and thus seemed more important than alcohols for cheese flavor. These results show that D. hansenii strains may have potential to be applied as cultures for increasing the nutty/malty flavor of cheese due to their production of aldehydes. However, due to large strain variations, production of flavor compounds has to be taken into consideration for selection of D. hansenii strains as starter cultures for cheese production. PMID:22950022

  2. Structure and thermodynamics of core-softened models for alcohols

    SciTech Connect

    Munaò, Gianmarco; Urbic, Tomaz

    2015-06-07

    The phase behavior and the fluid structure of coarse-grain models for alcohols are studied by means of reference interaction site model (RISM) theory and Monte Carlo simulations. Specifically, we model ethanol and 1-propanol as linear rigid chains constituted by three (trimers) and four (tetramers) partially fused spheres, respectively. Thermodynamic properties of these models are examined in the RISM context, by employing closed formulæ for the calculation of free energy and pressure. Gas-liquid coexistence curves for trimers and tetramers are reported and compared with already existing data for a dimer model of methanol. Critical temperatures slightly increase with the number of CH{sub 2} groups in the chain, while critical pressures and densities decrease. Such a behavior qualitatively reproduces the trend observed in experiments on methanol, ethanol, and 1-propanol and suggests that our coarse-grain models, despite their simplicity, can reproduce the essential features of the phase behavior of such alcohols. The fluid structure of these models is investigated by computing radial distribution function g{sub ij}(r) and static structure factor S{sub ij}(k); the latter shows the presence of a low−k peak at intermediate-high packing fractions and low temperatures, suggesting the presence of aggregates for both trimers and tetramers.

  3. Hydrophobic and hydrophilic interactions in aqueous mixtures of alcohols at a hydrophobic surface.

    PubMed

    Ballal, Deepti; Chapman, Walter G

    2013-09-21

    Aqueous solutions of alcohols are interesting because of their anomalous behavior that is believed to be due to the molecular structuring of water and alcohol around each other in solution. The interfacial structuring and properties are significant for application in alcohol purification processes and biomolecular structure. Here we study aqueous mixtures of short alcohols (methanol, ethanol, 1-propanol, and 2-propanol) at a hydrophobic surface using interfacial statistical associating fluid theory which is a perturbation density functional theory. The addition of a small amount of alcohol decreases the interfacial tension of water drastically. This trend in interfacial tension can be explained by the structure of water and alcohol next to the surface. The hydrophobic group of an added alcohol preferentially goes to the surface preserving the structure of water in the bulk. For a given bulk alcohol concentration, water mixed with the different alcohols has different interfacial tensions with propanol having a lower interfacial tension than methanol and ethanol. 2-propanol is not as effective in decreasing the interfacial tension as 1-propanol because it partitions poorly to the surface due to its larger excluded volume. But for a given surface alcohol mole fraction, all the alcohol mixtures give similar values for interfacial tension. For separation of alcohol from water, methods that take advantage of the high surface mole fraction of alcohol have advantages compared to separation using the vapor in equilibrium with a water-alcohol liquid.

  4. Modeling microbial ethanol production by E. coli under aerobic/anaerobic conditions: applicability to real postmortem cases and to postmortem blood derived microbial cultures.

    PubMed

    Boumba, Vassiliki A; Kourkoumelis, Nikolaos; Gousia, Panagiota; Economou, Vangelis; Papadopoulou, Chrissanthy; Vougiouklakis, Theodore

    2013-10-10

    The mathematical modeling of the microbial ethanol production under strict anaerobic experimental conditions for some bacterial species has been proposed by our research group as the first approximation to the quantification of the microbial ethanol production in cases where other alcohols were produced simultaneously with ethanol. The present study aims to: (i) study the microbial ethanol production by Escherichia coli under controlled aerobic/anaerobic conditions; (ii) model the correlation between the microbial produced ethanol and the other higher alcohols; and (iii) test their applicability in: (a) real postmortem cases that had positive BACs (>0.10 g/L) and co-detection of higher alcohols and 1-butanol during the original ethanol analysis and (b) postmortem blood derived microbial cultures under aerobic/anaerobic controlled experimental conditions. The statistical evaluation of the results revealed that the formulated models were presumably correlated to 1-propanol and 1-butanol which were recognized as the most significant descriptors of the modeling process. The significance of 1-propanol and 1-butanol as descriptors was so powerful that they could be used as the only independent variables to create a simple and satisfactory model. The current models showed a potential for application to estimate microbial ethanol - within an acceptable standard error - in various tested cases where ethanol and other alcohols have been produced from different microbes.

  5. Microemulsion system for topical delivery of thai mango seed kernel extract: development, physicochemical characterisation and ex vivo skin permeation studies.

    PubMed

    Leanpolchareanchai, Jiraporn; Padois, Karine; Falson, Françoise; Bavovada, Rapepol; Pithayanukul, Pimolpan

    2014-10-24

    A microemulsion system containing Thai mango seed kernel extract (MSKE, cultivar "Fahlun") was developed and characterised for the purpose of topical skin delivery. The MSKE-loaded microemulsions were prepared by using the spontaneous emulsification method. Isopropyl myristate (IPM) was selected as the oil phase. A polyoxyethylene sorbitan monooleate and sorbitan monododecanoate (1:1, w/w) system was used as the surfactant phase; an aqueous mixture of different cosurfactants (absolute ethanol, 96.3% v/v ethanol, 1-propanol, 2-propanol or 1,2-propanediol) at a weight ratio of 1:1 was used as the aqueous phase. Among the cosurfactants studied, the 1-propanol aqueous mixture had the largest microemulsion region (48.93%) in the pseudo-ternary phase diagram. Microemulsions containing 1% MSKE demonstrated good physicochemical stability during a six-month study period at 25 ± 2 °C/60% ± 5% RH. The ex vivo skin permeation study demonstrated that the microemulsions exhibited a potent skin enhancement effect allowing MSKE to penetrate skin layers up to 60-fold higher compared with the control. Neither skin irritation nor skin corrosion was observed in ex vivo studies. The present study revealed that IPM-based microemulsion systems may be promising carriers to enhance skin penetration and delivering MSKE for topical treatment.

  6. Sensing properties of monolayer borophane nanosheet towards alcohol vapors: A first-principles study.

    PubMed

    Nagarajan, V; Chandiramouli, R

    2017-05-01

    The electronic properties of borophane nanosheet and adsorption behavior of three distinct alcohol vapors namely methanol, ethanol and 1-propanol on borophane nanosheet is studied using density functional theory method for the first time. The state-of-the-art provides insights on to the development of new two dimensional materials with the surface passivation on boron nanostructures. The density of states spectrum provides a clear perception on charge transfer upon adsorption of alcohol vapors on borophane nanosheets. The monolayer of borophane band gap widens upon adsorption of alcohol vapors, which can be used for the detection for volatile organic vapors. The adsorption properties of alcohol vapors on borophane base material are analyzed in terms of natural bond orbital, average energy gap variation, adsorption energy and energy gap. The most suitable adsorption sites of methanol, ethanol and 1-propanol molecules on borophane nanosheet are investigated in atomistic level. The adsorption of alcohol molecules on borophane nanosheet is found to be more favorable. The findings suggest that the monolayer borophane nanosheet can be utilized to detect the presence of alcohol vapors in the atmosphere.

  7. Evolution of volatile compounds in gluten-free bread: From dough to crumb.

    PubMed

    Pico, Joana; Martínez, Mario M; Bernal, José; Gómez, Manuel

    2017-07-15

    Understanding the evolution of volatile compounds from dough to crumb is necessary in order to improve the weak aroma of gluten-free breads. Additionally, sensitive analytical methods are required to detect small changes. In the present study, a solvent extraction method combined with GC/MS was selected to examine the evolution of 31 principal volatile compounds from the beginning of fermentation to the end of baking in maize starch bread. During fermentation, only hexanal, hexanoic acid, benzaldehyde, benzyl alcohol, furfural and furfuryl alcohol remained constant whereas the rest became more abundant. After baking, 2,3-butanedione, 1-propanol, 2-methyl-1-propanol, 3/2-methyl-1-butanol and ethyl octanoate were evaporated whereas the other volatile compounds increased. The alcohols from fermentation, 2,3-butanedione, acetoin, acetic acid, isobutyric acid and ethyl octanoate, were the main volatile compounds in dough; all of them were formed during fermentation. In crumb, alongside those compounds, hexanal, 1-octen-3-ol and nonanal, produced from lipid oxidation, were also important contributors.

  8. Efficient yet accurate approximations for ab initio calculations of alcohol cluster thermochemistry.

    PubMed

    Umer, Muhammad; Kopp, Wassja A; Leonhard, Kai

    2015-12-07

    We have calculated the binding enthalpies and entropies of gas phase alcohol clusters from ethanol to 1-decanol. In addition to the monomers, we have investigated dimers, tetramers, and pentamers. Geometries have been obtained at the B3LYP/TZVP level and single point energy calculations have been performed with the Resolution of the Identity-MP2 (RIMP2) method and basis set limit extrapolation using aug-cc-pVTZ and aug-cc-pVQZ basis sets. Thermochemistry is calculated with decoupled hindered rotor treatment for large amplitude motions. The results show three points: First, it is more accurate to transfer the rigid-rotor harmonic oscillator entropies from propanol to longer alcohols than to compute them with an ultra-fine grid and tight geometry convergence criteria. Second, the computational effort can be reduced considerably by using dimerization energies of longer alcohols at density functional theory (B3LYP) level plus a RIMP2 correction obtained from 1-propanol. This approximation yields results almost with the same accuracy as RIMP2 - both methods differ for 1-decanol only 0.4 kJ/mol. Third, the entropy of dimerization including the hindered rotation contribution is converged at 1-propanol with respect to chain length. This allows for a transfer of hindered rotation contributions from smaller alcohols to longer ones which reduces the required computational and man power considerably.

  9. Determination of coenzyme Q10, alpha-tocopherol and cholesterol in biological samples by coupled-column liquid chromatography with coulometric and ultraviolet detection.

    PubMed

    Edlund, P O

    1988-03-04

    Coenzyme (Co) Q10, Co Q10H2, alpha-tocopherol and cholesterol were dissociated from lipoproteins in plasma by treatment with 1-propanol. The supernatant obtained was injected directly for determination of Co Q10 and Co Q10H2. Precolumn reduction with borohydride was used for determination of total Co Q10 simultaneously with alpha-tocopherol and cholesterol. Total Co Q10 in freeze-dried myocardial biopsies was determined after extraction with 1-propanol and oxidation of Co Q10H2 with ferric chloride. The chromatographic system comprised two reversed-phase columns and a three-electrode coulometric detector and a UV detector coupled in series. A pre-fractionation on the first column protected the coulometric detector from contamination and reduced the time for analysis by eliminating strongly retained solutes. The coulometric electrodes were operated in the oxidation-reduction-oxidation mode, and the last electrode was used for detection of alpha-tocopherol, Co Q10 and Co Q10H2, while cholesterol was detected by UV at 215 nm. The fast isolation procedure made it possible to determine the reduced and oxidized forms of Co Q10 in plasma. Quantitative recoveries were obtained for all the analytes studied and normal levels were determined with a coefficient of variation of 2-3%.

  10. Mechanistic insights into aqueous phase propanol dehydration in H-ZSM-5 zeolite

    SciTech Connect

    Mei, Donghai; Lercher, Johannes A.

    2016-10-06

    Aqueous phase dehydration of 1-propanol over H-ZSM-5 zeolite was investigated using density functional theory (DFT) calculations. The water molecules in the zeolite pores prefer to aggregate via the hydrogen bonding network and be protonated at the Brønsted acidic sites (BAS). Two typical configurations, i.e., dispersed and clustered, of water molecules were identified by ab initio molecular dynamics simulation of the mimicking aqueous phase H-ZSM-5 zeolite unit cell with 20 water molecules per unit cell. DFT calculated Gibbs free energies suggest that the dimeric propanol-propanol, the propanol-water complex, and the trimeric propanol-propanol-water are formed at high propanol concentrations, which provide a kinetically feasible dehydration reaction channel of 1-propanol to propene. However, calculation results also indicate that the propanol dehydration via the unimolecular mechanism becomes kinetically discouraged due to the enhanced stability of the protonated dimeric propanol and the protonated water cluster acting as the BAS site for alcohol dehydration reaction. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

  11. Fluorescence and CD spectroscopic analysis of the alpha-chymotrypsin stabilization by the ionic liquid, 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide.

    PubMed

    De Diego, Teresa; Lozano, Pedro; Gmouh, Said; Vaultier, Michel; Iborra, José L

    2004-12-30

    The stability of alpha-chymotrypsin in the ionic liquid, 1-ethyl-3-methyl-imidizolium bis[(trifluoromethyl)sulfonyl]amide ([emim][NTf2]), was studied at 30 and 50 degrees C and compared with the stability in other liquid media, such as water, 3 M sorbitol, and 1-propanol. The kinetic analysis of the enzyme stability pointed to the clear denaturative effect of 1-propanol, while both 3M sorbitol and [emim][NTf2] displayed a strong stabilizing power. For the first time, it is shown that enzyme stabilization by ionic liquids seems to be related to the associated structural changes of the protein that can be observed by differential scanning calorimetry (DSC) and fluorescence and circular dichroism (CD). The [emim][NTf2] enhanced both the melting temperature and heat capacity of the enzyme compared to the other media assayed. The fluorescence spectra clearly showed the ability of [emim][NTf2] to compact the native structural conformation of alpha-chymotrypsin, preventing the usual thermal unfolding which occurs in other media. Changes in the secondary structure of this beta/beta protein, as quantified by the CD spectra, pointed to the great enhancement (up 40% with respect to that in water) of beta-strands in the presence of the ionic liquid, which reflects its stabilization power.

  12. Combination effects of nitrocompounds, pyromellitic diimide, and 2-bromoethanesulfonate on in vitro ruminal methane production and fermentation of a grain-rich feed.

    PubMed

    Zhang, Dan-Feng; Yang, Hong-Jian

    2012-01-11

    An L(16) (4(5)) orthogonal experimental design was used to evaluate combination effects of nitroethane (0-15 mM), 2-nitroethanol (0-15 mM), 2-nitro-1-propanol (0-15 mM), pyromellitic diimide (0-0.07 mM), and 2-bromoethanesulfonate (0-0.05 mM) on in vitro ruminal fermentation of a grain-rich feed. In vitro dry matter disappearance was adversely affected by these inhibitors, while cumulative gas production was not affected. Volatile fatty acid production was increased by nitroethane and 2-bromoethanesulfonate in a dose-dependent manner and was decreased by 2-nitroethanol and pyromellitic diimide. All inhibitor treatments increased the molar acetate proportion, while decreasing proportions of propionate and butyrate; hydrogen recovery was decreased by 36.9-45.2%; and methane production was reduced by 95.2-99.2%. The methanogenesis inhibition ranked: nitroethane > 2-nitroethanol > 2-nitro-1-propanol > 2-bromoethanesulfonate > pyromellitic diimide; combined concentrations of 5, 5, 5, 0.02, and 0.03 mM, respectively, gave the optimal inhibiting efficiency. These results may provide a reference to develop effective mitigation of methane emission from ruminants.

  13. Electron beam induced synthesis of uranium dioxide nanoparticles: Effect of solvent composition

    NASA Astrophysics Data System (ADS)

    Rath, M. C.; Keny, S. J.; Naik, D. B.

    2016-09-01

    The effect of various compositions of solvents was investigated on the electron beam induced synthesis of uranium dioxide, UO2 nanoparticles. The synthesis was carried out at different pHs from 2 to 7 in the aqueous solutions containing 10 mM uranyl nitrate and 10% 2-propanol. The formation of UO2 nanoparticles was found to occur only in the pH range from 2.5 to 3.7. Experiments were also carried out in the aqueous solutions containing various other alcohols (10% v/v) such as methanol, ethanol, 1-propanol, 1-butanol or tert-butanol as well as in solutions containing 10 mM sodium formate at pH 3.4. The formation of UO2 nanoparticles in the aqueous solutions was found to occur only in the presence of ethanol, 1-propanol, 2-propanol or 1-butanol. It is therefore confirmed that the electron beam induced synthesis of UO2 nanoparticles strongly depends on the solvent compositions as well as the pH of the medium.

  14. Electrochemical properties of poly(3,4-ethylenedioxythiophene) nanofiber non-woven web formed by electrospinning.

    PubMed

    Nguyen, Hoang Dung; Ko, Jung Min; Kim, Hong Jung; Kim, Seok Ki; Cho, Seung Hyun; Nam, Jae Do; Lee, Jun Young

    2008-09-01

    Electrically conducting nano (micro) poly(3,4-ethylenedioxythiophene) (PEDOT) fiber non-woven web was fabricated using the electrospinning technique by applying high voltage of 10 to 30 kV to the electrospinning solution. To investigate the effects of various conditions on formation and properties of PEDOT fiber non-woven web, we changed the solvent or other components and their concentrations. We used 1-propanol or 1-butanol as a solvent and poly(vinyl pyrrolidone) (PVP) as a matrix polymer to prepare the electrospinning solution. The electrical conductivity of the electro-spun PEDOT non-woven web was as high as 7.5 S/cm when 1-propanol was used as the solvent. Electrochemical capacitor was assembled using one pair of the PEDOT non-woven webs as the electrodes by a simple stack method, where metal plates were used as current collectors. We observed the electrochemical charge and discharge behavior of the capacitor, confirming that the PEDOT non-woven web can be used as the electrode for flexible electrochemical capacitor.

  15. 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.

  16. Multi-walled carbon nanotubes covalently bonded cellulose composite for chemical vapor sensor

    NASA Astrophysics Data System (ADS)

    Yun, Sungryul; Yang, Sang Yeol; Kim, Jaehwan

    2010-04-01

    A cellulose solution was prepared by dissolving cotton pulp in LiCl/ N,N-Dimethylacetamide (DMAc) solution, and functionalized multi-walled carbon nanotubes (MWCNTs) were reacted with N, N-Carbonyldiimidazoles to obtain MWCNTs-imidazolides. By acylation of cellulose with MWCNTs-imidazolides, MWCNTs were covalently bonded with cellulose chains. Using the product, MWCNTs covalently bonded cellulose composite (M/C) composite was fabricated with mechanical stretching to align MWCNTs with cellulose. Finally, inter-digital comb electrode was formed on the composite via lift-off process. Chemo-electrical properties of the M/C composite in response of absorption of the volatile vapors corresponding to 1-propanol, 1-butanol, methanol and ethanol were investigated. Due to sensitive and reversible expansion/contraction of the M/C composite matrix in response to absorption of each analyte, the M/C composite showed fast and reversible change in chemo-electrical property. The ranking of relative resistance response of the composite was methanol < ethanol < 1-propanol < 1-butanol.

  17. 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.

  18. 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.

  19. Biodegradation of VOCs from printing press air by an on-site pilot plant bioscrubber and laboratory scale continuous yeast cultures.

    PubMed

    Granström, Tom; Lindberg, Pia; Nummela, Jyri; Jokela, Jouni; Leisola, Matti

    2002-01-01

    The volatile organic compound composition (VOCs) of printing press air was found to contain mostly ethanol, but also ethyl acetate, 1-propanol, 2-propanol, 1-methoxy-2-propanol and 3-ethoxy-1-propanol. A pilot plant bioscrubber inoculated with a mixed microbial population was constructed on-site. The bioscrubber was able to treat the polluted gas efficiently. It, however, suffered from strong wall growth and blockages in the column. The efficiencies of the pilot plant and a bioreactor is compared. The yeasts Candida guilliermondii and Saccharomyces cerevisiae known to tolerate ethanol were selected instead of mixed population to avoid the wall growth a nd blockages inthe bioreactor. The removal of the VOCs both individually and as a complex mixture was tested in a microcultivation system and in continuous chemostat cultures with and without cell recycling. The Candida yeast could use all the compounds as a carbon source while growth of S. cerevisiae was markedly slower on the methoxylated and ethoxylated propanols. Best total removal of the VOCs was 99% and achieved by C. guilliermondii. The only compound that was not totally removable in the chemostat experiment with C. guilliermondii was 1-methoxy-2-propanol. In laboratory scale the total and volumetric removal of VOCs by C. guilliermondii was more efficient compared to the pilot plant encouraging to scale up and applying the yeast bioreactor to real field conditions.

  20. 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.

  1. Phase equilibrium measurements on twelve binary mixtures

    SciTech Connect

    Giles, N.F.; Wilson, H.L.; Wilding, W.V.

    1996-11-01

    Phase equilibrium measurements have been performed on twelve binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following binary systems at two temperatures each: ethanethiol + propylene; nitrobenzene + methanol; pyridine + ethyl acetate; octane + tert-amyl methyl ether; diisopropyl ether + butane; 1,3-dichloro-2-propanol + epichlorohydrin; 2,3-dichloro-1-propanol + epichlorohydrin; 2,3-epoxy-1-propanol + epichlorohydrin; 3-chloro-1,2-propanediol + epichlorohydrin; methanol + hydrogen cyanide. For these systems, equilibrium vapor and liquid phase compositions were derived from the PTx data using the Soave equation of state to represent the vapor phase and the Wilson, NRTL, or Redlich-Kister activity coefficient model to represent the liquid phase. The infinite dilution activity coefficient of methylamine in N-methyl-2-pyrrolidone was determined at three temperatures by performing PTx measurements on the N-methyl-2-pyrrolidone was determined at three temperatures by performing PTx measurements on the N-methyl-2-pyrrolidone-rich half of the binary. Liquid-liquid equilibrium studies were made on the triethylene glycol + 1-pentene system at two temperatures by directly analyzing samples taken from each liquid phase.

  2. Asymmetric criticality of binary ionic solutions containing 1-butyl-3-methylimidazolium tetrafluoroborate and alcohol.

    PubMed

    Yin, Tianxiang; Xu, Chen; Lv, Hekun; Liu, Shixia; Wang, Mingjie; Chen, Zhiyun; Shen, Weiguo

    2014-09-07

    The liquid-liquid coexistence curves for binary solutions {1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) + 1-propanol} and {1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) + 2-propanol} have been precisely measured. The values of the critical exponents β obtained from the liquid-liquid equilibrium data in the critical region confirmed the 3D-Ising universality. The isobaric heat capacities per unit volume were measured for {[C4mim][BF4] + 1-propanol (or 2-propanol, 1,3-propanediol, 1,4-butanediol)} in both critical and non-critical regions. The experimental results indicate a major solvophobic contribution to the criticality for the studied ionic solutions. The complete scaling theory was applied to well represent the asymmetric behavior of the diameter of the coexistence curves with the consideration of the heat capacity contribution. It was found that the contribution of the heat capacity related term in the ionic solution decreased with the increase of the permittivity of alcohol and was more important in the description of the asymmetry of the coexistence curve of the ionic solutions than that of the molecular solutions.

  3. Efficient yet accurate approximations for ab initio calculations of alcohol cluster thermochemistry

    NASA Astrophysics Data System (ADS)

    Umer, Muhammad; Kopp, Wassja A.; Leonhard, Kai

    2015-12-01

    We have calculated the binding enthalpies and entropies of gas phase alcohol clusters from ethanol to 1-decanol. In addition to the monomers, we have investigated dimers, tetramers, and pentamers. Geometries have been obtained at the B3LYP/TZVP level and single point energy calculations have been performed with the Resolution of the Identity-MP2 (RIMP2) method and basis set limit extrapolation using aug-cc-pVTZ and aug-cc-pVQZ basis sets. Thermochemistry is calculated with decoupled hindered rotor treatment for large amplitude motions. The results show three points: First, it is more accurate to transfer the rigid-rotor harmonic oscillator entropies from propanol to longer alcohols than to compute them with an ultra-fine grid and tight geometry convergence criteria. Second, the computational effort can be reduced considerably by using dimerization energies of longer alcohols at density functional theory (B3LYP) level plus a RIMP2 correction obtained from 1-propanol. This approximation yields results almost with the same accuracy as RIMP2 — both methods differ for 1-decanol only 0.4 kJ/mol. Third, the entropy of dimerization including the hindered rotation contribution is converged at 1-propanol with respect to chain length. This allows for a transfer of hindered rotation contributions from smaller alcohols to longer ones which reduces the required computational and man power considerably.

  4. Oxygen reduction reaction on highly-durable Pt/nanographene fuel cell catalyst synthesized employing in-liquid plasma

    NASA Astrophysics Data System (ADS)

    Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Kano, Hiroyuki; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

    2016-09-01

    We recently have established ultrahigh-speed synthesis method of nanographene materials employing in-liquid plasma, and reported high durability of Pt/nanographene composites as a fuel cell catalyst. Crystallinity and domain size of nanographene materials were essential to their durability. However, their mechanism is not clarified yet. In this study, we investigated the oxygen reduction reaction using three-types of nanographene materials with different crystallinity and domain sizes, which were synthesized using ethanol, 1-propanol and 1-butanol, respectively. According to our previous studies, the nanographene material synthesized using the lower molecular weight alcohol has the higher crystallinity and larger domain size. Pt nanoparticles were supported on the nanographene surfaces by reducing 8 wt% H2PtCl6 diluted with H2O. Oxygen reduction current densities at a potential of 0.2 V vs. RHE were 5.43, 5.19 and 3.69 mA/cm2 for the samples synthesized using ethanol, 1-propanol and 1-butanol, respectively. This means that the higher crystallinity nanographene showed the larger oxygen reduction current density. The controls of crystallinity and domain size of nanographene materials are essential to not only their durability but also highly efficiency as catalyst electrodes.

  5. Investigation of chemical modifiers for the direct determination of arsenic in fish oil using high-resolution continuum source graphite furnace atomic absorption spectrometry.

    PubMed

    Pereira, Éderson R; de Almeida, Tarcísio S; Borges, Daniel L G; Carasek, Eduardo; Welz, Bernhard; Feldmann, Jörg; Campo Menoyo, Javier Del

    2016-04-01

    High-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) has been applied for the development of a method for the determination of total As in fish oil samples using direct analysis. The method does not use any sample pretreatment, besides dilution with 1-propanole, in order to decrease the oil viscosity. The stability and sensitivity of As were evaluated using ruthenium and iridium as permanent chemical modifiers and palladium added in solution over the sample. The best results were obtained with ruthenium as the permanent modifier and palladium in solution added to samples and standard solutions. Under these conditions, aqueous standard solutions could be used for calibration for the fish oil samples diluted with 1-propanole. The pyrolysis and atomization temperatures were 1400 °C and 2300 °C, respectively, and the limit of detection and characteristic mass were 30 pg and 43 pg, respectively. Accuracy and precision of the method have been evaluated using microwave-assisted acid digestion of the samples with subsequent determination by HR-CS GF AAS and ICP-MS; the results were in agreement (95% confidence level) with those of the proposed method.

  6. Single-walled carbon nanotube-based polymer monoliths for the enantioselective nano-liquid chromatographic separation of racemic pharmaceuticals.

    PubMed

    Ahmed, Marwa; Yajadda, Mir Massoud Aghili; Han, Zhao Jun; Su, Dawei; Wang, Guoxiu; Ostrikov, Kostya Ken; Ghanem, Ashraf

    2014-09-19

    Single-walled carbon nanotubes were encapsulated into different polymer-based monolithic backbones. The polymer monoliths were prepared via the copolymerization of 20% monomers, glycidyl methacrylate, 20% ethylene glycol dimethacrylate and 60% porogens (36% 1-propanol, 18% 1,4-butanediol) or 16.4% monomers (16% butyl methacrylate, 0.4% sulfopropyl methacrylate), 23.6% ethylene glycol dimethacrylate and 60% porogens (36% 1-propanol, 18% 1,4-butanediol) along with 6% single-walled carbon nanotubes aqueous suspension. The effect of single-walled carbon nanotubes on the chiral separation of twelve classes of pharmaceutical racemates namely; α- and β-blockers, antiinflammatory drugs, antifungal drugs, dopamine antagonists, norepinephrine-dopamine reuptake inhibitors, catecholamines, sedative hypnotics, diuretics, antihistaminics, anticancer drugs and antiarrhythmic drugs was investigated. The enantioselective separation was carried out under multimodal elution to explore the chiral recognition capabilities of single-walled carbon nanotubes using reversed phase, polar organic and normal phase chromatographic conditions using nano-liquid chromatography. Baseline separation was achieved for celiprolol, chlorpheniramine, etozoline, nomifensine and sulconazole under multimodal elution conditions. Satisfactory repeatability was achieved through run-to-run, column-to-column and batch-to-batch investigations. Our findings demonstrate that single-walled carbon nanotubes represent a promising stationary phase for the chiral separation and may open the field for a new class of chiral selectors.

  7. Structure and thermodynamics of core-softened models for alcohols.

    PubMed

    Munaò, Gianmarco; Urbic, Tomaz

    2015-06-07

    The phase behavior and the fluid structure of coarse-grain models for alcohols are studied by means of reference interaction site model (RISM) theory and Monte Carlo simulations. Specifically, we model ethanol and 1-propanol as linear rigid chains constituted by three (trimers) and four (tetramers) partially fused spheres, respectively. Thermodynamic properties of these models are examined in the RISM context, by employing closed formulæ for the calculation of free energy and pressure. Gas-liquid coexistence curves for trimers and tetramers are reported and compared with already existing data for a dimer model of methanol. Critical temperatures slightly increase with the number of CH2 groups in the chain, while critical pressures and densities decrease. Such a behavior qualitatively reproduces the trend observed in experiments on methanol, ethanol, and 1-propanol and suggests that our coarse-grain models, despite their simplicity, can reproduce the essential features of the phase behavior of such alcohols. The fluid structure of these models is investigated by computing radial distribution function gij(r) and static structure factor Sij(k); the latter shows the presence of a low-k peak at intermediate-high packing fractions and low temperatures, suggesting the presence of aggregates for both trimers and tetramers.

  8. 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.

  9. Effects of alcohols on the stability and low-frequency local motions that control the slow changes in structural dynamics of ferrocytochrome c.

    PubMed

    Jain, Rishu; Sharma, Deepak; Kumar, Rajesh

    2013-10-01

    To determine the effects of alcohols on the low-frequency local motions that control slow changes in structural dynamics of native-like compact states of proteins, we have studied the effects of alcohols on structural fluctuation of M80-containing Ω-loop by measuring the rate of thermally driven CO dissociation from a natively folded carbonmonoxycytochrome c under varying concentrations of alcohols (methanol, ethanol, 1-propanol, 2-propanol, 3°-butanol, 2,2,2-trifluoroethanol). As alcohol is increased, the rate coefficient of CO dissociation (k(diss)) first decreases in subdenaturing region and then increases on going from subdenaturing to denaturing milieu. This decrease in k(diss) is more for 2,2,2-trifluroethanol and 1-propanol and least for methanol, indicating that the first phase of motional constraint is due to the hydrophobicity of alcohols and intramolecular protein cross-linking effect of alcohols, which results in conformational entropy loss of protein. The thermal denaturation midpoint for ferrocytochrome c decreases with increase in alcohol, indicating that alcohol decrease the global stability of protein. The stabilization free energy (ΔΔG) in alcohols' solution was calculated from the slope of the Wyman-Tanford plot and water activity. The m-values obtained from the slope of ΔΔG versus alcohols plot were found to be more negative for longer and linear chain alcohols, indicating destabilization of proteins by alcohols through disturbance of hydrophobic interactions and hydrogen bonding.

  10. Solvent and temperature effects on ion association and mobility of 2,6-lutidinium chloride in non-aqueous solvents

    NASA Astrophysics Data System (ADS)

    Moreira, L.; Leitäo, R. E.; Martins, F.

    Molar conductivity values (Λm) of 2,6-lutidinium chloride at ten different concentrations ranging from 0.001 to 0.01 mol dm-3, in several solvents and temperatures are reported for: seven solvents (dimethyl sulphoxide, acetonitrile, propylene carbonate, N,N-dimethylacetamide, ethanol, 1-propanol and 1-butanol) at five different temperatures (60.00, 65.00, 70.00, 75.00 and 80.00°C) and three additional solvents (nitromethane, 2-methyl-1-propanol and 2-ethoxyethanol) at 60.00°C. Molar conductivities at infinite dilution ( ), association constants (KA) and respective errors are also determined. The temperature dependence of ILM0002 and KA shows positive, negative and negligible trends. ILM0003 versus viscosity plots reveal a breakdown of Walden's rule. KA is markedly dependent on the solvent's features, revealing strong deviations from the predictions of classical dielectric theories. It is reasoned that specific ion-solvent-solvent interactions may play an important role.

  11. Effects of nitrate or nitro supplementation, with or without added chlorate, on Salmonella enterica serovar Typhimurium and Escherichia coli in swine feces.

    PubMed

    Anderson, Robin C; Jung, Yong S; Oliver, Christy E; Horrocks, Shane M; Genovese, Kenneth J; Harvey, Roger B; Callaway, Todd R; Edrington, Thomas S; Nisbet, David J

    2007-02-01

    The effects of coincubating the active agent of an experimental chlorate product with nitrate or select nitro compounds, possible inducers and competing substrates for the targeted respiratory nitrate reductase, on concentrations of experimentally inoculated Salmonella enterica serovar Typhimurium and indigenous Escherichia coli were determined. Studies were completed in swine fecal suspensions as a prelude to the administration of these inhibitors to pigs. Results confirmed the bactericidal effect of chlorate (5 to 10 mM) against these fecal enterobacteria, reducing (P < 0.05) concentrations by > 2 log CFU ml(-1) after 3 to 6 h of incubation. An effect (P < 0.05) of pH was observed, with considerable regrowth of Salmonella and E. coli occurring after 24 h of incubation in suspensions buffered to pH 7.1 but not in suspensions buffered to pH 6.5 or 5.6. A 24-h coincubation of fecal suspensions with 5 to 10 mM chlorate and as little as 2.5 mM nitrate or 10 to 20 mM 2-nitro-1-propanol, 2-nitroethanol, and, sometimes, nitroethane decreased (P < 0.05) Salmonella but not necessarily E. coli concentrations. 2-Nitro-1-propanol and 2-nitroethanol exhibited inhibitory activity against Salmonella and E. coli by an undetermined mechanism, even in the absence of added chlorate.

  12. Switchable polarity solvent (SPS) systems: probing solvatoswitching with a spiropyran (SP)-merocyanine (MC) photoswitch.

    PubMed

    Boyd, Alaina R; Jessop, Philip G; Dust, Julian M; Buncel, Erwin

    2013-09-28

    The switchable polarity solvent (SPS) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and an alcohol (e.g. 1-propanol) reversibly switches to a higher polarity ionic liquid, [DBUH(+)][RCO3(-)], when treated with CO2. A long-lived species with unique properties was detected in an investigation into the use of SPS to control the lifetime of the merocyanine (MC) form in a spiropyran (SP)-MC molecular photoswitch. Irradiation of SP in 1-propanol (PrOH) in the presence of DBU generates a new species (λmax = 420 nm). This species converts to MC upon bubbling with CO2, which produces [DBUH(+)][PrOCOO(-)]. It is proposed that a mixture of 1,2 and 1,4 alkoxide addition products form as a result of nucleophilic attack on the conjugated diene system of MC, where alkoxide formation arises from equilibration of highly basic DBU and the alcohol. These adducts revert to MC upon application of CO2 or addition of acid. Determination of the overall equilibrium constant for alkoxide adduct formation involving DBU was afforded through Benesi-Hildebrand analysis.

  13. Biodegradation of bisphenol A and other bisphenols by a gram-negative aerobic bacterium

    SciTech Connect

    Lobos, J.H.; Leib, T.K. ); Tahmun Su )

    1992-06-01

    A novel bacterium designated strain MV1 was isolated from a sludge enrichmet takes from the wastewater treatment plant at a plastics manufacturing facility and shown to degrade 2,2-bis(4-hydroxyphenyl)propane (4,4[prime]-isopropylidenediphenol or bisphenol A). Strain MV1 is a gram-negative, aerobic bacillus that grows on bisphenol A as a sole source of carbon and energy. Total carbon analysis for bisphenol A degradation demonstrated that 60% of the carbon was mineralized to CO[sub 2], 20% was associated with the bacterial cells, and 20% was converted to soluble organic compounds. Metabolic intermediates detected in the culture medium during growth on bisphenol A were identified as 4-hydroxybenzoic acid, 4-hydroxyacetophenone, 2,2-bis(4-hydroxyphenyl)-1-propanol, and 2,3-bis(4-hydroxyphenyl)-1,2-propanediol. Most of the bisphenol A degraded by strain MV1 is cleaved in some way to form 4-hydroxybenzoic acid and 4-hydroxyacetophenone, which are subsequently mineralized or assimilated into cell carbon. In addition, about 20% of the bisphenol A is hydroxylated to form 2,2-bis(4-hydroxyphenyl)-1-propanol, which is slowly biotransformed to 2,3-bis(4-hydroxyphenyl)-1,2-propanediol. Cells that were grown on bisphenol A degraded a variety of bisphenol alkanes, hydroxylated benzoic acids, and hydroxylated acetophenones during resting-cell assays. Transmission electron microscopy of cells grown on bisphenol A revealed lipid storage granules and intracytoplasmic membranes.

  14. Gaseous anion chemistry. Hydrogen-deuterium exchange in mono- and dialcohol alkoxide ions: ionization reactions in dialcohols

    SciTech Connect

    Lloyd, J.R.; Agosta, W.C.; Field, F.H.

    1980-08-15

    The subject of this work is H-D exchange in certain gaseous anions using D/sub 2/ as the exchanging agent. The anions involved are produced from ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethanol, 1-propanol, and 1-butanol. Spectra and postulated ionization reactions for these mono- and dialcohols are given. Hydrogen-deuterium exchange occurs in the (M - 1)/sup -/ and (2M - 1)/sup -/ ions of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The amount of exchange occurring is 3-8 times greater in (2M - 1)/sup -/ than in (M - 1)/sup -/. The amount of H-D exchange occurring in ethanol, 1-propanol, and 1-butanol is small or zero in the (2M - 1)/sup -/ ions and in the (M - 1)/sup -/ ion for 1-butanol (the only (M - 1)/sup -/ ion which could be examined experimentally). The amount of exchange occurring in the (2M - 1)/sup -/ and (M - 1)/sup -/ ions from ethylene glycol is not affected by the total pressure or composition of the reaction mixture in the ionization chamber of the mass spectrometer. A novel hydrogen-bridging mechanism is suggested to account for the observed exchange occurring in the dialcohols.

  15. 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.

  16. Potassium sorbate reduces production of ethanol and 2 esters in corn silage.

    PubMed

    Hafner, Sasha D; Franco, Roberta B; Kung, Limin; Rotz, C Alan; Mitloehner, Frank

    2014-12-01

    The objective of this work was to evaluate the effects of biological and chemical silage additives on the production of volatile organic compounds (VOC; methanol, ethanol, 1-propanol, methyl acetate, and ethyl acetate) within corn silage. Recent work has shown that silage VOC can contribute to poor air quality and reduce feed intake. Silage additives may reduce VOC production in silage by inhibiting the activity of bacteria or yeasts that produce them. We produced corn silage in 18.9-L bucket silos using the following treatments: (1) control (distilled water); (2) Lactobacillus buchneri 40788, with 400,000 cfu/g of wet forage; (3) Lactobacillus plantarum MTD1, with 100,000 cfu/g; (4) a commercial buffered propionic acid-based preservative (68% propionic acid, containing ammonium and sodium propionate and acetic, benzoic, and sorbic acids) at a concentration of 1 g/kg of wet forage (0.1%); (5) a low dose of potassium sorbate at a concentration of 91 mg/kg of wet forage (0.0091%); (6) a high dose of potassium sorbate at a concentration of 1g/kg of wet forage (0.1%); and (7) a mixture of L. plantarum MTD1 (100,000 cfu/g) and a low dose of potassium sorbate (91 mg/kg). Volatile organic compound concentrations within silage were measured after ensiling and sample storage using a headspace gas chromatography method. The high dose of potassium sorbate was the only treatment that inhibited the production of multiple VOC. Compared with the control response, it reduced ethanol by 58%, ethyl acetate by 46%, and methyl acetate by 24%, but did not clearly affect production of methanol or 1-propanol. The effect of this additive on ethanol production was consistent with results from a small number of earlier studies. A low dose of this additive does not appear to be effective. Although it did reduce methanol production by 24%, it increased ethanol production by more than 2-fold and did not reduce the ethyl acetate concentration. All other treatments increased ethanol production

  17. Effect of immobilization support, water activity, and enzyme ionization state on cutinase activity and enantioselectivity in organic media.

    PubMed

    Vidinha, Pedro; Harper, Neil; Micaelo, Nuno M; Lourenco, Nuno M T; da Silva, Marco D R Gomes; Cabral, Joaquim M S; Afonso, Carlos A M; Soares, Claudio M; Barreiros, Susana

    2004-02-20

    We studied the reaction between vinyl butyrate and 2-phenyl-1-propanol in acetonitrile catalyzed by Fusarium solani pisi cutinase immobilized on zeolites NaA and NaY and on Accurel PA-6. The choice of 2-phenyl-1-propanol was based on modeling studies that suggested moderate cutinase enantioselectivity towards this substrate. With all the supports, initial rates of transesterification were higher at a water activity (a(w)) of 0.2 than at a(w) = 0.7, and the reverse was true for initial rates of hydrolysis. By providing acid-base control in the medium through the use of solid-state buffers that control the parameter pH-pNa, which we monitored using an organo-soluble chromoionophoric indicator, we were able, in some cases, to completely eliminate dissolved butyric acid. However, none of the buffers used were able to improve the rates of transesterification relative to the blanks (no added buffer) when the enzyme was immobilized at an optimum pH of 8.5. When the enzyme was immobilized at pH 5 and exhibited only marginal activity, however, even a relatively acidic buffer with a pK(a) of 4.3 was able to restore catalytic activity to about 20% of that displayed for a pH of immobilization of 8.5, at otherwise identical conditions. As a(w) was increased from 0.2 to 0.7, rates of transesterification first increased slightly and then decreased. Rates of hydrolysis showed a steady increase in that a(w) range, and so did total initial reaction rates. The presence or absence of the buffers did not impact on the competition between transesterification and hydrolysis, regardless of whether the butyric acid formed remained as such in the reaction medium or was eliminated from the microenvironment of the enzyme through conversion into an insoluble salt. Cutinase enantioselectivity towards 2-phenyl-1-propanol was indeed low and was not affected by differences in immobilization support, enzyme protonation state, or a(w).

  18. Odorous gaseous emissions as influence by process condition for the forced aeration composting of pig slaughterhouse sludge

    SciTech Connect

    Blazy, V.; Guardia, A. de; Benoist, J.C; Daumoin, M.; Lemasle, M.; Wolbert, D.; Barrington, S.

    2014-07-15

    Highlights: • The gaseous emissions produced by various composting process conditions were characterized and quantified. • Nine compounds were potentially odorous: TMA, NH{sub 3}, 2-pentanone, 1-propanol-2-methyl, acetophenone and sulphur forms. • The tested composting process conditions reduced odour emissions by a factor of 5–10. • A reduction of 10{sup 5} to 10{sup 6} is required to reach an odour threshold limit at peak event emissions. • Both aeration rate and bulking agent had the most impact on reducing odour emissions. - Abstract: Compost sustainability requires a better control of its gaseous emissions responsible for several impacts including odours. Indeed, composting odours have stopped the operation of many platforms and prevented the installation of others. Accordingly, present technologies collecting and treating gases emitted from composting are not satisfactory and alternative solutions must be found. Thus, the aim of this paper was to study the influence of composting process conditions on gaseous emissions. Pig slaughterhouse sludge mixed with wood chips was composted under forced aeration in 300 L laboratory reactors. The process conditions studied were: aeration rate of 1.68, 4.03, 6.22, 9.80 and 13.44 L/h/kg of wet sludge; incorporation ratio of 0.55, 0.83 and 1.1 (kg of wet wood chips/kg of wet sludge), and; bulking agent particles size of <10, 10 < 20 and 20 < 30 mm. Out-going gases were sampled every 2 days and their composition was analysed using gas chromatography coupled with mass spectrometry (GC–MS). Fifty-nine compounds were identified and quantified. Dividing the cumulated mass production over 30 days of composting, by odour threshold, 9 compounds were identified as main potential odour contributors: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone, 1-propanol-2-methyl, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide and acetophenone. Five gaseous compounds were correlated with both aeration rate and

  19. Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

    PubMed

    Sadeghi, Rahmat; Ebrahimi, Nosaibah

    2011-11-17

    A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are

  20. Efficacy of hand disinfectants against vancomycin-resistant enterococci in vitro.

    PubMed

    Kampf, G; Höfer, M; Wendt, C

    1999-06-01

    Vancomycin-resistant enterococci (VRE) may be spread within a hospital via the contaminated hands of the healthcare worker. Effective hand disinfectants are necessary to break chains of transmission. We determined the bactericidal activity of 1-propanol, chlorhexidine digluconate (0.5 and 4%). Sterillium (45% 2-propanol, 30% 1-propanol and 0.2% mecetronium etilsulphate), Skinsept F (70% 2-propanol, 0.5% chlorhexidine digluconate and 0.45% hydrogen peroxide) and Hibisol (70% 2-propanol and 0.5% chlorhexidine gluconate) against 11 clonally distinct enterococcal isolates in a quantitative suspension test. Four isolates were vancomycin susceptible, four were vanA and the remainder vanB positive. Eight isolates were identified as Enterococcus faecium, two as Enterococcus faecalis and one as Enterococcus gallinarum. The investigator was blinded to the species and the genotype. Four parallel experiments were carried out for each isolate, each preparation, each dilution and each reaction time. 1-Propanol (60%), Sterillium, Skinsept F and Hibisol were all highly bactericidal after 15 and 30 s against VRE and vancomycin-susceptible enterococci (VSE) with reduction factors (RF) > 6.4, even in dilution of 50% (v/v). No significant difference was observed between vanA isolates, vanB isolates and VSE. Chlorhexidine digluconate (0.5% and 4%) was found to be less bactericidal after 30, 60 and 300 sec (RF < or = 2.5). The vanB genotype isolates were found to be significantly more susceptible to chlorhexidine (0.5%) than the vanA isolates (60 sec; one-way ANOVA model; P = 0.05). After 300 sec the vanB genotype isolates were found to be significantly more susceptible to chlorhexidine (0.5%) than the other two genotype isolates (P = 0.016). The vanA isolates were found to be significantly more susceptible to chlorhexidine (4%) than the vanB isolates (300 s; P = 0.024). E. faecium was found to be less susceptible to chlorhexidine than E. faecalis at all concentrations and reaction

  1. Use of a flor velum yeast for modulating colour, ethanol and major aroma compound contents in red wine.

    PubMed

    Moreno, Juan; Moreno-García, Jaime; López-Muñoz, Beatriz; Mauricio, Juan Carlos; García-Martínez, Teresa

    2016-12-15

    The most important and negative effect of the global warming for winemakers in warm and sunny regions is the observed lag between industrial and phenolic grape ripeness, so only it is possible to obtain an acceptable colour when the ethanol content of wine is high. By contrast, the actual market trends are to low ethanol content wines. Flor yeast growing a short time under velum conditions, decreases the ethanol and volatile acidity contents, has a favorable effect on the colour and astringency and significantly changes the wine content in 1-propanol, isobutanol, acetaldehyde, 1,1-diethoxiethane and ethyl lactate. The Principal Component Analysis of six enological parameters or five aroma compounds allows to classify the wines subjected to different velum formation conditions. The obtained results in two tasting sessions suggest that the flor yeast helps to modulate the ethanol, astringency and colour and supports a new biotechnological perspective for red winemakers.

  2. Metabolic Engineering of Microorganisms for the Production of Higher Alcohols

    PubMed Central

    Choi, Yong Jun; Lee, Joungmin; Jang, Yu-Sin

    2014-01-01

    ABSTRACT Due to the increasing concerns about limited fossil resources and environmental problems, there has been much interest in developing biofuels from renewable biomass. Ethanol is currently used as a major biofuel, as it can be easily produced by existing fermentation technology, but it is not the best biofuel due to its low energy density, high vapor pressure, hygroscopy, and incompatibility with current infrastructure. Higher alcohols, including 1-propanol, 1-butanol, isobutanol, 2-methyl-1-butanol, and 3-methyl-1-butanol, which possess fuel properties more similar to those of petroleum-based fuel, have attracted particular interest as alternatives to ethanol. Since microorganisms isolated from nature do not allow production of these alcohols at high enough efficiencies, metabolic engineering has been employed to enhance their production. Here, we review recent advances in metabolic engineering of microorganisms for the production of higher alcohols. PMID:25182323

  3. Prebiotic Oxidative Polymerization of 2,3 Dimercaptopropanol on the Surface of Iron(III) Hydroxide Oxide

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    1994-01-01

    The oxidation of 2,3-Dimercapto-1-propanol by ferric ions on the surface of iron (III) hydroxide oxide yielded polydisulfide polymers. This polymerization occured readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron (III) hydroxide oxide (20 mg, 160 micro mole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the mineral phase. Reactions at higher dithiol concentrations with the same ratio of dithiol to mineral gave a higher yield of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis will be discussed.

  4. Diffusion in mixed solvents. II - The heat of mixing parameter

    NASA Technical Reports Server (NTRS)

    Carapellucci, P. A.

    1975-01-01

    Correlation of second-order rate constants for many reactions involving electron transfer between organic molecules, solvated electron reactions, iodine diffusion coefficients, and triplet state electron transfer reactions has been made with the heat of mixing parameter (HMP) for the aqueous binary solvent systems. The aqueous binary solvents studied are those containing methanol or ethanol (type I solvent); 1-propanol or tert-butyl alcohol (type II solvent); or sucrose or glycerol (type III solvent). A plot of the HMP vs. the diffusion parameter for each reaction yields superimposable curves for these reactions in a particular solvent mixture over the entire solvent mixture range, irrespective of the value of the reaction's rate constant or diffusion coefficient in water.

  5. 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.

  6. Electron emission and fragmentation of molecules in intense laser fields

    NASA Astrophysics Data System (ADS)

    Ueda, K.; Prümper, G.; Hatamoto, T.; Okunishi, M.; Mathur, D.

    2007-06-01

    We have constructed an apparatus for high-resolution electron spectroscopy and electron-ion coincidence experiments on gas-phase molecules in intense laser fields. The apparatus comprises an electron time-of-flight (TOF) spectrometer and an ion TOF spectrometer with a position detector, placed on either side of an effusive molecular beam. The ionizing radiation is either the fundamental (800 nm wavelength) of a Ti:sapphire laser or frequency doubled 400-nm light, with pulse durations of ~ 150 fs and the repetition rate of 1 kHz. We have investigated the electron emission and fragmentation of linear alcohol molecules, methanol, ethanol and 1-propanol, in laser fields with peak intensities up to ~ 1×10 14 W/cm2. Details of our apparatus are described along with an overview of some recent results.

  7. 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.

  8. Removal characteristics of CO2 using aqueous MEA/AMP solutions in the absorption and regeneration process.

    PubMed

    Choi, Won-Joon; Seo, Jong-Beom; Jang, Sang-Yong; Jung, Jong-Hyeon; Oh, Kwang-Joong

    2009-01-01

    The carbon dioxide (CO2) removal efficiency, reaction rate, and CO2 loading into aqueous blended monoethanolamine (MEA) + 2-amino-2-methyl-1-propanol (AMP) solutions to enhance absorption characteristics of MEA and AMP were carried out by the absorption/regeneration process. As a result, compared to aqueous MEA and AMP solutions, aqueous blended MEA + AMP solutions have a higher CO2 loading than MEA and a higher reaction rate than AMP. The CO2 loading of rich amine of aqueous 18 wt.% MEA + 12 wt.% AMP solution was 0.62 mol CO2/mol amine, which is 51.2% more than 30 wt.% MEA (0.41 mol CO2/mol amine). Consequently, blending MEA and AMP could be an effective way to design considering economical efficiency and used to operate absorber for a long time.

  9. Diagnosis by Volatile Organic Compounds in Exhaled Breath from Lung Cancer Patients Using Support Vector Machine Algorithm.

    PubMed

    Sakumura, Yuichi; Koyama, Yutaro; Tokutake, Hiroaki; Hida, Toyoaki; Sato, Kazuo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

    2017-02-04

    Monitoring exhaled breath is a very attractive, noninvasive screening technique for early diagnosis of diseases, especially lung cancer. However, the technique provides insufficient accuracy because the exhaled air has many crucial volatile organic compounds (VOCs) at very low concentrations (ppb level). We analyzed the breath exhaled by lung cancer patients and healthy subjects (controls) using gas chromatography/mass spectrometry (GC/MS), and performed a subsequent statistical analysis to diagnose lung cancer based on the combination of multiple lung cancer-related VOCs. We detected 68 VOCs as marker species using GC/MS analysis. We reduced the number of VOCs and used support vector machine (SVM) algorithm to classify the samples. We observed that a combination of five VOCs (CHN, methanol, CH₃CN, isoprene, 1-propanol) is sufficient for 89.0% screening accuracy, and hence, it can be used for the design and development of a desktop GC-sensor analysis system for lung cancer.

  10. Nonionic gelation agents prepared from hydroxypropyl guar gum.

    PubMed

    Kono, Hiroyuki; Hara, Hideyuki; Hashimoto, Hisaho; Shimizu, Yuuichi

    2015-03-06

    Nonionic gels were prepared from hydroxypropyl guar gum (HPG) with different molar substitution degrees by crosslinking with ethylene glycol diglycidyl ether (EGDE). FTIR and solid-state NMR spectroscopy revealed that the crosslinking degree of HPG gels increased with the amount of EGDE used during the reaction; this result was also confirmed by the water mobility in the swollen gels. Rheological characterization revealed behaviors typical of true gels, and their viscoelastic behaviors strongly depended on the crosslinking degree. The HPG gels absorbed buffers, aqueous saline, and water, and the absorption was not affected by the ionic strength or pH of the solution. In addition, HPG gels with high crosslinking degrees and molar substitution degrees exhibited gelation ability toward protic organic solvents such as methanol, ethanol, and 1-propanol. These HPG gels may find application as gelation agents for many industrial uses.

  11. Experimental Determination of Densities and Isobaric Vapor-Liquid Equilibria of Methyl Acetate and Ethyl Acetate with Alcohols (C3 and C4) at 0.3 MPa

    NASA Astrophysics Data System (ADS)

    Susial, Pedro; Estupiñan, Esteban J.; Castillo, Victor D.; Rodríguez-Henríquez, José J.; Apolinario, José C.

    2013-10-01

    The densities and excess volumes were determined at 298.15 K for the methyl acetate + 1-propanol, methyl acetate + 1-butanol, and ethyl acetate + 1-butanol mixtures. The vapor-liquid equilibria data at 0.3 MPa for these binary systems were obtained using a stainless steel equilibrium still. The activity coefficients were obtained from the experimental data using the Hayden and O’Connell method and the Yen and Woods equation. The binary systems in this study showed positive deviations from ideality. The experimental VLE data were verified with the point-to-point test of van Ness using the Barker routine and the Fredenslund criterion. The different versions of the UNIFAC and the ASOG group contribution models were applied.

  12. Dielectric absorption in mixtures of anisole with some primary alcohols at microwave frequency

    NASA Astrophysics Data System (ADS)

    Chaube, H. A.; Rana, V. A.; Gadani, D. H.

    2011-12-01

    Dielectric properties of binary mixtures of anisole with methanol (MeOH), 1-propanol (1-PrOH), 1-butanol (1-BuOH) and 1-heptanol (1-HeOH) over an entire concentration range have been studied at a fixed temperature 40°C. The dielectric constant (ε‧) and dielectric loss (ε″) of the binary mixtures of polar liquids have been determined at a microwave frequency of 9.1 GHz. The static dielectric permittivity (ε 0) of the liquid samples was also determined using a precision LCR meter. Determined values of static dielectric permittivity (ε 0) and dielectric permittivity (ε*) at 9.1 GHz frequency were used to evaluate relaxation time (τ) and high frequency limit dielectric permittivity (ε ∞). Dielectric parameters were interpreted in terms of molecular interaction between the anisole and alcohol molecules.

  13. PMR-15 polyimide modifications for improved prepreg tack

    NASA Technical Reports Server (NTRS)

    Vannucci, R. D.

    1982-01-01

    The use of mixed solvents and of modified monomeric ester reactants was investigated as a means of improving the tack and drape retention characteristics of PMR-15 polyimide prepreg. Methanol, ethanol, 1-propanol and 1-butanol were used to prepare the esters, prepreg solutions, and T-300 graphite fabric and Celion 6000 unidirectional fiber prepregs. The tack retention characteristics of the T-300 fabric prepreg after exposure to simulated use conditions were determined using a simple lap shear test. Drape was qualitatively assessed by visually monitoring the deformability of the prepreg. Thermo-oxidative stability and mechanical properties retention of the Celion 6000 grahite fiber composites were determined as a function of exposure time in air at 600 F.

  14. 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.

  15. Catalytic activity of carbon nanotubes in the conversion of aliphatic alcohols

    NASA Astrophysics Data System (ADS)

    Zhitnev, Yu. N.; Tveritinova, E. A.; Chernyak, S. A.; Savilov, S. V.; Lunin, V. V.

    2016-06-01

    Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C2-C4 alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified.

  16. Shock Hugoniot equations of state for binary water-alcohol liquid mixtures

    NASA Astrophysics Data System (ADS)

    Moore, David; Bolme, Cynthia; Brown, Kathryn; McGrane, Shawn; Schulze, Peter

    2015-06-01

    Shock Hugoniot data were obtained using laser generated shock and ultrafast dynamic ellipsometry (UDE) methods for several non-ideal water-alcohol liquid mixtures, using methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol (a.k.a., 2-methyl-2-propanol or tert-butanol). The sound speeds of the mixtures were obtained using Brillouin scattering when not available in the literature. The shock and particle velocities obtained from the UDE data were compared to expectations of the universal liquid Hugoniot (ULH) and to literature shock (plate impact) data where available. The shock Hugoniot trends for all these mixtures, represented as deviations from predictions of the ULH, versus fraction of alcohol are quite similar to each other and suggest that complex hydrogen bonding networks in water-alcohol mixtures alter the compressibility of the mixtures. Data and trends will be presented. LA-UR-15-20328.

  17. Controlling surface energy of glass substrates to prepare superhydrophobic and transparent films from silica nanoparticle suspensions.

    PubMed

    Ogihara, Hitoshi; Xie, Jing; Saji, Tetsuo

    2015-01-01

    We fabricated superhydrophobic and transparent silica nanoparticle (SNP) films on glass plates via spray-coating technique. When suspensions containing 1-propanol and hydrophobic SNPs were sprayed over glass plates that were modified with dodecyl groups, superhydrophobic and transparent SNP films were formed on the substrates. Surface energy of the glass plates had a significant role to obtain superhydrophobic and transparent SNP films. SNP films did not show superhydrophobicity when bare glass plates were used as substrates, because water droplets tend to adhere the exposed part of the hydrophilic glass plate. Glass plates having extreme low surface energy were not also suitable because suspension solution was repelled from the substrates, which resulted in forming non-uniform SNP films.

  18. Characterization of volatile components in makgeolli, a traditional Korean rice wine, with or without pasteurization, during storage.

    PubMed

    Park, Hye-Jung; Lee, Sang Mi; Song, Sang Hoon; Kim, Young-Suk

    2013-05-08

    Changes in the volatile components of unpasteurized and pasteurized makgeolli during 30 days of storage were investigated by gas chromatography-mass spectrometry (GC-MS) and GC-olfactometry (GC-O). A total of 11 odor-active compounds such as 3-methyl-1-butanol (isoamyl alcohol), 2-methyl-1-butanol, 2,3-butanediol, butanoic acid, 3-methylbutanoic acid (isovaleric acid), 2-methylbutanoic acid, 3-(methylthio)-1-propanol (methionol), 2-phenylethanol, ethyl decanoate, ethyl dodecanoate, and ethyl tetradecanoate were determined in both the pasteurized and unpasteurized makgeolli during 30 days of storage. Although there were no significant differences in the concentrations of odor-active compounds at the initial storage time, most of odor-active compounds were more significantly increased in unpasteurized makgeolli compared to the pasteurized one during the storage period.

  19. Method for producing high surface area chromia materials for catalysis

    DOEpatents

    Gash, Alexander E.; Satcher, Joe; Tillotson, Thomas; Hrubesh, Lawrence; Simpson, Randall

    2007-05-01

    Nanostructured chromium(III)-oxide-based materials using sol-gel processing and a synthetic route for producing such materials are disclosed herein. Monolithic aerogels and xerogels having surface areas between 150 m.sup.2/g and 520 m.sup.2/g have been produced. The synthetic method employs the use of stable and inexpensive hydrated-chromium(III) inorganic salts and common solvents such as water, ethanol, methanol, 1-propanol, t-butanol, 2-ethoxy ethanol, and ethylene glycol, DMSO, and dimethyl formamide. The synthesis involves the dissolution of the metal salt in a solvent followed by an addition of a proton scavenger, such as an epoxide, which induces gel formation in a timely manner. Both critical point (supercritical extraction) and atmospheric (low temperature evaporation) drying may be employed to produce monolithic aerogels and xerogels, respectively.

  20. Highly sensitive gas chromatographic determination of ethanol in human urine samples.

    PubMed

    Zilly, Michael; Langmann, Peter; Lenker, Ulrike; Satzinger, Verena; Schirmer, Diana; Klinker, Hartwig

    2003-12-25

    In order to evaluate recent alcohol consumption, a very sensitive and specific gas chromatographic method for ethanol determination in human urine samples was developed. The non-invasive method was performed without any pretreatment and carried out on a Stabilwax capillary column, 30 m x 0.53 mm x 1.0 microm film thickness. Helium was used as carrier gas with a constant inlet pressure of 27.72 kPa (0.277 bar) and a flame ionization detector (FID). Quantification was performed with the use of acetonitrile as an internal standard (IS). The calibration curve was linear throughout the concentration range from 0.5 to 500 mg/l. The calculated intra- and inter-day coefficients of variation were below 8%. A clear chromatographic separation of ethanol from methanol, acetone, 1-propanol and 2-propanol was achieved.

  1. Specific solute solvent interactions and dual fluorescence of electron donor substituted bis-pyrazoquinoline in binary mixed solvents

    NASA Astrophysics Data System (ADS)

    Rotkiewicz, Krystyna; Rettig, Wolfgang; Köhler, Gottfried; Rechthaler, Karl; Danel, Andrzej; Grabka, Danuta

    2004-12-01

    Some extended electron donor and acceptor substituted π-electron systems, composed of a dimethyl- or diethylanilino (DMA or DEA, respectively) group as electron donor and bis-pyrazoloquinoline (DPPQ) or bis-pyrazolopyridine (DMPP) derivatives as acceptors, were studied with the aim to elucidate the contributions of various solute interactions with solvent molecules upon intramolecular charge separation. Steady state and time resolved fluorescence studies were performed for DMA-DPPQ, DMA-DMPP and DEA-DMPP in alcohols and their binary mixtures with heptane. The decay kinetics of the fluorescence of DMA-DPPQ was also studied in neat 1-propanol in dependence of the temperature between 170 and 293 K. Several different fluorescent species, which were ascribed to different complexes with alcohol molecules, contribute to the fluorescence of the various compounds in these binary mixtures and account for the complex fluorescence decay. A simplified consecutive model is proposed to explain the decay behaviour of the excited species.

  2. Alcohol vapours sensor based on thin polyaniline salt film and quartz crystal microbalance.

    PubMed

    Ayad, Mohamad M; Torad, Nagy L

    2009-06-15

    A sensor based on the quartz crystal microbalance (QCM) technique was developed for detection of a number of primary aliphatic alcohols such as ethanol, methanol, 1-propanol, and 2-propanol vapours. Detection was based on a sensitive and a thin film of polyaniline, emeraldine salt (ES), coated the QCM electrode. The frequency shifts (Delta f) of the QCM were increased due to the vapour absorption into the ES film. The values of Delta f were found to be linearly correlated with the concentrations of alcohols vapour in mg L(-1). The changes in frequency are due to the hydrophilic character of the ES and the electrostatic interaction as well as the type of the alcohol. The sensor shows a good reproducibility and reversibility. The diffusion and diffusion coefficient (D) of different alcohols vapour were determined. It was found that the sensor follows Fickian kinetics.

  3. A re-appraisal of the concept of ideal mixtures through a computer simulation study of the methanol-ethanol mixtures

    NASA Astrophysics Data System (ADS)

    Požar, Martina; Lovrinčević, Bernarda; Zoranić, Larisa; Mijaković, Marijana; Sokolić, Franjo; Perera, Aurélien

    2016-08-01

    Methanol-ethanol mixtures under ambient conditions of temperature and pressure are studied by computer simulations, with the aim to sort out how the ideality of this type of mixtures differs from that of a textbook example of an ideal mixture. This study reveals two types of ideality, one which is related to simple disorder, such as in benzene-cyclohexane mixtures, and another found in complex disorder mixtures of associated liquids. It underlines the importance of distinguishing between concentration fluctuations, which are shared by both types of systems, and the structural heterogeneity, which characterises the second class of disorder. Methanol-1propanol mixtures are equally studied and show a quasi-ideality with many respect comparable to that of the methanol-ethanol mixtures, hinting at the existence of a super-ideality in neat mono-ol binary mixtures, driven essentially by the strong hydrogen bonding and underlying hydroxyl group clustering.

  4. Enhancement of radiopharmaceutical excretion by chemical interventions

    SciTech Connect

    Oster, Z.H.; Som, P.; Brill, A.B.; Sacker, D.F.; Atkins, H.L.

    1982-01-01

    The goal was to find methods of decreasing the radiation dose after radionuclide studies, by giving a compound that will increase the rate of excretion of the radionuclide. Sprague - 1 Dawley rats were given Tc-99m pertechnetate, Ga-67 citrate or Tl-201 chloride intravenously followed at intervals of 1 to 24 hours by one of the following compounds: desferroxamine (DFO), 2,3-dimercapto-1-propanol (BAL), triethylene tetraamine hexaacetic acid (TETHA), stannous tartarate, bleomycin (BLEO), 2,3-dimercaptosuccinic acid (DMSA), diethylene-triaminepentaacetic acid (DTPA), DTPA+SnCl.2H/sub 2/O, dihydroxybenzoic acid (DHB), and ferric-cyanoferrate (IT)(Prussian blue, PB). All the agents except PB are chelators. Some of these agents enhance excretion through the urinary tract (DFO), while most are excreted through the bile. PB was shown to increase Cs excrection through the G.I. tract. (ACR)

  5. Metabolic engineering of microorganisms for the production of higher alcohols.

    PubMed

    Choi, Yong Jun; Lee, Joungmin; Jang, Yu-Sin; Lee, Sang Yup

    2014-09-02

    Due to the increasing concerns about limited fossil resources and environmental problems, there has been much interest in developing biofuels from renewable biomass. Ethanol is currently used as a major biofuel, as it can be easily produced by existing fermentation technology, but it is not the best biofuel due to its low energy density, high vapor pressure, hygroscopy, and incompatibility with current infrastructure. Higher alcohols, including 1-propanol, 1-butanol, isobutanol, 2-methyl-1-butanol, and 3-methyl-1-butanol, which possess fuel properties more similar to those of petroleum-based fuel, have attracted particular interest as alternatives to ethanol. Since microorganisms isolated from nature do not allow production of these alcohols at high enough efficiencies, metabolic engineering has been employed to enhance their production. Here, we review recent advances in metabolic engineering of microorganisms for the production of higher alcohols.

  6. Photoelectron circular dichroism of isopropanolamine

    NASA Astrophysics Data System (ADS)

    Catone, D.; Turchini, S.; Contini, G.; Prosperi, T.; Stener, M.; Decleva, P.; Zema, N.

    2017-01-01

    Spectroscopies based on circular polarized light are sensitive to the electronic and structural properties of chiral molecules. Photoelectron circular dichroism (PECD) is a powerful technique that combines the chiral sensitivity of the circular polarized light and the electronic information obtained by photoelectron spectroscopy. An experimental and theoretical PECD study of the outer valence and C 1s core states of 1-amino-2-propanol in the gas phase is presented. The experimental dichroic dispersions in the photoelectron kinetic energy are compared with theoretical calculations employing a multicentric basis set of B-spline functions and a Kohn-Sham Hamiltonian. In order to understand analogies and differences in the dichroism of structural isomers bearing the same functional groups, a comparison with previous PECD study of valence band of 2-amino-1-propanol is carried out.

  7. Modification of bactericidal fatty acids by an enzyme of Staphylococcus aureus.

    PubMed

    Mortensen, J E; Shryock, T R; Kapral, F A

    1992-04-01

    Certain strains of Staphylococcus aureus produce an enzyme capable of inactivating the bactericidal fatty acids produced in staphylococcal abscesses by esterification to various alcohols. The enzyme, called FAME (fatty acid modifying enzyme), has a pH optimum between 5.5 and 6.0 and a temperature optimum of about 40 degrees C. Enzyme activity is not affected by edetic acid or by the presence or absence of sodium and potassium ions. Although FAME can utilise methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or cholesterol as substrates, cholesterol appears to be the preferred substrate. FAME esterifies without being an esterase operating in reverse. Strains capable of producing the enzyme can synthesise it in trypticase soy broth and in a chemically defined medium, but not necessarily in equal amounts. FAME production is correlated with the ability of a strain to grow and survive within the tissues.

  8. H-bonded supramolecular assembly via proton transfer: Isolation, X-ray crystallographic characterization and SOD mimic activity of [Cu(dipic)2]2[PA-H]4·5H2O

    NASA Astrophysics Data System (ADS)

    Siddiqi, Zafar A.; Khalid, Mohd; Shahid, M.; Kumar, Sarvendra; Sharma, Prashant K.; Siddique, Armeen; Anjuli

    2013-02-01

    The title proton transfer complex was isolated from the reaction of CuCl2·2H2O with pyridine-2,6-dicarboxylic acid (dipic-H2) in presence of 3-amino-1-propanol (PA) under reflux condition. It was thoroughly characterized by FAB-mass, FT-IR, electronic (ligand field), EPR spectroscopic and X-ray crystallographic techniques. The complex crystallizes in the space group C1c1 of the monoclinic system. The unit cell parameters are, a = 17.247(5), b = 20.058(5) Å, c = 15.320(4) Å and β = 109.235(5)°. Extensive H-bonding between the complex anion [Cu(dipic)2]2- and the surrounding cations [PA-H]+ results in a 3D network, supported with additional π-π interactions of the ligand (dipic)2- neighboring units. The SOD mimic activity of the present complex was also examined using NBT assay.

  9. By-product inhibition effects of ethanolic fermentation by Saccharomyces cerevisiae

    SciTech Connect

    Maiorella, B.; Blanch, H.W.; Wilke, C.R.

    1983-01-01

    Inhibition by secondary fermentation products may limit the ultimate productivity of new glucose to ethanol fermentation processes. New processes are under development whereby ethanol is selectively removed from the fermenting broth to eliminate ethanol inhibition effects. These processes can concentrate minor secondary products to the point where they become toxic to the yeast. Vacuum fermentation selectively concentrates nonvolatile products in the fermentation broth. Membrane fermentation systems may concentrate large molecules which are sterically blocked from membrane transport. Extractive fermentation systems, employing nonpolar solvents, may concentrate small organic acids. By-product production rates and inhibition levels in continuous fermentation with Saccharomyces cerevisiae have been determined for acetaldehyde, glycerol, formic, lactic, and acetic acids, 1-propanol, 2-methyl-1-butanol, and 2,3- butanediol to assess the potential effects of these by-products on new fermentation processes. Mechanisms are proposed for the various inhibition effects observed. (Refs. 15).

  10. By-product inhibition effects on ethanolic fermentation by Saccharomyces cerevisiae

    SciTech Connect

    Mairoella, B.; Blanch, H.W.; Wilke, C.R.

    1983-01-01

    Inhibition by secondary fermentation products may limit the ultimate productivity of new glucose to ethanol fermentation processes. New processes are under development whereby ethanol is selectively removed from the fermenting broth to eliminate ethanol inhibition effects. These processes can concentrate minor secondary products to the point where they become toxic to the yeast. Vacuum fermentation selectively concentrates nonvolatile products in the fermentation broth. Membrane fermentation systems may concentrate large molecules which are sterically blocked from membrane transport. Extractive fermentation systems, employing nonpolar solvents, may concentrate small organic acids. By-product production rates and inhibition levels in continuous fermentation with Saccharomyces cerevisiae have been determined for acetaldehyde, glycerol, formic, lactic, and acetic acids, 1-propanol, 2-methyl-1-butanol, and 2,3-butanediol to assess the potential effects of these by-products on new fermentation processes. Mechanisms are proposed for the various inhibition effects observed.

  11. Analysis of pharmaceutical preparations containing antihistamine drugs by micellar liquid chromatography.

    PubMed

    Martínez-Algaba, C; Bermúdez-Saldaña, J M; Villanueva-Camañas, R M; Sagrado, S; Medina-Hernández, M J

    2006-02-13

    Rapid chromatographic procedures for analytical quality control of pharmaceutical preparations containing antihistamine drugs, alone or together with other kind of compounds are proposed. The method uses C18 stationary phases and micellar mobile phases of cetyltrimethylammonium bromide (CTAB) with either 1-propanol or 1-butanol as organic modifier. The proposed procedures allow the determination of the antihistamines: brompheniramine, chlorcyclizine, chlorpheniramine, diphenhydramine, doxylamine, flunarizine, hydroxyzine, promethazine, terfenadine, tripelennamine and triprolidine, in addition to caffeine, dextromethorphan, guaifenesin, paracetamol and pyridoxine in different pharmaceutical presentations (tablets, capsules, suppositories, syrups and ointments). The methods require minimum handling sample and are rapid (between 3 and 12 min at 1 mLmin(-1) flow rate) and reproducible (R.S.D. values<5%). Limits of detection are lower than 1 microgmL(-1) and the recoveries of the analytes in the pharmaceutical preparations are in the range 100+/-10%.

  12. SO3H-functionalized ionic liquid: efficient catalyst for bagasse liquefaction.

    PubMed

    Long, Jinxing; Guo, Bin; Teng, Junjiang; Yu, Yinghao; Wang, Lefu; Li, Xuehui

    2011-11-01

    Liquefaction is a process for the production of biofuel or value-added biochemicals from non-food biomass. SO(3)H-, COOH-functionalized and HSO(4)-paired imidazolium ionic liquids were shown to be efficient catalysts for bagasse liquefaction in hot compressed water. Using SO(3)H-functionalized ionic liquid, 96.1% of bagasse was liquefied and 50.6% was selectively converted to low-boiling biochemicals at 543 K. The degree of liquefaction and selectivity for low-boiling products increased and the average molecular weight of the tetrahydrofuran soluble products decreased with increasing acidic strength of ionic liquids. Analysis of products and comparative characterization of raw materials and residues suggested that both catalytic liquefaction and hydrolysis processes contribute to the high conversion of bagasse. A possible liquefaction mechanism based on the generation of 3-cyclohexyl-1-propanol, one of the main products, is proposed.

  13. Resolution enhancement for low-temperature scanning microscopy by cryo-immersion.

    PubMed

    Metzger, Michael; Konrad, Alexander; Skandary, Sepideh; Ashraf, Imran; Meixner, Alfred J; Brecht, Marc

    2016-06-13

    Here we report a simple way to enhance the resolution of a confocal scanning microscope under cryogenic conditions. Using a microscope objective (MO) with high numerical aperture (NA = 1.25) and 1-propanol as an immersion fluid with low freezing temperature we were able to reach an imaging resolution at 160 K comparable to ambient conditions. The MO and the sample were both placed inside the inner chamber of the cryostat to reduce distortions induced by temperature gradients. The image quality of our commercially available MO was further enhanced by scanning the sample (sample scanning) in contrast to beam scanning. The ease of the whole procedure marks an essential step towards the development of cryo high-resolution microscopy and correlative light and electron cryo microscopy (cryoCLEM).

  14. Diagnosis by Volatile Organic Compounds in Exhaled Breath from Lung Cancer Patients Using Support Vector Machine Algorithm

    PubMed Central

    Sakumura, Yuichi; Koyama, Yutaro; Tokutake, Hiroaki; Hida, Toyoaki; Sato, Kazuo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

    2017-01-01

    Monitoring exhaled breath is a very attractive, noninvasive screening technique for early diagnosis of diseases, especially lung cancer. However, the technique provides insufficient accuracy because the exhaled air has many crucial volatile organic compounds (VOCs) at very low concentrations (ppb level). We analyzed the breath exhaled by lung cancer patients and healthy subjects (controls) using gas chromatography/mass spectrometry (GC/MS), and performed a subsequent statistical analysis to diagnose lung cancer based on the combination of multiple lung cancer-related VOCs. We detected 68 VOCs as marker species using GC/MS analysis. We reduced the number of VOCs and used support vector machine (SVM) algorithm to classify the samples. We observed that a combination of five VOCs (CHN, methanol, CH3CN, isoprene, 1-propanol) is sufficient for 89.0% screening accuracy, and hence, it can be used for the design and development of a desktop GC-sensor analysis system for lung cancer. PMID:28165388

  15. Characterization of a tannase from Emericella nidulans immobilized on ionic and covalent supports for propyl gallate synthesis.

    PubMed

    Gonçalves, Heloísa Bressan; Jorge, João Atílio; Pessela, Benevides Costa; Lorente, Glória Fernandez; Guisán, José Manuel; Guimarães, Luis Henrique Souza

    2013-04-01

    The extracellular tannase from Emericela nidulans was immobilized on different ionic and covalent supports. The derivatives obtained using DEAE-Sepharose and Q-Sepharose were thermally stable from 60 to 75 °C, with a half life (t50) >24 h at 80 °C at pH 5.0. The glyoxyl-agarose and amino-glyoxyl derivatives showed a thermal stability which was lower than that observed for ionic supports. However, when the stability to pH was considered, the derivatives obtained from covalent supports were more stable than those obtained from ionic supports. DEAE-Sepharose and Q-Sepharose derivatives as well as the free enzyme were stable in 30 and 50 % (v/v) 1-propanol. The CNBr-agarose derivative catalyzed complete tannic acid hydrolysis, whereas the Q-Sepharose derivative catalyzed the transesterification reaction to produce propyl gallate (88 % recovery), which is an important antioxidant.

  16. 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.

  17. Capture of carbon dioxide by amine-impregnated as-synthesized MCM-41.

    PubMed

    Wei, Jianwen; Liao, Lei; Xiao, Yu; Zhang, Pei; Shi, Yao

    2010-01-01

    The novel carbon dioxide (CO2) adsorbents with a high capture efficiency were prepared through impregnating the as-synthesized MCM-41 with three kinds of amines, namely diethylenetriamine (DETA), triethylenetetramine (TETA) and 2-amino-2-methyl-1-propanol (AMP). The resultant samples were characterized by small angle X-ray diffraction and low temperature N2 adsorption. The synthesis way not only saves the energy or extractor to remove the template but also is environmentally friendly due to the absence of the potential pollutants such as toluene. CO2 capture was investigated in a dynamic packed column. The sample impregnated by TETA showed the highest adsorption capacity, approximately 2.22 mmol/g at 60 degrees C due to its highest amino-groups content among the three amines. The CO2 adsorption behavior was also investigated with the deactivation model, which showed an excellent prediction for the breakthrough curves.

  18. Fast Scanning Calorimetry study of non-equilibrium relaxation in fragile organic liquids

    NASA Astrophysics Data System (ADS)

    Sadtchenko, Vlad; Bhattacharya, Deepanjan; O'Reilly, Liam

    2013-03-01

    Fast scanning calorimetry (FSC), capable of heating rates in excess of 1000000 K/s, was combined with vapor deposition technique to investigate non-equilibrium relaxation in micrometer thick viscous liquid films of several organic compounds (e.g.2-ethyl-1-hexanol, Toluene, and 1-propanol) under high vacuum conditions. Rapid heating of samples, vapor deposited at temperatures above their standard glass softening transition (Tg), resulted in observable endotherms which onset temperatures were strongly dependent on heating rate and the deposition temperature. Furthermore, all of the studied compounds were characterized by distinct critical deposition temperatures at which observation of endotherm became impossible. Based on the results of these studies, we have developed a simple model which makes it possible to infer the equilibrium enthalpy relaxation times for liquids from FSC data. We will discuss implications of these studies for contemporary models of non-equilibrium relaxation in glasses and supercooled liquids. Supported by NSF Grant 1012692.

  19. Uniform particles of pure and silica-coated cholesterol.

    PubMed

    Uskoković, Vuk; Matijević, Egon

    2007-11-15

    Uniform crystalline colloidal cholesterol particles of narrow size distribution were obtained by precipitation. The method consisted of adding a miscible non-solvent (water) into cholesterol solutions of different alcohols and acetone, without any additives. The properties of the resulting particles depended in a sensitive way on the concentration of all reactants, temperature, pH, ionic strength, and aging time. The major observed effects were due to the solubility of cholesterol, which was strongly affected by the solvent mixture and temperature. Precipitation in 1-propanol/water system yielded stable dispersions of well-defined particles, which were used to evaluate the effects of different experimental parameters on their properties. Aging of stable dispersions resulted in multi-layered aggregation of the primary platelets, the degree and rate of which process was strongly affected by temperature. Finally, it was shown that the colloidal cholesterol particles could be coated with homogeneous silica layers in order to alter their surface characteristics.

  20. Rapid purification of iodinated ligands for cyclic nucleotide radioimmunoassays

    SciTech Connect

    Wilson, S.P.

    1988-01-01

    The tyrosine methyl esters of succinyl cyclic AMP and succinyl cyclic GMP were iodinated by the chloramine T method and individually applied to C18 cartridges. A solution of 1-propanol/0.1 M sodium acetate pH 4.75 (17.5:82.5) was then pumped onto each cartridge and the eluate collected. A large peak of radioactivity, containing primarily the monoiodo and diiodo derivatives, was eluted. Radioactivity in peak fractions was greater than or equal to 95% the monoiodo derivative and represented 20 to 25% of the starting radioactivity. Contamination by the native cyclic nucleotide analogs was less than 5%. These peak fractions containing primarily monoiodinated products worked well in cyclic nucleotide radioimmunoassays. This fractionation required less than 30 min.

  1. In Situ Enrichment of Phosphopeptides on MALDI Plates Functionalized by Reactive Landing of Zirconium(IV)–n-Propoxide Ions

    PubMed Central

    Blacken, Grady R.; Volný, Michael; Vaisar, Tomáš; Sadílek, Martin; Tureček, František

    2008-01-01

    We report substantial in situ enrichment of phosphopeptides in peptide mixtures using zirconium oxide coated plates for detection by MALDI-TOF mass spectrometry. The novel feature of this approach rests on the specific preparation of zirconium oxide coatings using reactive landing on stainless steel support of gas-phase positive ions produced by electrospray of zirconium(IV)–n-propoxide solutions in 1-propanol. Reactive landing was found to produce durable functionalized surfaces for selective phosphopeptide capture and desorption–ionization by MALDI. Enrichment factors on the order of 20–90 were achieved for several monophosphorylated peptides relative to abundant nonphosphorylated peptides in tryptic digests. We demonstrate the ability of the zirconium oxide functionalized MALDI surfaces to facilitate detection of enriched phosphopeptides in mid-femtomole amounts of α-casein digests per MALDI spot. PMID:17569507

  2. High-performance thin-layer chromatography method for inositol phosphate analysis.

    PubMed

    Hatzack, F; Rasmussen, S K

    1999-12-24

    A simple and inexpensive high-performance thin-layer chromatography (HPTLC) method for the analysis of inositol mono- to hexakisphosphates on cellulose precoated plates is described. Plates were developed in 1-propanol-25% ammonia solution-water (5:4:1) and substance quantities as low as 100-200 pmol were detected by molybdate staining. Chromatographic mobilities of nucleotides and phosphorylated carbohydrates were also characterized. Charcoal treatment was employed to separate nucleotides from inositol phosphates with similar R(F) values prior to HPTLC analysis. Practical application of the HPTLC system is demonstrated by analysis of grain extracts from wild type and low-phytate mutant barley as well as phytate degradation products resulting from barley phytase activity.

  3. Analysis of concentration characteristics in ultrasonic atomization by droplet diameter distribution.

    PubMed

    Yasuda, Keiji; Bando, Yoshiyuki; Yamaguchi, Soyoko; Nakamura, Masaaki; Oda, Akiyoshi; Kawase, Yasuhito

    2005-01-01

    The droplet diameter distribution and concentration characteristics in ultrasonic atomization were experimentally studied. The samples were aqueous solutions of methanol, ethanol and 1-propanol. The diameter distribution of atomized droplets showed the normal distribution, and the median diameter and standard deviation were expressed by means of the ultrasonic condition and the liquid properties. The concentration characteristic in ultrasonic atomization was analyzed by using the model of shell and core to the atomized droplet, where the former and latter consist of solute and solution, respectively. The value, which was surface solute amount in droplet multiplied by the molecular volume, increased with increasing solute molar fraction in bulk liquid and was independent of alcohol kinds. The rate of accompanying liquid and the solute molar fraction in accompanied liquid were estimated from the diameter distribution and the surface solute amount in droplet.

  4. Application of a mathematical topological pattern of antihistaminic activity for the selection of new drug candidates and pharmacology assays.

    PubMed

    Duart, María J; García-Domenech, Ramón; Galvez, Jorge; Aleman, Pedro A; Martín-Algarra, Rafael V; Antón-Fos, Gerardo M

    2006-06-15

    Molecular topology was used to achieve a mathematical model capable of classifying compounds according to their antihistaminic activity and low sedative effects. By application of this model of activity to databases containing chemical reagents and drugs exhibiting other pharmacological activity, we selected 30 compounds with possible antihistaminic activity. After those with possible sedative effects were discarded, activity tests were performed with five chemical reagents and three drugs searching for in vivo antihistaminic activity. The obtained results indicate that compounds such as 4-[(E)-2-(1,3-benzothiazol-2-yl)vinyl]-N,N-dimethylaniline (AH2), 2-ethyl-9,10-dimethoxyanthracene (AH4), and 2,4-bis(alpha,alpha-dimethylbenzyl)phenol (AH5) showed antihistaminic activity above terfenadine, the reference drug, whereas others, for instance, pergolide, miconazole, trihexyphenidyl, 2-(dibenzylamino-3-phenyl-1-propanol (AH1), and N-benzylquininium chloride (AH3), were less active than terfenadine.

  5. [Effectiveness of alcoholic hand disinfectants against methicillin resistant Staphylococcus aureus].

    PubMed

    Kampf, G; Jarosch, R; Rüden, H

    1997-03-01

    In order to determine the efficacy of hand disinfectants based on alcohol against three MRSA strains and 3 methicillin-susceptible S. aureus strains (MSSA), 1-propanol (60%) as well as Sterillium and Spitaderm were investigated in the quantitative suspension test at various dilutions and reactions times (15, 30 and 60s). All undiluted disinfectants revealed reduction factors > 6 against MRSA and MSSA after 30s. Diluted disinfectants (50%) were significantly less effective against MRSA at short reaction times (15 s) (p < 0.05). Sterillium in a dilution of 50% did not reach 5 reduction factors against either MRSA or MSSA after 30 s. The impact of an appropriate use of hand disinfectants in order to break chains of infections with MRSA is obvious.

  6. Improved solvent formulations for efficient CO₂ absorption and low-temperature desorption.

    PubMed

    Barzagli, Francesco; Di Vaira, Massimo; Mani, Fabrizio; Peruzzini, Maurizio

    2012-09-01

    This experimental study describes efficient CO₂ capture by 2-amino-2-methyl-1-propanol (AMP)/piperazine (PZ) in ethylene glycol monoethyl ether (EGMEE, 2-ethoxyethanol) containing approximately 15 wt % of water. In these experiments, the solvent is continuously circulated between the absorber (packed-bed reactor at 30, 40, or 45 °C) and the desorber (at 80, 85, or 90 °C). The CO₂ -solvent reaction equilibria have been investigated by using ¹³C NMR spectroscopy, which provides confirmatory evidence that the formation of mono- and biscarbamate derivatives of PZ accounts for most of the CO₂ absorbed by the AMP/PZ/EGMEE/H₂O blend. The solid-state structures of AMP carbamate and of the carbonate salt of protonated AMP have been determined by using XRD. Both AMPCO₂(-) and CO(3)(2-) species completely convert to the monoalkyl carbonates on dissolving the respective salts in methanol, ethanol, or ethylene glycol.

  7. Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form.

    PubMed

    Takeya, Satoshi; Fujihisa, Hiroshi; Yamawaki, Hiroshi; Gotoh, Yoshito; Ohmura, Ryo; Alavi, Saman; Ripmeester, John A

    2016-08-01

    The crystal structure and phase transition of cubic structure II (sII) binary clathrate hydrates of methane (CH4 ) and propanol are reported from powder X-ray diffraction measurements. The deformation of host water cages at the cubic-tetragonal phase transition of 2-propanol+CH4 hydrate, but not 1-propanol+CH4 hydrate, was observed below about 110 K. It is shown that the deformation of the host water cages of 2-propanol+CH4 hydrate can be explained by the restriction of the motion of 2-propanol within the 5(12) 6(4) host water cages. This result provides a low-temperature structure due to a temperature-induced symmetry-lowering transition of clathrate hydrate. This is the first example of a cubic structure of the common clathrate hydrate families at a fixed composition.

  8. Identification and characterization of stress degradants of lacosamide by LC-MS and ESI-Q-TOF-MS/MS: development and validation of a stability indicating RP-HPLC method.

    PubMed

    Ramisetti, Nageswara Rao; Kuntamukkala, Ramakrishna; Lakshetti, Sridhar; Sripadi, Prabhakar

    2014-07-01

    The current study dealt with the degradation behavior of lacosamide (LAC) under ICH prescribed stress conditions. LAC was found to be labile under acid and base hydrolytic stress conditions, while it was stable to neutral hydrolytic, oxidative, photolytic and thermal stress. In total, seven degradation products (DPs) were formed, which were separated on a C18 column using a stability-indicating method. LC-MS analyses indicated that one of the DPs had the same molecular mass as that of the drug. Structural characterization of DPs was carried out using ESI-Q-TOF-MS/MS technique. The degradation pathways and mechanisms of degradation of the drug were delineated by carrying out the degradation in different co-solvents viz. methanol, deuterated methanol, ethanol, 1-propanol and acetonitrile. The developed LC method was validated for the determination of related substances and assay of LAC as per ICH guidelines. This study demonstrates a comprehensive approach of LAC degradation studies during its development phase.

  9. Comparing the effects of various fuel alcohols on the natural attenuation of Benzene Plumes using a general substrate interaction model

    NASA Astrophysics Data System (ADS)

    Gomez, Diego E.; Alvarez, Pedro J. J.

    2010-04-01

    The effects of five fuel alcohols (methanol, ethanol, 1-propanol, iso-butanol and n-butanol) on the natural attenuation of benzene were compared using a previously developed numerical model (General Substrate Interaction Module — GSIM) and a probabilistic sensitivity analysis. Simulations with a 30 gal dissolving LNAPL (light non-aqueous phase liquid) source consisting of a range of gasoline blends (10% and 85% v:v alcohol content) suggest that all fuel alcohols can hinder the natural attenuation of benzene, due mainly to accelerated depletion of dissolved oxygen and a decrease in the specific degradation rate for benzene (due to catabolite repression and metabolic flux dilution). Simulations for blends with 10% alcohol, assuming a homogeneous sandy aquifer, inferred maximum benzene plume elongations (relative to a regular gasoline release) of 26% for ethanol, 47% for iso-butanol, 147% for methanol, 188% for 1-propanol, and 265% for n-butanol. The corresponding elongation percentages for blends with 85% alcohol were generally smaller (i.e., 25%, 54%, 135%, 163%, and 181%, respectively), reflecting a lower content of benzene in the simulated release. Benzene plume elongation and longevity were more pronounced in the presence of alcohols that biodegrade slower (e.g., propanol and n-butanol), forming longer and more persistent alcohol plumes. Conversely, ethanol and iso-butanol exhibited the lowest potential to hinder the natural attenuation of benzene, illustrating the significant effect that a small difference in chemical structure (e.g., isomers) can have on biodegradation. Overall, simulations were highly sensitive to site-specific biokinetic coefficients for alcohol degradation, which forewarns against generalizations about the level of impact of specific fuel alcohols on benzene plume dynamics.

  10. 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%.

  11. The impact of the structuring of hydrotropes in water on the mesoscale solubilisation of a third hydrophobic component.

    PubMed

    Buchecker, Thomas; Krickl, Sebastian; Winkler, Robert; Grillo, Isabelle; Bauduin, Pierre; Touraud, Didier; Pfitzner, Arno; Kunz, Werner

    2017-01-18

    In the present contribution, the pre-structuring of binary mixtures of hydrotropes and H2O is linked to the solubilisation of poorly water miscible compounds. We have chosen a series of short-chain alcohols as hydrotropes and benzyl alcohol, limonene and a hydrophobic azo-dye (Disperse Red 13) as organic compounds to be dissolved. A very weak pre-structuring is found for ethanol/H2O and 2-propanol/H2O mixtures. Pre-structuring is most developed for binary 1-propanol/H2O and tert-butanol/H2O mixtures and supports the bicontinuity model of alcohol-rich and water-rich domains as already postulated by Anisimov et al. Such a pre-structuring leads to a high solubilisation power for poorly water miscible components (limonene and Disperse Red, characterized by high octanol/water partition coefficients, log(P) values of 4.5 and 4.85), whereas a very weak pre-structuring leads to a high solubilisation power for slightly water miscible components (benzyl alcohol). This difference in solubilisation power can be linked to (i) the formation of mesoscale structures in the cases of ethanol and 2-propanol and (ii) the extension of pre-structures in the cases of 1-propanol and tert-butanol. Three different solubilisation mechanisms could be identified: bulk solubilisation, interface solubilisation and a combination of both. These supramolecular structures in binary and ternary systems were investigated by small-and-wide-angle X-ray and neutron scattering, dynamic light scattering and conductivity measurements (in the presence of small amounts of salt).

  12. Variation of some fermentative sulfur compounds in Italian "millesime" classic sparkling wines during aging and storage on lees.

    PubMed

    Fedrizzi, Bruno; Magno, Franco; Finato, Fabio; Versini, Giuseppe

    2010-09-08

    Fermentative sulfur compounds are recognized as strongly affecting wine aroma, mainly as off-flavors, but recently also as possible positive contributors to wine quality and typicity in still wines. Nevertheless, no evidence has been provided for the influence of these molecules on sparkling wine aroma, except for peculiar volatile thiols found in French Champagne. According to the traditional method, the second fermentation, occurring in sealed bottles, is the essence of the procedure. After this fermentation, sparkling wine is aged on yeast lees for a period ranging from a few months to several years so that yeast autolysis can take place. So far, no evidence is provided for the effect of yeast contact duration on the level of sulfur compounds. Following a HS-SPME/GC-MS method, 13 sulfur compounds, that is, ethylmercaptan, dimethyl sulfide, diethyl sulfide, dimethyl disulfide, diethyl disulfide, methyl thioacetate, ethyl thioacetate, 2-mercaptoethanol, 2-(methylthio)-1-ethanol, 3-(methylthio)-1-propanol, 4-(methylthio)-1-butanol, benzothiazole, and 5-(2-hydroxyethyl)-4-methylthiazole, were quantified in several Italian sparkling wines, produced according to the traditional method in two wineries from Trentino-South Tyrol, region. Additionally, the influence of winemaking technology differences and vintage effects on the evolution of the quoted sulfur compounds was considered. This investigation was carried out by coupling the HS-SPME data with those obtained by SPE method and relevant to other volatile compounds, which are considered as winemaking markers. This work furnished the first evidence of the effect of aging and lees contact at different storage temperatures on the levels of these analytes in sparkling wines. Significant increments were observed for dimethyl sulfide, diethyl sulfide, 2-(methylthio)-1-ethanol, 3-(methylthio)-1-propanol, and 4-(methylthio)-1-butanol during aging with a different variation slope possibly due to the remarkably different

  13. Effects of solvent hydrogen bonding, viscosity, and polarity on the dispersion and alignment of nanofluids containing Fe2O3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Christensen, Greg; Younes, Hammad; Hong, Haiping; Smith, Pauline

    2015-12-01

    It has been shown that the alignment of Iron (III) oxide (Fe2O3) nanoparticles in water (H2O) can enhance the thermal conductivity of nanofluids. To better understand solvent effects such as hydrogen bonding, viscosity, and polarity, nanofluids were prepared by mixing Fe2O3 nanoparticles and various solvents (water, ethanol, 1-propanol, isopropanol, 2-propanone, hexane, cyclohexane, ethylene glycol, glycerol, etc.), and the dispersions and alignments of the Fe2O3 nanoparticles in these solvents with and without an applied magnetic field were investigated using an optical microscope. The microscope images indicated that inter-molecule hydrogen bonding of the solvents with one OH group (water, ethanol, 1-propanol, and isopropanol) could help to disperse and align the Fe2O3 nanoparticles. The intra-molecular hydrogen bonding causes a dramatic increase in viscosity for fluids with multiple OH groups, such as ethylene glycol (C2H6O2) and glycerol (C3H8O3), and makes the Fe2O3 nanoparticles dispersion and alignment difficult. Adding water to those fluids could lead to significantly reduced viscosity and make the particles disperse and align well. Polarity studies indicated that higher polarity yields better dispersion and alignment of the Fe2O3 nanoparticles. Thermal studies showed that thermal conductivity of nanofluids containing metal oxide particles with hydrogen bonding in solvents is enhanced compared to the theoretically calculated data. Intermolecular hydrogen bonding between water and ethylene glycol increases the thermal conductivity of nanofluids while decreasing the fluid viscosity. The results also well explain why 50 wt. % water/50 wt. % ethylene glycol is an excellent commercial coolant. Since high thermal conductivity enhancement with minimal viscosity increase is the primary goal of heat transfer nanofluids, this current research may open new doors to better understanding of the fundamental nature of nanofluids.

  14. Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions.

    PubMed

    Sato, Bruno M; de Oliveira, Carolina G; Martins, Clarissa T; El Seoud, Omar A

    2010-02-28

    The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the "complex" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

  15. Effect of Initial Headspace O2 Level on the Growth and Volatile Metabolite Production of Leuconostoc Mesenteriodes and the Microbial and Sensorial Quality of Modified Atmosphere Packaged Par-Fried French Fries.

    PubMed

    Samapundo, Simbarashe; Mujuru, Felix Mugove; de Baenst, Ilse; Denon, Quenten; Devlieghere, Frank

    2016-02-01

    This study evaluated the effect of residual O2 level (0% to 5%) on microbial growth and volatile metabolite production on par-fried French fries packaged in a modified atmosphere with 60% CO2 (rest N2 ) at 4 °C. The results obtained showed that the initial headspace (IH) O2 level had an effect on growth of Leuconostoc mesenteroides on French fry simulation agar, whereby growth was slightly faster under 5% O2 . In terms of quantity, ethanol, 2-methyl-1-propanol, and dimethyl disulphide were the most significant volatile metabolites produced by L. mesenteroides. The production of ethanol by L. mesenteroides was highest on simulation agar packaged under low IH O2 levels (0% to 1%), indicating that the fermentative metabolism was induced under these conditions. In agreement with the results observed on the simulation medium, growth of native lactic acid bacteria was faster under an IH O2 level of 5%. In addition, ethanol, 2-methyl-1-propanol, and dimethyl disulphide were also quantitatively the most important volatile metabolites. However, in contrast, greater quantities of ethanol and dimethyl disulphide were produced on par-fried French fries packaged under 5% O2 . This was attributed to the limited growth of the native flora on the par-fried French fries under residual O2 levels of 0% and 1%. Although some significant differences (P < 0.05) occurred between the French fries packaged in 0%, 1%, and 5 % residual O2 during storage, all products were considered to be acceptable for consumption. The results of this study can be used to optimize the shelf-life of packaged chill stored potato products.

  16. Evaluating paint-sludge chars for adsorption of selected paint solvents

    SciTech Connect

    Kim, B.R.; Kalis, E.M.; Salmeen, I.T.; Kruse, C.W.; Demir, I.; Rostam-Abadi, M.; Carlson, S.L.

    1996-06-01

    At Ford, a study had been carried out to investigate the technical feasibility of converting paint sludge to activated char and reusing the char in paint spray-booth water to capture paint solvents from spray-booth air. As part of the study, several chars were made from a paint sludge and six dried paints to evaluate their effectiveness as adsorbents by conducting a series of liquid-phase adsorption experiments. Three commonly-used paint solvents and p-nitrophenol were selected as adsorbates. The three paint solvents were toluene, 2-methyl-1-propanol (iso-butanol), and 2-butoxyethanol (butylcellosolve). In this paper, the results of the pyrolysis and adsorption experiments are presented along with practical implications. The primary findings include the following: (1) Black-paint chars showed substantially larger surface area and higher adsorption capacity (based on total weight) than white-paint chars which had high ash contents due to the white pigment, titanium dioxide; (2) the adsorption capacity of the paint-sludge char was between those of black-paint and white-paint chars, and was 5--20% that of a commercial activated carbon; (3) titanium dioxide in white-paint chars did not improve the chars` affinity for hydrophilic compounds such as 2-methyl-1-propanol and 2-butoxyethanol; (4) coal could be added to paint sludge to improve the quality of the resulting char and to reduce ash content; and (5) the pyrolysis of paint sludge could present an attractive opportunity for reusing and recycling a waste product for pollution abatement and as a vehicle component.

  17. Aminoalcohol-Induced Activation of Organophosphorus Hydrolase (OPH) towards Diisopropylfluorophosphate (DFP)

    PubMed Central

    Li, Dandan; Zhang, Yunze; Song, Haitao; Lu, Liangqiu; Liu, Deli; Yuan, Yongze

    2017-01-01

    Aminoalcohols have been addressed as activating buffers for alkaline phosphatase. However, there is no record on the buffer activation regarding organophosphorus hydrolase (OPH). Here we reported the activating effects of aminoalcohols on OPH-catalyzed hydrolysis of diisopropylfluorophosphate (DFP), an analog molecule of G-type warfare agents. The kinetic parametors kcat, Vmax and kcat/Km in the OPH reaction were remarkably increased in the buffers (pH 8.0, 25°C) containing aminoalcohols with C2 between nitrogen (N) and oxygen (O) in their structures, including triethanolamine (TEA), diethanolamine, monoethanolamine, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, and triisopropanolamine. In contrast, much lower or no rate-enhancing effects were observed in the adding of amines, alcohols, amine/alcohol mixtures, or 3-amino-1-propanol (C3 between N and O). The 300 mM TEA further increased DFP-degrading activities of OPH mutants F132Y and L140Y, the previously reported OPH mutants with desirable activities towards DFP. However, the treatment of ethylenediaminetetraacetate (EDTA) markedly abolished the TEA-induced activation of OPH. The product fluoride effectively inhibited OPH-catalyzed hydrolysis of DFP by a linear mixed inhibition (inhibition constant Ki ~ 3.21 mM), which was partially released by TEA adding at initial or later reaction stage. The obtained results indicate the activation of OPH by aminoalcohol buffers could be attributed to the reduction of fluoride inhibition, which would be beneficial to the hydrolase-based detoxification of organophosphofluoridate. PMID:28085964

  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. Solubility of sugars and sugar alcohols in ionic liquids: measurement and PC-SAFT modeling.

    PubMed

    Carneiro, Aristides P; Held, Christoph; Rodríguez, Oscar; Sadowski, Gabriele; Macedo, Eugénia A

    2013-08-29

    Biorefining processes using ionic liquids (ILs) require proper solubility data of biomass-based compounds in ILs, as well as an appropriate thermodynamic approach for the modeling of such data. Carbohydrates and their derivatives such as sugar alcohols represent a class of compounds that could play an important role in biorefining. Thus, in this work, the pure IL density and solubility of xylitol and sorbitol in five different ILs were measured between 288 and 339 K. The ILs under consideration were 1-ethyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]), Aliquat dicyanamide, trihexyltetradecylphosphonium dicyanamide, and 1-ethyl-3-methylimidazolium trifluoroacetate. Comparison with the literature data was performed, showing good agreement. With the exception of [bmim][DCA], the solubility of these sugar alcohols in the other ILs is presented for the first time. The measured data as well as previously published solubility data of glucose and fructose in these ILs were modeled by means of PC-SAFT using a molecular-based associative approach for ILs. PC-SAFT was used in this work as it has shown to be applicable to model the solubility of xylitol and sorbitol in ILs (Paduszyński; et al. J. Phys. Chem. B 2013, 117, 7034-7046). For this purpose, three pure IL parameters were fitted to pure IL densities, activity coefficients of 1-propanol at infinite dilution in ILs, and/or xylitol solubility in ILs. This approach allows accurate modeling of the pure IL data and the mixture data with only one binary interaction parameter k(ij) between sugar and the IL or sugar alcohol and the IL. In cases where only the pure IL density and activity coefficients of 1-propanol at infinite dilution in ILs were used for the IL parameter estimation, the solubility of the sugars and sugar alcohols in the ILs could be predicted (k(ij) = 0 between sugar and the IL or sugar alcohol and the IL) with reasonable accuracy.

  20. Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils.

    PubMed

    Dandie, Catherine E; Weber, John; Aleer, Samuel; Adetutu, Eric M; Ball, Andy S; Juhasz, Albert L

    2010-11-01

    In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is

  1. Conversion of 1,3-Propylene Glycol on Rutile TiO2(110)

    SciTech Connect

    Chen, Long; Li, Zhenjun; Smith, R. Scott; Kay, Bruce D.; Dohnalek, Zdenek

    2014-10-09

    The adsorption of 1,3-propylene glycol (1,3-PG) on partially reduced TiO2(110) and its conversion to products have been studied by a combination of molecular beam dosing and temperature programmed desorption (TPD). When the Ti surface sites are saturated by 1,3-PG, ~80% of the molecules undergo further reactions to yield products that are liberated during the TPD ramp. In contrast to ethylene glycol (EG) and 1,2- propylene glycol (1,2-PG) that yield only alkenes and water at very low coverages (< 0.05 ML), two additional products, HCHO and C2H4, along with propylene (CH3CHCH2) and water are observed for 1,3-PG. Identical TPD line shapes and desorption yields for HCHO and C2H4 suggest that these products result from C-C bond cleavage and are coupled. At higher 1,3-PG coverages (> 0.1 ML), propanal (CH3CH2CHO) and two additional products, 1-propanol (CH3CH2CH2OH) and acrolein (CH2CHCHO), are observed. The desorption of 1-propanol is found to be coupled with the desorption of acrolein, suggesting that these products are formed by the disproportionation of two 1,3-PG molecules. The coverage dependent TPD results further show that propylene formation dominates at low coverages (< 0.3 ML), while the decomposition and disproportionation channels increase rapidly at higher coverages and reach yields comparable to that of propylene at the 1,3-PG saturation coverage of 0.5 ML. The observed surface chemistry clearly shows how the molecular structure of glycols influences their reaction pathways on oxide surfaces.

  2. Performance of short-chain alcohols versus acetonitrile in the surfactant-mediated reversed-phase liquid chromatographic separation of β-blockers.

    PubMed

    Ruiz-Ángel, M J; Torres-Lapasió, J R; Carda-Broch, S; García-Álvarez-Coque, M C

    2010-11-05

    Organic solvents are traditionally added to micellar mobile phases to achieve adequate retention times and peak profiles, in a chromatographic mode which has been called micellar liquid chromatography (MLC). The organic solvent content is limited to preserve the formation of micelles. However, at increasing organic solvent contents, the transition to a situation where micelles do not exist is gradual. Also, there is no reason to neglect the potentiality of mobile phases containing only surfactant monomers instead of micelles (high submicellar chromatography, HSC). This is demonstrated here for the analysis of β-blockers. The performance of four organic solvents (methanol, ethanol, 1-propanol, and acetonitrile) was compared in mobile phases containing the anionic surfactant sodium dodecyl sulphate in the MLC and HSC modes. The association of the organic solvent molecules with micelles gives rise to a significant loss in the elution strength of the organic solvent; whereas upon disruption of micelles, it tends to that observed in the hydro-organic mode. The elution behaviour of the β-blockers was modelled to predict the retention times. This allowed the detailed exploration of the selectivity and resolution of the chromatographic systems in relatively wide ranges of concentration of surfactant and organic solvent. The best performance in terms of resolution and analysis time was achieved using HSC with acetonitrile, being able to base-line resolve a mixture of eight β-blockers. Ethanol also provided a good separation performance, significantly improved with respect to methanol and 1-propanol. In contrast, the hydro-organic mode using acetonitrile or any of the short-chain alcohols could not succeed with the separation of the β-blockers, owing to the poorer selectivity and wider peaks.

  3. Anaerobic lactic acid degradation during ensilage of whole crop maize inoculated with lactobacillus buchneri inhibits yeast growth and improves aerobic stability

    PubMed

    Driehuis; Elferink; Spoelstra

    1999-10-01

    Aerobic deterioration of silages is initiated by (facultative) aerobic micro-organisms, usually yeasts, that oxidize the preserving organic acids. In this study, a Lactobacillus buchneri strain isolated from maize silage was evaluated for its potential as a bacterial inoculant that enhances aerobic stability of silages. In four experiments, chopped whole crop maize (30-43% dry matter (DM)) was inoculated with Lact. buchneri and ensiled in laboratory silos. Uninoculated silages served as controls. Analysis of silages treated with Lact. buchneri at levels of 103-106 cfu g-1 after about 3 months of anaerobic storage showedthat acetic acid and 1-propanol contents increased with inoculum levels above 104 cfu g-1,whereas lactic acid decreased. Propionic acid, silage pH and DM loss increased withinoculum levels above 105 cfu g-1. Time course experiments with maize inoculated with Lact. buchneri at 4 x 104-2 x 105 cfu g-1 showed that up to 7-14 d after ensiling, Lact. buchneri had no effect on silage characteristics. Thereafter, the lactic acid content of the inoculated silages declined and, simultaneously, acetic acid and, to a lesser extent, propionic acid and 1-propanol, accumulated. Inoculation reduced survival of yeasts during the anaerobic storage phase and inhibited yeast growth when the silage was exposed to O2, resulting in a substantial improvement in aerobic stability. The results indicate that the use of Lact. buchneri as a silage inoculant can enhance aerobic stability by inhibition of yeasts. The ability of the organism to ferment lactic acid to acetic acid appears to be an important underlying principle of this effect.

  4. Inactivation of murine norovirus by chemical biocides on stainless steel

    PubMed Central

    2009-01-01

    Background Human norovirus (NoV) causes more than 80% of nonbacterial gastroenteritis in Europe and the United States. NoV transmission via contaminated surfaces may be significant for the spread of viruses. Therefore, measures for prevention and control, such as surface disinfection, are necessary to interrupt the dissemination of human NoV. Murine norovirus (MNV) as a surrogate for human NoV was used to study the efficacy of active ingredients of chemical disinfectants for virus inactivation on inanimate surfaces. Methods The inactivating properties of different chemical biocides were tested in a quantitative carrier test with stainless steel discs without mechanical action. Vacuum-dried MNV was exposed to different concentrations of alcohols, peracetic acid (PAA) or glutaraldehyde (GDA) for 5 minutes exposure time. Detection of residual virus was determined by endpoint-titration on RAW 264.7 cells. Results PAA [1000 ppm], GDA [2500 ppm], ethanol [50% (v/v)] and 1-propanol [30% (v/v)] were able to inactivate MNV under clean conditions (0.03% BSA) on the carriers by ≥ 4 log10 within 5 minutes exposure time, whereas 2-propanol showed a reduced effectiveness even at 60% (v/v). Furthermore, there were no significant differences in virus reduction whatever interfering substances were used. When testing with ethanol, 1- and 2-propanol, results under clean conditions were nearly the same as in the presence of dirty conditions (0.3% BSA plus 0.3% erythrocytes). Conclusion Products based upon PAA, GDA, ethanol and 1-propanol should be used for NoV inactivation on inanimate surfaces. Our data provide valuable information for the development of strategies to control NoV transmission via surfaces. PMID:19583832

  5. Biodegradation of propanol and isopropanol by a mixed microbial consortium.

    PubMed

    Bustard, M T; McEvoy, E M; Goodwin, J A; Burgess, J G; Wright, P C

    2000-09-01

    The aerobic biodegradation of high concentrations of 1-propanol and 2-propanol (IPA) by a mixed microbial consortium was investigated. Solvent concentrations were one order of magnitude greater than any previously reported in the literature. The consortium utilized these solvents as their sole carbon source to a maximum cell density of 2.4 x 10(9) cells ml(-1). Enrichment experiments with propanol or IPA as carbon sources were carried out in batch culture and maximum specific growth rates (mumax) calculated. At 20 degrees C, mumax values were calculated to be 0.0305 h(-1) and 0.1093 h(-1) on 1% (v/v) IPA and 1-propanol, respectively. Growth on propanol and IPA was carried out between temperatures of 10 degrees C and 45 degrees C. Temperature shock responses by the microbial consortium at temperatures above 45 degrees C were demonstrated by considerable cell flocculation. An increase in propanol substrate concentration from 1% (v/v) to 2% (v/v) decreased the mumax from 0.1093 h(-1) to 0.0715 h(-1). Maximum achievable biodegradation rates of propanol and IPA were 6.11 x 10(-3)% (v/v) h(-1) and 2.72 x 10(-3)% (v/v) h(-1), respectively. Generation of acetone during IPA biodegradation commenced at 264 h and reached a maximum concentration of 0.4% (v/v). The results demonstrate the potential of mixed microbial consortia in the bioremediation of solvent-containing waste streams.

  6. Odorous gaseous emissions as influence by process condition for the forced aeration composting of pig slaughterhouse sludge.

    PubMed

    Blazy, V; de Guardia, A; Benoist, J C; Daumoin, M; Lemasle, M; Wolbert, D; Barrington, S

    2014-07-01

    Compost sustainability requires a better control of its gaseous emissions responsible for several impacts including odours. Indeed, composting odours have stopped the operation of many platforms and prevented the installation of others. Accordingly, present technologies collecting and treating gases emitted from composting are not satisfactory and alternative solutions must be found. Thus, the aim of this paper was to study the influence of composting process conditions on gaseous emissions. Pig slaughterhouse sludge mixed with wood chips was composted under forced aerationin 300 L laboratory reactors. The process conditions studied were: aeration rate of 1.68, 4.03, 6.22, 9.80 and 13.44 L/h/kg of wet sludge; incorporation ratio of 0.55, 0.83 and 1.1 (kg of wet wood chips/kg of wet sludge), and; bulking agent particles size of <10, 10<20 and 20<30 mm. Out-going gases were sampled every 2 days and their composition was analysed using gas chromatography coupled with mass spectrometry (GC-MS). Fifty-nine compounds were identified and quantified. Dividing the cumulated mass production over 30 days of composting, by odour threshold, 9 compounds were identified as main potential odour contributors: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone, 1-propanol-2-methyl, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide and acetophenone. Five gaseous compounds were correlated with both aeration rate and bulking agent to waste ratio: hydrogen sulphide, trimethylamine, ammonia, 2-pentanone and 1-propanol-2-methyl. However, dropping the aeration rate and increasing the bulking agent to waste ratio reduced gaseous odour emissions by a factor of 5-10, when the required threshold dilution factor ranged from 10(5) to 10(6), to avoid nuisance at peak emission rates. Process influence on emissions of dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide were poorly correlated with both aeration rate and bulking agent to waste ratio as a reaction with

  7. Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, 1 April--30 June 30 1996

    SciTech Connect

    1996-07-25

    A series of CuMgCeO{sub x} catalysts have been prepared by coprecipitating the corresponding metal nitrates with a mixed solution of potassium carbonate and potassium hydroxide. Kinetic studies of methanol and ethanol coupling reactions on K-Cu/MgO/CeO{sub 2} and MgO/CeO{sub 2} catalysts indicate that Cu enhances the rates of alcohol dehydrogenation. The cross-coupling reactions of acetaldehyde and {sup 13}C-labeled methanol produce singly-labeled propionaldehyde, suggesting that it forms by the condensation of acetaldehyde and a reactive intermediate derived from methanol. Isobutyraldehyde, a precursor to isobutanol, forms via the condensation of propionaldehyde and a reactive C{sub 1} intermediate resulting from methanol. CO{sub 2}, one of the reaction products, poisons both basic and metal sites on Ce-containing CuMgO{sub x} catalysts, resulting in decreases in the rates of both alcohol dehydrogenation (Cu sites) and chain-growth condensation reactions (basic sites). CO{sub 2} inhibits ethanol dehydrogenation on both low-Cu and high-Cu CuMgCeO{sub x} catalysts; however, CO{sub 2} has no effect on the activity of low-Cu Ce-free Cu-MgO{sub x} catalysts, suggesting that the Cu on CuMgCeO{sub x} catalysts is more likely to be oxidized by CO{sub 2} to Cu{sup +} species that can be subsequently stabilized by CeO{sub 2}. CO{sub 2} effects on high-pressure isobutanol synthesis from CO/H{sub 2} have been studied on low- and high-Cu CuMgCeO{sub x} catalysts at 320{degrees}C and 4.5 MPa. CO{sub 2} addition and removal on low- and high-Cu catalysts show similar directional effects on CO conversion. CO conversion is lower at all space velocities in the presence of CO{sub 2}, and removal Of CO{sub 2} from the feed partially recovers CO conversion. CO{sub 2} decreases methanol and isobutanol productivities on both catalysts. Addition of 1-propanol to CO/H{sub 2} feed increases isobutanol production, suggesting that 1-propanol is a precursor to isobutanol.

  8. Studies of solvent effects on reaction dynamics using ultrafast transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Harris, Don Ahmasi

    Ultrafast transient absorption spectroscopy was used to investigate the solvent dependent reaction dynamics of two prototypical chemical systems: (1) The ring-opening reaction of 1,3-cyclohexadiene, the isolated chromophore in Provitamin D, and (2) The photolysis of various Vitamin B12 cofactors. We investigated the influence of solvent polarity on the ground state conformational relaxation of 1,3,5-cis hexatriene subsequent to the ring opening of 1,3-cyclohexadiene in methanol and 1-propanol solvents. Comparisons to the conformational relaxation in alkane solvents studied earlier demonstrated a surprising influence of solvent polarity on single bond isomerization. Temperature dependent transient absorption measurements were performed on 1,3,5-cis hexatriene in cyclohexane and 1-propanol to determine the effect of solvent polarity on the activation energy barrier for ground state single bond isomerization. These measurements conclude that the polar solvent lowers the energy barrier for single bond isomerization allowing conformational relaxation to proceed faster in alcohol solvents compared to alkane solvents. With no perceived polar transition state for single bond isomerization, this result disagrees with the conventional view of solvation and differentiates the single bond isomerization dynamics of polyenes from alkanes. Transient absorption spectroscopy was also utilized to study the solvent effects in the photolysis of various B12 cofactors in different environments. We investigated the solvent dependent photolysis of adenosylcobalamin, methylcobalamin, and cyanocobalamin in water and ethylene glycol as a function of solvent temperature. In comparing the radical cage escape of adenosylcobalamin and cyanocobalamin, we determined a larger than expected hydrodynamic radii for the diffusing radicals in water compared to ethylene glycol, thus making necessary a revised perspective of solvent interaction with the diffusing radical. In addition, we investigated the

  9. Identification of intact high molecular weight glutenin subunits from the wheat proteome using combined liquid chromatography-electrospray ionization mass spectrometry.

    PubMed

    Lagrain, Bert; Brunnbauer, Markus; Rombouts, Ine; Koehler, Peter

    2013-01-01

    The present paper describes a method for the identification of intact high molecular weight glutenin subunits (HMW-GS), the quality determining proteins from the wheat storage proteome. The method includes isolation of HMW-GS from wheat flour, further separation of HMW-GS by reversed-phase high-performance liquid chromatography (RP-HPLC), and their subsequent molecular identification with electrospray ionization mass spectrometry using a quadrupole-time-of-flight mass analyzer. For HMW-GS isolation, wheat proteins were reduced and extracted from flour with 50% 1-propanol containing 1% dithiothreitol. HMW-GS were then selectively precipitated from the protein mixture by adjusting the 1-propanol concentration to 60%. The composition of the precipitated proteins was first evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis with Coomassie staining and RP-HPLC with ultraviolet detection. Besides HMW-GS (≥65%), the isolated proteins mainly contained ω5-gliadins. Secondly, the isolated protein fraction was analyzed by liquid chromatography-mass spectrometry. Optimal chromatographic separation of HMW-GS from the other proteins in the isolated fraction was obtained when the mobile phase contained 0.1% trifluoroacetic acid as ion-pairing agent. Individual HMW-GS were then identified by determining their molecular masses from the high-resolution mass spectra and comparing these with theoretical masses calculated from amino acid sequences. Using formic acid instead of trifluoroacetic acid in the mobile phase increased protein peak intensities in the base peak mass chromatogram. This allowed the detection of even traces of other wheat proteins than HMW-GS in the isolated fraction, but the chromatographic separation was inferior with a major overlap between the elution ranges of HMW-GS and ω-gliadins. Overall, the described method allows a rapid assessment of wheat quality through the direct determination of the HMW-GS composition and offers a basis for

  10. Alkylresorcinols in selected Polish rye and wheat cereals and whole-grain cereal products.

    PubMed

    Kulawinek, Mariola; Jaromin, Anna; Kozubek, Arkadiusz; Zarnowski, Robert

    2008-08-27

    The alkylresorcinol content and homologue composition in selected Polish rye and wheat cultivars and selected whole-grain cereal products were determined in this study. Cereal grains and whole-grain cereal products were extracted with acetone, whereas bread types were extracted with hot 1-propanol. The average alkylresorcinol content in tested rye (approximately 1100 mg/kg DM) and wheat (approximately 800 mg/kg DM) grains harvested in Poland was within the range previously reported in Swedish and Finnish samples. The total alkylresorcinol content in tested cereal products available on the Polish market varied from very low levels in barley grain-based foods up to 3000 mg/kg DM in wheat bran. The total alkylresorcinol content in 14 bread samples extracted with hot 1-propanol varied from approximately 100 mg/kg DM in whole bread made with honey up to approximately 650 mg/kg DM in whole-rye bread. Calculated ratios of C17:0 to C21:0 homologues, a useful parameter previously used to distinguish between rye and wheat cereals and their derived products, was about 1.2-1.4 in rye products, about 0.2 in wheat products, and varied between 0.2 and 0.6 in cereal-derived products containing a mixture of whole rye and/or wheat. The data set obtained were subsequently compared using cluster and principal component analysis, which allowed the tested cereal products to be classified into two major groups consisting of whole-rye or whole-wheat products, respectively. On the basis of that approach, mixed cereal products containing rye and wheat bran or whole rye and wheat flour were grouped between those two well-defined clusters. Our work not only provides a detailed examination of alkylresorcinols in selected Polish rye and wheat cultivars and selected whole-grain cereal products, but also demonstrates that this type of analysis accompanied by the use of proper statistical algorithms offers an objective way to evaluate the quality of whole-grain rye and/or wheat and their derived

  11. Picosecond reorientational dynamics of polar dye probes in binary aqueous mixtures

    NASA Astrophysics Data System (ADS)

    Dutt, G. B.; Doraiswamy, S.

    1992-02-01

    Picosecond time dependent fluorescence method has been used to measure the rotational reorientation times (τr) of three kinds of dye probes—oxazine 720 (a monocation), nile red (neutral but polar), and resorufin (a monoanion)—in a series of binary mixtures of water-amides, water-dipolar aprotics, and water-alcohols at 298 K. Most of the binary mixtures are characterized by the fact that at a particular composition (between 25% to 40% of the organic solvent in water), the viscosity (η) of the solution reaches a maximum value that is higher than the viscosities of the two solvents. As a consequence, the viscosity profile of the solution as a function of the organic solvent exhibits a bivaluedness, the extent of which is more, if the liquids are nearly isoviscous. The dielectric properties of the solution also change across the composition range. All the dyes show a near linear behavior of τr vs η in formamide-water, N-methylformamide-water, and methanol-water mixtures. A dual-valued profile for τr vs η is obtained for the cation oxazine 720 in the three dipolar aprotic mixtures (N, N-dimethylformamide-water, N, N-dimethylacetamide-water, and dimethylsulphoxide-water), with the rotational reorientation times being higher in the organic solvent-rich zone, compared to the corresponding isoviscous point in the water-rich zone. However, the anion resorufin shows a bivalued profile of τr vs η only in dimethylsulphoxide-water mixtures, while the neutral nile red shows a linear behavior in all the dipolar-aprotic water mixtures. A hook-type profile of τr vs η is seen for the anion resorufin in ethanol-, 1-propanol-, and 2-propanol-water mixtures and for the cation oxazine 720 in 1-propanol- and 2-propanol-water mixtures; but nile red shows no departure from linear behavior even in alcohol-water mixtures. The rotational dynamics of the cation oxazine 720 in dipolar aprotic-water mixtures is explained in terms of solvation since the dielectric friction is minimal

  12. 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

  13. Universal critical-like scaling of dynamic properties in symmetry-selected glass formers

    NASA Astrophysics Data System (ADS)

    Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J.; Paluch, Marian

    2008-11-01

    Evidence for a possible general validity of the critical-like behavior of dielectric relaxation time or viscosity τ,η∝(T-TC)-ϕ with ϕ →9 and TC1-propanol). Results presented explain the puzzling experimental artifacts supporting the dynamical scaling model [R. H. Colby, Phys. Rev. E 61, 1783 (2000); B. M. Erwin, R. H. Colby, J. Non-Cryst. Solids 307-310, 225 (2002)]. It is suggested that spin-glass-like systems may be linked to the discussed pattern.

  14. Lipid substrate specificity of phosphatidylethanolamine N-methyltransferase of Tetrahymena

    SciTech Connect

    Smith, J.D.

    1986-05-01

    The ciliate protozoan Tetrahymena thermophila forms about 60% of its phosphatidylcholine by methylation of phosphatidylethanolamine with S-adenosylmethionine using the enzyme phosphatidylethanolamine N-methyltransferase. Analogues of ethanolamine or of ethanolamine phosphate are incorporated into the phospholipids of Tetrahymena when cells are cultured in their presence. These compounds, 3-amino-1-propanol, 2-aminoethylphosphonate, 3-aminopropylphosphonate and N,N-dimethylaminoethylphosphonate replace from 50 to 75% of the ethanolamine phosphate in phosphatidylethanolamine. However, analysis of the phospholipids of lipid-altered Tetrahymena showed that none of the phosphatidylethanolamine analogues had been converted to the corresponding phosphatidylcholine analogue. No incorration of (/sup 14/C-CH/sub 3/)methionine into the phosphatidylcholine analogues could be demonstrated in vivo, nor was label from (/sup 3/H-CH/sub 3/)S-adenosylmethionine incorporated in virto. Thus, only phosphatidylethanolamine and its monomethyl and dimethyl derivatives have been found to be substrates for the phosphatidylethanoiamine N-methyltransferase. The enzyme therefore requires a phospholipid substrate containing an ester linkage between the alkylamine and phosphorus, with the amino group required to be ..beta.. to the alcohol.

  15. A Very Stable High Throughput Taylor Cone-jet in Electrohydrodynamics

    NASA Astrophysics Data System (ADS)

    Morad, M. R.; Rajabi, A.; Razavi, M.; Sereshkeh, S. R. Pejman

    2016-12-01

    A stable capillary liquid jet formed by an electric field is an important physical phenomenon for formation of controllable small droplets, power generation and chemical reactions, printing and patterning, and chemical-biological investigations. In electrohydrodynamics, the well-known Taylor cone-jet has a stability margin within a certain range of the liquid flow rate (Q) and the applied voltage (V). Here, we introduce a simple mechanism to greatly extend the Taylor cone-jet stability margin and produce a very high throughput. For an ethanol cone-jet emitting from a simple nozzle, the stability margin is obtained within 1 kV for low flow rates, decaying with flow rate up to 2 ml/h. By installing a hemispherical cap above the nozzle, we demonstrate that the stability margin could increase to 5 kV for low flow rates, decaying to zero for a maximum flow rate of 65 ml/h. The governing borders of stability margins are discussed and obtained for three other liquids: methanol, 1-propanol and 1-butanol. For a gravity-directed nozzle, the produced cone-jet is more stable against perturbations and the axis of the spray remains in the same direction through the whole stability margin, unlike the cone-jet of conventional simple nozzles.

  16. Effect of Water Miscible Organic Solvents on p-Nitrophenol Hydroxylase (CYP2E1) Activity in Rat Liver Microsomes

    PubMed Central

    Patil, Pranali G.; Kamble, S. H.; Shah, T. S.; Iyer, K. R.

    2015-01-01

    Organic solvents used for solubilization of the substrates/NCEs are known to affect the activity of cytochrome P450 enzymes. Further, this effect varies with the solvents used, the substrates and CYP450 isoforms in question. In the present study, we have investigated the effect of ten commonly used water miscible organic solvents (methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, acetone, dimethyl sulphoxide, N,N-dimethyl formamide, dioxane and polyethylene glycol 400) on p-nitrophenol hydroxylase activity at 0, 0.1, 0.25, 0.5, 0.75 and 1% v/v concentration in rat liver microsomes. All the solvents studied showed concentration dependent inhibition of the p-nitrophenol hydroxylase activity except acetonitrile which showed activation of the activity at concentration range studied. Out of ten solvents studied, dioxane was found to be the most inhibitory solvent (inhibition >90% at 0.25% v/v concentration). Overall, solvents like dimethyl sulphoxide, dimethyl formamide and dioxane appeared to be unsuitable for characterizing p-nitrophenol hydroxylase (CYP2E1-mediated) reactions due to a high degree of inhibition. On the other hand, methanol and acetonitrile at concentrations <0.5% v/v appeared to be appropriate solvents for substrate solubilization while evaluating CYP2E1-mediated catalysis. The results of this study imply that caution should be exercised while choosing solvents for dissolution of substrate during enzyme studies in liver microsomes. PMID:26180273

  17. Screening for potential hazard effects from four nitramines on human eye and skin.

    PubMed

    Fjellsbø, Lise Marie; Van Rompay, An R; Hooyberghs, Jef; Nelissen, Inge; Dusinska, Maria

    2013-06-01

    Amines have potential to be used in CO2 capture and storage (CCS) technology, but as they can be released into the environment and be degraded into more toxic compounds, such as nitrosamines and nitramines, there have been concerns about their negative impact on human health. We investigated the potential toxic effects from acute exposure to dimethylnitramine (DMA-NO2), methylnitramine (MA-NO2), ethanolnitramine (MEA-NO2) and 2-methyl-2-(nitroamino)-1-propanol (AMP-NO2). The eye irritation, and skin sensitization, irritation and corrosion potential of these substances have been evaluated in vitro using the Bovine Corneal Opacity and Permeability (BCOP) assay, VITOSENS® assay, Reconstructed Human Epidermis (RHE) skin irritation test and Corrositex Skin corrosion test, respectively. Exposure to DMA-NO2 induced a mild eye irritation response, while MA-NO2, MEA-NO2 and AMP-NO2 were shown to be very severe eye irritants. MA-NO2 and MEA-NO2 were tested for skin sensitization and found to be non-sensitizers to the skin. In addition, none of the four test substances was irritant or corrosive to the skin.

  18. On the atmospheric degradation of multifunctional organic compounds by NO3 and SO4- radicals in aqueous solution

    NASA Astrophysics Data System (ADS)

    Schöne, Luisa; Stieger, Bastian; Weller, Christian; Herrmann, Hartmut

    2014-05-01

    The atmospheric decomposition and transformation of a large number of organic compounds is initiated by radicals in the gas and aqueous phase. With increasing degree of oxidation and functionalization, organics become less volatile and more water soluble and partition into aqueous particles and cloud droplets where the oxidation by radicals continues. NO3 and SO4- radicals dominate the atmospheric aqueous phase besides OH radicals. Within this work, temperature dependent kinetic investigations were conducted by use of a laser flash photolysis laser long path absorption (LFPLLPA) setup. Second order rate constants for the reactions of 3-methoxy-1-propanol, diethylether, methylpropylether, 2-methyloxirane-2-carbaldehyde, 2,3-dihydroxy-2-methylpropanal, pyruvic, glyoxylic and glycolic acid as well as glyoxal, methylglyoxal and glycolaldehyde with NO3 and SO4- radicals were measured in a temperature range of 278 and 318 K applying pseudo-first order kinetics. The reactivity of the acids and their anions were investigated separately adjusting the pH to pH 1 or pH 8 for the acid or the anion form, respectively. From these measurements, activation parameters were derived. Measured k2nd range from 106 - 108 M1 s1. The kinetic and thermodynamic parameters as well as reaction mechanisms will be discussed within this contribution.

  19. Chromatographic efficiency comparison of polyhedral oligomeric silsesquioxanes-containing hybrid monoliths via photo- and thermally-initiated free-radical polymerization in capillary liquid chromatography for small molecules.

    PubMed

    Wang, Hongwei; Ou, Junjie; Liu, Zhongshan; Lin, Hui; Peng, Xiaojun; Zou, Hanfa

    2015-09-04

    Monolithic poly(methacrylate epoxy cyclosiloxane-co-polyhedral oligomeric silsesquioxanes) (epoxy-MA-POSS) capillary columns have been prepared via either photo- or thermally-initiated polymerization of the corresponding monomers using a 1-propanol/PEG 400 mixture as porogens. Photochemical polymerization was accomplished by irradiation of the UV-transparent capillary for 10min at room temperature, while thermal polymerization was performed at 55°C, 60°C or 65°C for 18h. The evaluation of chromatographic property for two hybrid epoxy-MA-POSS monoliths was carried out. The results indicate that hybrid monoliths fabricated by photochemical initiation exhibit higher column efficiency (97,000-98,400plates/m) than those synthesized by thermal polymerization (41,100-48,000plates/m) in cLC. The higher efficiency of photo-initiated hybrid monoliths is closely related to lower eddy dispersion (A-term) and mass transfer resistance (C-term).

  20. Volatile compounds in whole meal bread crust: The effects of yeast level and fermentation temperature.

    PubMed

    Nor Qhairul Izzreen, M N; Hansen, Se S; Petersen, Mikael A

    2016-11-01

    The influence of fermentation temperatures (8°C, 16°C, and 32°C) and yeast levels (2%, 4%, and 6% of the flour) on the formation of volatile compounds in the crust of whole meal wheat bread was investigated. The fermentation times were regulated to optimum bread height for each treatment. The volatile compounds were extracted by dynamic headspace extraction and analyzed by gas chromatography-mass spectrometry. The results were evaluated using multivariate data analysis and ANOVA. In all crust samples 28 volatile compounds out of 58 compounds were identified and the other 30 compounds were tentatively identified. Higher fermentation temperatures promoted the formation of Maillard reaction products 3-methyl-1-butanol, pyrazine, 2-ethylpyrazine, 2-ethyl-3-methylpyrazine, 2-vinylpyrazine, 3-hydroxy-2-butanone, 3-(methylsulfanyl)-propanal, and 5-methyl-2-furancarboxaldehyde whereas at lower temperature (8°C) the formation of 2- and 3-methylbutanal was favored. Higher levels of yeast promoted the formation of 3-methyl-1-butanol, 2-methyl-1-propanol and 3-(methylsulfanyl)-propanal, whereas hexanal was promoted in the crust fermented with lower yeast level.

  1. Volatile organic compounds emitted by filamentous fungi isolated from flooded homes after Hurricane Sandy show toxicity in a Drosophila bioassay.

    PubMed

    Zhao, G; Yin, G; Inamdar, A A; Luo, J; Zhang, N; Yang, I; Buckley, B; Bennett, J W

    2016-10-17

    Superstorm Sandy provided an opportunity to study filamentous fungi (molds) associated with winter storm damage. We collected 36 morphologically distinct fungal isolates from flooded buildings. By combining traditional morphological and cultural characters with an analysis of ITS sequences (the fungal DNA barcode), we identified 24 fungal species that belong to eight genera: Penicillium (11 species), Fusarium (four species), Aspergillus (three species), Trichoderma (two species), and one species each of Metarhizium, Mucor, Pestalotiopsis, and Umbelopsis. Then, we used a Drosophila larval assay to assess possible toxicity of volatile organic compounds (VOCs) emitted by these molds. When cultured in a shared atmosphere with growing cultures of molds isolated after Hurricane Sandy, larval toxicity ranged from 15 to 80%. VOCs from Aspergillus niger 129B were the most toxic yielding 80% mortality to Drosophila after 12 days. The VOCs from Trichoderma longibrachiatum 117, Mucor racemosus 138a, and Metarhizium anisopliae 124 were relatively non-toxigenic. A preliminary analysis of VOCs was conducted using solid-phase microextraction-gas chromatography-mass spectrometry from two of the most toxic, two of the least toxic, and two species of intermediate toxicity. The more toxic molds produced higher concentrations of 1-octen-3-ol, 3-octanone, 3-octanol, 2-octen-1-ol, and 2-nonanone; while the less toxic molds produced more 3-methyl-1-butanol and 2-methyl-1-propanol, or an overall lower amount of volatiles. Our data support the hypothesis that at certain concentrations, some VOCs emitted by indoor molds are toxigenic.

  2. Water miscible mono alcohols' effect on the proteolytic performance of Bacillus clausii serine alkaline protease.

    PubMed

    Duman, Yonca Avci; Kazan, Dilek; Denizci, Aziz Akin; Erarslan, Altan

    2014-01-01

    In this study, our investigations showed that the increasing concentrations of all examined mono alcohols caused a decrease in the Vm, kcat and kcat/Km values of Bacillus clausii GMBE 42 serine alkaline protease for casein hydrolysis. However, the Km value of the enzyme remained almost the same, which was an indicator of non-competitive inhibition. Whereas inhibition by methanol was partial non-competitive, inhibition by the rest of the alcohols tested was simple non-competitive. The inhibition constants (KI) were in the range of 1.32-3.10 M, and the order of the inhibitory effect was 1-propanol>2-propanol>methanol>ethanol. The ΔG(≠) and ΔG(≠)E-T values of the enzyme increased at increasing concentrations of all alcohols examined, but the ΔG(≠)ES value of the enzyme remained almost the same. The constant Km and ΔG(≠)ES values in the presence and absence of mono alcohols indicated the existence of different binding sites for mono alcohols and casein on enzyme the molecule. The kcat of the enzyme decreased linearly by increasing log P and decreasing dielectric constant (D) values, but the ΔG(≠) and ΔG(≠)E-T values of the enzyme increased by increasing log P and decreasing D values of the reaction medium containing mono alcohols.

  3. Tuning the Surface Properties of Graphene Oxide by Surface-Initiated Polymerization of Epoxides: An Efficient Method for Enhancing Gas Separation.

    PubMed

    Wu, Yu; Jia, Pan; Xu, Linli; Chen, Zhangyan; Xiao, Linhong; Sun, Jinhua; Zhang, Jun; Huang, Yong; Bielawski, Christopher W; Geng, Jianxin

    2017-02-08

    Here, we describe an in situ approach for growing polyepoxides from the surfaces of graphene oxide (GO) using a surface-initiated polymerization reaction. The polymerization methodology is facile and general as a broad range of epoxides carrying various functional groups have been successfully polymerized by simply adding GO powders in the epoxide monomers. The resultant polyepoxide grafted GO are found to show enhanced dispersibility in various common solvents and to exhibit increased d-spacing between the basal planes. In particular, grafting poly(2,3-epoxy-1-propanol) (PEP) to GO results in a composite (i.e., GO-g-PEP) that is dispersible in water and miscible with polyether block amide, i.e., Pebax MH 1657. Preliminary studies have indicated the membranes prepared using Pebax/GO-g-PEP composites exhibit enhanced CO2 permeabilities and selectivities in comparison to H2, O2, or N2. The excellent performance in gas separation is attributed to the layered structure of the GO-g-PEP sheets with enlarged d-spacing and the functional groups present on the PEP chains grafted to the surfaces of GO sheets.

  4. Photoelectron spectroscopy of liquid water, some alcohols, and pure nonane in free micro jets

    NASA Astrophysics Data System (ADS)

    Faubel, Manfred; Steiner, Björn; Toennies, J. Peter

    1997-06-01

    The recently developed technique of accessing volatile liquids in a high vacuum environment by using a very thin liquid jet is implemented to carry out the first measurements of photoelectron spectra of pure liquid water, methanol, ethanol, 1-propanol, 1-butanol, and benzyl alcohol as well as of liquid n-nonane. The apparatus, which consists of a commercial hemispherical (10 cm mean radius) electron analyzer and a hollow cathode discharge He I light source is described in detail and the problems of the sampling of the photoelectrons in such an environment are discussed. For water and most of the alcohols up to six different electronic bands could be resolved. The spectra of 1-butanol and n-nonane show two weakly discernable peaks from which the threshold ionization potential could be determined. A deconvolution of the photoelectron spectra is used to extract ionization potentials of individual molecular bands of molecules near the surface of the liquid and shifts of the order of 1 eV compared to the gas phase are observed. A molecular orientation for water molecules at the surface of liquid water is inferred from a comparison of the relative band strengths with the gas phase. Similar effects are also observed for some of the alcohols. The results are discussed in terms of a simple "Born-solvation" model.

  5. Free energies for the coordination of ligands to the magnesium of chlorophyll-a in solvents

    NASA Astrophysics Data System (ADS)

    Kobayashi, Rika; Reimers, Jeffrey R.

    2015-07-01

    The coordination of bases to chlorophyll magnesium modifies spectroscopic properties in solution as well as in situ in reaction centres. We evaluate the free energies of complexation of one or two pyridine, 1-propanol, diethyl ether or water solvent molecules at 298 and 150 K to rationalise observed phenomena. Various a priori dispersion-corrected density functional theory calculations are performed as well as second-order Møller-Plesset calculations, focusing on the effects of dispersion modifying the intermolecular interactions, of dispersion modifying solvation energies, of entropy, and of basis-set superposition error. A process of particular interest is magnesium complexation in ether at low temperature that is often exploited to assign the Q-band visible absorption spectrum of chlorophyll. Recently, we demonstrated that trace water interferes with this process, but the nature of the resulting complex could not be uniquely determined; here, it is identified as ether.Chlorophyll-a.H2O, consistent with interpretations based on our authoritative 2013 assignment.

  6. Capillary electrochromatography-atmospheric pressure ionization mass spectrometry of pesticides using a surfactant-bound monolithic column

    PubMed Central

    Gu, Congying; Shamsi, Shahab A.

    2011-01-01

    A surfactant bound poly (11-acrylaminoundecanoic acid-ethylene dimethacrylate) (AAUA-EDMA) monolithic column was simply prepared by in-situ co-polymerization of AAUA and EDMA with 1-propanol, 1,4-butanediol and water as porogens in 100 µm id fused silica capillary in one step. This column was used in capillary electrochromatography (CEC)-atmospheric pressure photoionization (APPI)-mass spectrometry system for separation and detection of N-methylcarbamates (NMCs) pesticides. Numerous parameters are optimized for CEC-APPI-MS. After evaluation of the mobile phase composition, sheath liquid composition and the monolithic capillary outlet position, a fractional factorial design (FFD) was selected as a screening procedure to identify factors of ionization source parameters, such as sheath liquid flow rate, drying gas flow rate, drying gas temperature, nebulizing gas pressure, vaporizer temperature, and capillary voltage, which significantly influence APPI-MS sensitivity. A face-centered central composite design (CCD) was further utilized to optimize the most significant parameters and predict the best sensitivity. Under optimized conditions signal-to-noise ratios (S/N) around 78 were achieved for an injection of 100 ng/mL of each pesticide. Finally, this CEC-APPI-MS method was successfully applied to the analysis of nine NMCs in spiked apple juice sample after solid phase extraction with recoveries in the range of 65 to 109%. PMID:20349511

  7. Biochemical pathways generating post-mortem volatile compounds co-detected during forensic ethanol analyses.

    PubMed

    Boumba, Vassiliki A; Ziavrou, Kallirroe S; Vougiouklakis, Theodore

    2008-01-30

    In this contribution are presented the fermentations of the main substrates present in a decaying corpse, namely carbohydrates, amino acids, glycerol and fatty acids, generating the post-mortem volatile compounds that could be detected along with ethanol during the forensic ethanol analysis. The available literature (preferably reviews) on microbial metabolic pathways (enzymes, substrates, conditions) that are implicated in the formation of these volatiles has been reviewed. The microbial formation of the following volatiles is supported by the presented biochemical data: ethanol, acetaldehyde, acetone, 2-propanol, 1-propanol, 1-butanol, isobutanol, isoamyl alcohol, d-amyl alcohol, acetate, propionate, butyrate, isobutyrate and ethyl esters (mainly ethyl acetate). The extracted information was correlated with the existing forensic literature on the post-mortem detected volatiles. The significance of the microbial produced volatiles on the selection of an appropriate internal standard for the ethanol analysis has been considered. Finally, the possible contribution of the presence of volatiles in the interpretation of ethanol analysis results in post-mortem cases is discussed.

  8. Sequential extraction and quantitative recovery of gliadins, glutenins, and other proteins from small samples of wheat flour.

    PubMed

    DuPont, Frances M; Chan, Ronald; Lopez, Rocio; Vensel, William H

    2005-03-09

    Methods to sequentially extract and fractionate wheat flour proteins were evaluated to reliably quantify gliadins, glutenins, and albumins/globulins in single flour samples. Compositions of the resulting protein fractions were analyzed by RP-HPLC combined with SDS-PAGE. Unknown proteins were identified by mass spectrometry or N-terminal sequencing. The best separation and recovery of discrete albumin/globulin, gliadin, and glutenin fractions from the same flour sample was achieved by extraction with 0.3 M NaI in 7.5% 1-propanol followed by 2% SDS, 25 mM DTT in 25 mM TRIS, pH 8.0, and precipitation of the solubilized proteins with ammonium acetate/methanol followed by acetone. Average flour composition for the variety Butte86 was 10% albumin/globulin, 40% gliadin, and 48% glutenin. This method should be useful for determining flour composition in diverse samples and evaluating relationships between proteins and end-use functionality.

  9. [Synthetic study of biologically important nitrogen containing natural products: development of new methodology and design of leading compounds for new pharmaceuticals].

    PubMed

    Nakagawa, Masako

    2003-04-01

    Synthetic study of biologically important nitrogen-containing natural products and development of new methodologies and design of leading compounds for new pharmaceuticals are described. The first total synthesis of eudistomines, manzamine C, martefragin A, cerebroside B1b, and symbioramide was accomplished and the absolute configurations of the stereogenic centers were determined. A novel methodology useful for the synthesis of alkaloids that have perhydroisoquinoline ring system such as manzamine A and B, and related alkaloids, nakadomarin A and dynemicin A, is presented. Sphingolipids, 4-stereoisomers of 1-phenyl-2-palmitoylamino-3-morpholino-1-propanol, were synthesized and antimalaria activity was investigated. Inhibition of DNA primase by sphingosine and its analogues is described. A new synthetic methodology for alkylation and reduction of imines has been developed, and the first example of a reagent-controlled enantioselective Pictet-Spengler reaction is described. Also novel and convenient methods using transition metal and rare earth metals including alkene metathesis, asymmetric Diels-Alder reaction, imino ene reaction, selective allylic halogenation, enantioselective Pictet-Spengler reaction, and enantioselective physostigmine synthesis are described.

  10. HS-SPME GC/MS characterization of volatiles in raw and dry-roasted almonds (Prunus dulcis).

    PubMed

    Xiao, Lu; Lee, Jihyun; Zhang, Gong; Ebeler, Susan E; Wickramasinghe, Niramani; Seiber, James; Mitchell, Alyson E

    2014-05-15

    A robust HS-SPME and GC/MS method was developed for analyzing the composition of volatiles in raw and dry-roasted almonds. Almonds were analyzed directly as ground almonds extracted at room temperature. In total, 58 volatiles were identified in raw and roasted almonds. Straight chain aldehydes and alcohols demonstrated significant but minimal increases, while the levels of branch-chain aldehydes, alcohols, heterocyclic and sulfur containing compounds increased significantly (500-fold) in response to roasting (p<0.05). Benzaldehyde decreased from 2934.6±272.5 ng/g (raw almonds) to 315.8±70.0 ng/g (averaged across the roasting treatments evaluated i.e. 28, 33 and 38 min at 138 °C) after roasting. Pyrazines were detected in only the roasted almonds, with the exception of 2,5-dimethylpyrazine, which was also found in raw almonds. The concentration of most alcohols increased in the roasted samples with the exception of 2-methyl-1-propanol, 3-methyl-1-butanol and 2-phenylethyl alcohol, which decreased 68%, 80%, and 86%, respectively.

  11. Prevention of Cardiac Hypertrophy by the Use of a Glycosphingolipid Synthesis Inhibitor in ApoE−/− Mice

    PubMed Central

    Mishra, Sumita; Bedja, Djahida; Amuzie, Christine; Avolio, Alberto; Chatterjee, Subroto

    2015-01-01

    ApoE−/− mice fed a high fat and high cholesterol (HFHC) diet (20% fat and 1.25% cholesterol) from 12 weeks of age to 36 weeks revealed an age-dependent increase in the left ventricular mass (LV mass) and decline in fractional shortening (FS%), which worsened with HFHC diet. These traits are indicative of maladaptive pathological cardiac hypertrophy and dysfunction. This was accompanied by loading of glycosphingolipids and increased gene expression of ANP, BNP in myocardial tissue. Masson’s trichrome staining revealed a significant increase in cardiomyocyte size and fibrosis. In contrast, treatment with 5 and 10 µM D-threo-1-phenyl-2-decanoylamino-3-morpholino-1-propanol (D-PDMP), an inhibitor of glucosylceramide synthase and lactosylceramide synthase, dose-dependently decreased the load of glycosphingolipids and preserved fractional shortening and maintained left ventricular mass to normal 12-week-old control levels over a 6 month treatment period. Our mechanistic studies showed that D-PDMP inhibited cardiac hypertrophy by inhibiting the phosphorylation of mitogen–activated protein kinase (MAPK). We propose that associating increased glycosphingolipid synthesis with cardiac hypertrophy could serve as a novel approach to prevent this phenotype in experimental animal models of diet -induced atherosclerotic heart disease. PMID:26253472

  12. A Search for Interstellar Monohydric Thiols

    NASA Astrophysics Data System (ADS)

    Gorai, Prasanta; Das, Ankan; Das, Amaresh; Sivaraman, Bhalamurugan; Etim, Emmanuel E.; Chakrabarti, Sandip K.

    2017-02-01

    It has been pointed out by various astronomers that a very interesting relationship exists between interstellar alcohols and the corresponding thiols (sulfur analog of alcohols) as far as the spectroscopic properties and chemical abundances are concerned. Monohydric alcohols such as methanol and ethanol are widely observed and 1-propanol was recently claimed to have been seen in Orion KL. Among the monohydric thiols, methanethiol (chemical analog of methanol) has been firmly detected in Orion KL and Sgr B2(N2) and ethanethiol (chemical analog of ethanol) has been observed in Sgr B2(N2), though the confirmation of this detection is yet to come. It is very likely that higher order thiols could be observed in these regions. In this paper, we study the formation of monohydric alcohols and their thiol analogs. Based on our quantum chemical calculation and chemical modeling, we find that the Tg conformer of 1-propanethiol is a good candidate of astronomical interest. We present various spectroscopically relevant parameters of this molecule to assist in its future detection in the interstellar medium.

  13. Dielectric Study of Alcohols Using Broadband Terahertz Time Domain Spectroscopy (THz-TDS).

    NASA Astrophysics Data System (ADS)

    Sarkar, Sohini; Saha, Debasis; Banerjee, Sneha; Mukherjee, Arnab; Mandal, Pankaj

    2016-06-01

    Broadband Terahertz-Time Domain Spectroscopy (THz-TDS) (1-10 THz) has been utilized to study the complex dielectric properties of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-octanol. Previous reports on dielectric study of alcohols were limited to 5 THz. At THz (1 THz = 33.33 wn = 4 meV) frequency range (0.1 to 15 THz), the molecular reorientation and several intermolecular vibrations (local oscillation of dipoles) may coexist and contribute to the overall liquid dynamics. We find that the Debye type relaxations barely contribute beyond 1 THz, rather three harmonic oscillators dominate the entire spectral range. To get insights on the modes responsible for the observed absorption in THz frequency range, we performed all atom molecular dynamics (MD) using OPLS force field and ab initio quantum calculations. Combined experimental and theoretical study reveal that the complex dielectric functions of alcohols have contribution from a) alkyl group oscillation within H-bonded network ( 1 THz), b) intermolecular H-bond stretching ( 5 THz) , and c) librational motions in alcohols. The present work, therefore, complements all previous studies on alcohols at lower frequencies and provides a clear picture on them in a broad spectral range from microwave to 10 THz.

  14. Voltammetric determination of ruthenium in the form of complexes with biologically active ligands

    SciTech Connect

    Medyantseva, E.P.; Budnikov, G.K.; Balakaeva, T.A.

    1992-02-10

    The interest in the analytical chemistry of ruthenium and its compounds has recently been increasing. Ruthenium compounds can be used an antitumor agents and in the treatment of tuberculosis and fungal infections. It has been suggested that there is a specific relationship between the reduction potentials of the compounds and their biological activity. Of greatest interest among the biologically active compounds are the compounds with nitrogen-containing heterocycles. In order to obtain information on the degree of oxidation of the central atom in the complexes and to select the optimum conditions for the determination of the mono- and bi-nuclear complexes of ruthenium compounds with biologically active ligands such as imidazole (Im), histidine (His), benzimidazole (BIm) and its methyl derivative [1,2(CH{sub 3}){sub 2} - BIm], benzohyroxamic acid (Bha), and 1-phenyl-2-methylamino-1-propanol or ephedrine (Eph) in the present work, the authors studied their electrochemical behavior at dropping mercury (dme) and a platinum electrodes. 6 refs., 1 fig., 2 tabs.

  15. A self-reducible and alcohol-soluble copper-based metal-organic decomposition ink for printed electronics.

    PubMed

    Shin, Dong-Hun; Woo, Seunghee; Yem, Hyesuk; Cha, Minjeong; Cho, Sanghun; Kang, Mingyu; Jeong, Sooncheol; Kim, Yoonhyun; Kang, Kyungtae; Piao, Yuanzhe

    2014-03-12

    We report a novel method for the synthesis of a self-reducible (thermally reducible without a reducing atmosphere) and alcohol-soluble copper-based metal-organic decomposition (MOD) ink for printed electronics. Alcohol-solvent-based conductive inks are necessary for commercial printing processes such as reverse offset printing. We selected copper(II) formate as a precursor and alkanolamine (2-amino-2-methyl-1-propanol) as a ligand to make an alcohol-solvent-based conductive ink and to assist in the reduction reaction of copper(II) formate. In addition, a co-complexing agent (octylamine) and a sintering helper (hexanoic acid) were introduced to improve the metallic copper film. The specific resistivity of copper-based MOD ink (Cuf-AMP-OH ink) after heat treatment at 350 °C is 9.46 μΩ·cm, which is 5.5 times higher than the specific resistivity of bulk copper. A simple stamping transfer was conducted to demonstrate the potential of our ink for commercial printing processes.

  16. Choline Essentiality and Its Requirement in Diets for Juvenile Parrot Fish (Oplegnathus fasciatus)

    PubMed Central

    Khosravi, Sanaz; Jang, Ji-Woong; Rahimnejad, Samad; Song, Jin-Woo; Lee, Kyeong-Jun

    2015-01-01

    A 12-wk feeding trial was conducted to evaluate the essentiality of choline supplementation in diets for parrot fish. Five isonitrogenous and isocaloric diets were supplemented with 0 (as control), 500, 1,000, and 2,000 mg choline per kg diet, and a positive control diet without choline contained 0.3% of 2-amino-2-methyl-1-propanol as choline biosynthesis inhibitor (designated as Con, C500, C1000, C2000 and Con+, respectively). Triplicate groups of fish (body weight, 8.8±0.01 g) were fed one of the experimental diets at a rate of 4% body weight twice daily. The fish fed Con+ diet revealed significantly lower growth performance and feed utilization efficiency than other fish groups. Supplementation of choline to the basal diet did not significantly influence fish growth. The highest liver lipid content was observed in fish fed the Con+ diet and inversely correlated with liver choline concentration although the differences were not significant. Also, significantly higher liver linoleic, eicosapentaenoic and docosahexaenoic acid contents were found in fish fed the Con+ diet. Innate immune parameters including respiratory burst and myeloperoxidase activities were not significantly affected by dietary choline levels. The findings in this study conclude that choline concentration of approximately 230 mg kg−1 diet meets the requirement of parrot fish. PMID:25924958

  17. Development and characterization of dilutable self-microemulsifying premicroemulsion systems (SMEPMS) as templates for preparation of nanosized particulates

    PubMed Central

    Lin, Shen-Fu; Chen, Ying-Chen; Ho, Hsiu-O; Huang, Wei-Yu; Sheu, Ming-Thau; Liu, Der-Zen

    2013-01-01

    The utilization of self-microemulsifying premicroemulsion systems (SMEPMS) as templates for preparing poorly water-soluble compounds in the nanosized range represents a promising strategy. Fenofibrate was formulated with n-butyl L-lactate, Tween 80, and a number of cosurfactants (ethanol, 1-propanol, and PEG 600), diluted with the water phase (either water or saccharide solution) and then subjected to a freeze-drying (FD) process to obtain SMEPMS nanosized particulates. Results demonstrated that the particle size after resuspension of these FD SMEPMS nanosized particulates in water was too large, so the addition of saccharide solutions (lactose, mannitol, glucose, sucrose, and trehalose) as the solid carrier to prevent particles from aggregating seemed to be necessary and workable due to steric hindrance and repulsion. However, instability of these resuspended FD nanosized particulates after 30–90 minutes still occurred, and the addition of 0.5% sodium lauryl sulfate in the resuspending medium was able to retard the aggregation and maintain the particle size within the nano-range. Evaluation by scanning electron microscopy and X-ray powder diffraction also confirmed the results. It was concluded that using an SMEPMS formulation with PEG 600 as the cosurfactant, and in the presence of a suitable saccharide as an anticaking agent and FD process were able to produce fenofibrate nanoparticles. PMID:24049445

  18. The Amino Acid Specificity for Activation of Phenylalanine Hydroxylase Matches the Specificity for Stabilization of Regulatory Domain Dimers.

    PubMed

    Zhang, Shengnan; Hinck, Andrew P; Fitzpatrick, Paul F

    2015-08-25

    Liver phenylalanine hydroxylase is allosterically activated by phenylalanine. The structural changes that accompany activation have not been identified, but recent studies of the effects of phenylalanine on the isolated regulatory domain of the enzyme support a model in which phenylalanine binding promotes regulatory domain dimerization. Such a model predicts that compounds that stabilize the regulatory domain dimer will also activate the enzyme. Nuclear magnetic resonance spectroscopy and analytical ultracentrifugation were used to determine the ability of different amino acids and phenylalanine analogues to stabilize the regulatory domain dimer. The abilities of these compounds to activate the enzyme were analyzed by measuring their effects on the fluorescence change that accompanies activation and on the activity directly. At concentrations of 10-50 mM, d-phenylalanine, l-methionine, l-norleucine, and (S)-2-amino-3-phenyl-1-propanol were able to activate the enzyme to the same extent as 1 mM l-phenylalanine. Lower levels of activation were seen with l-4-aminophenylalanine, l-leucine, l-isoleucine, and 3-phenylpropionate. The ability of these compounds to stabilize the regulatory domain dimer agreed with their ability to activate the enzyme. These results support a model in which allosteric activation of phenylalanine hydroxylase is linked to dimerization of regulatory domains.

  19. Preparation and characterization of alkyl methacrylate-based monolithic columns for capillary gas chromatography applications.

    PubMed

    Yusuf, Kareem; Aqel, Ahmad; A L Othman, Zeid; Badjah-Hadj-Ahmed, Ahmed Yacine

    2013-08-02

    Gas chromatography (GC) is considered the least common application of both polymer and silica-based monolithic columns. This study describes the fabrication of alkyl methacrylate monolithic materials for use as stationary phases in capillary gas chromatography. Following the deactivation of the capillary surface with 3-(trimethoxysilyl)propyl methacrylate (TMSM), the monoliths were formed by the co-polymerization of either hexyl methacrylate (HMA) or lauryl methacrylate (LMA) with different percentage of ethylene glycol dimethacrylate (EDMA) in presence of an initiator (azobisisobutyronitrile, AIBN) and a mixture of porogens include 1-propanol, 1,4-butanediol and water. The monoliths were prepared in 500mm length capillaries possessing inner diameters of 250μm. The efficiencies of the monolithic columns for low molecular weight compounds significantly improved as the percentage of crosslinker was increased, because of the greater proportion of pores less than 50nm. The columns containing lower percentages of crosslinker were able to rapidly separate a series of 8 alkane members in 0.7min, but the separation was less efficient for the light alkanes. Columns prepared with the lauryl methacrylate monomer yielded a different morphology for the monolith-interconnected channels. The channels were more branched, which increased the separation time, and unlike the other columns, allowed for temperature programming.

  20. Regulation of exosome release by glycosphingolipids and flotillins.

    PubMed

    Phuyal, Santosh; Hessvik, Nina P; Skotland, Tore; Sandvig, Kirsten; Llorente, Alicia

    2014-05-01

    Exosomes are released by cells after fusion of multivesicular bodies with the plasma membrane. The molecular mechanism of this process is still unclear. We investigated the role of sphingolipids and flotillins, which constitute a raft-associated family of proteins, in the release of exosomes. Interestingly, our results show that dl-threo-1-phenyl-2-decanoylamino-3-morpholino-1-propanol, an inhibitor of glucosylceramide synthase, seemed to affect the composition of exosomes released from PC-3 cells. However, the inhibition of ceramide formation from the de novo pathway by fumonisin B1 did not affect exosome secretion. Moreover, in contrast to findings obtained with other cell lines published so far, inhibition of neutral sphingomyelinase 2, an enzyme that catalyzes the formation of ceramide from sphingomyelin, did not inhibit the secretion of exosomes in PC-3 cells. Finally, small interfering RNA-mediated downregulation of flotillin-1 and flotillin-2 did not significantly change the levels of released exosomes as such, but seemed to affect the composition of exosomes. In conclusion, our results reveal the involvement of glycosphingolipids and flotillins in the release of exosomes from PC-3 cells, and indicate that the role of ceramide in exosome formation may be cell-dependent.

  1. Acid lipase from Candida viswanathii: production, biochemical properties, and potential application.

    PubMed

    de Almeida, Alex Fernando; Tauk-Tornisielo, Sâmia Maria; Carmona, Eleonora Cano

    2013-01-01

    Influences of environmental variables and emulsifiers on lipase production of a Candida viswanathii strain were investigated. The highest lipase activity (101.1 U) was observed at 210 rpm, pH 6.0, and 27.5°C. Other fermentation parameters analyzed showed considerable rates of biomass yield (Y L/S = 1.381 g/g), lipase yield (Y L/S = 6.892 U/g), and biomass productivity (P X = 0.282 g/h). Addition of soybean lecithin increased lipase production in 1.45-fold, presenting lipase yield (Y L/S ) of 10.061 U/g. Crude lipase presented optimal activity at acid pH of 3.5, suggesting a new lipolytic enzyme for this genus and yeast in general. In addition, crude lipase presented high stability in acid conditions and temperature between 40 and 45°C, after 24 h of incubation in these temperatures. Lipase remained active in the presence of organic solvents maintaining above 80% activity in DMSO, methanol, acetonitrile, ethanol, acetone, 1-propanol, isopropanol, and 2-propanol. Effectiveness for the hydrolysis of a wide range of natural triglycerides suggests that this new acid lipase has high potential application in the oleochemical and food industries for hydrolysis and/or modification of triacylglycerols to improve the nutritional properties.

  2. Comparison of monolithic silica and polymethacrylate capillary columns for LC.

    PubMed

    Moravcová, Dana; Jandera, Pavel; Urban, Jiri; Planeta, Josef

    2004-07-01

    Organic polymer monolithic capillary columns were prepared in fused-silica capillaries by radical co-polymerization of ethylene dimethacrylate and butyl methacrylate monomers with azobisisobutyronitrile as initiator of the polymerization reaction in the presence of various amounts of porogenic solvent mixtures and different concentration ratios of monomers and 1-propanol, 1,4-butanediol, and water. The chromatographic properties of the organic polymer monolithic columns were compared with those of commercial silica-based particulate and monolithic capillary and analytical HPLC columns. The tests included the determination of H-u curves, column permeabilities, pore distribution by inversed-SEC measurements, methylene and polar selectivities, and polar interactions with naphthalenesulphonic acid test samples. Organic polymer monolithic capillary columns show similar retention behaviour to chemically bonded alkyl silica columns for compounds with different polarities characterized by interaction indices, Ix, but have lower methylene selectivities and do not show polar interactions with sulphonic acids. The commercial capillary and analytical silica gel-based monolithic columns showed similar selectivities and provided symmetrical peaks, indicating no significant surface heterogeneities. To allow accurate characterization of the properties of capillary monolithic columns, the experimental data should be corrected for extra-column contributions. With 0.3 mm ID capillary columns, corrections for extra-column volume contributions are sufficient, but to obtain true information on the efficiency of 0.1 mm ID capillary columns, the experimental bandwidths should be corrected for extra-column contributions to peak broadening.

  3. Comparisons of amine solvents for post-combustion CO{sub 2} capture: A multi-objective analysis approach

    SciTech Connect

    Lee, Anita S; Eslick, John C; Miller, David C; Kitchin, John R

    2013-10-01

    Amine solvents are of great interest for post-combustion CO{sub 2} capture applications. Although the development of new solvents is predominantly conducted at the laboratory scale, the ability to assess the performance of newly developed solvents at the process scale is crucial to identifying the best solvents for CO{sub 2} capture. In this work we present a methodology to evaluate and objectively compare the process performance of different solvents. We use Aspen Plus, with the electrolyte-NRTL thermodynamic model for the solvent CO{sub 2} interactions, coupled with a multi-objective genetic algorithm optimization to determine the best process design and operating conditions for each solvent. This ensures that the processes utilized for the comparison are those which are best suited for the specific solvent. We evaluate and compare the process performance of monoethanolamine (MEA), diethanolamine (DEA), and 2-amino-2-methyl-1-propanol (AMP) in a 90% CO{sub 2} capture process from a 550 MW coal fired power plant. From our analysis the best process specifications are amine specific and with those specific, optimized specifications DEA has the potential to be a better performing solvent than MEA, with a lower energy penalty and lower capital cost investment.

  4. Insight into the structural deformations of beta-cyclodextrin caused by alcohol cosolvents and guest molecules.

    PubMed

    Zhang, Haiyang; Ge, Chunling; van der Spoel, David; Feng, Wei; Tan, Tianwei

    2012-03-29

    Beta-cyclodextrin (β-CD) is an ideal candidate for a host molecule, and it is used as such in drug delivery and separation technology. The structural behavior of free β-CD and host-guest complexes of β-CD with two isoflavonoid isomers (puerarin and daidzin) in aqueous alcohol solutions, covering methanol, ethanol, 2-propanol, and 1-propanol, was investigated through molecular dynamics (MD) simulations. The MD results highlighted aspects of the structural flexibility and rigidity of β-CD in different alcohol solutions. The alcohol residence time within the β-CD cavity, solvent distribution around β-CD, and guest-induced structural changes were analyzed. Interaction with puerarin endowed β-CD with a more rigid structure than with daidzin and a weaker ternary complex β-CD/puerarin/alcohol was formed with a local participation of water molecules. The retention behavior of puerarin and daidzin on a β-CD-coupled medium was determined via chromatographic experiments and simulation results provided a structural explanation for such interactions.

  5. Effects of polar and nonpolar groups on the solubility of organic compounds in soil organic matter

    USGS Publications Warehouse

    Chiou, C.T.; Kile, D.E.

    1994-01-01

    Vapor sorption capacities on a high-organic-content peat, a model for soil organic matter (SOM), were determined at room temperature for the following liquids: n-hexane, 1,4-dioxane, nitroethane, acetone, acetonitrile, 1-propanol, ethanol, and methanol. The linear organic vapor sorption is in keeping with the dominance of vapor partition in peat SOM. These data and similar results of carbon tetrachloride (CT), trichloroethylene (TCE), benzene, ethylene glycol monoethyl ether (EGME), and water on the same peat from earlier studies are used to evaluate the effect of polarity on the vapor partition in SOM. The extrapolated liquid solubility from the vapor isotherm increases sharply from 3-6 wt % for low-polarity liquids (hexane, CT, and benzene) to 62 wt % for polar methanol and correlates positively with the liquid's component solubility parameters for polar interaction (??P) and hydrogen bonding (??h). The same polarity effect may be expected to influence the relative solubilities of a variety of contaminants in SOM and, therefore, the relative deviations between the SOM-water partition coefficients (Kom) and corresponding octanol-water partition coefficients (Kow) for different classes of compounds. The large solubility disparity in SOM between polar and nonpolar solutes suggests that the accurate prediction of Kom from Kow or Sw (solute water solubility) would be limited to compounds of similar polarity.

  6. Microbiological and fermentation characteristics of togwa, a Tanzanian fermented food.

    PubMed

    Mugula, J K; Nnko, S A M; Narvhus, J A; Sørhaug, T

    2003-02-15

    Selected microbiological and metabolic characteristics of sorghum, maize, millet and maize-sorghum togwa were investigated during natural fermentation for 24 h. The process was predominated by lactic acid bacteria (LAB) and yeasts. The mesophiles, lactic acid bacteria, and yeasts increased and the Enterobacteriaceae decreased to undetectable levels within 24 h. The isolated microorganisms were tentatively identified as Lactobacillus plantarum, Lactobacillus brevis, Lactobacillus fermentum, Lactobacillus cellobiosus, Pediococcus pentosaceus, Weissella confusa, Issatchenkia orientalis, Saccharomyces cerevisiae, Candida pelliculosa and Candida tropicalis. The pH decreased from 5.24-5.52 to 3.10-3.34. Maltose increased initially and then decreased, fructose decreased and glucose levels increased during the first 12 h of fermentation. The organic acids detected during fermentation included DL-lactic, succinic, formic, pyruvic, citric, pyroglutamic and uric acid. Lactate was the predominant acid and increased significantly with time. The volatile organic compounds (VOC) detected included acetaldehyde, 2-methyl-propanal, 2-methyl-butanal, 3-methyl-butanal, ethanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, diacetyl and acetoin. Ethanol was the predominant VOC and it increased significantly with time.

  7. Catalytic wet oxidation: mathematical modeling of multicompound destruction.

    PubMed

    Yang, J; Hand, D W; Hokanson, D R; Crittenden, J C; Oman, E J

    2003-01-01

    A mathematical model of a three-phase catalytic reactor, CatReac, was developed for analysis and optimization of a catalytic oxidation reactor that is used in the International Space Station potable water processor. The packed-bed catalytic reactor, known as the volatile reactor assembly (VRA), is operated as a three-phase reactor and contains a proprietary catalyst, a pure-oxygen gas phase, and the contaminated water. The contaminated water being fed to the VRA primarily consists of acetic acid, acetone, ethanol, 1-propanol, 2-propanol, and propionic acid ranging in concentration from 1 to 10 mg/L. The Langmuir-Hinshelwood Hougen-Watson (L-H) (Hougen, 1943) expression was used to describe the surface reaction rate for these compounds. Single and multicompound short-column experiments were used to determine the L-H rate parameters and calibrate the model. The model was able to predict steady-state multicomponent effluent profiles for short and full-scale reactor experiments.

  8. Application of an isothermal, three-phase catalytic reactor model to predict unsteady-state fixed-bed performance.

    PubMed

    Yang, Ji; Hand, David W; Hokanson, David R; Crittenden, John C

    2003-01-15

    CatReac, a three-phase catalytic mathematical model, was developed for analysis and optimization of the volatile reactor assembly used in International Space Station water processor. This wet oxidation process is used to remove low molecular weight contaminants such as acetic acid, acetone, ethanol, 1-propanol, 2-propanol, and propionic acid, which are not removed by the other treatment processes. The Langmuir-Hinshelwood (Hinshelwood, C. N. The Kinetics of Chemical Change in Gaseous Systems, 3rd ed.; Oxford: London, 1933; pp 301-347) isothermal adsorption expression was successfully used to describe the reaction kinetics of compounds on the catalyst surface for the compounds mentioned above. Small-column experiments combined with the use of the Arrhenius equation were successfully used to predict the Langmuir-Hinshelwood parameters under different temperatures for a temperature range from 93 to 149 degrees C. Full-scale and small-column experiments were successfully used to validate the model predictions for unsteady-state fixed-bed operations.

  9. Development and validation of a direct headspace GC-FID method for the determination of sevoflurane, desflurane and other volatile compounds of forensic interest in biological fluids: application on clinical and post-mortem samples.

    PubMed

    Kovatsi, Leda; Giannakis, Dimitrios; Arzoglou, Vasileios; Samanidou, Victoria

    2011-05-01

    A simple and reliable headspace GC-flame ionization detection (HS-GC-FID) method has been developed and validated for the simultaneous determination of seven volatile compounds of forensic interest: sevoflurane, desflurane, ethanol, methanol, 1-propanol, acetone and acetaldehyde. All seven compounds including acetonitrile (internal standard) eluted within 10 min and were well resolved with no endogenous interference. Good linearity was observed in the range of 1-12 mg/dL for both anesthetics and 2.5-40 mg/dL for the other five analytes. The method showed good precision, sensitivity and repeatability. Most of the analytes remained stable during the storage of samples at 4°C. Desflurane and acetone degraded (>10%), when the samples remained on the autosampler for more than 2 and 3 h, respectively. The method was finally applied on clinical and post-mortem blood and urine samples. The clinical samples were collected both from patients who underwent surgery, as well as from the occupationally exposed medical and nursing staff of the university hospital, working in the operating rooms. The hospital staff samples were found negative for all compounds, while the patients' samples were found positive for the anesthetic administered to the patient. The post-mortem blood samples were found positive for ethanol and acetaldehyde.

  10. Gelation of charged catanionic vesicles prepared by a semispontaneous process.

    PubMed

    Huang, Zheng-Lin; Hong, Jhen-Yi; Chang, Chien-Hsiang; Yang, Yu-Min

    2010-02-16

    Various stable charged catanionic vesicles with mean zeta-potential values from +59 mV to -96 mV were successfully prepared from an ion-pair amphiphile (dodecyltrimethylammonium-dodecylsulfate, DTMA-DS) and different amounts of the component ionic surfactants (dodecyltrimethylammonium bromide and sodium dodecyl sulfate) by using a simple semispontaneous process with the aid of cosolvent (1-propanol) addition in water. With the ensuring positively and negatively charged catanionic vesicles, gelation of them by four water-soluble polymers with various charge and hydrophobic characteristics was systematically studied by the tube inversion and rheological characteristic analyses. Four phase maps, which show regions of phase separation, viscous solution, and gel by varying the vesicle composition and polymer content, were thereby constructed. Furthermore, the experimental results of the relaxation time and the storage modulus at 1 Hz for the viscous solutions and gel samples revealed that the interactions at play between charged catanionic vesicles and the water-soluble polymers are of electrostatic and hydrophobic origin. The phase maps and the rheological properties obtained for mixtures of charged catanionic vesicles and polymers may provide useful information for the potential application of catanionic vesicles in mucosal or transdermal delivery of drugs.

  11. In vitro study on the disinfectability of two split-septum needle-free connection devices using different disinfection procedures

    PubMed Central

    Engelhart, Steffen; Exner, Martin; Simon, Arne

    2015-01-01

    This in vitro study investigated the external disinfection of two needle-free connection devices (NFC) using Octeniderm® (spraying and wiping technique) vs. Descoderm® pads (wiping technique). The split-septum membrane of the NFC was contaminated with >105 CFU K. pneumoniae or S. epidermidis. The efficacy of the disinfection at 30 sec. exposure time was controlled by taking a swab sample and by flushing the NFC with sterile 0.9% sodium chloride solution. Disinfection with octenidine dihydrochloride 0.1 g, 1-Propanol 30.0 g, and 2-Propanol 45.0 g in 100 g solution was highly effective (CFU reduction ≥4 log) against both microorganisms, whereas the use of 63.1 g 2-Propanol in 100 ml solution led to residual contamination with S. epidermidis. Our investigation underlines that (i) in clinical practice disinfection of NFCs before use is mandatory, and that (ii) details of disinfection technique are of utmost importance regarding their efficacy. Our investigation revealed no significant differences between both split-septum NFC types. Clinical studies are needed to confirm a possible superiority of disinfectants with long-lasting residual antimicrobial activity. PMID:26693394

  12. A rapid and sensitive alcohol oxidase/catalase conductometric biosensor for alcohol determination.

    PubMed

    Hnaien, M; Lagarde, F; Jaffrezic-Renault, N

    2010-04-15

    A new conductometric biosensor has been developed for the determination of short chain primary aliphatic alcohols. The biosensor assembly was prepared through immobilization of alcohol oxidase from Hansenula sp. and bovine liver catalase in a photoreticulated poly(vinyl alcohol) membrane at the surface of interdigitated microelectrodes. The local conductivity increased rapidly after alcohol addition, reaching steady-state within 10 min. The sensitivity was maximal for methanol (0.394+/-0.004 microS microM(-1), n=5) and decreased by increasing the alcohol chain length. The response was linear up to 75 microM for methanol, 70 microM for ethanol and 65 microM for 1-propanol and limits of detection were 0.5 microM, 1 microM and 3 microM, respectively (S/N=3). No significant loss of the enzyme activities was observed after 3 months of storage at 4 degrees C in a 20mM phosphate buffer solution pH 7.2 (two or three measurements per week). After 4 months, 95% of the initial signal still remained. The biosensor response to ethanol was not significantly affected by acetic, lactic, ascorbic, malic, oxalic, citric, tartaric acids or glucose. The bi-enzymatic sensor was successfully applied to the determination of ethanol in different alcoholic beverages.

  13. Carbonic anhydrase promotes the absorption rate of CO2 in post-combustion processes.

    PubMed

    Vinoba, Mari; Bhagiyalakshmi, Margandan; Grace, Andrews Nirmala; Kim, Dae Hoon; Yoon, Yeoil; Nam, Sung Chan; Baek, Il Hyun; Jeong, Soon Kwan

    2013-05-09

    The rate of carbon dioxide (CO2) absorption by monoethanol amine (MEA), diethanol amine (DEA), N-methyl-2,2'-iminodiethanol (MDEA), and 2-amino-2-methyl 1-propanol (AMP) solutions was found to be enhanced by the addition of bovine carbonic anhydrase (CA), has been investigated using a vapor-liquid equilibrium (VLE) device. The enthalpy (-ΔHabs) of CO2 absorption and the absorption capacities of aqueous amines were measured in the presence and/or absence of CA enzyme via differential reaction calorimeter (DRC). The reaction temperature (ΔT) under adiabatic conditions was determined based on the DRC analysis. Bicarbonate and carbamate species formation mechanisms were elucidated by (1)H and (13)C NMR spectral analysis. The overall CO2 absorption rate (flux) and rate constant (kapp) followed the order MEA > DEA > AMP > MDEA in the absence or presence of CA. Hydration of CO2 by MDEA in the presence of CA directly produced bicarbonate, whereas AMP produced unstable carbamate intermediate, then underwent hydrolytic reaction and converted to bicarbonate. The MDEA > AMP > DEA > MEA reverse ordering of the enhanced CO2 flux and kapp in the presence of CA was due to bicarbonate formation by the tertiary and sterically hindered amines. Thus, CA increased the rate of CO2 absorption by MDEA by a factor of 3 relative to the rate of absorption by MDEA alone. The thermal effects suggested that CA yielded a higher activity at 40 °C.

  14. Vanadium haloperoxidases from brown algae of the Laminariaceae family.

    PubMed

    Almeida, M; Filipe, S; Humanes, M; Maia, M F; Melo, R; Severino, N; da Silva, J A; Fraústo da Silva, J J; Wever, R

    2001-07-01

    Vanadium haloperoxidases were extracted, purified and characterized from three different species of Laminariaceae--Laminaria saccharina (Linné) Lamouroux, Laminaria hyperborea (Gunner) Foslie and Laminaria ochroleuca de la Pylaie. Two different forms of the vanadium haloperoxidases were purified from L. saccharina and L. hyperborea and one form from L. ochroleuca species. Reconstitution experiments in the presence of several metal ions showed that only vanadium(V) completely restored the enzymes activity. The stability of some enzymes in mixtures of buffer solution and several organic solvents such as acetone, ethanol, methanol and 1-propanol was noteworthy; for instance, after 30 days at least 40% of the initial activity for some isoforms remained in mixtures of 3:1 buffer solution/organic solvent. The enzymes were also moderately thermostable, keeping full activity up to 40 degrees C. Some preliminary steady-state kinetic studies were performed and apparent Michaelis-Menten kinetic parameters were determined for the substrates iodide and hydrogen peroxide. Histochemical studies were also performed in fresh tissue sections from stipe and blade of L. hyperborea and L. saccharina, showing that haloperoxidase activity was concentrated in the external cortex near the cuticle, although some activity was also observed in the inner cortical region.

  15. Close Correlation between Heat Shock Response and Cytotoxicity in Neurospora crassa Treated with Aliphatic Alcohols and Phenols

    PubMed Central

    Meyer, U.; Schweim, P.; Fracella, F.; Rensing, L.

    1995-01-01

    In Neurospora crassa the aliphatic alcohols methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, ethylene glycol, glycerol, and allyl alcohol and the phenolic compounds phenol, hydroquinone, resorcinol, pyrogallol, phloroglucinol, sodium salicylate, and acetylsalicylic acid were analyzed with respect to their capacities to induce heat shock proteins (HSP) and to inhibit protein synthesis. Both the alcohols and phenols showed the greatest levels of HSP induction at concentrations which inhibited the overall protein synthesis by about 50%. The abilities of the different alcohols to induce the heat shock response are proportional to their lipophilicities: the lipophilic alcohol isobutanol is maximally inductive at about 0.6 M, whereas the least lipophilic alcohol, methanol, causes maximal induction at 5.7 M. The phenols, in general, show a higher capability to induce the heat shock response. The concentrations for maximal induction range between 25 mM (sodium salicylate) and 100 mM (resorcinol). Glycerol (4.1 M) shifted the concentration necessary for maximal HSP induction by hydroquinone from 50 to 200 mM. The results reveal that the induction of HSP occurs under conditions which considerably constrain cell metabolism. The heat shock response, therefore, does not represent a sensitive marker for toxicity tests but provides a good estimate for the extent of cell damage. PMID:16534981

  16. A polyphasic approach for assessing the suitability of bioremediation for the treatment of hydrocarbon-impacted soil.

    PubMed

    Adetutu, Eric M; Smith, Renee J; Weber, John; Aleer, Sam; Mitchell, James G; Ball, Andrew S; Juhasz, Albert L

    2013-04-15

    Bioremediation strategies, though widely used for treating hydrocarbon-contaminated soil, suffer from lack of biodegradation endpoint accountability. To address this limitation, molecular approaches of alkB gene analysis and pyrosequencing were combined with chemical approaches of bioaccessibility and nutrient assays to assess contaminant degrading capacity and develop a strategy for endpoint biodegradation predictions. In long-term hydrocarbon-contaminated soil containing 10.3 g C10-C36 hydrocarbons kg(-1), 454 pyrosequencing detected the overrepresentation of potential hydrocarbon degrading genera such as Pseudomonas, Burkholderia, Mycobacterium and Gordonia whilst amplicons for PCR-DGGE were detected only with alkB primers targeting Pseudomonas. This indicated the presence of potential microbial hydrocarbon degradation capacity in the soil. Using non-exhaustive extraction methods of 1-propanol and HP-β-CD for hydrocarbon bioaccessibility assessment combined with biodegradation endpoint predictions with linear regression models, we estimated 33.7% and 46.7% hydrocarbon removal respectively. These predictions were validated in pilot scale studies using an enhanced natural attenuation strategy which resulted in a 46.4% reduction in soil hydrocarbon content after 320 days. When predicted biodegradation endpoints were compared to measured values, there was no significant difference (P=0.80) when hydrocarbon bioaccessibility was assessed with HP-β-CD. These results indicate that a combination of molecular and chemical techniques that inform microbial diversity, functionality and chemical bioaccessibility can be valuable tools for assessing the suitability of bioremediation strategies for hydrocarbon-contaminated soil.

  17. Dynamics of glass-forming liquids. VIII. Dielectric signature of probe rotation and bulk dynamics in branched alkanes.

    PubMed

    Shahriari, Shervin; Mandanici, Andrea; Wang, Li-Min; Richert, Ranko

    2004-11-08

    We have measured the dielectric relaxation of several glass forming branched alkanes with very low dielectric loss in the frequency range 50 Hz-20 kHz. The molecular liquids of this study are 3-methylpentane, 3-methylheptane, 4-methylheptane, 2,3-dimethylpentane, and 2,4,6-trimethylheptane. All liquids display asymmetric loss peaks typical of supercooled liquids and slow beta relaxations of similar amplitudes. As an unusual feature, deliberate doping with 2-ethyl-1-hexanol, 5-methyl-2-hexanol, 2-methyl-1-butanol, 1-propanol, or 2-methyltetrahydrofuran at the 1 wt % level generates additional relaxation peaks at frequencies below those of the alpha relaxation. The relaxation times of these sub-alpha-peaks increase systematically with the size of the dopant molecules. Because these features are spectrally separate from the bulk dynamics, the rotational behavior and effective dipole moments of the probes can be studied in detail. For the alcohol guest molecules, the large relative rotational time scales and small effective dipole moments are indicative of hydrogen bonded clusters instead of individual molecules.

  18. Shock Hugoniot equations of state for binary water-alcohol liquid mixtures

    NASA Astrophysics Data System (ADS)

    Schulze, Peter A.; Ivanov, Trevor W.; Bolme, Cynthia A.; Brown, Kathryn E.; McGrane, Shawn D.; Moore, David S.

    2014-01-01

    Shock Hugoniot data were obtained using laser generated shock and ultrafast dynamic ellipsometry (UDE) methods for several non-ideal water-alcohol liquid mixtures, with the alcohols being methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol (a.k.a., 2-methyl-2-propanol or tert-butanol). The sound speeds of the mixtures were obtained using Brillouin scattering when not available in the literature. The shock and particle velocities obtained from the UDE data were compared to expectations of the universal liquid Hugoniot (ULH) and to literature shock (plate impact) data where available. The ethanol/water data were presented in a previous publication [Schulze et al., J. Phys. Chem. A 117, 6158-6163 (2013)]. The shock Hugoniot trends for all these mixtures, here represented as deviations from predictions of the ULH, versus fraction of alcohol are quite similar to each other and suggest that complex hydrogen bonding networks in alcohol-water mixtures alter the compressibility of the mixtures.

  19. 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.

  20. Oxidation, Reduction, and Condensation of Alcohols over (MO3)3 (M=Mo, W) Nanoclusters

    SciTech Connect

    Fang, Zongtang; Li, Zhenjun; Kelley, Matthew S.; Kay, Bruce D.; Li, Shenggang; Hennigan, Jamie M.; Rousseau, Roger J.; Dohnalek, Zdenek; Dixon, David A.

    2014-10-02

    The reactions of deuterated methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol and t-butanol over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally with temperature programmed desorption (TPD) and theoretically with coupled cluster CCSD(T) theory and density functional theory. The reactions of two alcohols per M3O9 cluster are required to provide agreement with experiment for D2O release, dehydrogenation and dehydration. The reaction begins with the elimination of water by proton transfers and forms an intermediate dialkoxy species which can undergo further reaction. Dehydration proceeds by a β hydrogen transfer to a terminal M=O. Dehydrogenation takes place via an α hydrogen transfer to an adjacent MoVI = O atom or a WVI metal center with redox involved for M = Mo and no redox for M = W. The two channels have comparable activation energies. H/D exchange to produce alcohols can take place after olefin is released or via the dialkoxy species depending on the alcohol and the cluster. The Lewis acidity of the metal center with WVI being larger than MoVI results in the increased reactivity of W3O9 over Mo3O9 for dehydrogenation and dehydration.

  1. 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.

  2. Aminiphilus circumscriptus gen. nov., sp. nov., an anaerobic amino-acid-degrading bacterium from an upflow anaerobic sludge reactor.

    PubMed

    Díaz, C; Baena, S; Fardeau, M-L; Patel, B K C

    2007-08-01

    Strain ILE-2(T) was isolated from an upflow anaerobic sludge bed reactor treating brewery wastewater. The motile, non-sporulating, slightly curved cells (2-4 x 0.1 microm) stained Gram-negative and grew optimally at 42 degrees C and pH 7.1 with 0.5 % NaCl. The strain required yeast extract for growth and fermented Casamino acids, peptone, isoleucine, arginine, lysine, alanine, valine, glutamate, histidine, glutamine, methionine, malate, fumarate, glycerol and pyruvate to acetate, propionate and minor amounts of branched-chain fatty acids. Carbohydrates, formate, acetate, propionate, butyrate, isovalerate, methanol, ethanol, 1-propanol, butanol, lactate, succinate, starch, casein, gelatin, xylan and a number of other amino acids were not utilized. The DNA G+C content of strain ILE-2(T) was 52.7 mol%. 16S rRNA gene sequence analysis revealed that ILE-2(T) was distantly related to members of the genera Aminobacterium (83 % similarity) and Aminomonas (85 % similarity) in the family Syntrophomonadaceae, order Clostridiales, phylum Firmicutes. On the basis of the results of our polyphasic analysis, strain ILE-2(T) represents a novel species and genus within the family Syntrophomonadaceae, for which the name Aminiphilus circumscriptus gen. nov., sp. nov. is proposed. The type strain of Aminiphilus circumscriptus is ILE-2(T) (=DSM 16581(T) =JCM 14039(T)).

  3. Biliary excretion of cadmium in rat. III. Effects of chelating agents and change in intracellular thiol content on billiary transport and tissue distribution of cadmium

    SciTech Connect

    Cherian, M.G.

    1980-03-01

    The effects of changes in sulfur-containing intracellular ligands on biliary excretion of cadmium were studied in rats. Injection of zinc or copper salts 24 h before intravenous injection of /sup 109/CdCl/sub 2/ (1 mg/kg Cd) decreased biliary excretion of Cd. Pretreatment with cysteine (25 mg/kg) had a similar effect. Depletion of intracellular thiol by injection of diethylmaleate had little effect. The effect of chelating agents on the pharmacokinetics of Cd depended on time of administration of the agents after exposure to Cd. When chelating agents were administered 1/2 h after Cd injection (before the synthesis of metallothionein), the thiol-containing agents (2,3-dimercapto-1-propanol (BAL), DL-penicillamine, N-acetylpenicillamine, and dithioerythritol increased the biliary excretion of Cd, while the carboxyl-containing ones (EDTA and nitrilotriacetate) increased the urinary excretion of Cd. BAL was the most effective chelating agent, but there was also an increase in the renal concentration of Cd. However, when these chelating agents were administered 24 h after Cd injection (after the synthesis of metallothionein), only BAL increased the biliary excretion of Cd. Renal and hepatic Cd concentrations decreased concurrently after BAL treatment.

  4. Purification of pectinase from mango (Mangifera indica L. cv. Chokanan) waste using an aqueous organic phase system: a potential low cost source of the enzyme.

    PubMed

    Amid, Mehrnoush; Abdul Manap, Mohd Yazid; Mustafa, Shuhaimi

    2013-07-15

    As a novel method of purification, an aqueous organic phase system (AOPS) was employed to purify pectinase from mango waste. The effect of different parameters, such as the alcohol concentration (ethanol, 1-propanol, and 2-propanol), the salt type and concentration (ammonium sulfate, potassium phosphate and sodium citrate), the feed stock crude load, the aqueous phase pH and NaCl concentration, were investigated in the recovery of pectinase from mango peel. The partition coefficient (K), selectivity (S), purification factor (PF) and yield (Y, %) were investigated in this study as important parameters for the evaluation of enzyme recovery. The desirable partition efficiency for pectinase purification was achieved in an AOPS of 19% (w/w) ethanol and 22% (w/w) potassium phosphate in the presence of 5% (w/w) NaCl at pH 7.0. Based on the system, the purification factor of pectinase was enhanced 11.7, with a high yield of 97.1%.

  5. Suitability of Macrolampis firefly and Pyrearinus click beetle luciferases for bacterial light off toxicity biosensor.

    PubMed

    Gabriel, Gabriele V M; Lopes, P S; Viviani, V R

    2014-01-15

    Bioluminescence is widely used in biosensors. For water toxicity analysis, the naturally bioluminescent bacteria Vibrio fischeri have been used extensively. We investigated the suitability of two new beetle luciferases for Escherichia coli light off biosensors: Macrolampis firefly and Pyrearinus termitilluminans click beetle luciferases. The bioluminescence detection assay using this system is very sensitive, being comparable or superior to V. fischeri. The luciferase of P. termitilluminans produces a strong and sustained bioluminescence that is useful for less sensitive and inexpensive assays that require integration of the emission, whereas Macrolampis luciferase displays a flash-like luminescence that is useful for fast and more sensitive assays. The effect of heavy metals and sanitizing agents was analyzed. Zinc, copper, 1-propanol, and iodide had inhibitory effects on bioluminescence and growth assays; however, in these cases the bioluminescence was not a very reliable indicator of cell growth and metabolic activity because these agents also inhibited the luciferase. On the other hand, mercury and silver strongly affected cell bioluminescence and growth but not the luciferase activity, indicating that bioluminescence was a reliable indicator of cell growth and metabolic activity in this case. Finally, bioluminescent E. coli immobilized in agarose matrix gave a more stable format for environmental assays.

  6. Study of O/W micro- and nano-emulsions based on propylene glycol diester as a vehicle for geranic acid.

    PubMed

    Jaworska, Małgorzata; Sikora, Elżbieta; Ogonowski, Jan; Konieczna, Monika

    2015-01-01

    Nano- and microemulsions containing as the oil phase caprylic/capric propylene glycol diesters (Crodamol PC) were investigated as potential vehicle for controlled release of geranic acid. The influence of emulsifiers and co-surfactants on stability of the emulsions was investigated. Different kind of polysorbates (ethoxylated esters of sorbitan and fatty acids) were applied as the emulsifiers. The short-chain alcohols (ethanol, 1-propanol, 1-butanol) were used as co-surfactants. The emulsions were prepared at ambient temperature (25°C), by the phase inversion composition method (PIC). The stable O/W high dispersed emulsion systems based on Crodamol PC, of mean droplets size less than 200 nm, were prepared. Microemulsions stabilized by the mixture of Polisorbat 80 and 1-butanol were characterized by the largest degree of dispersion (137 nm) and the lowest PDI value (0.094), at surfactant/co-surfactant: oil weight ratio 90:10. The stable nano-emulsion (mean droplet size of 33 nm) was obtained for surfactant: oil (S:O) weight ratio 90:10, without co-surfactant addition. This nano-emulsion was chosen to release studies. The obtained results showed that the prepared stable nano-emulsion can be used as a carrier for controlled release of geranic acid. The active substance release from the nano-emulsion and the oil solution, after 24 hours was 22%.

  7. 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.

  8. Characterization of warfarin unusual peak profiles on oligoproline chiral high performance liquid chromatography columns.

    PubMed

    Lao, Wenjian; Gan, Jay

    2010-10-15

    Unusual peak profiles of warfarin were characterized on two oligoproline chiral stationary phases (CSPs). The pattern of 1st peak (S(-)) broadening and the 2nd peak (R(+)) compression was observed under mobile phase of hexane (0.1% TFA)/2-propanol (IPA) on a triproline CSP 1, and with other alcohol modifier such as ethanol, 1-propanol, 1-butanol, 2-butanol, and tert-butanol as well. Through analyzing system peak of additives, the unusual peak profile was interpreted by perturbation of TFA additive system peak. The unusual peak profile was also found in enantioseparation of coumachlor and on a covalently bonded doubly tethered diproline CSP 2. The pattern of 1st peak (S(-)) broadening and the 2nd peak (R(+)) compression can change to pattern of 1st peak compression and the 2nd peak broadening from 15 to 50°C. Chiral separation of warfarin created nonlinear van't Hoff plots on CSP. No peak broadening/compression were observed with methyl tertiary butyl ether or ethyl acetate as the modifier. The peak shapes of the two warfarin enantiomers can thus be tuned by varying alcohol concentration and column temperature. High separation factor and resolution may be carried out to tune the peak profiles into Langmuir/anti-Langmuir band-shape composition. Using none hydrogen donor modifier may avoid interference of the TFA system peak.

  9. Characterization of key odorants in Chinese chixiang aroma-type liquor by gas chromatography-olfactometry, quantitative measurements, aroma recombination, and omission studies.

    PubMed

    Fan, Haiyan; Fan, Wenlai; Xu, Yan

    2015-04-15

    Chixiang aroma-type liquor is extensively welcomed by consumers owing to its typical fatty aroma, particularly in southern China. To our knowledge, no comprehensive characterization of aroma and flavor from chixiang aroma-type liquor has been published. It is still a confused question which components are the most important in characterizing its unique aroma. A total of 56 odorants were identified in chixiang aroma-type liquor by aroma extract dilution analysis (AEDA), and in different quantitative measurements, 34 aroma compounds were further demonstrated as important odorants according to odor activity values (OAVs). Furthermore, this research suggested that the aroma of chixiang aroma-type finished liquor could be successfully reconstituted by mixing 34 aroma compounds in the concentrations measured. Omission experiments further confirmed (E)-2-nonenal as the key odorant and revealed the significance of (E)-2-octenal and 2-phenylethanol for the overall aroma of chixiang aroma-type liquor. 3-(Methylthio)-1-propanol (methionol), diethyl 1,7-heptanedioate (diethyl pimelate), diethyl 1,8-octanedioate (diethyl suberate), and diethyl 1,9-nonanedioate (diethyl azelate), identified as the characteristic aromas of chixiang aroma-type liquor in 1995, had no effects on aroma based on omission/addition experiments.

  10. Enzymes extracted from apple peels have activity in reducing higher alcohols in Chinese liquors.

    PubMed

    Han, Qi'an; Shi, Junling; Zhu, Jing; Lv, Hongliang; Du, Shuangkui

    2014-10-01

    As the unavoidable byproducts of alcoholic fermentation, higher alcohols are unhealthy compounds widespread in alcoholic drinks. To investigate the activity of apple crude enzymes toward higher alcohols in liquors, five kinds of apple peels, namely, Fuji, Gala, Golden Delicious, Red Star, and Jonagold, were chosen to prepare enzymes, and three kinds of Chinese liquors, namely, Xifeng (containing 45% ethanol), Taibai (containing 50% ethanol), and Erguotou (containing 56% ethanol), were tested. Enzymes were prepared in the forms of liquid solution, powder, and immobilized enzymes using sodium alginate (SA) and chitosan. The treatment was carried out at 37 °C for 1 h. The relative amounts of different alcohols (including ethanol, 1-propanol, isobutanol, 1-butanol, isoamylol, and 1-hexanol) were measured using gas chromatography (GC). Conditions for preparing SA-immobilized Fuji enzymes (SA-IEP) were optimized, and the obtained SA-IEP (containing 0.3 g of enzyme) was continuously used to treat Xifeng liquor eight times, 20 mL per time. Significant degradation rates (DRs) of higher alcohols were observed at different degrees, and it also showed enzyme specificity according to the apple varieties and enzyme preparations. After five repeated treatments, the DRs of the optimized Fuji SA-IEP remained 70% for 1-hexanol and >15% for other higher alcohols.

  11. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions.

    PubMed

    Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

    2015-11-21

    We apply our recently developed generalized Flory-Huggins (FH) type theory for the competitive solvation of polymers by two mixed solvents to explain general trends in the variation of phase boundaries and solvent quality (quantified by the second osmotic virial coefficient B2) with solvent composition. The complexity of the theoretically predicted miscibility patterns for these ternary mixtures arises from the competitive association between the polymer and the solvents and from the interplay of these associative interactions with the weak van der Waals interactions between all components of the mixture. The main focus here lies in determining the influence of the free energy parameters for polymer-solvent association (solvation) and the effective FH interaction parameters {χαβ} (driving phase separation) on the phase boundaries (specifically the spinodals), the second osmotic virial coefficient B2, and the relation between the positions of the spinodal curves and the theta temperatures at which B2 vanishes. Our classification of the predicted miscibility patterns is relevant to numerous applications of ternary polymer solutions in industrial formulations and the use of mixed solvent systems for polymer characterization, such as chromatographic separation where mixed solvents are commonly employed. A favorable comparison of B2 with experimental data for poly(methyl methacrylate)/acetonitrile/methanol (or 1-propanol) solutions only partially supports the validity of our theoretical predictions due to the lack of enough experimental data and the neglect of the self and mutual association of the solvents.

  12. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions

    NASA Astrophysics Data System (ADS)

    Dudowicz, Jacek; Freed, Karl F.; Douglas, Jack F.

    2015-11-01

    We apply our recently developed generalized Flory-Huggins (FH) type theory for the competitive solvation of polymers by two mixed solvents to explain general trends in the variation of phase boundaries and solvent quality (quantified by the second osmotic virial coefficient B 2 ) with solvent composition. The complexity of the theoretically predicted miscibility patterns for these ternary mixtures arises from the competitive association between the polymer and the solvents and from the interplay of these associative interactions with the weak van der Waals interactions between all components of the mixture. The main focus here lies in determining the influence of the free energy parameters for polymer-solvent association (solvation) and the effective FH interaction parameters {χαβ} (driving phase separation) on the phase boundaries (specifically the spinodals), the second osmotic virial coefficient B 2 , and the relation between the positions of the spinodal curves and the theta temperatures at which B 2 vanishes. Our classification of the predicted miscibility patterns is relevant to numerous applications of ternary polymer solutions in industrial formulations and the use of mixed solvent systems for polymer characterization, such as chromatographic separation where mixed solvents are commonly employed. A favorable comparison of B 2 with experimental data for poly(methyl methacrylate)/acetonitrile/methanol (or 1-propanol) solutions only partially supports the validity of our theoretical predictions due to the lack of enough experimental data and the neglect of the self and mutual association of the solvents.

  13. High octane ethers from synthesis gas-derived alcohols. Final technical report, September 25, 1990--December 24, 1993

    SciTech Connect

    Klier, K.; Herman, R.G.

    1994-05-01

    The objective of the research was to develop the methodology for the catalytic synthesis of ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers. The last stage of the synthesis involves direct coupling of synthesis gas-derived methanol and isobutanol that has been previously demonstrated by us to occur over superacid catalysts to yield MIBE and smaller amounts of MTBE at moderate pressures and a mixture of methanol and isobutene at low pressures. A wide range of organic resin catalysts and inorganic oxide and zeolite catalysts have been investigated for activity and selectivity in directly coupling alcohols, principally methanol and isobutanol, to form ethers and in the dehydration of isobutanol to isobutene in the presence of methanol. All of these catalysts are strong acids, and it was found that the organic and inorganic catalysts operate in different, but overlapping, temperature ranges, i.e. mainly 60--120{degrees}C for the organic resins and 90--175{degrees}C for the inorganic catalysts. For both types of catalysts, the presence of strong acid centers is required for catalytic activity, as was demonstrated by lack of activity of fully K{sup +} ion exchanged Nafion resin and zirconia prior to being sulfated by treatment with sulfuric acid.

  14. A novel immobilization strategy for electrochemical detection of cancer biomarkers: DNA-directed immobilization of aptamer sensors for sensitive detection of prostate specific antigens.

    PubMed

    Yang, Zhugen; Kasprzyk-Hordern, Barbara; Goggins, Sean; Frost, Christopher G; Estrela, Pedro

    2015-04-21

    We report on a novel strategy for DNA aptamer immobilization to develop sensitive electrochemical detection of a protein biomarker, with prostate specific antigen (PSA) as a case biomarker. Thiolated single-stranded DNA (ssDNA) was co-immobilized with 3-mercapto-1-propanol on gold electrodes, and used as a scaffold for DNA aptamer attachment through hybridization of the aptamer overhang (so-called "DNA-directed immobilization aptamer sensors", DDIAS). In the approach, the complementary DNA aptamer against PSA was assembled by the probe ssDNA onto the electrode to detect PSA; or the probe ssDNA directly hybridized with a complementary DNA aptamer/PSA complex following their pre-incubation in solution, so-called 'on-chip' and 'in-solution' methods, respectively. A double stranded DNA intercalator with a ferrocenyl (Fc) redox marker was synthesized to evaluate the feasibility of the strategy. The results demonstrate that the 'in-solution' method offers a favourable medium (in a homogeneous solution) for the binding between the aptamer and PSA, which shows to be more efficient than the 'on-chip' approach. DDIAS shows promising analytical performance under optimized conditions, with a limit of detection in the range of fM and low non-specific adsorption.

  15. Thermodynamics of hydrogen bonding in hydrophilic and hydrophobic media.

    PubMed

    van der Spoel, David; van Maaren, Paul J; Larsson, Per; Tîmneanu, Nicusor

    2006-03-09

    The thermodynamics of hydrogen bond breaking and formation was studied in solutions of alcohol (methanol, ethanol, 1-propanol) molecules. An extensive series of over 400 molecular dynamics simulations with an aggregate length of over 900 ns was analyzed using an analysis technique in which hydrogen bond (HB) breaking is interpreted as an Eyring process, for which the Gibbs energy of activation DeltaG can be determined from the HB lifetime. By performing simulations at different temperatures, we were able to determine the enthalpy of activation DeltaH and the entropy of activation TDeltaS for this process from the Van't Hoff relation. The equilibrium thermodynamics was determined separately, based on the number of donor hydrogens that are involved in hydrogen bonds. Results (DeltaH) are compared to experimental data from Raman spectroscopy and found to be in good agreement for pure water and methanol. The DeltaG as well as the DeltaG are smooth functions of the composition of the mixtures. The main result of the calculations is that DeltaG is essentially independent of the environment (around 5 kJ/mol), suggesting that buried hydrogen bonds (e.g., in proteins) do not contribute significantly to protein stability. Enthalpically HB formation is a downhill process in all substances; however, for the alcohols there is an entropic barrier of 6-7 kJ/mol, at 298.15 K, which cannot be detected in pure water.

  16. Amplification of hofmeister effect by alcohols.

    PubMed

    Xu, Yun; Liu, Guangming

    2014-07-03

    We have demonstrated that Hofmeister effect can be amplified by adding alcohols to aqueous solutions. The lower critical solution temperature behavior of poly(N-isopropylacrylamide) has been employed as the model system to study the amplification of Hofmeister effect. The alcohols can more effectively amplify the Hofmeister effect following the series methanol < ethanol < 1-propanol < 2-propanol for the monohydric alcohols and following the series d-sorbitol ≈ xylitol ≈ meso-erythritol < glycerol < ethylene glycol < methanol for the polyhydric alcohols. Our study reveals that the relative extent of amplification of Hofmeister effect is determined by the stability of the water/alcohol complex, which is strongly dependent on the chemical structure of alcohols. The more stable solvent complex formed via stronger hydrogen bonds can more effectively differentiate the anions through the anion-solvent complex interactions, resulting in a stronger amplification of Hofmeister effect. This study provides an alternative method to tune the relative strength of Hofmeister effect besides salt concentration.

  17. Sensitive determination of parabens in human urine and serum using methacrylate monoliths and reversed-phase capillary liquid chromatography-mass spectrometry.

    PubMed

    Carrasco-Correa, Enrique Javier; Vela-Soria, Fernando; Ballesteros, Oscar; Ramis-Ramos, Guillermo; Herrero-Martínez, José Manuel

    2015-01-30

    A method for the determination of parabens in human urine and serum by capillary liquid chromatography (cLC) with UV-Vis and mass spectrometry (MS) detection using methacrylate ester-based monolithic columns has been developed. The influence of composition of polymerization mixture was studied. The optimum monolith was obtained with butyl methacrylate monomer at 60/40% (wt/wt) butyl methacrylate/ethylene dimethacrylate ratio and 50wt% porogens (composed of 36wt% of 1,4-butanediol, 54wt% 1-propanol and 10wt% water). Baseline resolution of analytes was achieved through a mobile phase of acetonitrile/water in gradient elution mode. Additionally, dispersive liquid-liquid microextraction (DLLME) was combined with both cLC-UV-Vis and cLC-MS to achieve the determination of parabens in human urine and serum samples with very low limits of detection. Satisfactory intra- and inter-day repeatabilities were obtained in UV-Vis and MS detection, although the latter provided lower detection limits (up to 300-fold) than the UV-Vis detection. Recoveries for the target analytes from spiked biological samples ranged from 95.2% to 106.7%. The proposed methodology for the ultra-low determination of parabens in human urine and serum samples is simple and fast, the consumption of reagents is very low, and very small samples can be analyzed.

  18. In Situ Focused Beam Reflectance Measurement (FBRM), Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) and Raman Characterization of the Polymorphic Transformation of Carbamazepine.

    PubMed

    Zhao, Yingying; Bao, Ying; Wang, Jingkang; Rohani, Sohrab

    2012-02-09

    The objective of this work was to study the polymorphic transformation of carbamazepine from Form II to Form III in 1-propanol during seeded isothermal batch crystallization. First, the pure Form II and Form III were obtained and characterized. Then their solubilities and metastable zone limits were measured by in-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and focused beam reflectance measurement (FBRM). A transition temperature at about 34.2 °C was deduced suggesting the enantiotropic nature of this compound over the studied temperature range. To quantify the polymorph ratio during the transformation process, a new in-situ quantitative method was developed to measure the fraction of Form II by Raman spectroscopy. Successful tracking of the nucleation of the stable form and the transformation from Form II to Form III during isothermal crystallization was achieved by Raman spectroscopy and FBRM. The results from these three in-situ techniques, FBRM, FTIR and Raman were consistent with each other. The results showed a strong dependency on the amount of seeds added during isothermal crystallization.

  19. Genotoxicity of three-carbon compounds evaluated in the SCE test in vitro

    SciTech Connect

    von der Hude, W.; Scheutwinkel, M.; Gramlich, U.; Fissler, B.; Basler, A.

    1987-01-01

    Three-carbon chemicals (chlorinated and nonchlorinated, saturated and unsaturated, hydroxy- and oxo-hydrocarbons) were assay for genotoxicity. The sister chromatid exchange test in vitro served as the test system. Without S9 mix, the nonchlorinated solvents 1-propanol, 2-propanol, and 2-propanone (acetone) did not increase the SCE frequencies. All chlorinated 3-C hydrocarbons, except 1,2,3-trichloropropane, proved to be potent SCE inducers in V79 cells without S9 mix. In the presence of S9 mix, the results obtained with the nonchlorinated solvents were also negative, whereas, 1,2,3-trichloropropane was transformed to SCE-inducing metabolites. The addition of S9 mix resulted in an increased SCE rate for 2,3-dichloropropanol, whereas genotoxicity of 2,3-dichloropropene, 1,2-dichloropropane, 1,3-dichloropropene, and 1,3-dichloropropanone was reduced. 1,3-dichloropropanol, 1,3-dichloropropene, and epichlorohydrin were substantially inactivated by S9 mix in the V79/SCE test. It can be concluded the reactivity of the saturated dichloro compounds in the SCE test depends on the degree of oxidation. There is no general difference between the reactivity of ..cap alpha..,..beta..-dichloro and ..cap alpha..,omega-dichloro compounds.

  20. 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.

  1. 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.

  2. 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.

  3. Klebsiella pneumoniae 1,3-propanediol:NAD+ oxidoreductase.

    PubMed Central

    Johnson, E A; Lin, E C

    1987-01-01

    Fermentative utilization of glycerol, a more reduced carbohydrate than aldoses and ketoses, requires the disposal of the two extra hydrogen atoms. This is accomplished by sacrificing an equal quantity of glycerol via an auxiliary pathway initiated by glycerol dehydratase. The product, 3-hydroxypropionaldehyde, is then reduced by 1,3-propanediol NAD+:oxidoreductase (1,3-propanediol dehydrogenase; EC 1.1.1.202), resulting in the regeneration of NAD+ from NADH. The pathway for the assimilation of glycerol is initiated by an NAD-linked dehydrogenase. In Klebsiella pneumoniae the two pathways are encoded by the dha regulon which is inducible only anaerobically. In this study 1,3-propanediol:NAD+ oxidoreductase was purified from cells grown anaerobically on glycerol. The enzyme was immunochemically distinct from the NAD-linked glycerol dehydrogenase and was an octamer or hexamer of a polypeptide of 45,000 +/- 3,000 daltons. When tested as a dehydrogenase, only 1,3-propanediol served as a substrate; no activity was detected with ethanol, 1-propanol, 1,2-propanediol, glycerol, or 1,4-butanediol. The enzyme was inhibited by chelators of divalent cations. An enzyme preparation inhibited by alpha,alpha'-dipyridyl was reactivated by the addition of Fe2+ or Mn2+ after removal of the chelator by gel filtration. As for glycerol dehydrogenase, 1,3-propanediol oxidoreductase is apparently inactivated by oxidation during aerobic metabolism, under which condition the enzyme becomes superfluous. Images PMID:3553154

  4. Sound absorption in nonelectrolyte aqueous solutions

    NASA Astrophysics Data System (ADS)

    Endo, Harumi; Honda, Kazuyuki

    2001-10-01

    We indicate that the curve fitting for Debye-type relaxation spectrum of sound absorption (SA) cannot sufficiently account for the observed data of nonelectrolyte aqueous solutions (NEAS). To solve these problems, we introduce the distribution function of relaxation time [DFRT, F(τ)] from a diffusion equation of concentration fluctuations using the fluctuation dispersion theory. The SA expression is described by four-adjustable parameters. By use of the mixtures of 1-propanol, t-butanol, and monobutyl triethylene glycol with water, our calculation of SA shows the best fit between the observed and calculated curves, compared with other models. It was found that at lower frequencies the SA behaves as the square root of frequency. The approximate expression of DFRT was expressed in terms of a power law of relaxation time, F(τ)∝τ-γ, which is the same as the expression of dielectric relaxation by Matsumoto and Higashi. Our exponent (γ) of relaxation time is varied from 5/2 in hydrophilic solutes to 3/2 in hydrophobic solutes. The power (γ) of relaxation time was regarded as a parameter to explain the hydrophobic and hydrophilic in the dissolved states of a solute. Our SA expression of γ=5/2 for solutes of a small correlation length leads to that of Romanov-Solov'ev, where the value of 5/2 is that of the Debye distribution for the relaxation time in the Romanov-Solov'ev model.

  5. A Very Stable High Throughput Taylor Cone-jet in Electrohydrodynamics.

    PubMed

    Morad, M R; Rajabi, A; Razavi, M; Sereshkeh, S R Pejman

    2016-12-05

    A stable capillary liquid jet formed by an electric field is an important physical phenomenon for formation of controllable small droplets, power generation and chemical reactions, printing and patterning, and chemical-biological investigations. In electrohydrodynamics, the well-known Taylor cone-jet has a stability margin within a certain range of the liquid flow rate (Q) and the applied voltage (V). Here, we introduce a simple mechanism to greatly extend the Taylor cone-jet stability margin and produce a very high throughput. For an ethanol cone-jet emitting from a simple nozzle, the stability margin is obtained within 1 kV for low flow rates, decaying with flow rate up to 2 ml/h. By installing a hemispherical cap above the nozzle, we demonstrate that the stability margin could increase to 5 kV for low flow rates, decaying to zero for a maximum flow rate of 65 ml/h. The governing borders of stability margins are discussed and obtained for three other liquids: methanol, 1-propanol and 1-butanol. For a gravity-directed nozzle, the produced cone-jet is more stable against perturbations and the axis of the spray remains in the same direction through the whole stability margin, unlike the cone-jet of conventional simple nozzles.

  6. The fabrication of monolithic capillary column based on poly (bisphenol A epoxy vinyl ester resin-co-ethylene glycol dimethacrylate) and its applications for the separation of small molecules in high performance liquid chromatography.

    PubMed

    Niu, Wenjing; Wang, Lijuan; Bai, Ligai; Yang, Gengliang

    2013-07-05

    A new polymeric monolith was synthesized in fused-silica capillary by in situ polymerization technique. In the polymerization, bisphenol A epoxy vinyl ester resin (VER) was used as the functional monomer, ethylene glycol dimethacrylate (EDMA) as the crosslinking monomer, 1,4-butanediol, 1-propanol and water as the co-porogens, and azobisisobutyronitrile (AIBN) as the initiator. The conditions of polymerization have been optimized. Morphology of the prepared poly (VER-co-EDMA) monolith was investigated by the scanning electron microscopy (SEM); pore properties were assayed by mercury porosimetry and nitrogen adsorption. The optimized poly (VER-co-EDMA) monolith showed a uniform structure, good permeability and mechanical stability. Then, the column was used as the stationary phase of high performance liquid chromatography (HPLC) to separate the mixture of benzene derivatives. The best column efficiency achieved for phenol was 235790 theoretical plates per meter. Baseline separations of benzene derivatives and halogenated benzene compounds under optimized isocratic mode conditions were achieved with high column efficiency. The column showed good reproducibility: the relative standard deviation (RSD) values based on the retention times (n=3) for run-to-run, column-to-column and batch-to-batch were less than 0.98, 1.68, 5.48%, respectively. Compared with poly (BMA-co-EDMA) monolithic column, the proposed monolith exhibited more efficiency in the separation of small molecules.

  7. Application of the multi-step EPD technique to fabricate thick TiO2 layers: effect of organic medium viscosity on the layer microstructure.

    PubMed

    Sadeghi, A A; Ebadzadeh, T; Raissi, B; Ghashghaie, S; Fateminia, S M A

    2013-02-14

    In the present study, electrophoretic deposition (EPD) was used to obtain dense layers of TiO(2) in four organic media-methanol, ethanol, 1-propanol, and butanol-with different TiO(2) nanoparticle concenterations of 1-8 g/L. Microstructural study of the obtained layers by scanning electron (SEM) and optical microscope (OM) revealed that the multistep EPD technique could effectively prevent crack formation across the layer compared with the single-step method and will consequently increase the critical cracking thickness (CCT). The quality of EPD layers was also affected by viscosity. According to SEM and atomic force microscope (AFM) results, as the viscosity of the medium increased, more compact layers were formed which can be attributed to the lower deposition rates in heavier alcohols. High deposition rate in methanol and ethanol was also confirmed by zeta potential results. Suspension viscosity was interestingly observed to control the threshold concentration above which crack formation would occur. These values were measured to be 3 and 5 g/L for methanol and ethanol, respectively. However, in suspensions based on more viscous alcohols, the threshold concentration increased to 8 g/L which implied the decisive role of medium on concentration limits. It indicates that by employing organic vehicles of higher viscosity it is possible to maintain the CCT values obtained in less viscous media with no need to decrease the colloidal concentration of the suspension.

  8. Propagation of dynamic nuclear polarization across the xenon cluster boundaries: elucidation of the spin-diffusion bottleneck.

    PubMed

    Pourfathi, M; Kuzma, N N; Kara, H; Ghosh, R K; Shaghaghi, H; Kadlecek, S J; Rizi, R R

    2013-10-01

    Earlier Dynamic Nuclear Polarization (DNP) experiments with frozen xenon/1-propanol/trityl mixtures have demonstrated spontaneous formation of pure xenon clusters above 120 K, enabling spectrally-resolved real-time measurements of (129)Xe nuclear magnetization in the clusters and in the surrounding radical-rich matrix. A spin-diffusion bottleneck was postulated to explain the peculiar time evolution of (129)Xe signals in the clusters as well as the apparent discontinuity of (129)Xe polarization across the cluster boundaries. A self-contained ab initio model of nuclear spin diffusion in heterogeneous systems is developed here, incorporating the intrinsic T1 relaxation towards the temperature-dependent equilibrium polarization and the spin-diffusion coefficients based on the measured NMR line widths and the known atomic densities in each compartment. This simple model provides the physical basis for the observed spin-diffusion bottleneck and is in a good quantitative agreement with the earlier measurements. A simultaneous fit of the model to the time-dependent NMR data at two different DNP frequencies provides excellent estimates of the cluster size, the intrinsic sample temperature, and (129)Xe T1 constants. The model was also applied to the NMR data acquired during relaxation towards the thermal equilibrium after the microwaves were turned off, to estimate T1 relaxation time constants inside and outside the clusters. Fitting the model to the data during and after DNP provides consistent estimates of the cluster size.

  9. Ethanol stimulates epithelial sodium channels by elevating reactive oxygen species.

    PubMed

    Bao, Hui-Fang; Song, John Z; Duke, Billie J; Ma, He-Ping; Denson, Donald D; Eaton, Douglas C

    2012-12-01

    Alcohol affects total body sodium balance, but the molecular mechanism of its effect remains unclear. We used single-channel methods to examine how ethanol affects epithelial sodium channels (ENaC) in A6 distal nephron cells. The data showed that ethanol significantly increased both ENaC open probability (P(o)) and the number of active ENaC in patches (N). 1-Propanol and 1-butanol also increased ENaC activity, but iso-alcohols did not. The effects of ethanol were mimicked by acetaldehyde, the first metabolic product of ethanol, but not by acetone, the metabolic product of 2-propanol. Besides increasing open probability and apparent density of active channels, confocal microscopy and surface biotinylation showed that ethanol significantly increased α-ENaC protein in the apical membrane. The effects of ethanol on ENaC P(o) and N were abolished by a superoxide scavenger, 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy (TEMPOL) and blocked by the phosphatidylinositol 3-kinase inhibitor LY294002. Consistent with an effect of ethanol-induced reactive oxygen species (ROS) on ENaC, primary alcohols and acetaldehyde elevated intracellular ROS, but secondary alcohols did not. Taken together with our previous finding that ROS stimulate ENaC, the current results suggest that ethanol stimulates ENaC by elevating intracellular ROS probably via its metabolic product acetaldehyde.

  10. Thermohalochromism of phenolate dyes conjugated with nitro-substituted aryl groups

    NASA Astrophysics Data System (ADS)

    Hermosilla, Laura; Rezende, Marcos Caroli; Machado, Vanderlei Gageiro; Stock, Rafaela I.

    2017-02-01

    The cationic halochromism and thermohalochromism of four phenolate dyes conjugated with aryl moieties substituted with one or two nitro groups were investigated in the presence of organic (tetra-n-butylammonium bromide and benzyltriethylammonium chloride) and inorganic (sodium perchlorate) salts, in hydrogen-bond donating (water, 1-propanol, 1-butanol and 2-propanol) and hydrogen-bond accepting (acetonitrile and dimethylsulfoxide) solvents. Although a positive halochromic response was observed in water for tetraalkylammonium salts, their thermohalochromic behavior was negligible. A negative halochromic behavior was observed for the dyes in all solvents, when the added cation was Na+. Plots of Δλmaxvs. c (Na+) allowed the apparent association constants for the solvated phenolate-cation pair to be estimated. In most cases, a positive thermohalochromism was observed in the range of 25-50 °C, exceptions being the more sterically hindered phenolate dyes in the less polar solvents 2-propanol and acetonitrile. The observed variations were rationalized by invoking the effect of temperature on the phenolate-cation, phenolate-solvent and cation-solvent interactions.

  11. Comparative Transcriptome Analysis of Methylibium petroleiphilum PM1 Exposed to the Fuel Oxygenates Methyl tert-Butyl Ether and Ethanol▿ †

    PubMed Central

    Hristova, Krassimira R.; Schmidt, Radomir; Chakicherla, Anu Y.; Legler, Tina C.; Wu, Janice; Chain, Patrick S.; Scow, Kate M.; Kane, Staci R.

    2007-01-01

    High-density whole-genome cDNA microarrays were used to investigate substrate-dependent gene expression of Methylibium petroleiphilum PM1, one of the best-characterized aerobic methyl tert-butyl ether (MTBE)-degrading bacteria. Differential gene expression profiling was conducted with PM1 grown on MTBE and ethanol as sole carbon sources. Based on microarray high scores and protein similarity analysis, an MTBE regulon located on the megaplasmid was identified for further investigation. Putative functions for enzymes encoded in this regulon are described with relevance to the predicted MTBE degradation pathway. A new unique dioxygenase enzyme system that carries out the hydroxylation of tert-butyl alcohol to 2-methyl-2-hydroxy-1-propanol in M. petroleiphilum PM1 was discovered. Hypotheses regarding the acquisition and evolution of MTBE genes as well as the involvement of IS elements in these complex processes were formulated. The pathways for toluene, phenol, and alkane oxidation via toluene monooxygenase, phenol hydroxylase, and propane monooxygenase, respectively, were upregulated in MTBE-grown cells compared to ethanol-grown cells. Four out of nine putative cyclohexanone monooxygenases were also upregulated in MTBE-grown cells. The expression data allowed prediction of several hitherto-unknown enzymes of the upper MTBE degradation pathway in M. petroleiphilum PM1 and aided our understanding of the regulation of metabolic processes that may occur in response to pollutant mixtures and perturbations in the environment. PMID:17890343

  12. Rotational Spectrum of Neopentyl Alcohol, (CH_3)_3CCH_2OH

    NASA Astrophysics Data System (ADS)

    Kisiel, Zbigniew; Pszczołkowski, Lech; Xue, Zhifeng; Suhm, Martin A.

    2012-06-01

    The rotational spectrum of neopentyl alcohol (2,2-dimethyl-1-propanol, (CH_3)_3CCH_2OH) has been investigated for the first time. This molecule differs from ethanol only in having the ^tBu group instead of the methyl group, and is likewise anticipated to exhibit two spectroscopic species, with trans and gauche hydroxyl orientation. Quantum chemistry computations predict the trans to be the more stable species. Rotational transitions of both species have now been assigned in supersonic expansion cm-wave FTMW experiment and in room temperature, mm-wave spectra up to 280 GHz. The supersonic expansion measurements with Ar carrier gas confirm that trans is the global minimum species. The trans spectrum is predominantly b-type, while the gauche is predominantly a-type and the frequencies of rotational transitions in both species appear to be perturbed in different ways. The results from effective and from coupled Hamiltonian fits for neopentyl alcohol are presented, and are compared with predictions from ab initio calculations.

  13. Liquid chromatographic analysis of coal surface properties. Quarterly progress report, January--March 1994

    SciTech Connect

    Kwon, K.C.; Martin, L.L.

    1994-05-01

    Experiments on flotation of 60--200 mesh treated Illinois No. 6 coal (PSOC-1539) and Wyodak coal (PSOC-1545) were performed. The coals were treated with 20-ppM alcohol aqueous solutions (soln) for 1-24 hours at the 0.002-g/min mass flow rate at 225C. Flotation of Illinois No. 6 coal, treated with 1-propanol aqueous solution, increases with treatment durations for the first 10 hours and then decreases. Flotation of Illinois No. 6 coal, treated with isopropanol soln increases with treatment durations for the first 18 hours and then levels off. Flotation of Illinois No. 6 coal, treated with butanol soln, increases with treatment durations. Flotation of 1-butanol-treated Illinois No. 6 coal is higher than that of t-butanol-treated Illinois No. 6 coal. Flotation of Illinois No. 6 coal, treated with 20-ppM-isobutanol 20-ppM-HCl soln, increases with treatment durations for the first 10 hours treatment period, and then decreases sharply with treatment durations. Flotation of Wyodak coal, treated with water only, increases with treatment durations. Effects of water treatment on flotation of Wyodak coal are significantly pronounced compared to Illinois No. 6 coal.

  14. A Pseudomonas putida strain genetically engineered for 1,2,3-trichloropropane bioremediation.

    PubMed

    Samin, Ghufrana; Pavlova, Martina; Arif, M Irfan; Postema, Christiaan P; Damborsky, Jiri; Janssen, Dick B

    2014-09-01

    1,2,3-Trichloropropane (TCP) is a toxic compound that is recalcitrant to biodegradation in the environment. Attempts to isolate TCP-degrading organisms using enrichment cultivation have failed. A potential biodegradation pathway starts with hydrolytic dehalogenation to 2,3-dichloro-1-propanol (DCP), followed by oxidative metabolism. To obtain a practically applicable TCP-degrading organism, we introduced an engineered haloalkane dehalogenase with improved TCP degradation activity into the DCP-degrading bacterium Pseudomonas putida MC4. For this purpose, the dehalogenase gene (dhaA31) was cloned behind the constitutive dhlA promoter and was introduced into the genome of strain MC4 using a transposon delivery system. The transposon-located antibiotic resistance marker was subsequently removed using a resolvase step. Growth of the resulting engineered bacterium, P. putida MC4-5222, on TCP was indeed observed, and all organic chlorine was released as chloride. A packed-bed reactor with immobilized cells of strain MC4-5222 degraded >95% of influent TCP (0.33 mM) under continuous-flow conditions, with stoichiometric release of inorganic chloride. The results demonstrate the successful use of a laboratory-evolved dehalogenase and genetic engineering to produce an effective, plasmid-free, and stable whole-cell biocatalyst for the aerobic bioremediation of a recalcitrant chlorinated hydrocarbon.

  15. Microscopic dynamics of the glass transition investigated by time-resolved fluorescence measurements of doped chromophores

    NASA Astrophysics Data System (ADS)

    Ye, Jing Yong; Hattori, Toshiaki; Nakatsuka, Hiroki; Maruyama, Yoshihiro; Ishikawa, Mitsuru

    1997-09-01

    The microscopic dynamics of several monomeric and polymeric glass-forming materials has been investigated by time-resolved fluorescence measurements of doped malachite green molecules in a wide temperature region. For monomers, 1-propanol, propylene glycol, and glycerol, and a polymer without side chains, poly- butadiene, the temperature dependence of nonradiative decay time of doped malachite green molecules behaves in a similar way through the glass-transition region. Besides a kink around the calorimetric glass-transition temperature Tg, another crossover at a critical temperature Tc about 30-50 K above Tg has been clearly observed. This experimental finding is in agreement with the prediction of the mode-coupling theory that a dynamical transition exists well above Tg. On the other hand, for the complex polymers with side chains, poly(vinyl acetate), poly(methyl acrylate), and poly(ethyl methacrylate), the crossover at Tg is less pronounced than those for the monomers and the polymer without side chains. Moreover, although we could not distinguish any singularities above Tg for these complex polymers, we observed another kink below Tg, which may be attributed to the side-chain motions.

  16. CEC separation of heterocyclic amines using methacrylate monolithic columns.

    PubMed

    Barceló-Barrachina, Elena; Moyano, Encarnación; Puignou, Lluís; Galceran, Maria Teresa

    2007-06-01

    Two methacrylate-based monolithic columns, one with a negatively charged group (sulfonic group) and another with a new monomer N,N-dimethylamino ethyl acrylate (DMAEA), were prepared and tested for the separation of basic compounds by CEC. This new monolithic stationary phase was prepared by the in situ polymerization of DMAEA with butyl methacrylate and ethylene dimethacrylate, using a ternary porogenic solvent consisting of water, 1-propanol and 1,4-butanediol. The performance of this column was evaluated by means of the analysis of a family of heterocyclic amines. Separation conditions such as pH, amount of organic modifier, ionic strength and elution mode (normal or counterdirectional flow) were studied. At the optimal running electrolyte composition, and using the counterdirectional mode, symmetrical electrochromatographic peaks were obtained, with the number of theoretical plates up to 30,000 and a good resolution between closely related peaks. The 2-acrylamido-2-methyl-1-propane-sulfonic acid column was used for CEC-MS, taking advantage of the compatibility of its elution mode (normal flow) with the MS coupling.

  17. Application of integrated comprehensive/multidimensional gas chromatography with mass spectrometry and olfactometry for aroma analysis in wine and coffee.

    PubMed

    Chin, Sung-Tong; Eyres, Graham T; Marriott, Philip J

    2015-10-15

    Component coelution in chromatographic analysis complicates identification and attribution of individual odour-active volatile molecules in complex multi-component samples. An integrated system incorporating comprehensive two-dimensional gas chromatography (GC × GC) and multidimensional gas chromatography (MDGC), with flame ionisation, olfactometry and mass spectrometry detection was developed to circumvent data correlation across different systems. Identification of potent odorants in Shiraz wine and the headspace of ground coffee are demonstrated as selected applications. Multiple solid-phase microextraction (SPME) sampling with GC-O located odour-active regions; GC × GC established the complexity of odour-active regions; MDGC provided high-resolution separation for each region; simultaneous 'O' and MS detection completed the analysis for target resolved peaks. Seven odour regions in Shiraz were analysed with MDGC-O/MS detection, revealing 11 odour volatiles through matching of mass spectrometry and retention indices from both separating dimensions, including acetic acid; octen-3-ol; ethyl octanoate; methyl-2-oxo-nonanoate; butanoic acid, 2-methylbutanoic acid, and 3-methylbutanoic acid; 3-(methylthio)-1-propanol; hexanoic acid; β-damascenone; and ethyl-3-phenylpropanoate. A capsicum odour in ground coffee was identified as 2-methoxy-3-isobutylpyrazine with a 5-fold increase in S/N of the odorant when acquired using a 6-time cumulative SPME sampling approach.

  18. Comparative studies on the alcohol types presence in Gracilaria sp. and rice fermentation using Sasad

    NASA Astrophysics Data System (ADS)

    Mansa, R.; Mansuit, H.; Sipaut, C. S.; Yee, C. F.; Yasir, S. M.

    2016-06-01

    Alternative fuel sources such as biofuels are needed in order to overcome environmental problem caused by fossil fuel consumption. Currently, most biofuel are produced from land based crops and there is a possibility that marine biomass such as macroalgae can be an alternative source for biofuel production. The carbohydrate in macroalgae can be broken down into simple sugar through thermo-chemical hydrolysis and enzymatic hydrolysis. Dilute-acid hydrolysis was believed to be the most available and affordable method. However, the process may release inhibitors which would affect alcohol yield from fermentation. Thus, this work was aimed at investigating if it is possible to avoid this critical pre-treatment step in macroalgae fermentation process by using Sasad, a local Sabahan fermentation agent and to compare the yield with rice wine fermentation. This work hoped to determine and compare the alcohol content from Gracilaria sp. and rice fermentation with Sasad. Rice fermentation was found containing ethanol and 2 - methyl - 1 - propanol. Fermentation of Gracilaria sp. had shown the positive presence of 3 - methyl - 1 - butanol. It was found that Sasad can be used as a fermentation agent for bioalcohol production from Gracilaria sp. without the need for a pretreatment step. However further investigations are needed to determine if pre-treatment would increase the yield of alcohol.

  19. Analysis of methanol and ethanol in virgin olive oil

    PubMed Central

    Gómez-Coca, Raquel B.; Cruz-Hidalgo, Rosario; Fernandes, Gabriel D.; Pérez-Camino, María del Carmen; Moreda, Wenceslao

    2014-01-01

    This work provides a short and easy protocol that allows the analysis of both methanol and ethanol in the static headspace of olive oil. The procedure avoids any kind of sample pre-treatment beyond that of heating the oil to allow a maximum volatile concentration in the headspace of the vials. The method's LOD is 0.55 mg kg−1 and its LOQ is 0.59 mg kg−1. Advantages of this method are:•Simultaneous determination of methanol and ethanol (the pre-existing Spanish specification UNE-EN 14110 only analyses methanol).•No need of equipment modifications (standard split injectors work perfectly). Use of a highly polar capillary GC column, leading in most cases to chromatograms in which only three dominant peaks are present – methanol, ethanol, and propanol (that is extremely positive for easy interpretation of results).•Use of an internal standard (1-propanol) to determine the concentration of the analytes, reducing the presence of error sources. PMID:26150954

  20. Effects of Fermentation Temperature on Key Aroma Compounds and Sensory Properties of Apple Wine.

    PubMed

    Peng, Bangzhu; Li, Fuling; Cui, Lu; Guo, Yaodong

    2015-12-01

    Fermentation temperature strongly affects yeast metabolism during apple wine making and thus aromatic and quality profiles. In this study, the temperature effect during apple wine making on both the key aroma compounds and sensory properties of apple wine were investigated. The concentration of nine key aroma compounds (ethyl acetate, isobutyl acetate, isopentylacetate, ethyl caprylate, ethyl 4-hydroxybutanoate, isobutylalcohol, isopentylalcohol, 3-methylthio-1-propanol, and benzeneethanol) in apple wine significantly increased with the increase of fermentation temperature from 17 to 20 °C, and then eight out of the nine key aroma compounds with an exception of ethyl 4-hydroxybutanoate, decreased when the temperature goes up 20 to 26 °C. Sensory analysis showed that the apple wine fermented at 20 °C had the highest acceptance for consumers. Fermentation at the temperature of 20 °C was therefore considered to be the most suitable condition using the selected yeast strain (Saccharomyces cerevisiae AP05) for apple wine making. Changes in the fermentation temperature can considerably affect the production of key aroma compounds and sensory profiles of apple wine. These results could help apple wine producers make better quality production for consumers at the optimal fermentation temperature.

  1. Acid Lipase from Candida viswanathii: Production, Biochemical Properties, and Potential Application

    PubMed Central

    de Almeida, Alex Fernando; Carmona, Eleonora Cano

    2013-01-01

    Influences of environmental variables and emulsifiers on lipase production of a Candida viswanathii strain were investigated. The highest lipase activity (101.1 U) was observed at 210 rpm, pH 6.0, and 27.5°C. Other fermentation parameters analyzed showed considerable rates of biomass yield (YL/S = 1.381 g/g), lipase yield (YL/S = 6.892 U/g), and biomass productivity (PX = 0.282 g/h). Addition of soybean lecithin increased lipase production in 1.45-fold, presenting lipase yield (YL/S) of 10.061 U/g. Crude lipase presented optimal activity at acid pH of 3.5, suggesting a new lipolytic enzyme for this genus and yeast in general. In addition, crude lipase presented high stability in acid conditions and temperature between 40 and 45°C, after 24 h of incubation in these temperatures. Lipase remained active in the presence of organic solvents maintaining above 80% activity in DMSO, methanol, acetonitrile, ethanol, acetone, 1-propanol, isopropanol, and 2-propanol. Effectiveness for the hydrolysis of a wide range of natural triglycerides suggests that this new acid lipase has high potential application in the oleochemical and food industries for hydrolysis and/or modification of triacylglycerols to improve the nutritional properties. PMID:24350270

  2. Effects of select nitrocompounds on in vitro ruminal fermentation during conditions of limiting or excess added reductant.

    PubMed

    Anderson, Robin C; Krueger, Nathan A; Stanton, Thaddeus B; Callaway, Todd R; Edrington, Thomas S; Harvey, Roger B; Jung, Yong Soo; Nisbet, David J

    2008-12-01

    Ruminal methane (CH(4)) production results in the loss of up to 12% of gross energy intake and contributes nearly 20% of the United States' annual emission of this greenhouse gas. We report the effects of select nitrocompounds on ruminal fermentation after 22 h in vitro incubation (39 degrees C) with or without additions of hydrogen (H(2)), formate or both. In incubations containing no added reductant, CH(4) production was inhibited 41% by 2-nitro-1-propanol (2NPOH) and >97% by 3-nitro-1-propionic acid (3NPA), nitroethane (NE) and 2-nitroethanol (2NEOH) compared to non-treated controls and H(2) did not accumulate. With formate as the sole added reductant, nitro-treatment reduced CH(4) production by >99% and caused 42% to complete inhibition of formate catabolism compared to controls, and the accumulation of H(2) increased slightly. Nitro-treatment decreased CH(4) production 57-98% from that of controls when supplied H(2) or formate plus H(2). Formate catabolism was decreased 42-84% from that in controls by all nitro-treatments except 3NPA with both formate and H(2). Greater than 97% of the added H(2) was catabolized within controls; >84% was catabolized in nitro-treated incubations. Acetate, propionate and butyrate accumulations were unaffected by nitro-treatment irregardless of reductant; however, effects on ammonia and branched chain fatty acid accumulations varied. These results suggest that nitro-treatment inhibited formate dehydrogenase/formate hydrogen lyase and hydrogenase activity.

  3. Catalytic conversion of aliphatic alcohols on carbon nanomaterials: The roles of structure and surface functional groups

    NASA Astrophysics Data System (ADS)

    Tveritinova, E. A.; Zhitnev, Yu. N.; Chernyak, S. A.; Arkhipova, E. A.; Savilov, S. V.; Lunin, V. V.

    2017-03-01

    Carbon nanomaterials with the structure of graphene and different compositions of the surface groups are used as catalysts for the conversion of C2-C4 aliphatic alcohols. The conversions of ethanol, propanol- 1, propanol-2, butanol-1, butanol-2, and tert-butanol on carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are investigated. Oxidized and nonoxidized multiwalled carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are synthesized. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning and transmission electronic microscopies, Brunauer-Emmett-Teller method, derivatographic analyses, and the pulsed microcatalytic method are used to characterize comprehensively the prepared catalysts. It was established that all of the investigated carbon nanomaterials (with the exception of nondoped carbon nanoflakes) are bifunctional catalysts for the conversion of aliphatic alcohols, and promote dehydration reactions with the formation of olefins and dehydrogenation reactions with the formation of aldehydes or ketones. Nanoflakes doped with nitrogen are inert with respect to secondary alcohols and tert-butanol. The role of oxygen-containing and nitrogen-containing surface groups, and of the geometrical structure of the carbon matrix of graphene nanocarbon materials in the catalytic conversion of aliphatic alcohols, is revealed. Characteristics of the conversion of aliphatic alcohols that are associated with their structure are identified.

  4. Determination of priority phenolic pollutants exploiting an in-syringe dispersive liquid-liquid microextraction-multisyringe chromatography system.

    PubMed

    González, Alba; Avivar, Jessica; Cerdà, Víctor

    2015-03-01

    An automatic phenolic compounds analyzer is presented. The system performs online magnetic-stirring-assisted dispersive liquid-liquid microextraction before multisyringe chromatography (MSC) using a monolithic Chromolith Flash RP-18e column. The extraction behavior of the following phenolic pollutants: phenol, 2-nitrophenol, 4-nitrophenol, 2-chlorophenol, 2,4-diclorophenol, and 2,4,6-trichlorophenol, has been studied. A critical comparison of extractants (tributyl phosphate, acetonitrile, hexane, and 1-chlorobutane) and disperser solvents (acetone, acetonitrile, ethanol, methanol, 1-propanol, and 2-propanol) was made. Tributyl phosphate and acetonitrile were chosen as the extractant and the disperser solvent, respectively, since these showed the best performance. Phenols were online back-extracted into NaOH and neutralized before multi-isocratic chromatographic separation. The proposed analyzer can be applied for wide linear working ranges, i.e., between 40 and 20,000 μg L(-1). The precision of the developed system has been proved, with maximum values for the intraday and interday precision of 4.4 % and 5.2 %, respectively, expressed as relative standard deviation, and high preconcentration factors (9.3-10.5) for most of the compounds studied. The method developed was successfully applied to natural water samples.

  5. Enhanced enteric properties and stability of shellac films through composite salts formation.

    PubMed

    Limmatvapirat, Sontaya; Limmatvapirat, Chutima; Puttipipatkhachorn, Satit; Nuntanid, Jurairat; Luangtana-Anan, Manee

    2007-11-01

    The objective of this study was to improve the properties of shellac by composite salts formation. The shellac samples were prepared in various salt forms by dissolving them with 2-amino-2-methyl-1-propanol (AMP) and ammonium hydroxide (AMN) at various ratios of AMP:AMN. The results demonstrated that aqueous solubility of the shellac salts was improved as the ratio of AMP:AMN increased. The absorbance ratio of the FTIR peaks assigned to CO stretching of carboxylate and carboxylic acid (ABS1556/ABS1716) was increased with the increase of the AMP fraction, suggesting that the solubility enhancement was due to more ionization of AMP salts. Moisture adsorption studies indicated that shellac salts were more hygroscopic as AMP content increased. After storage at 40 degrees C, 75% RH, the acid value and insoluble solid of AMP salts were relatively constant even after storage of up to 180 days, suggesting that AMP should protect polymerization. The ABS1556/ABS1716 values of the shellac salts were rapidly decreased after storage, especially for those consisting of a high percentage of AMN. Thus, AMP should bind much tighter at the carboxylate binding site as compared with AMN, resulting in more solubility and stability. In conclusion, optimized shellac properties could be easily accomplished by composite salts formation.

  6. Agonistic sensory effects of airborne chemicals in mixtures: odor, nasal pungency, and eye irritation.

    PubMed

    Cometto-Muñiz, J E; Cain, W S; Hudnell, H K

    1997-07-01

    Thresholds responses of odor, nasal pungency (irritation), and eye irritation were measured for single chemicals (1-propanol, 1-hexanol, ethyl acetate, heptyl acetate, 2-pentanone, 2-heptanone, toluene, ethyl benzene, and propyl benzene) and mixtures of them (two three-component mixtures, two six-component mixtures, and one nine-component mixture). Nasal pungency was measured in subjects lacking a functional sense of smell (i.e., anosmics) to avoid interference from olfaction. Various degrees of stimulus agonism (additive effects) were observed for each of the three sensory channels when testing mixtures. As the number of components and the lipophilicity of such components in the mixtures decreased, so did the degree of agonism. Synergistic stimulus agonism characterized the eye-irritation response for the most complex (the nine-component) and the most lipophilic (one of the six-component) mixtures. Physicochemical properties play a large role in the determination of sensitivity to airborne chemicals, particularly to their ability to evoke irritation. While this has revealed itself previously with respect to single chemicals, it seems to have relevance to mixtures as well.

  7. Effect of Agave tequilana age, cultivation field location and yeast strain on tequila fermentation process.

    PubMed

    Pinal, L; Cornejo, E; Arellano, M; Herrera, E; Nuñez, L; Arrizon, J; Gschaedler, A

    2009-05-01

    The effect of yeast strain, the agave age and the cultivation field location of agave were evaluated using kinetic parameters and volatile compound production in the tequila fermentation process. Fermentations were carried out with Agave juice obtained from two cultivation fields (CF1 and CF2), as well as two ages (4 and 8 years) and two Saccharomyces cerevisiae yeast strains (GU3 and AR5) isolated from tequila fermentation must. Sugar consumption and ethanol production varied as a function of cultivation field and agave age. The production of ethyl acetate, 1-propanol, isobutanol and amyl alcohols were influenced in varying degrees by yeast strain, agave age and cultivation field. Methanol production was only affected by the agave age and 2-phenylethanol was influenced only by yeast strain. This work showed that the use of younger Agave tequilana for tequila fermentation resulted in differences in sugar consumption, ethanol and volatile compounds production at the end of fermentation, which could affect the sensory quality of the final product.

  8. Characterization of kinetic parameters and the formation of volatile compounds during the tequila fermentation by wild yeasts isolated from agave juice.

    PubMed

    Arellano, Melchor; Pelayo, Carlos; Ramírez, Jesús; Rodriguez, Ingrid

    2008-08-01

    The production of aroma compounds during tequila fermentation using four native yeast strains isolated from agave juice was quantified at controlled (35 degrees C) and uncontrolled temperatures (room temperature) by gas chromatography (FID). Three of the four strains were identified as Saccharomyces cerevisiae (MTLI 1, MALI 1 and MGLI 1) and one as Kloeckera apiculata (MALI 2). Among the aroma compounds produced, acetaldehyde has the highest accumulation at the controlled temperature and before 50% of sugar was consumed. The S. cerevisiae strains produced ethyl acetate in almost the same quantity at a concentration of 5 mg/L and the K. apiculata produced six-times more (30 mg/L) than the S. cerevisiae strains, independent of the fermentation temperature. The rate and amount of 1-propanol, amyl alcohols and isobutanol production were affected by the type of yeast used. The K. apiculate strain produced 50% less of the higher alcohols than the Saccharomyces strains. The results obtained showed that indigenous isolated yeasts play an important role in the tequila flavor and suggest that mixtures of these yeasts may be used to produce tequila with a unique and desirable aroma.

  9. Optimization of the separation of a group of triazine herbicides by micellar capillary electrophoresis using experimental design and artificial neural networks.

    PubMed

    Frías-García, Sergio; Sánchez, M Jesús; Rodríguez- Delgado, Miguel Angel

    2004-04-01

    The micellar electrokinetic chromatography separation of a group of triazine compounds was optimized using a combination of experimental design (ED) and artificial neural network (ANN). Different variables affecting separation were selected and used as input in the ANN. A chromatographic exponential function (CEF) combining resolution and separation time was used as output to obtain optimal separation conditions. An optimized buffer (19.3 mM sodium borate, 15.4 mM disodium hydrogen phosphate, 28.4 mM SDS, pH 9.45, and 7.5% 1-propanol) provides the best separation with regard to resolution and separation time. Besides, an analysis of variance (ANOVA) approach of the MEKC separation, using the same variables, was developed, and the best capability of the combination of ED-ANN for the optimization of the analytical methodology was demonstrated by comparing the results obtained from both approaches. In order to validate the proposed method, the different analytical parameters as repeatability and day-to-day precision were calculated. Finally, the optimized method was applied to the determination of these compounds in spiked and nonspiked ground water samples.

  10. Lysozyme gelation in mixtures of tetramethylurea with protic solvents: Use of solvatochromic indicators to probe medium microstructure and solute solvent interactions

    NASA Astrophysics Data System (ADS)

    da Silva, Marcelo A.; El Seoud, Omar A.; Arêas, Elizabeth P. G.

    2007-09-01

    This work investigated the relationship between the structure of binary mixtures of tetramethylurea and protic solvents and their capacity to induce lysozyme gelation. In order to get an insight into the mechanism of gel formation, the solvatochromic behavior of zwitterionic probes, employed as simple models for the protein, was investigated. We studied two probes of similar p Ka's, but different hydrophobic character, namely 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate, RB, and 4-[2-(1-methylpyridinium-4-yl) ethenyl] phenolate, MC. The protic solvents used included water, 1-propanol and 2- n-butoxyethanol in the temperature range from 10 to 60 °C, and methanol, from 10 to 40 °C. In all cases, the dependence of the empirical solvent polarity parameter, ET, on mixture composition was non-ideal with negative deviation for TMU-water and positive deviation for TMU-organic solvent. For all binary mixtures, the deviation from linearity decreased as a function of increasing the temperature. In TMU/alcohol, the effect became more pronounced with increasing alcohol hydrophobicity.

  11. Electron spin-lattice relaxation of nitroxyl radicals in temperature ranges that span glassy solutions to low-viscosity liquids.

    PubMed

    Sato, Hideo; Bottle, Steven E; Blinco, James P; Micallef, Aaron S; Eaton, Gareth R; Eaton, Sandra S

    2008-03-01

    Electron spin-lattice relaxation rates, 1/T1, at X-band of nitroxyl radicals (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl and 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl) in glass-forming solvents (decalin, glycerol, 3-methylpentane, o-terphenyl, 1-propanol, sorbitol, sucrose octaacetate, and 1:1 water:glycerol) at temperatures between 100 and 300K were measured by long-pulse saturation recovery to investigate the relaxation processes in slow-to-fast tumbling regimes. A subset of samples was also studied at lower temperatures or at Q-band. Tumbling correlation times were calculated from continuous wave lineshapes. Temperature dependence and isotope substitution (2H and 15N) were used to distinguish the contributions of various processes. Below about 100K relaxation is dominated by the Raman process. At higher temperatures, but below the glass transition temperature, a local mode process makes significant contributions. Above the glass transition temperature, increased rates of molecular tumbling modulate nuclear hyperfine and g anisotropy. The contribution from spin rotation is very small. Relaxation rates at X-band and Q-band are similar. The dependence of 1/T1 on tumbling correlation times fits better with the Cole-Davidson spectral density function than with the Bloembergen-Purcell-Pound model.

  12. Electron spin lattice relaxation of nitroxyl radicals in temperature ranges that span glassy solutions to low-viscosity liquids

    NASA Astrophysics Data System (ADS)

    Sato, Hideo; Bottle, Steven E.; Blinco, James P.; Micallef, Aaron S.; Eaton, Gareth R.; Eaton, Sandra S.

    2008-03-01

    Electron spin-lattice relaxation rates, 1/ T1, at X-band of nitroxyl radicals (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl and 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl) in glass-forming solvents (decalin, glycerol, 3-methylpentane, o-terphenyl, 1-propanol, sorbitol, sucrose octaacetate, and 1:1 water:glycerol) at temperatures between 100 and 300 K were measured by long-pulse saturation recovery to investigate the relaxation processes in slow-to-fast tumbling regimes. A subset of samples was also studied at lower temperatures or at Q-band. Tumbling correlation times were calculated from continuous wave lineshapes. Temperature dependence and isotope substitution ( 2H and 15N) were used to distinguish the contributions of various processes. Below about 100 K relaxation is dominated by the Raman process. At higher temperatures, but below the glass transition temperature, a local mode process makes significant contributions. Above the glass transition temperature, increased rates of molecular tumbling modulate nuclear hyperfine and g anisotropy. The contribution from spin rotation is very small. Relaxation rates at X-band and Q-band are similar. The dependence of 1/ T1 on tumbling correlation times fits better with the Cole-Davidson spectral density function than with the Bloembergen-Purcell-Pound model.

  13. Correlation of Chemical and Physical Test Data for the Environmental Ageing of Tefzel (ETFE). Revised

    NASA Technical Reports Server (NTRS)

    Morgan, G. J.; Campion, R. P.

    1997-01-01

    In a similar approach to that used for the previously issued correlation report for Coflon (CAPP/M.10), this report aims to identify any correlations between mechanical property changes and chemical/morphological changes for Tefzel, using information supplied in other MERL and TRI project reports. Differences identified with Coflon behaviour will be of scientific interest as well as appropriate to project applications, as Tefzel and Coflon are chemical isomers. Owing to the considerable chemical resistance of Tefzel, much of its testing so far has been based on mechanical properties. Where changes have occurred, chemical analysis can now be targeted more effectively. Relevant test data collated here include: tensile modulus and related properties, permeation coefficients, % crystallinity, some crack growth resistance measurements, and other observations where significant. Fluids based on methanol and amine (Fluid G), a mixture of methane, carbon dioxide and hydrogen sulphide gases plus an aqueous amine solution (Fluid F), and an aromatic oil mix of heptane, cyclohexane, toluene and 1-propanol (Fluid I) have affected Tefzel to varying degrees, and are discussed in some detail herein.

  14. Health assessment for Velsicol Chemical Corporation (St. Louis Plant Site), Gratiot County, Michigan, Region 5. CERCLIS No. MID000722439. Preliminary report

    SciTech Connect

    Not Available

    1989-04-18

    The Velsicol Chemical Corporation (Velsicol) site is currently listed on the National Priorities List. More than 60 contaminants were found throughout the site, but polybrominated biphenyl (PBB) is the contaminant that caused the most concern. Phenols, calcium, magnesium, sodium (as chloride or bromium salts) and PBB were present in wastes. Soil samples collected had the following maximum concentrations (parts per million - ppm); PBB, 1,100; phenol, 4.2; lead, 11,100; hexabromebenzene, 56; 2,3-dibromo-1-propanol phosphate, 4,700; and dimethylaminoethylchloride hydrochloride (DMAE), 53. On-site ground water samples contained the following maximum concentrations (ppm): PBB, 0.013; chloride, 82,000; sulfate, 650; phenol, 1.2; DMAE, 20 and carbon tetrachloride, 0.080. Of various species of fish carp had the highest maximum PBB concentrations. Wildlife (mice, earthworms, a raccoon and ducks) in the area were found to be contaminated with PBB and/or DDT. The site is of potential public health concern because of the risk to human health that could result from possible human exposure to hazardous substances at levels that may result in adverse human health effects over time. Occupational exposure to many harmful contaminants, including PBB and DDT, has occurred and exposure to the general population may possibly still be occurring via ingestion of contaminated fish and wildlife.

  15. Experimental Measurement and Thermodynamic Modeling of the Solubility of Carbon Dioxide in Aqueous Alkanolamine Solutions in the High Gas Loading Region

    NASA Astrophysics Data System (ADS)

    Suleman, Humbul; Maulud, Abdulhalim Shah; Man, Zakaria

    2016-09-01

    The solubility of carbon dioxide in aqueous alkanolamine solutions was investigated in the high gas loading region based on experimental measurements and thermodynamic modeling. An experimental phase equilibrium study was performed to evaluate the absorption of carbon dioxide in aqueous solutions of five representative alkanolamines, including monoethanolamine, diethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol and piperazine. The carbon dioxide loadings of these solutions were determined for a wide range of pressures (62.5 kPa to 4150 kPa), temperatures (303.15 K to 343.15 K) and alkanolamine concentrations (2 M to 4 M). The results were found to be largely consistent with those previously reported in the literature. Furthermore, a hybrid Kent-Eisenberg model was developed for the correlation of the experimental data points. This new model incorporated an equation of state/excess Gibbs energy model for determining the solubility of carbon dioxide in the high-pressure-high gas loading region. This approach also used a single correction parameter, which was a function of the alkanolamine concentration. The results of this model were in excellent agreement with our experimental results. Most notably, this model was consistent with other reported values from the literature.

  16. Effect of high-pressure treatment and a bacteriocin-producing lactic culture on the odor and aroma of hispánico cheese: correlation of volatile compounds and sensory analysis.

    PubMed

    Avila, Marta; Garde, Sonia; Fernández-García, Estrella; Medina, Margarita; Nuñez, Manuel

    2006-01-25

    The effect on the volatile compounds and on the odor and aroma of Hispánico cheese of a high-pressure (HP) treatment (400 MPa for 5 min at 10 degrees C, applied to 15-day-old cheeses), by itself or combined with the addition of a bacteriocin-producing (BP) culture to milk, was investigated. HP-treated cheeses showed higher levels of hexanal, 3-hydroxy-2-pentanone, 2-hydroxy-3-pentanone, and hexane and lower levels of ethanal, ethanol, 1-propanol, ethyl acetate, ethyl butanoate, ethyl hexanoate, 2-pentanone, and butanoic acid than untreated cheeses. HP cheeses received higher "milky" odor descriptor scores and lower scores for odor quality and intensity and for "buttery", "yogurt-like", and "caramel" odor descriptors. Addition of the BP culture enhanced the formation of three aldehydes, three alcohols, three ethyl esters, and three ketones but decreased the levels of seven ketones and butanoic acid. BP cheeses received higher scores for aroma intensity and for "yogurt-like" and "cheesy" aroma descriptors. Principal component analysis showed the correlation between diketones and aroma descriptors "caramel", "buttery", and "milky" and between 3-methylbutanal and the odor and aroma intensity scores and aroma descriptors "sheepy" and "meat broth".

  17. Analysis of some Italian lemon liquors (limoncello).

    PubMed

    Andrea, Versari; Nadia, Natali; Teresa, Russo Maria; Andrea, Antonelli

    2003-08-13

    The chemical composition of several commercial Italian Limoncellos, lemon-peel-based alcoholic beverages, was studied by chromatographic techniques. These methods allowed a rapid monitoring of Limoncello, giving information on quality markers and possible adulteration of the product. Quantitative data for more than 60 compounds are reported. Limoncellos were characterized by the presence of selected volatile (terpenes, aldehydes, alcohols) and nonvolatile compounds (psoralens, coumarins, phenolics, carbohydrates and acids). On the basis of their composition, the samples were grouped by PCA analysis in two sets; the first group showed a composition similar to lemon essential oils, with a high content of b-pinene, myrcene, trans-a-bergamottene, and b-bisabolene, and a low content in neral and geranial. The composition of the second group suggested the occurrence of oxidative phenomena and/or the addition of flavors. The presence of ethyl acetate, acetaldehyde, 2-methyl-1-propanol and glycerol showed that a fermentation probably occurred in the sugar syrup used to dilute the Limoncello after the extraction process.

  18. Fermentation Results and Chemical Composition of Agricultural Distillates Obtained from Rye and Barley Grains and the Corresponding Malts as a Source of Amylolytic Enzymes and Starch.

    PubMed

    Balcerek, Maria; Pielech-Przybylska, Katarzyna; Dziekońska-Kubczak, Urszula; Patelski, Piotr; Strąk, Ewelina

    2016-10-01

    The objective of this study was to determine the efficiency of rye and barley starch hydrolysis in mashing processes using cereal malts as a source of amylolytic enzymes and starch, and to establish the volatile profile of the obtained agricultural distillates. In addition, the effects of the pretreatment method of unmalted cereal grains on the physicochemical composition of the prepared mashes, fermentation results, and the composition of the obtained distillates were investigated. The raw materials used were unmalted rye and barley grains, as well as the corresponding malts. All experiments were first performed on a semi-technical scale, and then verified under industrial conditions in a Polish distillery. The fermentable sugars present in sweet mashes mostly consisted of maltose, followed by glucose and maltotriose. Pressure-thermal treatment of unmalted cereals, and especially rye grains, resulted in higher ethanol content in mashes in comparison with samples subjected to pressureless liberation of starch. All agricultural distillates originating from mashes containing rye and barley grains and the corresponding malts were characterized by low concentrations of undesirable compounds, such as acetaldehyde and methanol. The distillates obtained under industrial conditions contained lower concentrations of higher alcohols (apart from 1-propanol) than those obtained on a semi-technical scale.

  19. Metal cations for the determination of fluorescent phosphoinositides by capillary electrophoresis.

    PubMed

    Otieno, Anthony C; Quainoo, Emmanuel W; Mwongela, Simon M

    2008-12-01

    Phosphatidylinositol (PI) and its phosphorylated derivatives known as phosphoinositides (PIPs), are essential regulators of cell signaling and membrane trafficking, cytoskeletal dynamics, and nuclear functions. Disruption of PI metabolism is associated with disorders such as immune dysfunction, cardiovascular disease, and cancer; therefore, there is currently great interest in studying PIPs and their metabolic enzymes. Here, we describe a method for the separation of fluorescent PI and its seven fluorescent phosphorylated derivatives by CE-LIF. The CE method utilizes a Tris buffer and sodium deoxycholate in the presence of 30% 1-propanol and 5% of a dynamic coating reagent, EOTrol low reverse (EOTrol LR). It is simple, fast, highly sensitive, and it offers LODs in the order of 1.5 amol. The effect of cations such as lithium, sodium, potassium, cesium, barium, manganese, zinc, magnesium, calcium, spermine, and gentamicin were evaluated. Calcium and magnesium provided the best selectivity and resolution for the separation of the analytes while magnesium offered the best data reproducibility. The developed CE method would be useful in the studies of enzymatic activity in the PI and PIPs metabolic pathways using CE-based in vitro and CE cell-based assays, and/or for drug screening.

  20. The effect of temperature on ribose-5-phosphate isomerase from a mesophile, Thiobacillus thioparus, and a thermophile, Bacillus caldolyticus.

    PubMed

    Middaugh, C R; MacElroy, R D

    1976-06-01

    The enzyme ribose-5-phosphate isomerase [EC 5.3.1.6] was partially purified from a mesophilic organism, Thiobacillus thioparus, and from an extreme thermophile, Bacillus caldolyticus. The stability and kinetics of the two enzymes were compared with regard to temperature in the presence of a series of neutral salts and alcohols. The thermal stability of both enzymes was altered such that the salts (NH4)2SO4, NaCl, KCl, and LiCl increased stability, while LiBr, CaCl2, methanol, ethanol, and 1-propanol decreased stability. Ethylene glycol had little effect on the mesophilic enzyme, but increased the stability of the thermophilic protein. The kinetics of both enzymes were also affected by the salts and alcohols, and Arrhenius plots of two kinetic parameters, Km and Vmax, displayed discontinuities, or sharp changes in slope, at characteristic temperatures, TD. Neutral salts and alcohols altered the temperature of discontinuity in a sequence similar to that observed in studies of thermal stability. It is suggested that the slope change is due to temperature-dependent alterations in the enzymes at specific, but undefined, loci at the active site, although no evidence is offered for the absence of a larger conformation change in the entire enzyme.

  1. Higher-alcohols biorefinery: improvement of catalyst for ethanol conversion.

    PubMed

    Olson, Edwin S; Sharma, Ramesh K; Aulich, Ted R

    2004-01-01

    The concept of a biorefinery for higher-alcohol production is to integrate ethanol and methanol formation via fermentation and biomass gasification, respectively, with conversion of these simple alcohol intermediates into higher alcohols via the Guerbet reaction. 1-Butanol results from the self-condensation of ethanol in this multistep reaction occurring on a single catalytic bed. Combining methanol with ethanol gives a mixture of propanol, isobutanol, and 2-methyl-1-butanol. All of these higher alcohols are useful as solvents, chemical intermediates, and fuel additives and, consequently, have higher market values than the simple alcohol intermediates. Several new catalysts for the condensation of ethanol and alcohol mixtures to higher alcohols were designed and tested under a variety of conditions. Reactions of methanol-ethanol mixtures gave as high as 100% conversion of the ethanol to form high yields of isobutanol with smaller amounts of 1-propanol, the amounts in the mixture depending on the starting mixture. The most successful catalysts are multifunctional with basic and hydrogen transfer components.

  2. Conversion of Methanol, Ethanol and Propanol over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-06-04

    Renewable fuel from lignocellulosic biomass has recently attracted more attention due to its environmental and the potential economic benefits over the crude oil [1]. In particular the production of fuel range hydrocarbon (HC) from alcohol generated lots of interest since the alcohol can be produced from biomass via thermochemical [2] (mixed alcohol from gasification derived synthesis gas) as well as the biochemical routes [3] (alcohol fermentation). Along with the development of ZSM5 synthesis and the discovery of methanol-to-gasoline (MTG) process by Mobil in 1970’s triggered lots of interest in research and development arena to understand the reaction mechanisms of alcohols over zeolites in particular ZSM5 [4]. More detailed research on methanol conversion was extensively reported [5] and in recent times the research work can be found on ethanol [6] and other alcohols as well but comprehensive comparison of catalyst activity and the deactivation mechanism of the conversion of various alcohols over zeolites has not been reported. The experiments were conducted on smaller alcohols such as methanol, ethanol and 1-propanol over HZSM5. The experimental results on the catalyst activity and the catalyst deactivation mechanism will be discussed.

  3. Gene cloning and catalytic characterization of cold-adapted lipase of Photobacterium sp. MA1-3 isolated from blood clam.

    PubMed

    Kim, Young Ok; Khosasih, Vivia; Nam, Bo-Hye; Lee, Sang-Jun; Suwanto, Antonius; Kim, Hyung Kwoun

    2012-12-01

    A lipase-producing Photobacterium strain (MA1-3) was isolated from the intestine of a blood clam caught at Namhae, Korea. The lipase gene was cloned by shotgun cloning and encoded 340 amino acids with a molecular mass of 38,015 Da. It had a very low sequence identity with other bacterial lipases, with the exception of that of Photobacterium lipolyticum M37 (83.2%). The MA1-3 lipase was produced in soluble form when Escherichia coli cells harboring the gene were cultured at 18°C. Its optimum temperature and pH were 45°C and pH 8.5, respectively. Its activation energy was calculated to be 2.69 kcal/mol, suggesting it to be a cold-adapted lipase. Its optimum temperature, temperature stability, and substrate specificity were quite different from those of M37 lipase, despite the considerable sequence similarities. Meanwhile, MA1-3 lipase performed a transesterification reaction using olive oil and various alcohols including methanol, ethanol, 1-propanol, and 1-butanol. In the presence of t-butanol as a co-solvent, this lipase produced biodiesel using methanol and plant or waste oils. The highest biodiesel conversion yield (73%) was achieved using waste soybean oil and methanol at a molar ratio of 1:5 after 12 h using 5 units of lipase.

  4. Photophysical property and photostability of J-aggregate thin films of thiacyanine dyes prepared by the spin-coating method.

    PubMed

    Tani, Katsuhiko; Ito, Chizuru; Hanawa, Yasuhiro; Uchida, Mamoru; Otaguro, Kunihiko; Horiuchi, Hiroaki; Hiratsuka, Hiroshi

    2008-01-24

    By use of electrostatic interactions of dye molecules and poly(diallyldimethylammonium chloride) (PDDA), the spin-coating technique has been successfully applied to the preparation of stable J-aggregate thin films of thiacarbocyanine dyes on a polycarbonate or quartz plate. The J-aggregate thin films were prepared by the spin-coating of PDDA aqueous solution on dye thin films prepared on a substrate by the spin-coating of 2,2,3,3-tetrafluoro-1-propanol solution of dyes. Photophysical properties of the dye thin films and J-aggregate thin films were studied by measuring the fluorescence spectra, quantum yields, and lifetimes. Coherent size of the J-aggregates was estimated to be 3-12 by means of the absorption bandwidth (full width at half maximum) or radiative lifetime. Photostability of the J-aggregate thin films was also studied in terms of photodegradation efficiency under argon and oxygen in comparison with the dye thin films, and J-aggregate thin films were found to be more stable than the corresponding dye thin films.

  5. Effect of Water Miscible Organic Solvents on p-Nitrophenol Hydroxylase (CYP2E1) Activity in Rat Liver Microsomes.

    PubMed

    Patil, Pranali G; Kamble, S H; Shah, T S; Iyer, K R

    2015-01-01

    Organic solvents used for solubilization of the substrates/NCEs are known to affect the activity of cytochrome P450 enzymes. Further, this effect varies with the solvents used, the substrates and CYP450 isoforms in question. In the present study, we have investigated the effect of ten commonly used water miscible organic solvents (methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, acetone, dimethyl sulphoxide, N,N-dimethyl formamide, dioxane and polyethylene glycol 400) on p-nitrophenol hydroxylase activity at 0, 0.1, 0.25, 0.5, 0.75 and 1% v/v concentration in rat liver microsomes. All the solvents studied showed concentration dependent inhibition of the p-nitrophenol hydroxylase activity except acetonitrile which showed activation of the activity at concentration range studied. Out of ten solvents studied, dioxane was found to be the most inhibitory solvent (inhibition >90% at 0.25% v/v concentration). Overall, solvents like dimethyl sulphoxide, dimethyl formamide and dioxane appeared to be unsuitable for characterizing p-nitrophenol hydroxylase (CYP2E1-mediated) reactions due to a high degree of inhibition. On the other hand, methanol and acetonitrile at concentrations <0.5% v/v appeared to be appropriate solvents for substrate solubilization while evaluating CYP2E1-mediated catalysis. The results of this study imply that caution should be exercised while choosing solvents for dissolution of substrate during enzyme studies in liver microsomes.

  6. Solvent Effect on the Photolysis of Riboflavin.

    PubMed

    Ahmad, Iqbal; Anwar, Zubair; Ahmed, Sofia; Sheraz, Muhammad Ali; Bano, Raheela; Hafeez, Ambreen

    2015-10-01

    The kinetics of photolysis of riboflavin (RF) in water (pH 7.0) and in organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol, ethyl acetate) has been studied using a multicomponent spectrometric method for the assay of RF and its major photoproducts, formylmethylflavin and lumichrome. The apparent first-order rate constants (k obs) for the reaction range from 3.19 (ethyl acetate) to 4.61 × 10(-3) min(-1) (water). The values of k obs have been found to be a linear function of solvent dielectric constant implying the participation of a dipolar intermediate along the reaction pathway. The degradation of this intermediate is promoted by the polarity of the medium. This indicates a greater stabilization of the excited-triplet states of RF with an increase in solvent polarity to facilitate its reduction. The rate constants for the reaction show a linear relation with the solvent acceptor number indicating the degree of solute-solvent interaction in different solvents. It would depend on the electron-donating capacity of RF molecule in organic solvents. The values of k obs are inversely proportional to the viscosity of the medium as a result of diffusion-controlled processes.

  7. Control of propranolol intake by direct chromatographic detection of alpha-naphthoxylactic acid in urine.

    PubMed

    Ruiz-Angel, M J; Fernández-López, P; Murillo-Pulgarín, J A; García-Alvarez-Coque, M C

    2002-02-15

    A rapid chromatographic procedure with a C18 column, a mobile phase of 0.15 M sodium dodecyl sulfate (SDS)-10% (v/v) 1-propanol at pH 3 (0.01 M phosphate buffer), and fluorimetric detection, is reported for the control of propranolol (PPL) intake in urine samples, which are injected directly without any other treatment than filtration. The peak of PPL was only observed in samples taken a few hours after ingestion of the drug due to its extensive conjugation and metabolisation. The detection of several unconjugated PPL metabolites was therefore considered: desisopropylpropranolol (DIP), propranolol glycol (PPG), alpha-naphthoxylactic acid (NLT) and alpha-naphthoxyacetic acid (NAC). NLT showed the best characteristics: it eluted at a much shorter retention time than PPL, its concentration in urine samples was greater and it did not present any interference from endogeneous compounds in urine, common drugs or drugs administered in combination with PPL. The limit of quantification, measured as the concentration of analyte providing a relative standard deviation of 20%, was 24 ng/ml, and the day-to-day imprecision was below 4% for concentrations above 200 ng/ml. The procedure allows the routine control of PPL at therapeutic urine levels. Urinary excretion studies showed that the detection of NLT is possible at least up to 20-30 h after oral administration.

  8. A Very Stable High Throughput Taylor Cone-jet in Electrohydrodynamics

    PubMed Central

    Morad, M. R.; Rajabi, A.; Razavi, M.; Sereshkeh, S. R. Pejman

    2016-01-01

    A stable capillary liquid jet formed by an electric field is an important physical phenomenon for formation of controllable small droplets, power generation and chemical reactions, printing and patterning, and chemical-biological investigations. In electrohydrodynamics, the well-known Taylor cone-jet has a stability margin within a certain range of the liquid flow rate (Q) and the applied voltage (V). Here, we introduce a simple mechanism to greatly extend the Taylor cone-jet stability margin and produce a very high throughput. For an ethanol cone-jet emitting from a simple nozzle, the stability margin is obtained within 1 kV for low flow rates, decaying with flow rate up to 2 ml/h. By installing a hemispherical cap above the nozzle, we demonstrate that the stability margin could increase to 5 kV for low flow rates, decaying to zero for a maximum flow rate of 65 ml/h. The governing borders of stability margins are discussed and obtained for three other liquids: methanol, 1-propanol and 1-butanol. For a gravity-directed nozzle, the produced cone-jet is more stable against perturbations and the axis of the spray remains in the same direction through the whole stability margin, unlike the cone-jet of conventional simple nozzles. PMID:27917956

  9. A capillary electrophoretic system based on a novel microemulsion for the analysis of coenzyme Q10 in human plasma by electrokinetic chromatography.

    PubMed

    Lucangioli, Silvia; Flor, Sabrina; Sabrina, Flor; Contin, Mario; Mario, Contin; Tripodi, Valeria; Valeria, Tripodi

    2009-06-01

    A new analytical method for determination of coenzyme Q10 (2,3-dimethoxy-5-methyl-6-decaprenyl-1,4-benzoquinone, CoQ10) in human plasma was developed based on CE using a double tensioactive microemulsion. CoQ10 was quantitatively extracted into 1-propanol/hexane and quantified by MEEKC. The microemulsion was prepared by mixing 1.4% w/w sodium bis(2-ethylhexyl) sulfosuccinate, 4% w/w cholic acid, 1% w/w octane, 8.5% w/w butanol, 0.1% w/w PVA and 85% w/w 10 mM Tris buffer at pH 9.0. The optimized electrophoretic conditions included the use of an uncoated silica capillary of 60 cm total length and 75 mum id, an applied voltage of 20 kV, room temperature and 214 nm ultraviolet detection. Selectivity, linearity, LOD, LOQ, precision and accuracy were evaluated as the parameters of validation. Owing to its simplicity and reliability, the proposed method can be an advantageous alternative to the traditional methodology for the quantitation of CoQ10 in human plasma with good accuracy and precision.

  10. Characterization of an organic phase peroxide biosensor based on horseradish peroxidase immobilized in Eastman AQ.

    PubMed

    Konash, Anastassija; Magner, Edmond

    2006-07-15

    Due to their frequent occurrence in food, cosmetics and pharmaceutical products, and their poor solubility in water, the detection of peroxides in organic solvents has aroused significant interest. For diagnostics or on-site testing, a fast and specific experimental approach is required. Although aqueous peroxide biosensors are well known, they are usually not suitable for nonaqueous applications due to their instability. Here we describe an organic phase biosensor for hydrogen peroxide based on horseradish peroxidase immobilized in an Eastman AQ 55 polymer matrix. Rotating disc amperometry was used to examine the effect of the solvent properties, the amount and pH of added buffer, the concentration of peroxide and ferrocene dimethanol, and the amount of Eastman AQ 55 and of enzyme on the response of the biosensor to hydrogen peroxide. The response of the biosensor was limited by diffusion. Linear responses (with detection limits to hydrogen peroxide given in parentheses) were obtained in methanol (1.2 microM), ethanol (0.6 microM), 1-propanol (2.8 microM), acetone (1.4 microM), acetonitrile (2.6 microM), and ethylene glycol (13.6 microM). The rate of diffusion of ferrocene dimethanol was more constrained than the rate of diffusion of hydrogen peroxide, resulting in a comparatively narrow linear range. The main advantages of the sensor are its ease of use and a high degree of reproducibility, together with good operational and storage stability.

  11. Viscosities of aqueous blended amines

    SciTech Connect

    Hsu, C.H.; Li, M.H.

    1997-07-01

    Solutions of alkanolamines are an industrially important class of compounds used in the natural gas, oil refineries, petroleum chemical plants, and synthetic ammonia industries for the removal of acidic components like CO{sub 2} and H{sub 2}S from gas streams. The viscosities of aqueous mixtures of diethanolamine (DEA) + N-methyldiethanolamine (MDEA), DEA + 2-amino-2-methyl-1-propanol (AMP), and monoethanolamine (MEA) + 2-piperidineethanol (2-PE) were measured from 30 C to 80 C. A Redlich-Kister equation for the viscosity deviation was applied to represent the viscosity. On the basis of the available viscosity data for five ternary systems, MEA + MDEA + H{sub 2}O, MEA + AMP + H{sub 2}O, DEA + MDEA + H{sub 2}O, DEA + AMP + H{sub 2}O, and MEA + 2-PE + H{sub 2}O, a generalized set of binary parameters were determined. For the viscosity calculation of the systems tested, the overall average absolute percent deviation is about 1.0% for a total of 499 data points.

  12. Solubility of nitrous oxide in alkanolamine aqueous solutions

    SciTech Connect

    Tsai, T.C.; Ko, J.J.; Wang, H.M.; Lin, C.Y.; Li, M.H.

    2000-04-01

    The solubility of nitrous oxide (N{sub 2}O) in alkanolamine aqueous solutions has been measured at (30, 35, and 40) C. The systems studied are monoethanolamine, diethanolamine, diisopropanolamine, triethanolamine, and 2-amino-2-methyl-1-propanol aqueous solutions. The concentration of amine for monoethanolamine ranges from (1 to 6) kmol/m{sup 3} and for other amines from (0.5 to 3) kmol/m{sup 3}. The accuracy of the measurement is estimated to be {+-}2%. A semiempirical model of the excess Henry's constant proposed by Wang et al. (1992) was used to correlate the solubility of N{sub 2}O in amine solutions. The parameters of the correlation were determined from the measured solubility data and the available data in the open literature. For a wide temperature range from (15 to 75) C, the obtained correlation has been shown to represent reasonably the solubility of N{sub 2}O in six amine aqueous solutions: MEA, DEA, DIPA, TEA, MDEA, and AMP. For the purpose of process design, the obtained correlations are, in general, satisfactory for estimating the solubility of N{sub 2}O in amine solutions, which in turn can be used to estimate the correct free-gas solubility of CO{sub 2} in amines.

  13. Densities of aqueous blended amines

    SciTech Connect

    Hsu, C.H.; Li, M.H.

    1997-05-01

    Solutions of alkanolamines are an industrially important class of compounds used in the natural gas and synthetic ammonia industries and petroleum chemical plants for the removal of CO{sub 2} and H{sub 2}S from gas streams. The densities of aqueous mixtures of diethanolamine (DEA) + N-methyldiethanolamine (MDEA) + water, DEA + 2-amino-2-methyl-1-propanol (AMP) + water, and monoethanolamine (MEA) + 2-piperidineethanol (2-PE) + water were measured from 30 C to 80 C. A Redlich-Kister equation of the excess volume was applied to represent the density. Based on the available density data for five ternary systems: MEA + MDEA + H{sub 2}O, MEA + AMP + H{sub 2}O, DEA + MDEA + H{sub 2}O, DEA + AMP + H{sub 2}O, and MEA + 2-PE + H{sub 2}O, a generalized set of binary parameters were determined. The density calculations show quite satisfactory results. The overall average absolute percent deviation is about 0.04% for a total of 686 data points.

  14. Use of micellar liquid chromatography to analyze oxolinic acid, flumequine, marbofloxacin and enrofloxacin in honey and validation according to the 2002/657/EC decision.

    PubMed

    Tayeb-Cherif, K; Peris-Vicente, J; Carda-Broch, S; Esteve-Romero, J

    2016-07-01

    A micellar liquid chromatographic method was developed for the analysis of oxolinic acid, flumequine, marbofloxacin and enrofloxacin in honey. These quinolines are unethically used in beekeeping, and a zero-tolerance policy to antibiotic residues in honey has been stated by the European Union. The sample pretreatment was a 1:1 dilution with a 0.05M SDS at pH 3 solution, filtration and direct injection, thus avoiding extraction steps. The quinolones were eluted without interferences using mobile phase of 0.05M SDS/12.5% 1-propanol/0.5% triethylamine at pH 3, running at 1mL/min under isocratic room through a C18 column. The analytes were detected by fluorescence. The method was successfully validated according to the requirements of the European Union Decision 2002/657/EC in terms of: specificity, linearity (r(2)>0.995), limit of detection and decision limit (0.008-0.070mg/kg), lower limit of quantification (0.02-0.2mg/kg), detection capability (0.010-0.10mg/kg), recovery (82.1-110.0%), precision (<9.4%), matrix effects, robustness (<10.4%), and stability. The procedure was applied to several commercial honey supplied by a local supermarket, and the studied antibiotics were not detected. Therefore, the method was rapid, simple, safe, eco friendly, reliable and useful for the routine analysis of honey samples.

  15. Bismuth Dimercaptopropanol (BisBAL) Inhibits the Expression of Extracellular Polysaccharides and Proteins by Brevundimonas diminuta: Implications for Membrane Microfiltration

    SciTech Connect

    Badireddy, Appala R.; Chellam, Shankararaman; Yanina, Svetlana; Gassman, Paul L.; Rosso, Kevin M.

    2008-02-15

    A 2:1 molar ratio preparation of bismuth with a lipophilic dithiol (3-dimercapto-1-propanol, BAL)significantly reduced extracellular polymeric substances (EPS) expression by Brevundimonas diminuta in suspended cultures at levels just below the minimum inhibitory concentration (MIC). Total polysaccharides and proteins secreted by B. diminuta decreased by approximately 95% over a 5-day period when exposed to the bismuth-BAL chelate (BisBAL) at near MIC (12 μM). Fourier-transform infrared spectroscopy (FTIR) suggested that a possible mechanism of biofilm disruption by BisBAL is the inhibition of carbohydrate Oacetylation. FTIR also revealed extensive homology between EPS samples with and without BisBAL treatment, with proteins, polysaccharides, and peptides varying predominantly only in the amount expressed. EPS secretion decreased following BisBAL treatment as verified by atomic force microscopy and scanning electron microscopy. Without BisBAL treatment, a slime-like EPS matrix secreted by B. diminuta resulted in biofouling and inefficient hydrodynamic backwashing of microfiltration membranes.

  16. Determination of oxolinic acid, danofloxacin, ciprofloxacin, and enrofloxacin in porcine and bovine meat by micellar liquid chromatography with fluorescence detection.

    PubMed

    Terrado-Campos, David; Tayeb-Cherif, Khaled; Peris-Vicente, Juan; Carda-Broch, Samuel; Esteve-Romero, Josep

    2017-04-15

    A method was developed for the determination of oxolinic acid, danofloxacin, ciprofloxacin and enrofloxacin by micellar liquid chromatography - fluorescence detection in commercial porcine and bovine meat. The samples were ultrasonicated in a micellar solution, free of organic solvent, to extract the analytes, and the supernatant was directly injected. The quinolones were resolved in <22min using a mobile phase of 0.05M SDS - 7.5% 1-propanol - 0.5% triethylamine buffered at pH 3, running through a C18 column at 1mL/min using isocratic mode. The method was validated by the in terms of: selectivity, calibration range (0.01-0.05 to 0.5mg/kg), linearity (r(2)>0.9998), trueness (89.3-105.1%), precision (<8.3%), decision limit (<12% over the maximum residue limit), detection capability (<21% over the maximum residue limit), ruggedness (<5.6%) and stability. The procedure was rapid, eco-friendly, safe and easy-to-handle.

  17. Determination of eight triazine herbicide residues in cereal and vegetable by micellar electrokinetic capillary chromatography with on-line sweeping.

    PubMed

    Fang, Rou; Chen, Guan-hua; Yi, Ling-xiao; Shao, Yu-xiu; Zhang, Li; Cai, Qing-hong; Xiao, Jing

    2014-02-15

    A new method was developed for the determination of eight triazine herbicide residues in cereal and vegetable samples by on-line sweeping technique in micellar electrokinetic capillary chromatography (MEKC). Some factors affecting analyte enrichment and separation efficiency were examined. The optimum buffer was composed of 25 mM borate, 15 mM phosphate, 40 mM sodium dodecylsulfate (SDS) and 3% (v/v) of 1-propanol at pH 6.5. The separation voltage was 20 kV and the sample was injected at 0.5 psi for 240 s. The detection wavelength was set at 220 nm with the capillary temperature being at 25 °C. Under the optimized conditions, the enrichment factors were achieved from 479 to 610. The limits of detection (LODs, S/N = 3) ranged from 0.02 to 0.04 ng/g and the limits of quantification (LOQs) of eight triazine herbicides were all 0.1 ng/g. The average recoveries of spiked samples were 82.8-96.8%. This method has been successfully applied to the determination of the triazine herbicide residues in cereal and vegetable samples.

  18. Simultaneous isocratic separation of phenolic acids and flavonoids using micellar liquid chromatography.

    PubMed

    Hadjmohammadi, Mohammad Reza; Nazari, S Saman S J

    2013-12-01

    The simultaneous isocratic separation of a mixture of five phenolic acids and four flavonoids (two important groups of natural polyphenolic compounds with very different polarities) was investigated in three different RPLC modes using a hydro-organic mobile phase, and mobile phases containing SDS at concentrations below and above the critical micellar concentration (submicellar LC and micellar LC (MLC), respectively). In the hydro-organic mode, methanol and acetonitrile; in the submicellar mode methanol; and in the micellar mode, methanol and 1-propanol were examined individually as organic modifiers. Regarding the other modes, MLC provided more appropriate resolutions and analysis time and was preferred for the separation of the selected compounds. Optimization of separation in MLC was performed using an interpretative approach for each alcohol. In this way, the retention of phenolic acids and flavonoids were modeled using the retention factors obtained from five different mobile phases, then the Pareto optimality method was applied to find the best compatibility between analysis time and quality of separation. The results of this study showed some promising advantages of MLC for the simultaneous separation of phenolic acids and flavonoids, including low consumption of organic solvent, good resolution, short analysis time, and no requirement of gradient elution.

  19. Treating exposure to chemical warfare agents: Implications for health care providers and community emergency planning

    SciTech Connect

    Munro, N.B.; Watson, A.P.; Ambrose, K.R.; Griffin, G.D. )

    1990-11-01

    Current treatment protocols for exposure to nerve and vesicant agents found in the US stockpile of unitary chemical weapons are summarized, and the toxicities of available antidotes are evaluated. The status of the most promising of the new nerve agent antidotes is reviewed. In the US, atropine and pralidoxime compose the only approved antidote regimen for organophosphate nerve agent poisoning. Diazepam may also be used if necessary to control convulsions. To avoid death, administration must occur within minutes of substantial exposure together with immediate decontamination. Continuous observation and repeated administration of antidotes are necessary as symptoms warrant. Available antidotes do not necessarily prevent respiratory failure or incapacitation. The toxicity of the antidotes themselves and the individualized nature of medical care preclude recommending that autoinjectors be distributed to the general public. In addition, precautionary administration of protective drugs to the general population would not be feasible or desirable. No antidote exists for poisoning by the vesicant sulfur mustard (H, HD, HT); effective intervention can only be accomplished by rapid decontamination followed by palliative treatment of symptoms. British anti-Lewisite (BAL) (2,3-dimercapto-1-propanol) is the antidote of choice for treatment of exposure to Lewisite, another potent vesicant. Experimental water-soluble BAL analogues have been developed that are less toxic than BAL. Treatment protocols for each antidote are summarized in tabular form for use by health care providers.

  20. Liquid-phase synthesis of cobalt oxide nanoparticles.

    PubMed

    Sinkó, Katalin; Szabó, Géza; Zrínyi, Miklós

    2011-05-01

    Various liquid-phase syntheses of CoO and Co3O4 nanoparticles have been studied. The experiments focus on two synthesis routes: the coprecipitation and the sol-gel methods combined with thermal decomposition. The effect of synthesis route, the type of precursors (cobalt nitrate/chloride) and precipitation agent (carbonate, hydroxide, oxalic acid, and ammonia), the chemical compositions, pH, application of surfactants (PDMS, Triton X-100, NaDS, NaDBS, TTAB, ethyl acetate, citric acid), and the heat treatments on the properties of particles were investigated. The particle size and distribution have been determined by dynamic light scattering (DLS). The phases and the morphology of products have been analysed by XRD and SEM. The coprecipitation technique is less able to shape the particles than sol-gel technique. PDMS can be applied efficiently as surfactant in preparation methods. The finest particles (around 85 nm) with narrow polydispersity (70-100 nm) and spherical shape could be achieved by using sol-gel technique in medium of 1-propanol and ethyl acetate.

  1. Physico-chemical and microbiological characterization of spontaneous fermentation of Cellina di Nardò and Leccino table olives

    PubMed Central

    Bleve, Gianluca; Tufariello, Maria; Durante, Miriana; Perbellini, Ezio; Ramires, Francesca A.; Grieco, Francesco; Cappello, Maria S.; De Domenico, Stefania; Mita, Giovanni; Tasioula-Margari, Maria; Logrieco, Antonio F.

    2014-01-01

    Table olives are one of the most important traditional fermented vegetables in Europe and their world consumption is constantly increasing. In the Greek style, table olives are obtained by spontaneous fermentations, without any chemical debittering treatment. Evolution of sugars, organic acids, alcohols, mono, and polyphenol compounds and volatile compounds associated with the fermentative metabolism of yeasts and bacteria throughout the natural fermentation process of the two Italian olive cultivars Cellina di Nardò and Leccino were determined. A protocol was developed and applied aimed at the technological characterization of lactic acid bacteria (LAB) and yeast strains as possible candidate autochthonous starters for table olive fermentation from Cellina di Nardò and Leccino cultivars. The study of the main physic-chemical parameters and volatile compounds during fermentation helped to determine chemical descriptors that may be suitable for monitoring olive fermentation. In both the analyzed table olive cultivars, aldehydes proved to be closely related to the first stage of fermentation (30 days), while higher alcohols (2-methyl-1-propanol; 3-methyl-1-butanol), styrene, and o-cymene were associated with the middle stage of fermentation (90 days) and acetate esters with the final step of olive fermentation (180 days). PMID:25389422

  2. Defining maximum levels of higher alcohols in alcoholic beverages and surrogate alcohol products.

    PubMed

    Lachenmeier, Dirk W; Haupt, Simone; Schulz, Katja

    2008-04-01

    Higher alcohols occur naturally in alcoholic beverages as by-products of alcoholic fermentation. Recently, concerns have been raised about the levels of higher alcohols in surrogate alcohol (i.e., illicit or home-produced alcoholic beverages) that might lead to an increased incidence of liver diseases in regions where there is a high consumption of such beverages. In contrast, higher alcohols are generally regarded as important flavour compounds, so that European legislation even demands minimum contents in certain spirits. In the current study we review the scientific literature on the toxicity of higher alcohols and estimate tolerable concentrations in alcoholic beverages. On the assumption that an adult consumes 4 x 25 ml of a drink containing 40% vol alcohol, the maximum tolerable concentrations of 1-propanol, 1-butanol, 2-butanol, isobutanol, isoamyl alcohol and 1-hexanol in such a drink would range between 228 and 3325 g/hl of pure alcohol. A reasonable preliminary guideline level would be 1000 g/hl of pure alcohol for the sum of all higher alcohols. This level is higher than the concentrations usually found in both legal alcoholic beverages and surrogate alcohols, so that we conclude that scientific data are lacking so far to consider higher alcohols as a likely cause for the adverse effects of surrogate alcohol. The limitations of our study include the inadequate toxicological data base leading to uncertainties during the extrapolation of toxicological data between the different alcohols, as well as unknown interactions between the different higher alcohols and ethanol.

  3. Evaluation of the bactericidal effect of five products for surgical hand disinfection according to prEN 12054 and prEN 12791.

    PubMed

    Marchetti, M G; Kampf, G; Finzi, G; Salvatorelli, G

    2003-05-01

    Surgical hand disinfection (with an alcohol-based hand rub) and surgical handwash (with an antiseptic-based liquid soap) are accepted measures to reduce the risk for surgical site infections. The new European Standards allow a comparison of their antimicrobial efficacy. The bactericidal activity of surgical hand rubs [Sterillium and Softaman, (active ingredient=alcohols)] and handwashes [Derman plus (triclosan), Hibiscrub (chlorhexidine) and Betadine (PVP-iodine)] was tested according to the prEN 12054 suspension test using Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Enterococcus hirae, and to prEN 12791 for the effect on resident skin flora in comparison with 1-propanol, 60% (v/v). All five products achieved a reduction of test bacteria within 3 min of >10(5)-fold so fulfilling prEN 12054. However, only Hibiscrub, Sterillium and Softa Man met the requirements of prEN 12791, giving a mean reduction of resident micro-organisms (immediate and sustained effect) which was not significantly lower than the reference alcohol (P>0.1; Wilcoxon matched-pairs signed-rank test). Sterillium was significantly more effective than the reference alcohol (immediate and sustained affect). Products for surgical hand disinfection may have equal antimicrobial activity in suspension tests but show large differences under practical conditions. Healthcare workers should not rely on results from suspension tests when deciding on a product for surgical hand disinfection.

  4. New organic aerogels based upon a phenolic-furfural reaction

    SciTech Connect

    Hrubesh, L.W.

    1994-09-01

    The aqueous polycondensation of (1) resorcinol with formaldehyde and (2) melamine with formaldehyde are two proven synthetic routes for the formation of organic aerogels. Recently, we have discovered a new type of organic aerogel based upon a phenolic-furfural (PF) reaction. This sol-gel polymerization has a major advantage over past approaches since it can be conducted in alcohol (e.g., 1-propanol), thereby eliminating the need for a solvent exchange step prior to supercritical drying from carbon dioxide. The resultant aerogels are dark brown in color and can be converted to a carbonized version upon pyrolysis in an inert atmosphere. BET surface areas of 350--600 m{sup 2}/g have been measured, and transmission electron microscopy reveals an interconnected structure of irregularly-shaped particles or platelets with {approximately}10 nm dimensions. Thermal conductivities as low as 0.015 W/m-K have been recorded for PF aerogels under ambient conditions. This paper describes the chemistry-structure-property relationships of these new materials in detail.

  5. The Search for a Volatile Human Specific Marker in the Decomposition Process.

    PubMed

    Rosier, E; Loix, S; Develter, W; Van de Voorde, W; Tytgat, J; Cuypers, E

    2015-01-01

    In this study, a validated method using a thermal desorber combined with a gas chromatograph coupled to mass spectrometry was used to identify the volatile organic compounds released during decomposition of 6 human and 26 animal remains in a laboratory environment during a period of 6 months. 452 compounds were identified. Among them a human specific marker was sought using principle component analysis. We found a combination of 8 compounds (ethyl propionate, propyl propionate, propyl butyrate, ethyl pentanoate, pyridine, diethyl disulfide, methyl(methylthio)ethyl disulfide and 3-methylthio-1-propanol) that led to the distinction of human and pig remains from other animal remains. Furthermore, it was possible to separate the pig remains from human remains based on 5 esters (3-methylbutyl pentanoate, 3-methylbutyl 3-methylbutyrate, 3-methylbutyl 2-methylbutyrate, butyl pentanoate and propyl hexanoate). Further research in the field with full bodies has to corroborate these results and search for one or more human specific markers. These markers would allow a more efficiently training of cadaver dogs or portable detection devices could be developed.

  6. Production of fermentation aroma compounds by Saccharomyces cerevisiae wine yeasts: effects of yeast assimilable nitrogen on two model strains.

    PubMed

    Carrau, Francisco M; Medina, Karina; Farina, Laura; Boido, Eduardo; Henschke, Paul A; Dellacassa, Eduardo

    2008-11-01

    The contribution of yeast fermentation metabolites to the aromatic profile of wine is well documented; however, the biotechnological application of this knowledge, apart from strain selection, is still rather limited and often contradictory. Understanding and modeling the relationship between nutrient availability and the production of desirable aroma compounds by different strains must be one of the main objectives in the selection of industrial yeasts for the beverage and food industry. In order to overcome the variability in the composition of grape juices, we have used a chemically defined model medium for studying yeast physiological behavior and metabolite production in response to nitrogen supplementation so as to identify an appropriate yeast assimilable nitrogen level for strain differentiation. At low initial nitrogen concentrations, strain KU1 produced higher quantities of esters and fatty acids whereas M522 produced higher concentrations of isoacids, gamma-butyrolactone, higher alcohols and 3-methylthio-1-propanol. We propose that although strains KU1 and M522 have a similar nitrogen consumption profile, they represent useful models for the chemical characterization of wine strains in relation to wine quality. The differential production of aroma compounds by the two strains is discussed in relation to their capacity for nitrogen usage and their impact on winemaking. The results obtained here will help to develop targeted metabolic footprinting methods for the discrimination of industrial yeasts.

  7. Evaluation of the water and organic liquids extraction efficiency of Spirulina maxima dyes using thermostated micro thin-layer chromatography.

    PubMed

    Zarzycki, Paweł K; Zarzycka, Magdalena B

    2008-01-01

    Thermostated micro thin-layer chromatography was applied for separation and quantification studies of Spirulina maxima dyes isolated from pharmaceutical formulation by a simple one-step liquid extraction. The isolation process was performed using a number of liquids, including water; 10 mM water solutions of native alpha-, beta-, and gamma-cyclodextrin and their hydroxypropyl derivatives; and a number of common organic liquids characterized by different polarity, namely, methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, acetone, tetrahydrofuran, dichloromethane, toluene, and n-hexane. Chromatographic studies were performed on RP18W plates working inside a small thermostated horizontal chamber allowing a development distance of 45 mm. Using a mobile phase consisting of acetone-n-hexane (30 + 70, v/v) and 40 degrees C separation temperature, plate peak capacity of at least 15 spots/lane and developing time <5 min were obtained. Validation data indicated that under such conditions, with an office scanner used for chromatogram digitalization, spot quantification could be accurately performed within an analyte mass range of 2 factors. The raw quantitative data obtained from microchromatograms acquired under visible light conditions were explored using cluster analysis and principal components analysis. Chemometric investigations revealed that the best extraction liquids for isolation of dye mixtures from Spirulina samples were methanol, ethanol, tetrahydrofuran, and dichloromethane. Moreover, it was found that the liquids' parachor values could be used for estimation of the dye extraction efficiency from complex samples.

  8. A sialic acid assay in isolation and purification of bovine k-casein glycomacropeptide: a review.

    PubMed

    Nakano, Takuo; Ozimek, Lech

    2014-01-01

    Sialic acid is a carbohydrate moiety of k-casein glycomacropeptide (GMP), which is a 64 amino acid residue C-terminal sialylated phosphorylated glycopeptide released from k-casein by the action of chymosin during cheese making. GMP lacks aromatic amino acids including phenylalanine, tyrosine, and tryptophan. Because of its unique amino acid composition and various biological activities, GMP is thought to be a potential ingredient for dietetic foods (e.g., a food for PKU patients) and pharmaceuticals. Thus, increased attention has been given to the development of techniques to purify GMP. In this review, techniques of GMP purification described in patents and scientific research papers were introduced. A sialic acid assay is the important method to track GMP isolation and purification processes, for which the thiobarbituric acid reaction with 1-propanol as a chromophore extracting solvent is an inexpensive, practical and specific technique. Sephacryl S-200 gel filtration chromatography, cellulose acetate electrophoresis, and sodium dodecyl sulfate polyacrylamide gel electrophoresis are the major techniques to identify sialic acid specific to GMP. Sephacryl S-200 chromatography and cellulose acetate electrophoresis are also used to detect GMP sialic acid in whey pearmeate and whey added commercial margarine samples. Future research includes development of an economical industrial scale method to produce high purity GMP.

  9. CO2 capture in alkanolamine-RTIL blends via carbamate crystallization: route to efficient regeneration.

    PubMed

    Hasib-ur-Rahman, Muhammad; Larachi, Faïçal

    2012-10-16

    One of the major drawbacks of aqueous alkanolamine based CO(2) capture processes is the requirement of significantly higher energy of regeneration. This weakness can be overcome by separating the CO(2)-captured product to regenerate the corresponding amine, thus avoiding the consumption of redundant energy. Replacing aqueous phase with more stable and practically nonvolatile imidazolium based room-temperature ionic liquid (RTIL) provided a viable approach for carbamate to crystallize out as supernatant solid. In the present study, regeneration capabilities of solid carbamates have been investigated. Diethanolamine (DEA) carbamate as well as 2-amino-2-methyl-1-propanol (AMP) carbamate were obtained in crystalline form by bubbling CO(2) in alkanolamine-RTIL mixtures. Hydrophobic RTIL, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf(2)N]), was used as aqueous phase substituent. Thermal behavior of the carbamates was observed by differential scanning calorimetry and thermogravimetric analysis, while the possible regeneration mechanism has been proposed through (13)C NMR and FTIR analyses. The results showed that decomposition of DEA-carbamate commenced at lower temperature (∼55 °C), compared to that of AMP-carbamate (∼75 °C); thus promising easy regeneration. The separation of carbamate as solid phase can offer two-way advantage by letting less volume to regenerate as well as by narrowing the gap between CO(2) capture and amine regeneration temperatures.

  10. Rat serum alkaline phosphatase electrophoretic fractions: variations with feeding, starvation and cellulose fibre ingestion.

    PubMed

    Martins, M J; Dias, P O; Hipólito-Reis, C

    1998-12-01

    The effect of feeding, starvation and fibre ingestion on alkaline phosphatase (ALP) activity (E.C. 3.1.3.1) was studied in Wistar rat serum. Using identical assay conditions for total ALP activity determination and for electrophoretic ALP isoenzymes/fractions activity calculation, alpha- and beta-naphthyl phosphates and p-nitrophenyl phosphate were used as substrates and 2-amino-2-methyl-1-propanol/HCI was used as buffer, respectively. Total activity with beta-naphthyl phosphate was significantly higher than with alpha-naphthyl phosphate and p-nitrophenyl phosphate; with alpha-naphthyl phosphate it was significantly higher than with p-nitrophenyl phosphate. With all substrates, fed animals had significantly higher total activity than starving ones. Electrophoresis allowed the separation of two fractions. The second fraction activity was significantly higher in the fed group than in the starving ones, irrespective of the substrate used. Starving animals with fibre showed higher values of this fraction than starving animals without fibre, the difference reaching statistical significance with alpha-naphthyl phosphate. The first fraction predominated in both starved groups and the second in the fed group. The second fraction was identified as intestinal ALP. We conclude that the mechanical stimulation of the digestive tract appears to influence the passage of intestinal ALP to serum. The experimental conditions used enable quantification of electrophoretic fractions based on total activity. Activity depends on the substrate used.

  11. Fluorescent-Protein Stabilization and High-Resolution Imaging of Cleared, Intact Mouse Brains

    PubMed Central

    Schwarz, Martin K.; Scherbarth, Annemarie; Sprengel, Rolf; Engelhardt, Johann; Theer, Patrick; Giese, Guenter

    2015-01-01

    In order to observe and quantify long-range neuronal connections in intact mouse brain by light microscopy, it is first necessary to clear the brain, thus suppressing refractive-index variations. Here we describe a method that clears the brain and preserves the signal from proteinaceous fluorophores using a pH-adjusted non-aqueous index-matching medium. Successful clearing is enabled through the use of either 1-propanol or tert-butanol during dehydration whilst maintaining a basic pH. We show that high-resolution fluorescence imaging of entire, structurally intact juvenile and adult mouse brains is possible at subcellular resolution, even following many months in clearing solution. We also show that axonal long-range projections that are EGFP-labelled by modified Rabies virus can be imaged throughout the brain using a purpose-built light-sheet fluorescence microscope. To demonstrate the viability of the technique, we determined a detailed map of the monosynaptic projections onto a target cell population in the lateral entorhinal cortex. This example demonstrates that our method permits the quantification of whole-brain connectivity patterns at the subcellular level in the uncut brain. PMID:25993380

  12. Sequential extraction of inorganic arsenic compounds and methyl arsenate in human urine using mixed-mode monolithic silica spin column coupled with gas chromatography-mass spectrometry.

    PubMed

    Namera, Akira; Takeuchi, Akito; Saito, Takeshi; Miyazaki, Shota; Oikawa, Hiroshi; Saruwatari, Tatsuro; Nagao, Masataka

    2012-09-01

    A sequential analytical method was developed for the detection of arsenite, arsenate, and methylarsenate in human urine by gas chromatography-mass spectrometry (GC-MS). The combination of a derivatization of trivalent arsenic compounds by 2,3-dithio-1-propanol (British antilewisite; BAL) and a reduction of pentavalent arsenic compounds (arsenate and methylarsenate) were accomplished to carry out the analysis of arsenic compounds in urine. The arsenic derivatives obtained using BAL were extracted in a stepwise manner using a monolithic spin column and analyzed by GC-MS. A linear curve was observed for concentrations of arsenic compounds of 2.0 to 200 ng/mL, where the correlation coefficients of calibration curves were greater than 0.996 (for a signal-to-noise (S/N) ratio >10). The detection limits were 1 ng/mL (S/N > 3). Recoveries of the targets in urine were in the range 91.9-106.5%, and RSDs of the intra- and interday assay for urine samples containing 5, 50, and 150 ng/mL of arsenic compounds varied between 2.95 and 13.4%. The results from real samples obtained from a patient suspected of having ingested As containing medications using this proposed method were in good agreement with those obtained using high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

  13. Propagation of Dynamic Nuclear Polarization across the Xenon Cluster Boundaries: Elucidation of the Spin-Diffusion Bottleneck

    PubMed Central

    Pourfathi, M.; Kuzma, N. N.; Kara, H.; Ghosh, R. K.; Shaghaghi, H.; Kadlecek, S. J.; Rizi, R. R.

    2013-01-01

    Earlier dynamic nuclear polarization (DNP) experiments with frozen xenon/1-propanol/trityl mixtures have demonstrated spontaneous formation of pure xenon clusters above 120 K, enabling spectrally-resolved real-time measurements of 129Xe nuclear magnetization in the clusters and in the surrounding radical-rich matrix. A spin-diffusion bottleneck was postulated to explain the peculiar time evolution of 129Xe signals in the clusters as well as the apparent discontinuity of 129Xe polarization across the cluster boundaries. A self-contained ab initio model of nuclear spin diffusion in heterogeneous systems is developed here, incorporating the intrinsic T1 relaxation towards the temperature-dependent equilibrium along with the spin-diffusion coefficients based on the measured NMR line widths and the known atomic densities in each compartment. This simple model provides the physical basis for the observed spin-diffusion bottleneck and is in a good quantitative agreement with the earlier measurements. A simultaneous fit of the model to the time-dependent NMR data at two different DNP frequencies provides excellent estimates of the cluster size, the intrinsic sample temperature, and 129Xe T1 constants. The model was also applied to the NMR data acquired during relaxation towards thermal equilibrium after microwaves were turned off to estimate T1 relaxation time constants inside and outside the clusters. Fitting the model to data during and after DNP provides estimates of cluster size that are in complete agreement. PMID:23981341

  14. Separation and purification of glucosinolates from crude plant homogenates by high-speed counter-current chromatography.

    PubMed

    Fahey, Jed W; Wade, Kristina L; Stephenson, Katherine K; Chou, F Edward

    2003-05-09

    Glucosinolates are anionic, hydrophilic plant secondary metabolites which are of particular interest due to their role in the prevention of cancer and other chronic and degenerative diseases. The separation and purification of glucosinolates from a variety of plant sources (e.g. seeds of broccoli, arugula and the horseradish tree), was achieved using high-speed counter-current chromatography (HSCCC). A high-salt, highly polar system containing 1-propanol-acetonitrile-saturated aqueous ammonium sulfate-water (1:0.5:1.2:1), was run on a semi-preparative scale and then transferred directly to preparative scale. Up to 7 g of a concentrated methanolic syrup containing about 10% glucosinolates was loaded on an 850-ml HSCCC column, and good separation and recovery were demonstrated for 4-methylsulfinylbutyl, 3-methylsulfinylpropyl, 4-methylthiobutyl, 2-propenyl and 4-(rhamnopyranosyloxy)benzyl glucosinolates. Multiple injections (5 to 6 times) were performed with well-preserved liquid stationary phase under centrifugal force. Pooled sequential runs with broccoli seed extract yielded about 20 g of its predominant glucosinolate, glucoraphanin, which was produced at > 95% purity and reduced to powdered form.

  15. Mobilization of lead by esters of meso-2,3-dimercaptosuccinic acid

    SciTech Connect

    Singh, P.K.; Jones, M.M.; Xu, Z.; Gale, G.R.; Smith, A.B.; Atkins, L.M. )

    1989-01-01

    An examination was made of the relative efficacies of 2,3-dimercapto-1-propanol (BAL) and three diesters (CH(SH)COOR)2; DMDMS, R = CH3; DEDMS, R = C2H5; and Di-PDMS, R = CH(CH3)2 of meso-2,3-dimercaptosuccinic acid (DMSA) in mobilizing freshly injected lead from mice. These diesters, like BAL, reduced the lead levels resulting from freshly injected lead in both the soft tissues (liver, kidneys, spleen, and brain) and the bone (tibia). After treatment with the dimethyl (DMDMS), the diethyl (DEDMS), and the diisopropyl (Di-PDMS) esters the lead content of each of the organs was significantly less than that present in the untreated controls. Each of the diesters reduced lead levels in the kidneys, liver, and spleen significantly below those levels found after BAL treatment. The action of the diesters in reducing brain lead levels was comparable to that of BAL. Di-PDMS was the most effective of these compounds and was significantly superior to BAL. Each of the esters was also significantly more effective than BAL in reducing the whole body level of lead.

  16. Photocatalytic degradation of Reactive Black 5 and Malachite Green with ZnO and lanthanum doped nanoparticles

    NASA Astrophysics Data System (ADS)

    Kaneva, N.; Bojinova, A.; Papazova, K.

    2016-02-01

    Here we report the preparation of ZnO particles with different concentrations of La3+ doping (0, 0.5 and 1 wt%) via sol-gel method. The nanoparticles are synthesized directly from Zn(CH3COO)2.2H2O in the presence of 1-propanol and triethylamine at 80°C. The conditions are optimized to obtain particles of uniform size, easy to isolate and purify. The nanoparticles are characterized by SEM, XRD and UV-Vis analysis. The photocatalytic properties of pure and La-doped ZnO are studied in the photobleaching of Malachite Green (MG) and Reactive Black 5 (RB5) dyes in aqueous solutions upon UV illumination. It is observed that the rate constant increases with the La loading up to 1 wt%. The doping helps to achieve complete mineralization of MG within a short irradiation time. 1 wt% La-doped ZnO nanoparticles show highest photocatalytic activity. The La3+ doped ZnO particles degrade faster RB5 than MG. The reason is weaker N=N bond in comparison with the C-C bond between the central carbon atom and N,N-dimethylaminobenzyl in MG. The as-prepared ZnO particles can find practical application in photocatalytic purification of textile wastewaters.

  17. Zeolitic imidazolate framework-71 nanocrystals and a novel SOD-type polymorph: solution mediated phase transformations, phase selection via coordination modulation and a density functional theory derived energy landscape.

    PubMed

    Schweinefuss, Maria E; Springer, Sergej; Baburin, Igor A; Hikov, Todor; Huber, Klaus; Leoni, Stefano; Wiebcke, Michael

    2014-03-07

    We report a rapid additive-free synthesis of nanocrystals (NCs) of RHO-type ZIF-71 () of composition [Zn(dcim)2] (dcim = 4,5-dichloroimidazolate) in 1-propanol as solvent at room temperature. NC- has a size of 30-60 nm and exhibits permanent microporosity with a surface area (SBET = 970 m(2) g(-1)) comparable to that of microcrystalline material. When kept under the mother solution NC- undergoes transformation into a novel SOD-type polymorph (), which in turn converts into known ZIF-72 () with lcs topology. It is shown that microcrystals (MCs) of can be favourably synthesised using 1-methylimidazole as a coordination modulator. NC- with size <200 nm was prepared using NC-ZIF-8 as a template with SOD topology in a solvent assisted ligand exchange-related process. DFT-assisted Rietveld analysis of powder XRD data revealed that novel polymorph possesses an unusual SOD framework conformation. was further characterised with regard to microporosity (SBET = 597 m(2) g(-1)) and thermal as well as chemical stability. DFT calculations were performed to search for further potentially existing but not-yet synthesised polymorphs in the [Zn(dcim)2] system.

  18. Engineering Escherichia coli for Microbial Production of Butanone

    PubMed Central

    Srirangan, Kajan; Liu, Xuejia; Akawi, Lamees; Bruder, Mark; Moo-Young, Murray

    2016-01-01

    To expand the chemical and molecular diversity of biotransformation using whole-cell biocatalysts, we genetically engineered a pathway in Escherichia coli for heterologous production of butanone, an important commodity ketone. First, a 1-propanol-producing E. coli host strain with its sleeping beauty mutase (Sbm) operon being activated was used to increase the pool of propionyl-coenzyme A (propionyl-CoA). Subsequently, molecular heterofusion of propionyl-CoA and acetyl-CoA was conducted to yield 3-ketovaleryl-CoA via a CoA-dependent elongation pathway. Lastly, 3-ketovaleryl-CoA was channeled into the clostridial acetone formation pathway for thioester hydrolysis and subsequent decarboxylation to form butanone. Biochemical, genetic, and metabolic factors affecting relative levels of ketogenesis, acidogenesis, and alcohologenesis under selected fermentative culture conditions were investigated. Using the engineered E. coli strain for batch cultivation with 30 g liter−1 glycerol as the carbon source, we achieved coproduction of 1.3 g liter−1 butanone and 2.9 g liter−1 acetone. The results suggest that approximately 42% of spent glycerol was utilized for ketone biosynthesis, and thus they demonstrate potential industrial applicability of this microbial platform. PMID:26896132

  19. Development and validation of a stability-indicating micellar liquid chromatographic method for the determination of timolol maleate in the presence of its degradation products.

    PubMed

    Rizk, Mohamed S; Merey, Hanan A; Tawakkol, Shereen M; Sweilam, Mona N

    2015-04-01

    A stability-indicating micellar liquid chromatographic (MLC) method was developed and validated for the quantitative determination of timolol maleate (TM) in the presence of its degradation products resulting from accelerated degradation in a run time not more than 8 min. TM was subjected to stress conditions of hydrolysis (including alkaline, acidic and thermal hydrolysis) and oxidation. An isocratic, rapid and mobile phase saving the micellar LC method was developed with a BioBasic phenyl column (150 × 1.0 mm, 5 µm particle size) and a micellar mobile phase composed of 0.1 M sodium dodecyl sulfate, 10% of 1-propanol and 0.1% of triethylamine in 0.035 M ortho-phosphoric acid. The flow rate of the mobile phase was 0.1 mL/min. UV detection was adjusted at 298 nm and performed at room temperature. The method has been validated according to the International Conference on Harmonisation guidelines. The method is successfully applied for the determination of TM in bulk powder and pharmaceutical dosage form.

  20. 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.

  1. Vertically aligned ZnO nanorod grown by hydrothermal based chemical method on glass substrate

    NASA Astrophysics Data System (ADS)

    Srivastava, R.; Majumdar, S.; Bhunia, S.

    2012-06-01

    A low-temperature and effective precursor-based method has been demonstrated to synthesize nanostructured ZnO. It is found that the morphology of ZnO precursors has a strong dependence on the reaction conditions that include the molar ratio of reagents, solvent, and reaction temperature. In this work, ZnO nanostructures were synthesized via hydrothermal based chemical method. Zinc acetate dehydrate [Zn(Ac)2 2H2O] and 1-propanol(C3H8O) were adopted for a seed layer growth on glass substrate via spin coating technique. Zinc nitrate hexahydrate [Zn(NO3)2 6H2O], hexamethylenetetramine(C6H12N4) and diethylamine(C4H11N) were adopted as synthesis precursors. The ZnO nanostructures obtained were characterized by scanning electronic microscopy (SEM) and the PL method. The SEM image of the sample showed that the thin film of ZnO on glass substrate has, predominantly, a nanometric rod-like morphology with hexagonal wurtzite structure.

  2. 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.

  3. Internal surface modification of zeolite MFI particles and membranes for gas separation

    NASA Astrophysics Data System (ADS)

    Kassaee, Mohamad H.

    Zeolites are a well-known class of crystalline oxide materials with tunable compositions and nanoporous structures, and have been used extensively in catalysis, adsorption, and ion exchange. The zeolite MFI is one of the well-studied zeolites because it has a pore size and structure suitable for separation or chemical conversion of many industrially important molecules. I synthesized MFI membranes with [h0h] out-of-plane orientation on α-alumina supports. The membranes were modified by the same procedures as used for MFI particles and with 1-butanol, 3-amino-1-propanol, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. The existence of functional groups in the pores of the zeolite was confirmed by PA-FTIR measurements. Permeation measurements of H2, N2, CO2, CH 4, and SF6, were performed at room temperature before and after modification. Permeation of n-butane, and i-butane were measured before and after modification with 1-butanol. For all of the studied gases, gas permeances decreased by 1-2 orders of magnitude compared to bare MFI membranes for modified membranes. This is a strong indication that the organic species in the MFI framework are interacting with or blocking the gas molecule transport through the MFI pores. The CO2/CH 4 permeation selectivity was close to the Knudsen selectivity (0.6) for the membranes before modification. CO2/CH4 selectivity increased for MFI/benzenemethanol modified membrane (1.0), whereas it decreased for the MFI/2-[(2-aminoethyl)amino]ethanol modified membrane (0.5). MFI/benzenemethanol crystals were shown to have a highest sorption capacity for CH4, whereas, MFI/2-[(2-aminoethyl)amino]ethanol crystals were shown to have a highest sorption capacity for CO2 over all other studied molecules Higher sorption of CH4 in MFI/benzenemethanol and higher sorption of CO2 in MFI/2-[(2-aminoethyl)amino]ethanol and their strong binding to the modified membrane are likely the reasons for observing higher and lower CO2/CH4 permeation

  4. Structural Insight into Guest Binding Sites in a Porous Homochiral Metal-Organic Material.

    PubMed

    Zhang, Shi-Yuan; Wojtas, Lukasz; Zaworotko, Michael J

    2015-09-23

    An enantiomeric pair of chiral metal-organic materials (CMOMs) based upon mandelate (man) and 4,4'-bipyridine (bpy) ligands, [Co2(S-man)2(bpy)3](NO3)2·guest (1S·guest) and [Co2(R-man)2(bpy)3](NO3)2·guest (1R·guest), have been prepared. The cationic frameworks exhibit one-dimensional chiral channels with dimensions of 8.0 Å × 8.0 Å. The pore chemistry is such that chiral surfaces lined with nitrate anions and phenyl groups create multiple binding sites for guest and/or solvent molecules. The performance of 1S and 1R with respect to resolution of racemic mixtures of 1-phenyl-1-propanol (PP) was studied by varying time, temperature, and the use of additives. Selectivity toward PP was determined by chiral HPLC with ee values of up to 60%. The binding sites and host-guest interactions were investigated through single-crystal X-ray structural analyses of guest-exchanged 1S and 1R. Crystallographically observed structural changes (e.g., the absolute configurations of the three PP binding sites switch from R, R, and S to R, R, and R/S) correlate with experimentally observed ee values of 33% and 60% for variants of 1S that contain PP and different solvent molecules, 1S·PPex and 1S·PPex', respectively. The fact that manipulation of guest solvent molecules, which in effect serve as cofactors, can modify chiral sites and increase enantioselectivity is likely to aid in the design of more effective CMOMs and processes for chiral separations.

  5. Redox effect on volatile compound formation in wine during fermentation by Saccharomyces cerevisiae.

    PubMed

    Fariña, Laura; Medina, Karina; Urruty, Maia; Boido, Eduardo; Dellacassa, Eduardo; Carrau, Francisco

    2012-09-15

    Although redox state is a well-known key process parameter in microbial activity, its impact on wine volatile aroma compounds produced during fermentation has not been studied in detail. In this study we report the effect of reductive and microaerobic conditions on wine aroma compound production using different initial amounts of yeast assimilable nitrogen (YAN: 180 and 400 mg N/l) in a simil grape must defined medium and two S. cerevisiae strains commonly used in wine-making. In batch fermentation culture conditions, reductive conditions were obtained using flasks plugged with Muller valves filled with sulphuric acid; while microaerobic conditions were attained with defined cotton plugs. It was found that significant differences in redox potential were obtained using the different plugs, and with variation of over 100 mV during the main fermentation period. Significant differences in the final concentration of higher alcohols, esters and fatty acids were attributed to differences in the redox state in the medium in both strains. A consistent increase in esters and medium chain fatty acids, as well as a decrease of higher alcohols and isoacids, was seen under reductive fermentation conditions. Interestingly, 1-propanol, δ-butyrolactone and ethyl lactate concentrations, showed no significant variation under the different redox conditions. A better understanding of the influence of redox state of the fermentation medium on the composition of volatile compounds in wine could enable improvement of vinification management. From a microbiological standpoint results presented here will contribute to the standardization of data models for the application of metabolic footprinting methods for wine yeast strain phenotyping and characterization.

  6. An ATR-FTIR Study on the Effect of Molecular Structural Variations on the CO2 Absorption Characteristics of Heterocyclic Amines, Part II

    PubMed Central

    Robinson, Kelly; McCluskey, Adam; Attalla, Moetaz I

    2012-01-01

    This paper reports on an ATR-FTIR spectroscopic investigation of the CO2 absorption characteristics of a series of heterocyclic diamines: hexahydropyrimidine (HHPY), 2-methyl and 2,2-dimethylhexahydropyrimidine (MHHPY and DMHHPY), hexahydropyridazine (HHPZ), piperazine (PZ) and 2,5- and 2,6-dimethylpiperazine (2,6-DMPZ and 2,5-DMPZ). By using in situ ATR-FTIR the structure–activity relationship of the reaction between heterocyclic diamines and CO2 is probed. PZ forms a hydrolysis-resistant carbamate derivative, while HHPY forms a more labile carbamate species with increased susceptibility to hydrolysis, particularly at higher CO2 loadings (>0.5 mol CO2/mol amine). HHPY exhibits similar reactivity toward CO2 to PZ, but with improved aqueous solubility. The α-methyl-substituted MHHPY favours HCO3− formation, but MHHPY exhibits comparable CO2 absorption capacity to conventional amines MEA and DEA. MHHPY show improved reactivity compared to the conventional α-methyl- substituted primary amine 2-amino-2-methyl-1-propanol. DMHHPY is representative of blended amine systems, and its reactivity highlights the advantages of such systems. HHPZ is relatively unreactive towards CO2. The CO2 absorption capacity CA (mol CO2/mol amine) and initial rates of absorption RIA (mol CO2/mol amine min−1) for each reactive diamine are determined: PZ: CA=0.92, RIA=0.045; 2,6-DMPZ: CA=0.86, RIA=0.025; 2,5-DMPZ: CA=0.88, RIA=0.018; HHPY: CA=0.85, RIA=0.032; MHHPY: CA=0.86, RIA=0.018; DMHHPY: CA=1.1, RIA=0.032; and HHPZ: no reaction. Calculations at the B3LYP/6-31+G** and MP2/6-31+G** calculations show that the substitution patterns of the heterocyclic diamines affect carbamate stability, which influences hydrolysis rates. PMID:22517608

  7. Study of the art: canine olfaction used for cancer detection on the basis of breath odour. Perspectives and limitations.

    PubMed

    Jezierski, Tadeusz; Walczak, Marta; Ligor, Tomasz; Rudnicka, Joanna; Buszewski, Bogusław

    2015-05-06

    Experimental studies using trained dogs to identify breath odour markers of human cancer, published in the recent decade, have been analyzed and compared with the authors' own results. Particular published studies differ as regards the experimental setup, kind of odour samples (breath, urine, tumor tissue, serum), sample collection methods, dogs' characteristics and dog training methods as well as in results presented in terms of detection sensitivity and specificity. Generally it can be stated that trained dogs are able to distinguish breath odour samples typical for patients with lung cancer and other cancers from samples typical for healthy humans at a 'better than by chance' rate. Dogs' indications were positively correlated with content of 2-pentanone and ethyl acetate (r = 0.97 and r = 0.85 respectively) and negatively correlated with 1-propanol and propanal in breath samples (r = -0.98 and -0.87 respectively). The canine method has some advantages as a potential cancer-screening method, due to its non-invasiveness, simplicity of odour sampling and storage, ease of testing and interpretation of results and relatively low costs. Disadvantages and limitations of this method are related to the fact that it is still not known exactly to which chemical compounds and/or their combinations the dogs react. So far it could not be confirmed that dogs are able to sniff out early preclinical cancer stages with approximately the same accuracy as already diagnosed cases. The detection accuracy may vary due to failure in conditioning of dogs, decreasing motivation or confounding factors. The dogs' performance should be systematically checked in rigorous double-blind procedures. Recommendations for methodological standardization have been proposed.

  8. Occurrence of chloropropanols in soy sauce and other foods in China between 2002 and 2004.

    PubMed

    Fu, Wu Sheng; Zhao, Yunfeng; Zhang, Gong; Zhang, Lei; Li, Jing Guang; Tang, Chang Dong; Miao, Hong; Ma, Jin Bo; Zhang, Qi; Wu, Yong Ning

    2007-08-01

    A survey of chloropropanols in soy sauce and some selected foods in China is reported. Thirty-seven traditionally brewed soy sauce samples contained 3-MCPD below the EC maximum limit (ML) of 0.02 mg kg(-1). All soy sauce samples (629) from retailers contained levels of 3-MCPD ranging between <0.005 (LOQ) and 189 mg kg(-1), and only 12.2% had levels in excess of the Chinese ML of 1.0 mg kg(-1) for acid hydrolyzed vegetable protein (acid HVP). This indicates that the necessary processing changes have been made to decrease levels of chloropropanols in soy sauce. 2-Monochloropropane-1,3-diol (2-MCPD), 1,3-dichloro-2-propanol (1,3-DCP) and 2,3-dichloro-1-propanol (2,3-DCP) were detected in 48.1 19.1 and 3.78% of the soy sauce samples, respectively; the highest levels being 20.3, 8.26 and 0.50 mg kg(-1), respectively. A good linear correlation was found between the amount of 3-MCPD and 2-MCPD, with the level of 3-MCPD being generally higher than that of other chloropropanols for the same soy sauce. Acid HVP contained 3-MCPD at a level of 0.010-117.7 mg kg(-1) (on a liquid basis) and 80% of samples contained levels exceeding 1.0 mg kg(-1). In some other foods investigated, relatively high levels of 3-MCPD were found in soy sauce powder, oyster sauce, beef products, instant noodle spices and health foods, ranging from 0.029 to 13.64 mg kg(-1). It is concluded that abnormal levels of 3-MCPD in soy sauce or other foods produced in China may result from acid hydrolysis or the addition of the contaminated acid HVP.

  9. DNA methylation analysis in rat kidney epithelial cells exposed to 3-MCPD and glycidol.

    PubMed

    Senyildiz, Mine; Alpertunga, Buket; Ozden, Sibel

    2016-11-24

    3-Monochloropropane-1,2-diol (3-MCPD) is a well-known food processing contaminant that has been regarded as a rat carcinogen, which is known to induce Leydig-cell and mammary gland tumors in males, as well as kidney tumors in both genders. 3-MCPD is highly suspected to be a non-genotoxic carcinogen. 2,3-Epoxy-1-propanol (glycidol) can be formed via dehalogenation from 3-MCPD. We aimed to investigate the cytotoxic effects of 3-MCPD and glycidol, then to demonstrate the possible epigenetic mechanisms with global and gene-specific DNA methylation in rat kidney epithelial cells (NRK-52E). IC50 value of 3-MCPD was determined as 48 mM and 41.39 mM, whereas IC50 value of glycidol was 1.67 mM and 1.13 mM by MTT and NRU test, respectively. Decreased global DNA methylation at the concentrations of 100 μM and 1000 μM for 3-MCPD and 100 μM and 500 μM for glycidol were observed after 48 h exposure by using 5-methylcytosine (5-mC) ELISA kit. Methylation changes were detected in promoter regions of c-myc and Rassf1a in 3-MCPD and glycidol treated NRK-52E cells by using methylation-specific PCR (MSP), whereas changes on gene expression of c-myc and Rassf1a were observed by using real-time PCR. However, e-cadherin, p16, VHL and p15 genes were unmethylated in their CpG promoter regions in response to treatment with 3-MCPD and glycidol. Alterations in DNA methylation might be key events in the toxicity of 3-MCPD and glycidol.

  10. Analytical method for the trace determination of esterified 3- and 2-monochloropropanediol and glycidyl fatty acid esters in various food matrices.

    PubMed

    Samaras, Vasilios G; Giri, Anupam; Zelinkova, Zuzana; Karasek, Lubomir; Buttinger, Gerhard; Wenzl, Thomas

    2016-09-30

    Fatty acid esters of 3-monochloro-1,2-propanediol (3-MCPDEs), of 2-monochloro-1,3-propanediol (2-MCPDEs) and of 2,3-epoxy-1-propanol or glycidol (GEs), which are considered to be deleterious to human health, may occur in a broad variety of food samples. A proper risk assessment of those substances requires the availability of robust occurrence data; in this respect concerns have been raised regarding the reliability of results obtained with the currently available methods to determine those substances in processed food. This article presents an indirect analytical procedure for the simultaneous determination of 3-MCPDEs, 2-MCPDEs and GEs in a wide variety of food products after extraction by pressurised liquid extraction (PLE) and determination by gas chromatography mass-spectrometry (GC-MS). For the differentiation of MCPDEs and GEs, the latter were first converted to monobromopropanediol esters (MBPDEs) in acid aqueous solution of sodium bromide. MCPDEs and MBPDEs were then hydrolysed under acidic conditions followed by derivatisation of the released free (non-esterified) form in ethyl acetate with phenyl boronic acid (PBA). Quantification of the analytes was carried out using the isotopic labelled analogues of both MCPDEs and GEs. Limits of detection (LODs) and limits of quantitation (LOQs) were in the range of 7-17mgkg(-1) and 13-31mgkg(-1) respectively, while the working range of the method was between LOQ and 1850mgkg(-1) expressed on fat basis. The developed method was successfully applied for the analysis of the target compounds in more than 650 different food samples covering the following commodities: bread and rolls, fine bakery wares, smoked fish products, fried and roasted meat, potato based snacks and fried potato products, cereal-based snacks and margarines.

  11. Towards the rational design of organic/inorganic interface for solid supported CO2 capture

    NASA Astrophysics Data System (ADS)

    He, Feng

    Monoethanolamine (MEA, HO(CH2)2NH2) aqueous solution based CO2 capture is the current technology used to mitigate power plants' green house gas emission. Solid based CO2 capture technique is regarded as a promising alternative, because it is more cost-effective and environmentally friendly than the solution based technique. Recently, solid-supported CO2 capture on MEA modified TiO 2 powders has been demonstrated [1]. It is believed that the main reaction pathway involved in solid-supported amine based CO2 capture is similar to the reaction in the amine solution, where the amine group reacts with CO2 to form carbamate (--NHCOO--). From the previous work on the MEA/TiO2 (110) system [2], it is found that MEA covered rutile TiO2 (110) did not capture CO 2. The main reaction pathway in this system was blocked because the amine group attached to the surface. In order to design a functional system, we proposed two possible mechanisms to free --NH2 from rutile TiO2 (110) surface. In this work, we investigated one of our six candidates, the 3-Amino-1-propanol (3AP, HO(CH2) 3NH2) molecule. The classical reactive force field (ReaxFF) [3] method has been employed to investigate the 3AP/TiO2 (110) system with emphasis on binding configurations and binding energies. We found that the amine group of 3AP did not attach to the rutile TiO2 (110) surface, indicating the CO2 capture capability of the 3AP/TiO 2 (110) system, which was confirmed by our experimental collaborators [4].

  12. Characterization of a new α-l-fucosidase isolated from Fusarium proliferatum LE1 that is regioselective to α-(1 → 4)-l-fucosidic linkage in the hydrolysis of α-l-fucobiosides.

    PubMed

    Shvetsova, Svetlana V; Shabalin, Konstantin A; Bobrov, Kirill S; Ivanen, Dina R; Ustyuzhanina, Nadezhda E; Krylov, Vadim B; Nifantiev, Nikolay E; Naryzhny, Stanislav N; Zgoda, Victor G; Eneyskaya, Elena V; Kulminskaya, Anna A

    2017-01-01

    Here, we report the biochemical characterization of a novel α-l-fucosidase with broad substrate specificity (FpFucA) isolated from the mycelial fungus Fusarium proliferatum LE1. Highly purified α-l-fucosidase was obtained from several chromatographic steps after growth in the presence of l-fucose. The purified α-l-fucosidase appeared to be a monomeric protein of 67 ± 1 kDa that was able to hydrolyze the synthetic substrate p-nitrophenyl α-l-fucopyranoside (pNPFuc), with Km = 1.1 ± 0.1 mM and kcat = 39.8 ± 1.8 s(-1). l-fucose, 1-deoxyfuconojirimycin and tris(hydroxymethyl)aminomethane inhibited pNPFuc hydrolysis, with inhibition constants of 0.2 ± 0.05 mM, 7.1 ± 0.05 nM, and 12.2 ± 0.1 mM, respectively. We assumed that the enzyme belongs to subfamily A of the GH29 family (CAZy database) based on its ability to hydrolyze practically all fucose-containing oligosaccharides used in the study and the phylogenetic analysis. We found that this enzyme was a unique α-l-fucosidase that preferentially hydrolyzes the α-(1 → 4)-L-fucosidic linkage present in α-L-fucobiosides with different types of linkages. As a retaining glycosidase, FpFucA is capable of catalyzing the transglycosylation reaction with alcohols (methanol, ethanol, and 1-propanol) and pNP-containing monosaccharides as acceptors. These features make the enzyme an important tool that can be used in the various modifications of valuable fucose-containing compounds.

  13. Effects of new Torulaspora delbrueckii killer yeasts on the must fermentation kinetics and aroma compounds of white table wine.

    PubMed

    Velázquez, Rocío; Zamora, Emiliano; Álvarez, María L; Hernández, Luis M; Ramírez, Manuel

    2015-01-01

    Torulaspora delbrueckii is becoming widely recommended for improving some specific characteristics of wines. However, its impact on wine quality is still far from satisfactory at the winery level, mostly because it is easily replaced by Saccharomyces cerevisiae-like yeasts during must fermentation. New T. delbrueckii killer strains were here isolated and selected for winemaking. They killed S. cerevisiae yeasts and were able to dominate and complete the fermentation of sterile grape must. Sequential yeast inoculation of non-sterile white must with T. delbrueckii followed by S. cerevisiae did not ensure T. delbrueckii dominance or wine quality improvement. Only a single initial must inoculation at high cell concentrations allowed the T. delbrueckii killer strains to dominate and complete the must fermentation to reach above 11% ethanol, but not the non-killer strains. None of the wines underwent malolactic fermentation as long as the must had low turbidity and pH. Although no statistically significant differences were found in the wine quality score, the S. cerevisiae-dominated wines were preferred over the T. delbrueckii-dominated ones because the former had high-intensity fresh fruit aromas while the latter had lower intensity, but nevertheless nice and unusual dried fruit/pastry aromas. Except for ethyl propanoate and 3-ethoxy-1-propanol, which were more abundant in the T. delbrueckii-dominated wines, most of the compounds with fresh fruit odor descriptors, including those with the greatest odor activity values (isoamyl acetate, ethyl hexanoate, and ethyl octanoate), were more abundant in the S. cerevisiae-dominated wines. The low relative concentrations of these fruity compounds made it possible to detect in the T. delbrueckii-dominated wines the low-relative-concentration compounds with dried fruit and pastry odors. An example was γ-ethoxy-butyrolactone which was significantly more abundant in these wines than in those dominated by S. cerevisiae.

  14. Time-dependent VOC-profile of decomposed human and animal remains in laboratory environment.

    PubMed

    Rosier, E; Loix, S; Develter, W; Van de Voorde, W; Tytgat, J; Cuypers, E

    2016-09-01

    A validated method using a thermal desorber combined with a gas chromatograph coupled to a mass spectrometer was used to identify the volatile organic compounds released in decomposed human and animal remains after 9 and 12 months in glass jars in a laboratory environment. This is a follow-up study on a previous report where the first 6 months of decomposition of 6 human and 26 animal remains was investigated. In the first report, out of 452 identified compounds, a combination of 8 compounds was proposed as human and pig specific. The goal of the current study was to investigate if these 8 compounds were still released after 9 and 12 months. The next results were noticed: 287 compounds were identified; only 9 new compounds were detected and 173 were no longer seen. Sulfur-containing compounds were less prevalent as compared to the first month of decomposition. The appearance of nitrogen-containing compounds and alcohols was increasingly evident during the first 6 months, and the same trend was seen in the following 6 months. Esters became less important after 6 months. From the proposed human and pig specific compounds, diethyl disulfide was only detected during the first months of decomposition. Interestingly, the 4 proposed human and pig specific esters, as well as pyridine, 3-methylthio-1-propanol and methyl(methylthio)ethyl disulfide were still present after 9 and 12 months of decomposition. This means that these 7 human and pig specific markers can be used in the development of training aids for cadaver dogs during the whole decomposition process. Diethyl disulfide can be used in training aids for the first month of decomposition.

  15. Characterization of hydroxypropylmethylcellulose (HPMC) using comprehensive two-dimensional liquid chromatography.

    PubMed

    Greiderer, Andreas; Steeneken, Linda; Aalbers, Tom; Vivó-Truyols, Gabriel; Schoenmakers, Peter

    2011-08-26

    Various hydroxyl-propylmethylcellulose (HPMC) polymers were characterized according to size and compositional distributions (percentage of methoxyl and hydroxyl-propoxyl substitution) by means of comprehensive two-dimensional liquid chromatography (LC×LC) using reversed-phase (RP) liquid chromatography in the first dimension and aqueous size-exclusion chromatography (aq-SEC) in the second dimension. RP separation was carried out in gradient-elution mode applying 0.05% TFA in water and 1-propanol, while 0.05% TFA in water was used as mobile phase in aqueous SEC. A two-position ten-port switching valve equipped with two storage loops was used to realize LC×LC. Detection of HPMC was accomplished by charged-aerosol detection (CAD). Data processing to visualize chromatograms was carried out using Matlab software. The significant influence of the LC×LC temperature on (the retention of) HPMC was studied using a column oven which allowed accurate temperature control. Due to the phenomenon of thermal gelation, which is a result of methyl and hydroxypropyl substitution of anhydroglucose units from the cellulose backbone, we were able to obtain additional, specific information on compositional characteristics of various HPMC samples. As the retention behaviour of gelated and non-gelated polymer proved to be different, the fraction of the polymer that is gelated in the chromatographic column could be monitored at different temperatures. Moreover, the temperature at which half of the polymer is gelated could be correlated with the cloud-point temperature. As a result, differences in inherent cloud points of modified cellulose can be used as a further distinguishing property in "temperature-responsive" LC×LC.

  16. Monte Carlo Simulation of Aqueous Dilute Solutions of Polyhydric Alcohols

    NASA Astrophysics Data System (ADS)

    Lilly, Arnys Clifton, Jr.

    In order to investigate the details of hydrogen bonding and solution molecular conformation of complex alcohols in water, isobaric-isothermal Monte Carlo simulations were carried out on several systems. The solutes investigated were ethanol, ethylene glycol, 1,2-propylene glycol, 1,3 -propylene glycol and glycerol. In addition, propane, which does not hydrogen bond but does form water hydrates, was simulated in aqueous solution. The complex alcohol-water systems are very nonideal in their behavior as a function of solute concentration down to very dilute solutions. The water model employed was TIP4P water^1 and the intermolecular potentials employed are of the Jorgensen type^2 in which the interactions between the molecules are represented by interaction sites usually located on nuclei. The interactions are represented by a sum of Coulomb and Lennard-Jones terms between all intermolecular pairs of sites. Intramolecular rotations in the solute are modeled by torsional potential energy functions taken from ethanol, 1-propanol and 2-propanol for C-O and C-C bond rotations. Quasi-component pair correlation functions were used to analyze the hydrogen bonding. Hydrogen bonds were classified as proton acceptor and proton donor bonds by analyzing the nearest neighbor pair correlation function between hydroxyl oxygen and hydrogen and between solvent-water hydrogen and oxygen. The results obtained for partial molar heats of solution are more negative than experimental values by 3.0 to 14 kcal/mol. In solution, all solutes reached a contracted molecular geometry with the OH groups generally on one side of the molecule. There is a tendency for the solute OH groups to hydrogen bond with water, with more proton acceptor bonds than proton donor bonds. The water -solute binding energies correlate with experimental measurements of the water-binding properties of the solute. ftn ^1Jorgensen, W. L. et al, J. Chem. Phys., 79, 926 (1983). ^2Jorgensen, W. L., J. Phys Chem., 87, 5304

  17. Preparation of a new polymeric ionic liquid-based monolith for stir cake sorptive extraction and its application in the extraction of inorganic anions.

    PubMed

    Huang, Xiaojia; Chen, Linli; Yuan, Dongxing; Bi, Shangshang

    2012-07-27

    In this study, a novel stir cake sorptive extraction (SCSE) sorbent based on polymeric ionic liquid-based monolith (PILM) for the extraction of inorganic anions was prepared. In the presence of a porogen solvent containing 1-propanol and dimethylformamid, an ionic liquid, 1-ally-3-methylimidazolium chloride was used as monomer to copolymerize in situ with ethylene dimethacrylate to form PILM. The effect of preparation conditions such as ratio of functional monomer to cross-linker, content of porogenic solvent on the extraction efficiencies were investigated in detail. The PILM was characterized by elemental analysis, scanning electron microscopy, mercury intrusion porosimetry and infrared spectroscopy. In order to investigate the extraction capacity of PILM-SCSE for inorganic anions, the SCSE was combined with ion chromatography with conductivity detection, F(-), Cl(-), NO(2)(-), Br(-), NO(3)(-), PO(4)(3-) and SO(4)(2-) were selected as detected solutes. Several extractive parameters, including pH values in sample matrix, desorption solvent, extraction and desorption time were optimized. The results showed that under the optimum experimental conditions, low detection limits (S/N=3) and quantification limits (S/N=10) of the proposed method for the target anions were achieved within the range of 0.11-2.08 and 0.37-6.88 μg/L, respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction inorganic anions. Finally, the proposed method was successfully used to detect different water samples include commercial purified water, tab water and river water. Acceptable recoveries and satisfactory repeatability were obtained. To the best of our knowledge, this is the first to use polymeric ionic liquid to enrich inorganic anions.

  18. Growth characteristics of Saccharomyces cerevisiae S288C in changing environmental conditions: auxo-accelerostat study.

    PubMed

    Kasemets, Kaja; Nisamedtinov, Ildar; Laht, Tiiu-Maie; Abner, Kristo; Paalme, Toomas

    2007-07-01

    The effect of individual environmental conditions (pH, pO(2), temperature, salinity, concentration of ethanol, propanol, tryptone and yeast extract) on the specific growth rate as well as ethanol and glycerol production rate of Saccharomyces cerevisiae S288C was mapped during the fermentative growth in aerobic auxo-accelerostat cultures. The obtained steady-state values of the glycerol to ethanol formation ratio (0.1 mol mol(-1)) corresponding to those predicted from the stoichiometric model of fermentative yeast growth showed that the complete repression of respiration was obtained in auxostat culture and that the model is suitable for calculation of Y(ATP) and Q(ATP) values for the aerobic fermentative growth. Smooth decrease in the culture pH and dissolved oxygen concentration (pO2) down to the critical values of 2.3 and 0.8%, respectively, resulted in decrease in growth yield (Y(ATP)) and specific growth rate, however the specific ATP production rate (Q(ATP)) stayed almost constant. Increase in the concentration of biomass (>0.8 g dwt l(-1)), propanol (>2 g l(-1)) or NaCl (>15 g l(-1)) lead at first to the decrease in the specific growth rate and Q(ATP), while Y(ATP) was affected only at higher concentrations. The observed decrease in Q(ATP) was caused by indirect rather than direct inhibition of glycolysis. The increase in tryptone concentration resulted in an increase in the specific growth rate from 0.44 to 0.62 h(-1) and Y(ATP) from 12.5 to 18.5 mol ATP g dwt(-1). This study demonstrates that the auxo-accelerostat method, besides being an efficient tool for obtaining the culture characteristics, provides also decent conditions for the experiments elucidating the control mechanisms of cell growth.

  19. New Cerium-Based Metal-Organic Scintillators for Radiation Detection

    SciTech Connect

    Boatner, Lynn A; Neal, John S; Ramey, Joanne Oxendine; Chakoumakos, Bryan C; Custelcean, Radu; Van Loef, Edgar; Markosyan, G

    2013-01-01

    We have previously shown that a new class of scintillating materials can be developed based on the synthesis and crystal growth of rare-earth metal-organic compounds. The first scintillator of this type consisted of single crystals of CeCl3(CH3OH)4 that were grown from a methanol solution. These crystals were shown to be applicable to both gamma-ray and fast neutron detection. Subsequently, metal-organic scintillators consisting of the compound LaBr3(CH3OH)4 activated with varying levels of Ce3+ and of CeBr3(CH3OH)4 were grown in single crystal form. We have now extended the development of this new class of scintillators to more complex organic components by reacting rare-earth halides such as CeCl3 or CeBr3 with different isomers of propanol and butanol including 1-propanol, isobutanol, n-butanol, and tert-butanol. The reaction of CeCl3 or CeBr3 with these organics results in the formation of new and relatively complex molecular crystals whose structures were determined using single-crystal X-ray diffraction. These new metal-organic scintillating materials were grown in single crystal form from solution, and their scintillation characteristics have been investigated using X-ray-excited luminescence plus energy spectra obtained with gamma-ray and alpha-particle sources. If the reactions between the inorganic and organic components are not carried out under very dry and highly controlled conditions, molecular structures can be formed that incorporate waters of hydration. The present observation of scintillation in these hydrated rare-earth metal-organic compounds is apparently an original finding, since we are not aware of any previous reports of scintillation being observed in a material that incorporates waters of hydration

  20. Cyanobacterial Blue Color Formation during Lysis under Natural Conditions

    PubMed Central

    Tsuji, Kiyomi; Tomita, Koji; Hasegawa, Masateru; Bober, Beata; Harada, Ken-Ichi

    2015-01-01

    Cyanobacteria produce numerous volatile organic compounds (VOCs), such as β-cyclocitral, geosmin, and 2-methylisoborneol, which show lytic activity against cyanobacteria. Among these compounds, only β-cyclocitral causes a characteristic color change from green to blue (blue color formation) in the culture broth during the lysis process. In August 2008 and September 2010, the lysis of cyanobacteria involving blue color formation was observed at Lake Tsukui in northern Kanagawa Prefecture, Japan. We collected lake water containing the cyanobacteria and investigated the VOCs, such as β-cyclocitral, β-ionone, 1-propanol, 3-methyl-1-butanol, and 2-phenylethanol, as well as the number of cyanobacterial cells and their damage and pH changes. As a result, the following results were confirmed: the detection of several VOCs, including β-cyclocitral and its oxidation product, 2,2,6-trimethylcyclohexene-1-carboxylic acid; the identification of phycocyanin based on its visible spectrum; the lower pH (6.7 and 5.4) of the lysed samples; and characteristic morphological change in the damaged cyanobacterial cells. We also encountered the same phenomenon on 6 September 2013 in Lake Sagami in northern Kanagawa Prefecture and obtained almost the same results, such as blue color formation, decreasing pH, damaged cells, and detection of VOCs, including the oxidation products of β-cyclocitral. β-Cyclocitral derived from Microcystis has lytic activity against Microcystis itself but has stronger inhibitory activity against other cyanobacteria and algae, suggesting that the VOCs play an important role in the ecology of aquatic environments. PMID:25662969

  1. Phase behavior and molecular dynamics simulation studies of new aqueous two-phase separation systems induced by HEPES buffer.

    PubMed

    Taha, Mohamed; Khoiroh, Ianatul; Lee, Ming-Jer

    2013-01-17

    Here, for the first time, we show that with addition of a biological buffer, 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES), into aqueous solutions of tetrahydrofuran (THF), 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone, the organic solvent can be excluded from water to form a new liquid phase. The phase diagrams have been determined at ambient temperature. In order to understand why and how a zwitterion solute (HEPES) induced phase separation of the investigated systems, molecular dynamics (MD) simulation studies are performed for HEPES + water + THF system. The MD simulations were conducted for the aqueous mixtures with 12 different compositions. The reliability of the simulation results of HEPES in pure water and beyond the phase separation mixtures was justified by comparing the densities obtained from MD with the experimental values. The simulation results of HEPES in pure THF and in a composition inside the phase separation region were justified qualitatively. Interestingly, all HEPES molecules entirely aggregated in pure THF. This reveals that HEPES is insoluble in pure THF, which is consistent with the experimental results. Even more interestingly, the MD simulation for the mixture with composition inside the phase separation region showed the formation of two phases. The THF molecules are squeezed out from the water network into a new liquid phase. The hydrogen bonds (HBs), HB lifetime, HB Gibbs energy (ΔG), radial distribution functions (RDFs), coordination numbers (CNs), electrostatic interactions, and the van der Waals interactions between the different species have been analyzed. Further, MD simulations for the other phase separation systems by choosing a composition inside the two liquids region for each system were also simulated. Our findings will therefore pave the way for designing new benign separation auxiliary agents.

  2. Construction of self-cloning bottom-fermenting yeast with low vicinal diketone production by the homo-integration of ILV5.

    PubMed

    Kusunoki, K; Ogata, T

    2012-10-01

    The vicinal diketones (VDK), such as diacetyl and 2,3-pentandione, impart an unpleasant butter-like flavour to beer. Typically, these are required to be reduced below the flavour thresholds during the maturation (lagering) stages of the brewing process. To shorten beer maturation time, we constructed a self-cloning, bottom-fermenting yeast with low VDK production by integrating ILV5, a gene encoding a protein that metabolizes α-acetolactate and α-aceto-α-hydroxybutyrate (precursors of VDK). A DNA fragment containing Saccharomyces cerevisiae-type ILV5 was inserted upstream of S. cerevisiae-type ILV2 in bottom-fermenting yeast to construct self-cloning strains with an increased copy number of ILV5. Via transformation, ILV2 was replaced with the sulfometuron methyl (SM) resistance gene SMR1B, which differs by a single nucleotide, to create SM-resistant transformants. The wort fermentation test, using the SC-ILV5-homo inserted transformant, confirmed a consecutive reduction in VDK and a shortening period during which VDK was reduced to within the threshold. The concentrations of ethyl acetate, isoamyl acetate, isoamyl alcohol, 1-propanol, isobutyl alcohol and active isoamyl alcohol (flavour components) were not changed when compared with the parent strain. We successfully constructed self-cloning brewer's yeast in which SC-ILV5 was homo-inserted. Using the transformed yeast, the concentration of VDK in fermenting wort was reduced, whereas the concentrations of flavour components were not affected. This genetically stable, low VDK-producing, self-cloning bottom-fermenting yeast would contribute to the shortening of beer maturation time without affecting important flavour components produced by brewer's yeast.

  3. [Preparation and evaluation of pepsin affinity organic polymer capillary monolithic column].

    PubMed

    Chi, Cuijie; Wang, Wei; Ji, Yibing

    2014-08-01

    The protein modified monolithic column in affinity capillary electrochromatography (CEC) has attracted considerable attention over the past decades because of its great enantioseparation ability. A porous polymethacrylate ester-based capillary monolithic column poly (glycidyl methacrylate-co-ethyleneglycol dimethacrylate) (poly (GMA-co-EDMA)) was prepared by in situ co-polymerization. The process was initiated thermally by azobisisobutyronitrile (AIBN). The polymerization mixture contained GMA as the function monomer and EDMA as the crosslinking agent with 1,4-butanediol and 1-propanol as the binary porogen solvent. Under the optimized reaction conditions, including the proportion of monomer and porogens, reaction temperature etc, the column exhibited a uniform structure, sufficient permeability and excel- lent pressure resistance. The separation of alkyl benzenes on the column was mainly based on typical reversed-phase chromatographic retention mechanism. The reproducibility and stability were good with RSDs less than 9. 0%. A pepsin functionalized organic polymer monolith was prepared by covalently bonded pepsin to poly(GMA-co-EDMA) monolith with glutaraldehyde as a spacer based on the activity of epoxide group. The enantioseparation performance of the pepsin affinity monolith for basic enantiomers has been investigated by CEC. Nefopam, amlodipine, citalopram and chlorpheniramine were resolved, and baseline separations of nefopam, amlodipine, citalopram were achieved. The influences of pH, operating voltage, temperature and sample quantity used on the chiral separation were studied. The chiral recognition mechanism of enantiomers on the monolithic column in CEC is discussed. This work developed a new method for the prepataion and application of protein affinity monolith in CEC.

  4. Thermodynamical and structural properties of binary mixtures of imidazolium chloride ionic liquids and alcohols from molecular simulation

    NASA Astrophysics Data System (ADS)

    Raabe, Gabriele; Köhler, Jürgen

    2008-10-01

    We have performed molecular dynamics simulations to determine the densities, excess energies of mixing, and structural properties of binary mixtures of the 1-alkyl-3-methylimidazolium chloride ionic liquids (ILs) [amim][Cl] and ethanol and 1-propanol in the temperature range from 298.15to363.15K. As in our previous work [J. Chem. Phys. 128, 154509 (2008)], our simulation studies are based on a united atom model from Liu et al. [Phys. Chem. Chem. Phys. 8, 1096 (2006)] for the 1-ethyl- and 1-butyl-3-methylimidazolium cations [emim+] and [bmim+], which we have extended to the 1-hexyl-3-methylimidazolium [hmim+] cation and combined with parameters of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] for the chloride anion [Cl-] and the force field by Khare et al. for the alcohols [J. Phys. Chem. B 108, 10071 (2004)]. With this, we provide both prediction for the densities of the mixtures that have mostly not been investigated experimentally yet and a molecular picture of the interactions between the alcohol molecules and the ions. The negative excess energies of all mixtures indicate an energetically favorable mixing of [amim][Cl] ILs and alcohols. To gain insight into the nonideality of the mixtures on the molecular level, we analyzed their local structures by radial and spatial distribution functions. These analyses show that the local ordering in these mixtures is determined by strong hydrogen-bond interactions between the chloride anion and the hydroxyls of the alcohols, enhanced interactions between the anion and the charged domain of the cation, and an increasing aggregation of the nonpolar alkyl tails of the alcohols and the cations with increasing cation size, which results in a segregation of polar and nonpolar domains.

  5. Application of cotton as a solid phase extraction sorbent for on-line preconcentration of copper in water samples prior to inductively coupled plasma optical emission spectrometry determination.

    PubMed

    Faraji, Mohammad; Yamini, Yadollah; Shariati, Shahab

    2009-07-30

    Copper, as a heavy metal, is toxic for many biological systems. Thus, the determination of trace amounts of copper in environmental samples is of great importance. In the present work, a new method was developed for the determination of trace amounts of copper in water samples. The method is based on the formation of ternary Cu(II)-CAS-CTAB ion-pair and adsorption of it into a mini-column packed with cotton prior applying inductively coupled plasma optical emission spectrometry (ICP-OES). The experimental parameters that affected the extraction efficiency of the method such as pH, flow rate and volume of the sample solution, concentration of chromazurol S (CAS) and cethyltrimethylammonium bromide (CTAB) as well as type and concentration of eluent were investigated and optimized. The ion-pair (Cu(II)-CAS-CTAB) was quantitatively retained on the cotton under the optimum conditions, then eluted completely using a solution of 25% (v/v) 1-propanol in 0.5 mol L(-1) HNO(3) and directly introduced into the nebulizer of the ICP-OES. The detection limit (DL) of the method for copper was 40 ng L(-1) (V(sample)=100mL) and the relative standard deviation (R.S.D.) for the determination of copper at 10 microg L(-1) level was found to be 1.3%. The method was successfully applied to determine the trace amounts of copper in tap water, deep well water, seawater and two different mineral waters, and suitable recoveries were obtained (92-106%).

  6. TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: Phase diagrams and molecular dynamic simulations

    NASA Astrophysics Data System (ADS)

    Taha, Mohamed; Lee, Ming-Jer

    2013-06-01

    Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol/acetonitrile/acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

  7. Ion Mobility-Mass Spectrometry Reveals the Energetics of Intermediates that Guide Polyproline Folding

    NASA Astrophysics Data System (ADS)

    Shi, Liuqing; Holliday, Alison E.; Glover, Matthew S.; Ewing, Michael A.; Russell, David H.; Clemmer, David E.

    2016-01-01

    Proline favors trans-configured peptide bonds in native proteins. Although cis/ trans configurations vary for non-native and unstructured states, solvent also influences these preferences. Water induces the all- cis right-handed polyproline-I (PPI) helix of polyproline to fold into the all- trans left-handed polyproline-II (PPII) helix. Our recent work has shown that this occurs via a sequential mechanism involving six resolved intermediates [Shi, L., Holliday, A.E., Shi, H., Zhu, F., Ewing, M.A., Russell, D.H., Clemmer, D.E.: Characterizing intermediates along the transition from PPI to PPII using ion mobility-mass spectrometry. J. Am. Chem. Soc. 136, 12702-12711 (2014)]. Here, we use ion mobility-mass spectrometry to make the first detailed thermodynamic measurements of the folding intermediates, which inform us about how and why this transition occurs. It appears that early intermediates are energetically favorable because of the hydration of the peptide backbone, whereas late intermediates are enthalpically unfavorable. However, folding continues, as the entropy of the system increases upon successive formation of each new structure. When PPII is immersed in 1-propanol, the PPII→PPI transition occurs, but this reaction occurs through a very different mechanism. Early on, the PPII population splits onto multiple pathways that eventually converge through a late intermediate that continues on to the folded PPI helix. Nearly every step is endothermic. Folding results from a stepwise increase in the disorder of the system, allowing a wide-scale search for a critical late intermediate. Overall, the data presented here allow us to establish the first experimentally determined energy surface for biopolymer folding as a function of solution environment.

  8. Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3.

    PubMed

    Docherty, Kenneth S; Wu, Wilbur; Lim, Yong Bin; Ziemann, Paul J

    2005-06-01

    The role of organic peroxides in secondary organic aerosol (SOA) formation from reactions of monoterpenes with O3 was investigated in a series of environmental chamber experiments. Reactions were performed with endocyclic (alpha-pinene and delta3-carene) and exocyclic (beta-pinene and sabinene) alkenes in dry and humid air and in the presence of the OH radical scavengers: cyclohexane, 1-propanol, and formaldehyde. A thermal desorption particle beam mass spectrometer was used to probe the identity and volatility of SOA components, and an iodometric-spectrophotometric method was used to quantify organic peroxides. Thermal desorption profiles and mass spectra showed that the most volatile SOA components had vapor pressures similar to pinic acid and that much of the SOA consisted of less volatile species that were probably oligomeric compounds. Peroxide analyses indicated that the SOA was predominantly organic peroxides, providing evidence that the oligomers were mostly peroxyhemiacetals formed by heterogeneous reactions of hydroperoxides and aldehydes. For example, it was estimated that organic peroxides contributed approximately 47 and approximately 85% of the SOA mass formed in the alpha- and beta-pinene reactions, respectively. Reactions performed with different OH radical scavengers indicated that most of the hydroperoxides were formed through the hydroperoxide channel rather than by reactions of stabilized Criegee intermediates. The effect of the OH radical scavenger on the SOA yield was also investigated, and the results were consistent with results of recent experiments and model simulations that support a mechanism based on changes in the [HO2]/[RO2] ratios. These are the first measurements of organic peroxides in monoterpene SOA, and the results have important implications for understanding the mechanisms of SOA formation and the potential effects of atmospheric aerosol particles on the environment and human health.

  9. Comparative Analysis of Salivary Alkaline Phosphatase in Post menopausal Women with and without Periodontitis

    PubMed Central

    Sophia, Khumukcham; Sudhakar, Uma; Jayakumar, Parvathee; Mathew, Danny

    2017-01-01

    Introduction Alkaline phosphatase is an intracellular destruction enzyme in the periodontium, and it takes part in the normal turnover of the periodontal ligament, alveolar bone, and root cementum formation and maintenance. Aim The aim of this case control study was to evaluate the enzyme Alkaline Phosphatase (ALP) level in saliva of post menopausal women with and without chronic periodontitis. Materials and Methods In this study, 40 individuals, satisfying the study inclusion and exclusion criteria, were recruited. They were categorically divided, on the basis of gingival index, probing pocket depth and clinical attachment level, into two groups: Group I (post menopausal women with a clinically healthy periodontium, n=20); and Group II (post menopausal women with generalized chronic periodontitis, n=20). Clinical parameters assessed were Plaque Index (PI), Gingival Index (GI), Clinical Attachment Level (CAL) and Probing Pocket Depth (PPD). Unstimulated salivary samples were obtained in which the ALP concentration was measured using p-Nitrophenylphosphate, and 2-amino-2-methyl-1-propanol reagents in Beckman and Coulter, AU 480 auto analyser. Mann-Whitney U test was used to find statistical difference with respect to all clinical parameters such as PI, GI, CAL, PPD and salivary ALP levels. Results The mean ALP in saliva was found to be higher in Group II compared to Group I and the difference was statistically significant with the p-value of 0.008. Conclusion A noteworthy increase in the ALP concentration was seen in saliva in our study (Group II) may be due to increased periodontal inflammation in post menopausal women. Thus salivary ALP can be taken as an additional biomarker to early diagnosis, development and progression of periodontitis especially among post menopausal women. PMID:28274061

  10. Decomposition degree of chlorofluorocarbon (CFC) and CFC replacements during recovery with surface-modified activated carbon

    SciTech Connect

    Tanada, Seiki; Kawasaki, Naohito; Nakamura, Takeo; Abe, Ikuo

    1996-02-10

    The recovery efficiency of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) and three CFC replacements (1,1-dichloro-1-fluoroethane, HCFC141b; 1,3-dichloro-1,1,2,2,3-pentafluoro-propane, HCFC225cb; and 2,2,3,3,3-pentafluoro-1-propanol, 5FP) were investigated on the basis of their degree of decomposition and adsorption isotherms. The authors prepared activated carbons with various surface polarities to elucidate the recovery efficiency, the amount adsorbed, and the degree of decomposition. The amount of CFC113 adsorbed onto untreated activated carbon was the largest of all. That of HCFC225cb adsorbed onto activated carbon treated with hydrogen gas was larger than that adsorbed onto untreated activated carbon and activated carbon treated with 6 N nitric acid. The amount of 5FP and HCFC141b adsorbed on the various activated carbons was not substantial. The degree of decomposition of CFC replacements using the untreated activated carbon except for HCFC225cb was the largest of all. In the case without the activated carbon, that of CFC and the CFC replacements increased in the order 5FP, CFC113 or HCFC225cb, and HCFC141b. It is concluded that the recovery of CFC replacements was possible using the surface-modified activated carbons rather than the untreated activated carbon. The degree of decomposition of the CFC replacements during recovery using the activated carbon depends on the relationship between the adsorption site of the surface of the activated carbon and the polarity, hydrophilic site, or hydrophobic site of the CFC replacement molecule.

  11. Effects of new Torulaspora delbrueckii killer yeasts on the must fermentation kinetics and aroma compounds of white table wine

    PubMed Central

    Velázquez, Rocío; Zamora, Emiliano; Álvarez, María L.; Hernández, Luis M.; Ramírez, Manuel

    2015-01-01

    Torulaspora delbrueckii is becoming widely recommended for improving some specific characteristics of wines. However, its impact on wine quality is still far from satisfactory at the winery level, mostly because it is easily replaced by Saccharomyces cerevisiae-like yeasts during must fermentation. New T. delbrueckii killer strains were here isolated and selected for winemaking. They killed S. cerevisiae yeasts and were able to dominate and complete the fermentation of sterile grape must. Sequential yeast inoculation of non-sterile white must with T. delbrueckii followed by S. cerevisiae did not ensure T. delbrueckii dominance or wine quality improvement. Only a single initial must inoculation at high cell concentrations allowed the T. delbrueckii killer strains to dominate and complete the must fermentation to reach above 11% ethanol, but not the non-killer strains. None of the wines underwent malolactic fermentation as long as the must had low turbidity and pH. Although no statistically significant differences were found in the wine quality score, the S. cerevisiae-dominated wines were preferred over the T. delbrueckii-dominated ones because the former had high-intensity fresh fruit aromas while the latter had lower intensity, but nevertheless nice and unusual dried fruit/pastry aromas. Except for ethyl propanoate and 3-ethoxy-1-propanol, which were more abundant in the T. delbrueckii–dominated wines, most of the compounds with fresh fruit odor descriptors, including those with the greatest odor activity values (isoamyl acetate, ethyl hexanoate, and ethyl octanoate), were more abundant in the S. cerevisiae–dominated wines. The low relative concentrations of these fruity compounds made it possible to detect in the T. delbrueckii–dominated wines the low-relative-concentration compounds with dried fruit and pastry odors. An example was γ-ethoxy-butyrolactone which was significantly more abundant in these wines than in those dominated by S. cerevisiae. PMID

  12. Involvement of Ganglioside GM3 in G2/M Cell Cycle Arrest of Human Monocytic Cells Induced by Actinobacillus actinomycetemcomitans Cytolethal Distending Toxin

    PubMed Central

    Mise, Koji; Akifusa, Sumio; Watarai, Shinobu; Ansai, Toshihiro; Nishihara, Tatsuji; Takehara, Tadamichi

    2005-01-01

    Actinobacillus actinomycetemcomitans produces a toxin called cytolethal distending toxin (CDT), which causes host cell DNA damage leading to the induction of DNA damage checkpoint pathways. CDT consists of three subunits, CdtA, CdtB, and CdtC. CdtB is the active subunit of CDT and exerts its effect as a nuclease that damages nuclear DNA, triggering cell cycle arrest. In the present study, we confirmed that the only combination of toxin proteins causing cell cycle arrest was that of all three recombinant CDT (rCDT) protein subunits. Furthermore, in order for rCDT to demonstrate toxicity, it was necessary for CdtA and CdtC to access the cell before CdtB. The coexistence of CdtA and CdtC was necessary for these subunits to bind to the cell. Cells treated with the glucosylceramide synthesis inhibitor 1-phenyl-2-palmitoylamino-3-morpholino-1-propanol showed resistance to the cytotoxicity induced by rCDT. Furthermore, LY-B cells, which are deficient in the biosynthesis of sphingolipid, also showed resistance to the cytotoxicity induced by rCDT. To evaluate the binding of each subunit for glucosylceramides, we performed thin-layer chromatography immunostaining. The results indicated that each subunit reacted with the glycosphingolipids GM1, GM2, GM3, Gb3, and Gb4. The rCDT mixture incubated with liposomes containing GM3 displayed partially reduced toxicity. These results indicate that GM3 can act as a CDT receptor. PMID:16040998

  13. Thermosolvatochromism of betaine dyes revisited: theoretical calculations of the concentrations of alcohol-water hydrogen-bonded species and application to solvation in aqueous alcohols.

    PubMed

    Bastos, Erick L; Silva, Priscilla L; El Seoud, Omar A

    2006-08-31

    Solvatochromic data of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB) in aqueous methanol, 1-propanol, 2-propanol, and 2-methyl-2-propanol at 25 degrees C were recalculated by employing a recently introduced model that explicitly considers the presence of 1:1 alcohol-water hydrogen-bonded species, ROH-W, in bulk solution and their exchange equilibria with water and alcohol in the probe solvation microsphere. The thermosolvatochromic behavior of RB in aqueous ethanol was measured in the temperature range from 10 to 60 degrees C; the results thus obtained were treated according to the same model. All calculations require reliable values of Kdissoc, the dissociation constant of the ROH-W species. This was previously calculated from the dependence of the density of the binary solvent mixture on its composition. Through the use of iteration, the volume of the hydrogen-bonded species, VROH-W, and Kdissoc are obtained simultaneously from the same set of experimental data. This approach may be potentially problematic because Kdissoc and VROH-W are highly correlated. Therefore, we introduced the following approach: (i) VROH-W was obtained from ab initio calculations, (ii) these volumes were corrected for the nonideal behavior of the binary solvent mixtures at different temperatures, (iii) corrected VROH-W values were employed as a constant in the equation used to calculate Kdissoc (from density vs binary solvent mixture composition). VROH-W calculated by the COSMO-RS solvation model fitted the density data better than those calculated by the IEFPCM model. In all aqueous alcohols, solvation by ROH-W is favored over that by the two precursor solvents. In aqueous ethanol, a temperature increase resulted in a gradual desolvation of RB, due to a decrease in the hydrogen-bonding of both components of the mixture. The microscopic polarities of ROH-W are much closer to those of the precursor alcohols.

  14. Methanomicrobium antiquum sp. nov., a hydrogenotrophic methanogen isolated from deep sedimentary aquifers in a natural gas field.

    PubMed

    Mochimaru, Hanako; Tamaki, Hideyuki; Katayama, Taiki; Imachi, Hiroyuki; Sakata, Susumu; Kamagata, Yoichi

    2016-11-01

    A mesophilic, hydrogenotrophic methanogen, designated strain MobHT, was isolated from sediments derived from deep sedimentary, natural-gas-bearing aquifers in Japan. Strain MobHT utilized H2/CO2 or formate, but not ethanol, 1-propanol, 2-propanol, 2-butanol or cyclopentanol, for growth and methane production. In addition, acetate and tungsten were required for growth. Yeast extract stimulated the growth, but was not required. The cells were weakly motile with multiple flagella, presented as a curved-rod-shaped (0.8×2.0 µm) and occurred singly or in pairs. Strain MobHT grew at 15-40 °C (optimum 35 °C) and at pH 5.9-7.9 (optimum pH 7.0-7.5). The sodium chloride range for growth was 0-5.8 % (optimum 2 %). The G+C content of the genomic DNA was 37.6 mol%. In the phylogenetic tree based on the 16S rRNA gene sequences, strain MobHT clustered together with Methanomicrobium mobile (95.4 % in sequence similarity), and formed a distinct clade from Methanolacinia petrolearia SEBR 4847T (95.6 %) and Methanolacinia paynteri G-2000T (95.4 %). The two species of the genus Methanolacinia utilized 2-propanol, whereas strain MobHT and Methanomicrobium mobile, the sole species of the genus Methanomicrobium, do not. Based on phenotypic and phylogenetic features, we propose a novel species for the isolate with the name, Methanomicrobiumantiquum sp. nov. The type strain is MobHT (=DSM 21220T=NBRC 104160T).

  15. Structure-activity relationships of new 1-substitutedmethyl-4-[5-(N-methyl-N-propylamino)pentyloxy]piperidines and selected 1-[(N-substituted-N-methyl)-3-propyloxy]-5-(N-methy-l-N-propyl)-pentanediamines as H3 -antagonists.

    PubMed

    Masłowska-Lipowicz, Iwona; Walczyński, Krzysztof

    2014-01-01

    Novel, potent non-imidazole histamine H3 receptor antagonists have been prepared and in vitro tested as H3 -receptor antagonists (the electrically evoked contraction of the guinea-pig jejunum). The present compounds contain a 4-hydroxypiperidine core, which behaves as a conformationally restricted version of the 3-amino-1-propanol moiety common to the many previously described non-imidazole H3 ligands. Detailed structure-activity studies revealed that 1-(2-benzofuranylmethyl)- 5c (pA2 = 8.47 ± 0.05) and 1-(3-benzofuranylmethyl)-4-[5-(N-methyl-N-propyl)pentyloxy]piperidine 5d (pA2 = 8.15 ± 0.07) exhibit high potency for the H3 histamine receptor. In addition, the potency of selected 1-[(N-substituted-N-methyl)-3-propyloxy]-5-(N-methyl-N-propyl)pentanediamines as antagonist of the H3 histamine receptor was also evaluated. Replacement of the 4-hydroxypiperidine of the leads 7 and 5c by a highly flexible 3-(methylamino)propyloxy chain yields compounds 6a (pA2 = 8.02) and 6b (pA2 = 6.23) with higher and lower potency than their piperidine analogues (7, pA2 = 7.79; 5c, pA2 = 8.47), respectively. The histaminergic H1 antagonism of selected compounds 5c, 5d and 6a has been established on the isolated guinea-pig ileum by conventional methods; the pA2 values have compared with the potency of pyrilamine. None of them showed any H1 -antagonistic activity (pA2 < 4; for pyrilamine pA2 = 8.5).

  16. Transformation of Isopropylamine to l-Alaninol by Pseudomonas sp. Strain KIE171 Involves N-Glutamylated Intermediates

    PubMed Central

    de Azevedo Wäsch, Susana I.; van der Ploeg, Jan R.; Maire, Tere; Lebreton, Alice; Kiener, Andreas; Leisinger, Thomas

    2002-01-01

    Pseudomonas sp. strain KIE171 was able to grow with isopropylamine or l-alaninol [S-(+)-2-amino-1-propanol] as the sole carbon source, but not with d-alaninol. To investigate the hypothesis that l-alaninol is an intermediate in the degradation of isopropylamine, two mini-Tn5 mutants unable to utilize both isopropylamine and l-alaninol were isolated. Whereas mutant KIE171-BI transformed isopropylamine to l-alaninol, mutant KIE171-BII failed to do so. The two genes containing a transposon insertion were cloned, and the DNA regions flanking the insertions were sequenced. Two clusters, one comprising eight ipu (isopropylamine utilization) genes (ipuABCDEFGH) and the other encompassing two genes (ipuI and orf259), were identified. Comparisons of sequences of the deduced Ipu proteins and those in the database suggested that isopropylamine is transported into the cytoplasm by a putative permease, IpuG. The next step, the formation of γ-glutamyl-isopropylamide from isopropylamine, ATP, and l-glutamate, was shown to be catalyzed by IpuC, a γ-glutamylamide synthetase. γ-Glutamyl-isopropylamide is then subjected to stereospecific monooxygenation by the hypothetical four-component system IpuABDE, thereby yielding γ-glutamyl-l-alaninol [γ(l-glutamyl)-l-hydroxy-isopropylamide]. Enzymatic hydrolysis by a hydrolase, IpuF, was shown to finally liberate l-alaninol and to regenerate l-glutamate. No gene(s) encoding an enzyme for the next step in the degradation of isopropylamine was found in the ipu clusters. Presumably, l-alaninol is oxidized by an alcohol dehydrogenase to yield l-2-aminopropionaldehyde or it is deaminated by an ammonia lyase to propionaldehyde. Genetic evidence indicated that the aldehyde formed is then further oxidized by the hypothetical aldehyde dehydrogenases IpuI and IpuH to either l-alanine or propionic acid, compounds which can be processed by reactions of the intermediary metabolism. PMID:11976110

  17. The exometabolome of Clostridium thermocellum reveals overflow metabolism at high cellulose loading

    SciTech Connect

    Holwerda, Evert K.; Thorne, Philip G.; Olson, Daniel G.; Amador-Noguez, Daniel; Engle, Nancy L.; Tschaplinski, Timothy J.; van Dijken, Johannes P.; Lynd, Lee R.

    2014-10-21

    Background: Clostridium thermocellum is a model thermophilic organism for the production of biofuels from lignocellulosic substrates. The majority of publications studying the physiology of this organism use substrate concentrations of ≤10 g/L. However, industrially relevant concentrations of substrate start at 100 g/L carbohydrate, which corresponds to approximately 150 g/L solids. To gain insight into the physiology of fermentation of high substrate concentrations, we studied the growth on, and utilization of high concentrations of crystalline cellulose varying from 50 to 100 g/L by C. thermocellum. Results: Using a defined medium, batch cultures of C. thermocellum achieved 93% conversion of cellulose (Avicel) initially present at 100 g/L. The maximum rate of substrate utilization increased with increasing substrate loading. During fermentation of 100 g/L cellulose, growth ceased when about half of the substrate had been solubilized. However, fermentation continued in an uncoupled mode until substrate utilization was almost complete. In addition to commonly reported fermentation products, amino acids - predominantly L-valine and L-alanine - were secreted at concentrations up to 7.5 g/L. Uncoupled metabolism was also accompanied by products not documented previously for C. thermocellum, including isobutanol, meso- and RR/SS-2,3-butanediol and trace amounts of 3-methyl-1-butanol, 2-methyl-1-butanol and 1-propanol. We hypothesize that C. thermocellum uses overflow metabolism to balance its metabolism around the pyruvate node in glycolysis. In conclusion: C. thermocellum is able to utilize industrially relevant concentrations of cellulose, up to 93 g/L. We report here one of the highest degrees of crystalline cellulose utilization observed thus far for a pure culture of C. thermocellum, the highest maximum substrate utilization rate and the highest amount of isobutanol produced by a wild-type organism.

  18. 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

  19. Model aging and oxidation effects on varietal, fermentative, and sulfur compounds in a dry botrytized red wine.

    PubMed

    Fedrizzi, Bruno; Zapparoli, Giacomo; Finato, Fabio; Tosi, Emanuele; Turri, Arianna; Azzolini, Michela; Versini, Giuseppe

    2011-03-09

    From harvest until wine arrives to the consumer, oxygen plays a crucial role in the definition of the final aroma. In the present research, the effect of the model oxidative aging on a dry red Botrytis wine, such as Italian Amarone, was considered. Amarone wine was submitted to model oxidative aging and then analyzed with two different approaches (SPE-GC-MS and HS-SPME/GC-MS). The same sampling plan was adopted to study the model aging of the same Amarone wine in anaerobic conditions. The HS-SPME/GC-MS method was applied to investigate for the first time the effect of the oxidative aging on a vast number of fermentative sulfur compounds. This research highlighted peculiar evolutions for several volatile compounds. In particular, benzaldehyde showed a sensitive increment during the oxidative aging, with a rate much higher than that reported for non-Botrytis red wines. On the other hand, several sulfides (dimethyl sulfide, 3-(methylthio)-1-propanol, etc.) disappeared after just 15 days of oxidative aging. A wine oxidation marker such as 3-(methylthio)-propanal was not found in any of the oxidized wines; conversely methionol-S-oxide was tentatively identified. This evidence has not been mentioned in the literature. A possible involvement of grape withering process and Botrytis in these mechanisms was supposed: a dry red wine, produced from the same but without any grape withering process and Botrytis infection (e.g., Bardolino wine), was submitted to oxidative aging and analysis. This red wine showed an evolution similar to those reported in the literature for dry red wines but significantly different from the Amarone wine.

  20. Quantification of melamine in drinking water and wastewater by micellar liquid chromatography.

    PubMed

    Beltrán-Martinavarro, Beatriz; Peris-Vicente, Juan; Rambla-Alegre, Maria; Marco-Peiró, Sergio; Esteve-Romero, Josep; Carda-Broch, Samuel

    2013-01-01

    Because of the large potential health impact caused by deliberate contamination with the synthetic chemical melamine of different products for human and animal consumption, the World Health Organization and the Food and Agriculture Organization of the United Nations provided a range of recommendations in order to facilitate obtaining needed data, among which was the determination of the background levels of melamine in drinking water and wastewater (December 4, 2008). A chromatographic procedure using a C18 column, a micellar mobile phase consisting of sodium dodecyl sulfate (0.1 M), and 1-propanol (7.5%) buffered at pH 3, and detection by absorbance at 210 nm is reported in this paper for the quantification of melamine in drinking water and wastewater. Samples were filtered and directly injected into the chromatographic system, thus avoiding an extraction procedure. The optimal mobile phase composition was obtained by a chemometrics approach that considered the retention factor, efficiency, and peak shape. Melamine was eluted in about 6.2 min without interferences. Validation was performed following U.S. Food and Drug Administration guidelines. The analytical parameters studied were linearity (0.03-5 microg/mL, R2 = 0.998), LOD (13 nglmL), intraday and interday accuracy (between 4.1 and 12.2%), intraday and interday precision (less than 14.8%), and robustness (RSD < 5.1% for retention time and <9.0% for area). The proposed methodology was successfully applied for analysis of local wastewater and drinking water, in which no melamine was found.

  1. Effect of Crown Ethers on Structure, Stability, Activity, and Enantioselectivity of Subtilisin Carlsberg in Organic Solvents

    PubMed Central

    Santos, Angélica M.; Vidal, Michael; Pacheco, Yamaris; Frontera, Joel; Báez, Carlos; Ornellas, Olivia; Barletta, Gabriel

    2015-01-01

    Colyophilization or codrying of subtilisin Carlsberg with the crown ethers 18-crown-6, 15-crown-5, and 12-crown-4 substantially improved enzyme activity in THF, acetonitrile, and 1,4-dioxane in the transesterification reactions of N-acetyl-L-phenylalanine ethylester and 1-propanol and that of (±)-1-phenylethanol and vinylbutyrate. The acceleration of the initial rate, V0, ranged from less than 10-fold to more than 100-fold. All crown ethers activated subtilisin substantially, which excludes a specific macrocyclic effect from being responsible. The secondary structure of subtilisin was studied by Fourier-transform infrared (FTIR) spectroscopy. 18-Crown-6 and 15-crown-5 led to a more nativelike structure of subtilisin in the organic solvents employed when compared with that of the dehydrated enzyme obtained from buffer alone. However, the high level of activation with 12-crown-4 where this effect was not observed excluded overall structural preservation from being the primary cause of the observed enzyme activation. The conformational mobility of subtilisin was investigated by performing thermal denaturation experiments in 1,4-dioxane. Although only a small effect of temperature on subtilisin structure was observed for the samples prepared with or without 12-crown-4, both 18-crown-6 and 15-crown-5 caused the enzyme to denature at quite low temperatures (38°C and 56°C, respectively). No relationship between this property and V0 was evident, but increased conformational mobility of the protein decreased its storage stability. The possibility of a “molecular imprinting” effect was also tested by removing 18-crown-6 from the subtilisin-18-crown-6 colyophilizate by washing. V0 was only halved as a result of this procedure, an effect insignificant compared with the ca. 80-fold rate enhancement observed prior to washing in THF. This suggests that molecular imprinting is likely the primary cause of sub-tilisin activation by crown ethers, as recently suggested. PMID

  2. A silica-supported, switchable, and recyclable hydroformylation-hydrogenation catalyst.

    PubMed

    Sandee, A J; Reek, J N; Kamer, P C; van Leeuwen, P W

    2001-09-05

    A homogeneous hydroformylation catalyst, designed to produce selectively linear aldehydes, was covalently tethered to a polysilicate support. The immobilized transition-metal complex [Rh(A)CO]+(1+)), in which A is N-(3-trimethoxysilane-n-propyl)-4,5-bis(diphenylphosphino)phenoxazine, was prepared both via the sol-gel process and by covalent anchoring to silica. 1+ was characterized by means of (31)P and (29)Si MAS NMR, FT-IR, and X-ray photoelectron spectroscopy. Polysilicate immobilized Rh(A) performed as a selective hydroformylation catalyst showing an overall selectivity for the linear aldehyde of 94.6% (linear to branched aldehyde ratio of 65). In addition 1-nonanol, obtained via the hydrogenation of the corresponding aldehyde, was formed as an unexpected secondary product (3.6% at 20% conversion). Under standard hydroformylation conditions, 1+ and HRh(A)(CO)(2)(1) coexist on the support. This dual catalyst system performed as a hydroformylation/hydrogenation sequence catalyst (Z), giving selectively 1-nonanol from 1-octene; ultimately, 98% of 1-octene was converted to mainly 1-nonanal and 97% of the nonanal was hydrogenated to 1-nonanol. The addition of 1-propanol completely changes Z in a hydroformylation catalyst (X), which produces 1-nonanal with an overall selectivity of 93%, and completely suppresses the reduction reaction. If the atmosphere is changed from CO/H(2) to H(2) the catalyst system is switched to the hydrogenation mode (Y), which shows a clean and complete hydrogenation of 1-octene and 1-nonanal within 24 h. The immobilized catalyst can be recycled and the system can be switched reversibly between the three "catalyst modes" X, Y, and Z, completely retaining the catalyst performance in each mode.

  3. Cyanobacterial blue color formation during lysis under natural conditions.

    PubMed

    Arii, Suzue; Tsuji, Kiyomi; Tomita, Koji; Hasegawa, Masateru; Bober, Beata; Harada, Ken-ichi

    2015-04-01

    Cyanobacteria produce numerous volatile organic compounds (VOCs), such as β-cyclocitral, geosmin, and 2-methylisoborneol, which show lytic activity against cyanobacteria. Among these compounds, only β-cyclocitral causes a characteristic color change from green to blue (blue color formation) in the culture broth during the lysis process. In August 2008 and September 2010, the lysis of cyanobacteria involving blue color formation was observed at Lake Tsukui in northern Kanagawa Prefecture, Japan. We collected lake water containing the cyanobacteria and investigated the VOCs, such as β-cyclocitral, β-ionone, 1-propanol, 3-methyl-1-butanol, and 2-phenylethanol, as well as the number of cyanobacterial cells and their damage and pH changes. As a result, the following results were confirmed: the detection of several VOCs, including β-cyclocitral and its oxidation product, 2,2,6-trimethylcyclohexene-1-carboxylic acid; the identification of phycocyanin based on its visible spectrum; the lower pH (6.7 and 5.4) of the lysed samples; and characteristic morphological change in the damaged cyanobacterial cells. We also encountered the same phenomenon on 6 September 2013 in Lake Sagami in northern Kanagawa Prefecture and obtained almost the same results, such as blue color formation, decreasing pH, damaged cells, and detection of VOCs, including the oxidation products of β-cyclocitral. β-Cyclocitral derived from Microcystis has lytic activity against Microcystis itself but has stronger inhibitory activity against other cyanobacteria and algae, suggesting that the VOCs play an important role in the ecology of aquatic environments.

  4. Genome-scale analyses of butanol tolerance in Saccharomyces cerevisiae reveal an essential role of protein degradation

    PubMed Central

    2013-01-01

    Background n-Butanol and isobutanol produced from biomass-derived sugars are promising renewable transport fuels and solvents. Saccharomyces cerevisiae has been engineered for butanol production, but its high butanol sensitivity poses an upper limit to product titers that can be reached by further pathway engineering. A better understanding of the molecular basis of butanol stress and tolerance of S. cerevisiae is important for achieving improved tolerance. Results By combining a screening of the haploid S. cerevisiae knock-out library, gene overexpression, and genome analysis of evolutionary engineered n-butanol-tolerant strains, we established that protein degradation plays an essential role in tolerance. Strains deleted in genes involved in the ubiquitin-proteasome system and in vacuolar degradation of damaged proteins showed hypersensitivity to n-butanol. Overexpression of YLR224W, encoding the subunit responsible for the recognition of damaged proteins of an ubiquitin ligase complex, resulted in a strain with a higher n-butanol tolerance. Two independently evolved n-butanol-tolerant strains carried different mutations in both RPN4 and RTG1, which encode transcription factors involved in the expression of proteasome and peroxisomal genes, respectively. Introduction of these mutated alleles in the reference strain increased butanol tolerance, confirming their relevance in the higher tolerance phenotype. The evolved strains, in addition to n-butanol, were also more tolerant to 2-butanol, isobutanol and 1-propanol, indicating a common molecular basis for sensitivity and tolerance to C3 and C4 alcohols. Conclusions This study shows that maintenance of protein integrity plays an essential role in butanol tolerance and demonstrates new promising targets to engineer S. cerevisiae for improved tolerance. PMID:23552365

  5. Biodegradation of the gasoline oxygenates methyl tert-butyl ether, ethyl tert-butyl ether, and tert-amyl methyl ether by propane-oxidizing bacteria.

    PubMed

    Steffan, R J; McClay, K; Vainberg, S; Condee, C W; Zhang, D

    1997-11-01

    Several propane-oxidizing bacteria were tested for their ability to degrade gasoline oxygenates, including methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). Both a laboratory strain and natural isolates were able to degrade each compound after growth on propane. When propane-grown strain ENV425 was incubated with 20 mg of uniformly labeled [14C]MTBE per liter, the strain converted > 60% of the added MTBE to 14CO2 in < 30 h. The initial oxidation of MTBE and ETBE resulted in the production of nearly stoichiometric amounts of tert-butyl alcohol (TBA), while the initial oxidation of TAME resulted in the production of tert-amyl alcohol. The methoxy methyl group of MTBE was oxidized to formaldehyde and ultimately to CO2. TBA was further oxidized to 2-methyl-2-hydroxy-1-propanol and then 2-hydroxy isobutyric acid; however, neither of these degradation products was an effective growth substrate for the propane oxidizers. Analysis of cell extracts of ENV425 and experiments with enzyme inhibitors implicated a soluble P-450 enzyme in the oxidation of both MTBE and TBA. MTBE was oxidized to TBA by camphor-grown Pseudomonas putida CAM, which produces the well-characterized P-450cam, but not by Rhodococcus rhodochrous 116, which produces two P-450 enzymes. Rates of MTBE degradation by propane-oxidizing strains ranged from 3.9 to 9.2 nmol/min/mg of cell protein at 28 degrees C, whereas TBA was oxidized at a rate of only 1.8 to 2.4 nmol/min/mg of cell protein at the same temperature.

  6. Formation of H3O+ from alcohols and ethers induced by intense laser fields.

    PubMed

    Shirota, Tatsuro; Mano, Narutoshi; Tsuge, Masashi; Hoshina, Kennosuke

    2010-03-15

    The processes of H(3)O(+) production from alcohols (ethanol, 2-propanol, 1-propanol, 2-butanol) and ethers (diethyl ether and ethyl methyl ether), and their deuterium-substituted species, by intense laser fields (800 nm, 100 fs, approximately 1 x 10(14) W/cm) were investigated through time-of-flight (TOF) mass spectrometry. H(3)O(+) formation was observed for all these compounds except for ethyl methyl ether. From the analysis of TOF signals of H((3-n))D(n)O(+) (n = 0, 1, 2, and 3) that have expanding tails with increasing flight time, it has been confirmed that the reaction proceeds through metastable dissociation from the intermediate species C(2)H((5-m))D(m)O(+)(m = 0-5). The common shape of the H((3-n))D(n)O(+) signal profiles contains two major distributions in the time constant, i.e., fast and slow components of <50 ns and approximately 500 ns, respectively. The H((3-n))D(n)O(+) branching ratio is interpreted to be the result of complete scrambling of four hydrogen atoms at the C-C site in C(2)H(4)-OH(+), and partial exchange (18-38%) of a hydrogen atom in the OH group with four other hydrogen atoms within 1 ns prior to H((3-n))D(n)O(+) production. Ab initio calculations for the isomers and transition states of C(2)H(5)O(+) were also performed, and the observed H((3-n))D(n)O(+) production mechanism has been discussed. In addition, a stable isomer having a complex structure and two isomerization pathways were discovered to contribute to the H(3)O(+) formation process.

  7. The exometabolome of Clostridium thermocellum reveals overflow metabolism at high cellulose loading

    DOE PAGES

    Holwerda, Evert K.; Thorne, Philip G.; Olson, Daniel G.; ...

    2014-10-21

    Background: Clostridium thermocellum is a model thermophilic organism for the production of biofuels from lignocellulosic substrates. The majority of publications studying the physiology of this organism use substrate concentrations of ≤10 g/L. However, industrially relevant concentrations of substrate start at 100 g/L carbohydrate, which corresponds to approximately 150 g/L solids. To gain insight into the physiology of fermentation of high substrate concentrations, we studied the growth on, and utilization of high concentrations of crystalline cellulose varying from 50 to 100 g/L by C. thermocellum. Results: Using a defined medium, batch cultures of C. thermocellum achieved 93% conversion of cellulose (Avicel)more » initially present at 100 g/L. The maximum rate of substrate utilization increased with increasing substrate loading. During fermentation of 100 g/L cellulose, growth ceased when about half of the substrate had been solubilized. However, fermentation continued in an uncoupled mode until substrate utilization was almost complete. In addition to commonly reported fermentation products, amino acids - predominantly L-valine and L-alanine - were secreted at concentrations up to 7.5 g/L. Uncoupled metabolism was also accompanied by products not documented previously for C. thermocellum, including isobutanol, meso- and RR/SS-2,3-butanediol and trace amounts of 3-methyl-1-butanol, 2-methyl-1-butanol and 1-propanol. We hypothesize that C. thermocellum uses overflow metabolism to balance its metabolism around the pyruvate node in glycolysis. In conclusion: C. thermocellum is able to utilize industrially relevant concentrations of cellulose, up to 93 g/L. We report here one of the highest degrees of crystalline cellulose utilization observed thus far for a pure culture of C. thermocellum, the highest maximum substrate utilization rate and the highest amount of isobutanol produced by a wild-type organism.« less

  8. Multiple alcohol dehydrogenases but no functional acetaldehyde dehydrogenase causing excessive acetaldehyde production from ethanol by oral streptococci.

    PubMed

    Pavlova, Sylvia I; Jin, Ling; Gasparovich, Stephen R; Tao, Lin

    2013-07-01

    Ethanol consumption and poor oral hygiene are risk factors for oral and oesophageal cancers. Although oral streptococci have been found to produce excessive acetaldehyde from ethanol, little is known about the mechanism by which this carcinogen is produced. By screening 52 strains of diverse oral streptococcal species, we identified Streptococcus gordonii V2016 that produced the most acetaldehyde from ethanol. We then constructed gene deletion mutants in this strain and analysed them for alcohol and acetaldehyde dehydrogenases by zymograms. The results showed that S. gordonii V2016 expressed three primary alcohol dehydrogenases, AdhA, AdhB and AdhE, which all oxidize ethanol to acetaldehyde, but their preferred substrates were 1-propanol, 1-butanol and ethanol, respectively. Two additional dehydrogenases, S-AdhA and TdhA, were identified with specificities to the secondary alcohol 2-propanol and threonine, respectively, but not to ethanol. S. gordonii V2016 did not show a detectable acetaldehyde dehydrogenase even though its adhE gene encodes a putative bifunctional acetaldehyde/alcohol dehydrogenase. Mutants with adhE deletion showed greater tolerance to ethanol in comparison with the wild-type and mutant with adhA or adhB deletion, indicating that AdhE is the major alcohol dehydrogenase in S. gordonii. Analysis of 19 additional strains of S. gordonii, S. mitis, S. oralis, S. salivarius and S. sanguinis showed expressions of up to three alcohol dehydrogenases, but none showed detectable acetaldehyde dehydrogenase, except one strain that showed a novel ALDH. Therefore, expression of multiple alcohol dehydrogenases but no functional acetaldehyde dehydrogenase may contribute to excessive production of acetaldehyde from ethanol by certain oral streptococci.

  9. ELISA assays and alcohol: increasing carbon chain length can interfere with detection of cytokines.

    PubMed

    von Maltzan, Kristine; Pruett, Stephen B

    2011-02-01

    Enzyme-linked immunosorbent assays (ELISAs) are frequently used in studies on cytokine production in response to treatment of cell cultures or laboratory animals. When an ELISA assay is performed on cell culture supernatants, samples often contain the treatment agents. The purpose of the present study was to determine if some of the agents evaluated might inhibit cytokine detection by interfering with the ELISA, leaving the question of whether cytokine production was inhibited unanswered. Mouse and human cytokine ELISA kits from BD Biosciences were used according to the manufacturer's instructions. Cytokine proteins were subjected to one to five carbon alcohols at 86.8mM (methanol, ethanol, 1-propanol, 2-propanol, n-butanol, and n-pentanol). After treating cell cultures with alcohols of different carbon chain lengths, we found that some of the alcohols interfered with measurement of some cytokines by ELISA, thus making their effects on cytokine production by cells in culture unclear. Increasing carbon chain length of straight chain alcohols positively correlated with their ability to inhibit detection of tumor necrosis factor alpha (TNF-α) and interleukin 10 (IL-10), but not with the detection of interleukin 6 (IL-6), interleukin 8, (IL-8), and interleukin 12 (IL-12). To avoid misinterpretation of treatment effects, ELISA assays should be tested with the reference protein and the treatment agent first, before testing biological samples. These results along with other recent results we obtained using circular dichroism indicate that alcohols with two or more carbons can directly alter protein conformation enough to disrupt binding in an ELISA (shown in the present study) or to inhibit ligand-induced conformational changes (results not shown). Such direct effects have not been given enough consideration as a mechanism of ethanol action in the immune system.

  10. Volatile sulphur compounds and pathways of L-methionine catabolism in Williopsis yeasts.

    PubMed

    Tan, Amelia W J; Lee, Pin-Rou; Seow, Yi-Xin; Ong, Peter K C; Liu, Shao-Quan

    2012-08-01

    Volatile sulphur compounds (VSCs) are important to the food industry due to their high potency and presence in many foods. This study assessed for the first time VSC production and pathways of L: -methionine catabolism in yeasts from the genus Williopsis with a view to understanding VSC formation and their potential flavour impact. Five strains of Williopsis saturnus (var. saturnus, var. subsufficiens, var. suavolens, var. sargentensis and var. mrakii) were screened for VSC production in a synthetic medium supplemented with L: -methionine. A diverse range of VSCs were produced including dimethyl disulphide, dimethyl trisulphide, 3-(methylthio)-1-propanal (methional), 3-(methylthio)-1-propanol (methionol), 3-(methylthio)-1-propene, 3-(methylthio)-1-propyl acetate, 3-(methylthio)-1-propanoic acid (methionic acid) and ethyl 3-(methylthio)-1-propanoate, though the production of these VSCs varied between yeast strains. W. saturnus var. saturnus NCYC22 was selected for further studies due to its relatively high VSC production. VSC production was characterised step-wise with yeast strain NCYC22 in coconut cream at different L: -methionine concentrations (0.00-0.20%) and under various inorganic sulphate (0.00-0.20%) and nitrogen (ammonia) supplementation (0.00-0.20%), respectively. Optimal VSC production was obtained with 0.1% of L: -methionine, while supplementation of sulphate had no significant effect. Nitrogen supplementation showed a dramatic inhibitory effect on VSC production. Based on the production of VSCs, the study suggests that the Ehrlich pathway of L: -methionine catabolism is operative in W. saturnus yeasts and can be manipulated by adjusting certain nutrient parameters to control VSC production.

  11. Post-translational Activation of Glutamate Cysteine Ligase with Dimercaprol: A Novel Mechanism of Inhibiting Neuroinflammation in vitro.

    PubMed

    McElroy, Pallavi B; Sri Hari, Ashwini; Day, Brian J; Patel, Manisha

    2017-02-15

    Neuroinflammation and oxidative stress are hallmarks of various neurological diseases. However, whether and how the redox processes control neuroinflammation is incompletely understood. We hypothesized that increasing cellular glutathione (GSH) levels would inhibit neuroinflammation. A series of thiol compounds were identified to elevate cellular GSH levels by a novel approach i.e. post-translational activation of glutamate cysteine ligase (GCL), the rate-limiting enzyme in GSH biosynthesis. These small thiolcontaining compounds were examined for their ability to increase intracellular GSH levels in a murine microglial cell line (BV2), of which dimercaprol [2,3-dimercapto-1-propanol (DMP)] was found to be the most effective compound. DMP increased GCL activity, decreased LPS-induced production of pro-inflammatory cytokines and iNOS induction in BV2 cells in a concentrationdependent manner. DMP's ability to elevate GSH levels and attenuate LPS-induced proinflammatory cytokine production was inhibited by buthionine sulfoximine, an inhibitor of GCL. DMP increased the expression of GCL holoenzyme without altering the expression of its subunits or Nrf2 target proteins (NQO1 and HO-1), suggesting a post-translational mechanism. DMP attenuated LPS-induced mitogen activated protein (MAP) kinase activation in BV2 cells suggesting the MAP kinase pathway as the signaling mechanism underlying DMP's effect. Finally, DMP's ability to increase GSH via GCL activation was observed in mixed cerebrocortical cultures and N27 dopaminergic cells. Together, the data demonstrate a novel mechanism of GSH elevation by posttranslational activation of GCL. Post-translational activation of GCL offers a novel targeted approach to control inflammation in chronic neuronal disorders associated with impaired adaptive responses.

  12. Development and validation of an analytical method for the separation and determination of major bioactive curcuminoids in Curcuma longa rhizomes and herbal products using non-aqueous capillary electrophoresis.

    PubMed

    Anubala, S; Sekar, R; Nagaiah, K

    2014-06-01

    A simple, fast and efficient non-aqueous capillary electrophoresis method (NACE) was developed for the simultaneous determination of three major bioactive curcuminoids (CMNs) in Curcuma longa rhizomes and its herbal products. Good separation, resolution and reproducibility were achieved with the background electrolyte (BGE) consisting a mixture of 15.0 mM sodium tetraborate and 7.4 mM sodium hydroxide (NaOH) in 2:10:15 (v/v/v) of water, 1-propanol, and methanol. The influences of background electrolyte, sodium hydroxide, water, sodium dodecyl sulfate and hydroxylpropyl-β-cyclodextrin on separations were investigated. The separation was carried out in a fused-silica capillary tube with reverse polarity. Hydrodynamic injection of 25mbar for 12s was used for injecting samples and a voltage of 28 kV was applied for separation. The ultrasonication method was used for the extraction of CMNs from the turmeric herbal products and the extract was filtered and directly injected without any further treatments. The limits of detection and quantification were less than 5.0 and 14.6 µg/ml respectively for all CMNs. The percentage recoveries for CMNs were >97.2% (%RSD, <2.62). The results obtained by the method were compared with existing spectrophotometric and HPLC methods. The related compounds in the extract did not interfere in the determination of CMNs. The proposed NACE method is better than existing chromatographic and electrophoretic methods in terms of simple electrophoretic medium, fast analysis and good resolution.

  13. Ruminal Fermentation of Anti-Methanogenic Nitrate- and Nitro-Containing Forages In Vitro

    PubMed Central

    Anderson, Robin C.; Ripley, Laura H.; Bowman, Jan G. P.; Callaway, Todd R.; Genovese, Kenneth J.; Beier, Ross C.; Harvey, Roger B.; Nisbet, David J.

    2016-01-01

    Nitrate, 3-nitro-1-propionic acid (NPA) and 3-nitro-1-propanol (NPOH) can accumulate in forages and be poisonous to animals if consumed in high enough amounts. These chemicals are also recognized as potent anti-methanogenic compounds, but plants naturally containing these chemicals have been studied little in this regard. Presently, we found that nitrate-, NPA-, or NPOH-containing forages effectively decreased methane production, by 35–87%, during in vitro fermentation by mixed cultures of ruminal microbes compared to fermentation by cultures incubated similarly with alfalfa. Methane production was further decreased during the incubation of mixed cultures also inoculated with Denitrobacterium detoxificans, a ruminal bacterium known to metabolize nitrate, NPA, and NPOH. Inhibition of methanogens within the mixed cultures was greatest with the NPA- and NPOH-containing forages. Hydrogen accumulated in all the mixed cultures incubated with forages containing nitrate, NPA or NPOH and was dramatically higher, exceeding 40 μmol hydrogen/mL, in mixed cultures incubated with NPA-containing forage but not inoculated with D. detoxificans. This possibly reflects the inhibition of hydrogenase-catalyzed uptake of hydrogen produced via conversion of 50 μmol added formate per milliliter to hydrogen. Accumulations of volatile fatty acids revealed compensatory changes in fermentation in mixed cultures incubated with the nitrate-, NPA-, and NPOH-containing forages as evidenced by lower accumulations of acetate, and in some cases, higher accumulations of butyrate and lower accumulations of ammonia, iso-buytrate, and iso-valerate compared to cultures incubated with alfalfa. Results reveal that nitrate, NPA, and NPOH that accumulate naturally in forages can be made available within ruminal incubations to inhibit methanogenesis. Further research is warranted to determine if diets can be formulated with nitrate-, NPA-, and NPOH-containing forages to achieve efficacious mitigation

  14. Preparation of an adsorbent based on polymeric ionic liquid for the simultaneous extraction of acidic, basic and neutral pollutants.

    PubMed

    Chen, Lei; Huang, Xiaojia

    2016-09-30

    In this study, coextraction of acidic, basic and neutral pollutants was realized with a new adsorbent based on polymeric ionic liquid (PIL). In the presence of a porogen solvent containing 1-propanol and 1,4-butanediol, an ionic liquid, 1-vinyl-3-octylimidazolium tetrafluoraborate was used as monomer to copolymerize with dual cross-linkers (divinylbenzene and N,N-methylene-bisacrylamide) to form the adsorbent for stir cake sorptive extraction (SCSE). Phenols, aromatic amines and parabens were selected as acidic, basic and neutral model analytes, respectively. The effects of preparation conditions and extraction parameters on the extraction performance of SCSE/PIL were investigated thoroughly. Under the optimized conditions, the prepared adsorbent showed satisfactory coextraction performance to the selected analytes with multiply interactions. At the same time, simple and sensitive analytical method for simultaneous determination of phenols, aromatic amines and parabens in environmental water samples was developed by the combination of SCSE/PIL with high-performance liquid chromatography with diode array detection. Low limits of detection (S/N=3) and quantification limits (S/N=10) of the proposed method for the targeted analytes were achieved within the range of 0.064-0.30μg/L and 0.21-0.99μg/L, respectively. The precision of the proposed method was evaluated in terms of intra- and inter-assay variability calculated as relative standard deviation (RSD), and it was found that the RSD values were all below 10%. Ultimately, the applicability of developed method was successfully confirmed by analyzing lake, reservoir and river water samples. Recoveries obtained for the determination of targeted analytes in spiking samples ranged from 70.0% to 112%, with RSDs within the range of 1.6-9.8%.

  15. Inhibition of glucosylceramide synthase eliminates the oncogenic function of p53 R273H mutant in the epithelial-mesenchymal transition and induced pluripotency of colon cancer cells

    PubMed Central

    Hosain, Salman B.; Khiste, Sachin K.; Uddin, Mohammad B.; Vorubindi, Vindya; Ingram, Catherine; Zhang, Sifang; Hill, Ronald A.; Gu, Xin; Liu, Yong-Yu

    2016-01-01

    Missense mutation of tumor suppressor p53, which exhibits oncogenic gain-of-function (GOF), not only promotes tumor progression, but also diminishes therapeutic efficacies of cancer treatments. However, it remains unclear how a p53 missense mutant contributes to induced pluripotency of cancer stem cells (CSCs) in tumors exposed to chemotherapeutic agents. More importantly, it may be possible to abrogate the GOF by restoring wild-type p53 activity, thereby overcoming the deleterious effects resulting from heterotetramer formation, which often compromises the efficacies of current approaches being used to reactivate p53 function. Herewith, we report that p53 R273H missense mutant urges cancer cells to spawn CSCs. SW48/TP53 cells, which heterozygously carry the p53 R273H hot-spot mutant (R273H/+, introduced by a CRISPR/Casp9 system), were subchronically exposed to doxorubicin in cell culture and in tumor-bearing mice. We found that p53-R273H (TP53-Dox) cells were drug-resistant and exhibited epithelial-mesenchymal transition (EMT) and increased numbers of CSCs (CD44v6+/CD133+), which resulted in enhanced wound healing and tumor formation. Inhibition of glucosylceramide synthase with d-threo-1-phenyl-2-decanoylamino-3-morpholino-1-propanol (PDMP) sensitized p53-R273H cancer cells and tumor xenografts to doxorubicin treatments. Intriguingly, PDMP treatments restored wild-type p53 expression in heterozygous R273H mutant cells and in tumors, decreasing CSCs and sensitizing cells and tumors to treatments. This study demonstrated that p53-R273H promotes EMT and induced pluripotency of CSCs in cancer cells exposed to doxorubicin, mainly through Zeb1 and β-catenin transcription factors. Our results further indicate that restoration of p53 through inhibition of ceramide glycosylation might be an effective treatment approach for targeting cancers heterozygously harboring TP53 missense mutations. PMID:27517620

  16. 1,2-Ethanediol and 1,3-Propanediol Conversions over (MO3)3 (M = Mo, W) Nanoclusters: A Computational Study.

    PubMed

    Fang, Zongtang; Zetterholm, Patrick; Dixon, David A

    2016-03-24

    The dehydration and dehydrogenation reactions of one and two 1,2-ethanediol and 1,3-propanediol molecules on (MO3)3 (M = Mo, W) nanoclusters have been studied computationally using density functional and coupled cluster (CCSD(T)) theory. The reactions are initiated by the formation of a Lewis acid-base complex with an additional hydrogen bond. Dehydration is the dominant reaction proceeding via a metal bisdiolate. Acetaldehyde, the major product for 1,2-ethanediol, is produced by α-hydrogen transfer from one CH2 group to the other. For 1,3-propanediol, the C-C bond breaking pathways to produce C2H4 and HCH═O simultaneously and proton transfer to generate propylene oxide have comparable barrier energies. The barrier to produce propanal from the propylene oxide complex is less than that for epoxide release from the cluster. On the Mo3O9 cluster, a redox reaction channel for 1,2-ethanediol to break the C-C bond to form two formaldehyde molecules and then to produce C2H4 is slightly more favorable than the formation of acetaldehyde. For W(VI), the energy barrier for the reduction pathway is larger due to the lower reducibility of W3O9. Similar reduction on Mo(VI) for 1,3-propanediol to form propene is not a favorable pathway compared with the other pathways as additional C-H bond breaking is required in addition to breaking a C-C bond. The dehydrogenation and dehydration activation energies for the selected glycols are larger than the reactions of ethanol and 1-propanol on the same clusters. The CCSD(T) method is required because density functional theory with the M06 and B3LYP functionals does not predict quantitative energies on the potential energy surface. The M06 functional performs better than does the B3LYP functional.

  17. Effects of disinfectants and detergents on skin irritation.

    PubMed

    Slotosch, Caroline M; Kampf, Günter; Löffler, Harald

    2007-10-01

    We investigated the biological response of regular human skin to alcohol-based disinfectants and detergents in a repetitive test design. Using non-invasive diagnostic tools such as transepidermal water loss, laser-Doppler flowmetry and corneometry, we quantified the irritative effects of a propanol-based hand disinfectant (Sterillium), its propanol mixture (2-propanol 45% w/w and 1-propanol 30% w/w), sodium lauryl sulfate (SLS) 0.5% and distilled water. The substances were applied in a 2-D patch test in a repetitive occlusive test design to the back. Additionally, we performed a wash test on the forearms that was supposed to mimic the skin affection in the normal daily routine of health care workers. In this controlled half-side test design, we included the single application of the hand rub, SLS 0.5% and water as well as a tandem application of the same substances. Patch test and wash test showed similar results. The alcohol-based test preparations showed minimal irritation rather comparable to the application of water. However, the detergent SLS produced stronger barrier disruption, erythema and dryness than the alcohol-based preparations. There was no additional irritation at the combined use of SLS and disinfectants. By contrary, there was even a decrease in barrier disruption and erythema induced by the tandem application of SLS followed by alcohol-based disinfection compared with the use of SLS alone. These findings show a less irritant effect of alcohol-based disinfectants on the skin than detergents. Our study shows that there is no summation of irritating effects of a common detergent and propanol and that the combination of washing and disinfection has a rather protective aspect compared with washing alone.

  18. Testing of the World Health Organization-recommended formulations for surgical hand preparation and proposals for increased efficacy.

    PubMed

    Suchomel, M; Kundi, M; Allegranzi, B; Pittet, D; Rotter, M L

    2011-10-01

    The 2009 World Health Organization (WHO) Guidelines on hand hygiene in health care recommend alcohol-based hand rubs for both hygienic and pre-surgical hand treatment. Two formulations based on ethanol 80% v/v and 2-propanol 75% v/v are proposed for local preparation in healthcare settings where commercial products are not available or too expensive. Both formulations and our suggested modifications (using mass rather than volume percent concentrations) were evaluated for their conformity with the efficacy requirements of the forthcoming amendment of the European Norm (EN) 12791, i.e. non-inferiority of a product when compared with a reference procedure (1-propanol 60% v/v for 3 min) immediately and 3 h after antisepsis. In this study, the WHO-recommended formulations were tested for 3 min and 5 min. Neither formulation met the efficacy requirements of EN 12791 with 3 min application. Increasing the respective concentrations to 80 w/w (85% v/v) and 75 w/w (80% v/v), together with a prolonged application of 5 min, rendered the immediate effect of both formulations non-inferior to the reference antisepsis procedure. This was not the case with the 3h effect, which remained significantly inferior to the reference. Although the original formulations do not meet the efficacy requirements of EN 12791, the clinical significance of this finding deserves further clinical trials. To comply with the requirement of EN 12791, an amendment to the formulations is possible by increasing the alcohol concentrations through changing volume into mass percent and prolonging the duration of application from 3 min to 5 min.

  19. Molybdenum complexes of 1,2-bis(diphenylphosphino)benzene. Mononuclear molybdenum(II) species formed by facile metal-metal bond cleavage of the (Mo-/sup 4/Mo)/sup 4+/ core

    SciTech Connect

    Bakir, M.; Cotton, F.A.; Cudahy, M.M.; Simpson, C.Q.; Smith, T.J.; Vogel, E.F.; Walton, R.A.

    1988-07-27

    The quadruply bonded dimolybdenum(II) complexes K/sub 4/Mo/sub 2/Cl/sub 8/, (NH/sub 4/)/sub 5/MoCl/sub 9/ /times/ H/sub 2/O, and (NH/sub 4/)/sub 4/Mo/sub 2/Br/sub 8/ react with 1,2-C/sub 6/H/sub 4/(PPh/sub 2/)/sub 2/(dppbe) in methanol at room temperature to afford /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ complexes (X = Cl, Br), which do not isomerize to the /beta/ isomers. Under more forcing reactions conditions (refluxing 1-propanol), these same reactions give mononuclear trans-MoX/sub 2/(dppbe)/sub 2/ in good yield (ca. 50%) together with some (MoOX(dppbe)/sub 2/)X /times/ nH/sub 2/O. An alternative synthetic strategy for the preparation of /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ involves the reaction of Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ with dppbe and Me/sub 3/SiX in THF. The compound MoCl/sub 2/(dppbe)/sub 2/ forms crystals in space group P2/sub 1//n, with the following unit cell parameters: a = 10.884 (2) /angstrom/, b = 12.753 (2) /angstrom/, c = 18.141 (4) /angstrom/, /beta/ = 91.43 (2)/degree/, V = 2517 (2) /angstrom//sup 3/, and Z = 2. The centrosymmetric trans molecule has Mo-Cl = 2.410 (1) /angstrom/, Mo-P = 2.481 (1), 2.511 (1) /angstrom/, and P-Mo-P(intra-ring) = 78.68 (4)/degree/. 25 refs., 1 fig., 4 tabs.

  20. Measurement of nitrosamine and nitramine formation from NOx reactions with amines during amine-based carbon dioxide capture for postcombustion carbon sequestration.

    PubMed

    Dai, Ning; Shah, Amisha D; Hu, Lanhua; Plewa, Michael J; McKague, Bruce; Mitch, William A

    2012-09-04

    With years of full-scale experience for precombustion CO(2) capture, amine-based technologies are emerging as the prime contender for postcombustion CO(2) capture. However, concerns for postcombustion applications have focused on the possible contamination of air or drinking water supplies downwind by potentially carcinogenic N-nitrosamines and N-nitramines released following their formation by NO(x) reactions with amines within the capture unit. Analytical methods for N-nitrosamines in drinking waters were adapted to measure specific N-nitrosamines and N-nitramines and total N-nitrosamines in solvent and washwater samples. The high levels of amines, aldehydes, and nitrite in these samples presented a risk for the artifactual formation of N-nitrosamines during sample storage or analysis. Application of a 30-fold molar excess of sulfamic acid to nitrite at pH 2 destroyed nitrite with no significant risk of artifactual nitrosation of amines. Analysis of aqueous morpholine solutions purged with different gas-phase NO and NO(2) concentrations indicated that N-nitrosamine formation generally exceeds N-nitramine formation. The total N-nitrosamine formation rate was at least an order of magnitude higher for the secondary amine piperazine (PZ) than for the primary amines 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA) and the tertiary amine methyldiethanolamine (MDEA). Analysis of pilot washwater samples indicated a 59 μM total N-nitrosamine concentration for a system operated with a 25% AMP/15% PZ solvent, but only 0.73 μM for a 35% MEA solvent. Unfortunately, a greater fraction of the total N-nitrosamine signal was uncharacterized for the MEA-associated washwater. At a 0.73 μM total N-nitrosamine concentration, a ~25000-fold reduction in concentration is needed between washwater units and downwind drinking water supplies to meet proposed permit limits.

  1. Isolation and characterization of a thermophilic bacterium which oxidizes acetate in syntrophic association with a methanogen and which grows acetogenically on H/sub 2/-CO/sub 2/

    SciTech Connect

    Lee, M.J.; Zinder, S.H.

    1988-01-01

    The authors previously described a thermophilic (60/sup 0/C), syntrophic, two-membered culture which converted acetate to methane via a two-step mechanism in which acetate was oxidized to H/sub 2/ and CO/sub 2/. While the hydrogenotrophic methanogen Methanobacterium sp. strain THF in the biculture was readily isolated, we were unable to find a substrate that was suitable for isolation of the acetate-oxidizing member of the biculture. In this study, we found that the biculture grew on ethylene glycol, and an acetate-oxidizing, rod-shape bacterium (AOR) was isolated from the biculture by dilution into medium containing ethylene glycol as the growth substrate. When the axenic culture of the AOR was recombined with a pure culture of Methanobacterium sp. strain THF, the reconstituted biculture grew on acetate and converted it to CH/sub 4/. The AOR used ethylene glycol, 1,2-propanediol, formate, pyruvate, glycine-betaine, and H/sub 2/-CO/sub 2/ as growth substrates. Acetate was the major fermentation product detected from these substrates, except for 1,2-propanediol, which was converted to 1-propanol and propionate. N,N-Dimethylglycine was also formed from glycine-betaine. Acetate was formed in stoichiometric amounts during growth on H/sub 2/-CO/sub 2/, demonstrating that the AOR is an acetogen. This reaction, which was carried out by the pure culture of the AOR in the presence of high partial pressures of H/sub 2/, was the reverse of the acetate oxidation reaction carried out by the AOR when hydrogen partial pressures were kept low by coculturing it with Methanobacterium sp. strain THF. The DNA base composition of the AOR was 47 mol% guanine plus cytosine, and no cytochromes were detected.

  2. The same microbiota and a potentially discriminant metabolome in the saliva of omnivore, ovo-lacto-vegetarian and Vegan individuals.

    PubMed

    De Filippis, Francesca; Vannini, Lucia; La Storia, Antonietta; Laghi, Luca; Piombino, Paola; Stellato, Giuseppina; Serrazanetti, Diana I; Gozzi, Giorgia; Turroni, Silvia; Ferrocino, Ilario; Lazzi, Camilla; Di Cagno, Raffaella; Gobbetti, Marco; Ercolini, Danilo

    2014-01-01

    The salivary microbiota has been linked to both oral and non-oral diseases. Scant knowledge is available on the effect of environmental factors such as long-term dietary choices on the salivary microbiota and metabolome. This study analyzed the microbial diversity and metabolomic profiles of the saliva of 161 healthy individuals who followed an omnivore or ovo-lacto-vegetarian or vegan diet. A large core microbiota was identified, including 12 bacterial genera, found in >98% of the individuals. The subjects could be stratified into three "salivary types" that differed on the basis of the relative abundance of the core genera Prevotella, Streptococcus/Gemella and Fusobacterium/Neisseria. Statistical analysis indicated no effect of dietary habit on the salivary microbiota. Phylogenetic beta-diversity analysis consistently showed no differences between omnivore, ovo-lacto-vegetarian and vegan individuals. Metabolomic profiling of saliva using (1)H-NMR and GC-MS/SPME identified diet-related biomarkers that enabled a significant discrimination between the 3 groups of individuals on the basis of their diet. Formate, urea, uridine and 5-methyl-3-hexanone could discriminate samples from omnivores, whereas 1-propanol, hexanoic acid and proline were characteristic of non-omnivore diets. Although the salivary metabolome can be discriminating for diet, the microbiota has a remarkable inter-individual stability and did not vary with dietary habits. Microbial homeostasis might be perturbed with sub-standard oral hygiene or other environmental factors, but there is no current indication that a choice of an omnivore, ovo-lacto-vegetarian or vegan diet can lead to a specific composition of the oral microbiota with consequences on the oral homeostasis.

  3. Radical intermediates in the addition of OH to propene: photolytic precursors and angular momentum effects.

    PubMed

    Brynteson, M D; Womack, C C; Booth, R S; Lee, S-H; Lin, J J; Butler, L J

    2014-05-08

    We investigate the photolytic production of two radical intermediates in the reaction of OH with propene, one from addition of the hydroxyl radical to the terminal carbon and the other from addition to the center carbon. In a collision-free environment, we photodissociate a mixture of 1-bromo-2-propanol and 2-bromo-1-propanol at 193 nm to produce these radical intermediates. The data show two primary photolytic processes occur: C-Br photofission and HBr photoelimination. Using a velocity map imaging apparatus, we measured the speed distribution of the recoiling bromine atoms, yielding the distribution of kinetic energies of the nascent C3H6OH radicals + Br. Resolving the velocity distributions of Br((2)P(1/2)) and Br((2)P(3/2)) separately with 2 + 1 REMPI allows us to determine the total (vibrational + rotational) internal energy distribution in the nascent radicals. Using an impulsive model to estimate the rotational energy imparted to the nascent C3H6OH radicals, we predict the percentage of radicals having vibrational energy above and below the lowest dissociation barrier, that to OH + propene; it accurately predicts the measured velocity distribution of the stable C3H6OH radicals. In addition, we use photofragment translational spectroscopy to detect several dissociation products of the unstable C3H6OH radicals: OH + propene, methyl + acetaldehyde, and ethyl + formaldehyde. We also use the angular momenta of the unstable radicals and the tensor of inertia of each to predict the recoil kinetic energy and angular distributions when they dissociate to OH + propene; the prediction gives an excellent fit to the data.

  4. Myelin-associated glycoprotein (MAG) protects neurons from acute toxicity using a ganglioside-dependent mechanism.

    PubMed

    Mehta, Niraj R; Nguyen, Thien; Bullen, John W; Griffin, John W; Schnaar, Ronald L

    2010-03-17

    Myelin-associated glycoprotein (MAG), a protein expressed on the innermost wrap of myelin, contributes to long-term axon stability as evidenced by progressive axon degeneration in Mag-null mice. Recently, MAG was also found to protect axons from acute toxic insults. In the current study, rat dorsal root ganglion neurons were cultured on control substrata and substrata adsorbed with myelin proteins. Neurons on myelin-adsorbed surfaces were resistant to acute degeneration of neurites induced by vincristine, a cancer chemotherapeutic agent with neuropathic side effects. Myelin-mediated protection was reversed by anti-MAG antibody and was absent when cells were cultured on extracts from Mag-null mouse myelin, confirming the protective role of MAG. Gangliosides (sialylated glycosphingolipids) are one functional class of axonal receptors for MAG. In the current studies, a direct role for gangliosides in mediating the acute protective effects of MAG was established. Treatment of neurons with sialidase, an enzyme that cleaves the terminal sialic acids required for MAG binding, reversed MAG's protective effect, as did treatment with (1R,2R)-1-phenyl-2-hexadecanoylamino-3-pyrrolidino-1-propanol, an inhibitor of glycosphingolipid biosynthesis. In contrast, treatment with phosphatidylinositol-specific phospholipase C, an enzyme that cleaves Nogo receptors (NgR, another class of MAG receptor), or with a peptide inhibitor of an NgR-associated signaling molecule p75(NTR), failed to diminish MAG-mediated protection. Inhibiting the Rho-associated protein kinase ROCK reversed protection. We conclude that MAG protects neurites from acute toxic insult via a ganglioside-mediated signaling pathway that involves activation of RhoA. Understanding MAG-mediated protection may provide opportunities to reduce axonal damage and loss.

  5. Improved intervention of atherosclerosis and cardiac hypertrophy through biodegradable polymer-encapsulated delivery of glycosphingolipid inhibitor

    PubMed Central

    Foss, C.A.; Pomper, M.G.; Bhattacharya, R.; Yarema, K.J.; Chatterjee, S.

    2015-01-01

    D-Threo-1-phenyl-2-decanoylamino-3-morpholino-1-propanol (D-PDMP), a glycosphingolipid synthesis inhibitor, holds promise for the treatment of atherosclerosis and cardiac hypertrophy but rapid in vivo clearance has severely hindered translation to the clinic. To overcome this impediment, we used a materials-based delivery strategy wherein D-PDMP was encapsulated within a biodegradable polymer composed of poly ethylene glycol (PEG) and sebacic acid (SA). PEG-SA was formulated into nanoparticles that were doped with 125I-labeled PEG to allow in vivo bio-distribution and release kinetics of D-PDMP to be determined by using γ-scintigraphy and subsequently, by mass spectrometry. Polymer-encapsulation increased the residence time of D-PDMP in the body of a treated mouse from less than one hour to at least four hours (and up to 48 h or longer). This substantially increased in vivo longevity provided by polymer encapsulation resulted in an order of magnitude gain in efficacy for interfering with atherosclerosis and cardiac hypertrophy in apoE−/− mice fed a high fat and high cholesterol (HFHC) diet. These results establish that D-PDMP encapsulated in a biodegradable polymer provides a superior mode of delivery compared to unconjugated D-PDMP by way of increased gastrointestinal absorption and increased residence time thus providing this otherwise rapidly cleared compound with therapeutic relevance in interfering with atherosclerosis, cardiac hypertrophy, and probably other diseases associated with the deleterious effects of abnormally high glycosphingolipid biosynthesis or deficient catabolism. PMID:26111596

  6. Fabrication and evaluation of an organic monolithic column based upon the polymerisation of hexyl methacrylate with 1,6-hexanediol ethoxylate diacrylate for the separation of small molecules by capillary liquid chromatography.

    PubMed

    Alshitari, Wael; Quigley, Cristina Legido; Smith, Norman

    2015-08-15

    This paper describes the fabrication of a new porous monolith, prepared in 100μm i.d. capillaries by the co-polymerisation of hexyl methacrylate with 1,6-hexanediol ethoxylate diacrylate, poly (HMA-co-1,6 HEDA), in the presence of azobisisobutyronitrile, 1, 4-butanediol and 1-propanol were used as porogens for the monoliths; the monoliths were then used as a stationary phase for capillary liquid chromatography. Two cross linkers namely 1,6 HEDA and EDMA were utilised in order to investigate the effects of cross linker length on the separation efficiency of small molecules, and it was found that the efficiency of the separation improved tenfold when using the longer cross linker, 1,6 HEDA. This improvement is associated with the increase in number of methylene groups which resulted in an increased number of mesopores, less than 50nm. The 1,6 HEDA based monolith showed a high porosity (90%) and no evidence of swelling or shrinking with the use of organic solvents. Moreover, the 1,6 HEDA monolith demonstrated high reproducibility for the separation of the retained compounds anisole and naphthalene; these showed retention time RSDs of 1.79% and 2.74% respectively. The fabricated monolith also demonstrated high selectivity for neutral non-polar molecules, weak acids, and basic molecules. The asymmetry factors for basic molecules (nortriptyline and amitriptyline) were 1.5 and 1.3 respectively, indicating slight tailing, which is often noticeable on silica based phases due to secondary interactions between basic moieties and the hydroxyl groups of the silica.

  7. Modulation of [3H]MK-801 binding to NMDA receptors in vivo and in vitro.

    PubMed

    Murray, F; Kennedy, J; Hutson, P H; Elliot, J; Huscroft, I; Mohnen, K; Russell, M G; Grimwood, S

    2000-06-02

    [3H]MK-801 binding in vivo was used to determine the occupancy of NMDA receptor ligands shown to allosterically modulate binding in vitro. ED(50) values (mg/kg) were obtained for the channel blockers (+)-5-methyl-10,11-dihydro-5,4-dibenzo[a,d]cyclohepten-5,10-imine maleate ((+)-MK-801, 0.2), 1-(1-phenylcyclohexyl)piperidine (phencyclidine, PCP, 1.7) and ketamine (4.4). Antagonists at the glutamate (DL-(2-carboxypiperazine-4-yl)propyl-1-phosphonate (DL-CPP, 5.7)) and glycine site (7-Chloro-4-hydroxy-3-(3-phenoxy)-phenyl-2(H)quinolinone (L-701,324, 14.1), 3R(+)cis-4-methyl-pyrrollid-2-one (L-687,414, 15.1)) inhibited [3H]MK-801 binding in vivo to varying maximum levels (69%, 103% and 45%, respectively). NR2B subunit-selective compounds acting at the ifenprodil site inhibited [3H]MK-801 in vivo by a maximum of 52-72% and gave ED(50) values (mg/kg) of: (+/-)-(1S*, 2S*)-1-(4-hydroxyphenyl)-2-(4-hydroxy-4-phenylpiperidino)-1-propanol ((+/-)CP-101,606), 1.9; (+/-)-(3R, 4S)-3-[4-(4-fluorophenyl)-4-hydroxypiperidin-1-yl]chroman-4,7-diol ((+/-)CP-283,097), 1.8; (+/-)-(R*, S*)-alpha-(4-hydroxyphenyl)-beta-methyl-4-(phenylmethyl)-1-piperidine propanol ((+/-)Ro 25-6981), 1.0; ifenprodil, 6.0. The glycine site agonist D-serine stimulated binding to 151% of control with an ED(50) of 1.7 mg/kg. Results show that [3H]MK-801 binding in vivo may be used to measure receptor occupancy of ligands acting not only within the ion channel but also at modulatory sites on the NMDA receptor complex.

  8. Time-activity relationships to VOC personal exposure factors

    NASA Astrophysics Data System (ADS)

    Edwards, Rufus D.; Schweizer, Christian; Llacqua, Vito; Lai, Hak Kan; Jantunen, Matti; Bayer-Oglesby, Lucy; Künzli, Nino

    Social and demographic factors have been found to play a significant role in differences between time-activity patterns of population subgroups. Since time-activity patterns largely influence personal exposure to compounds as individuals move across microenvironments, exposure subgroups within the population may be defined by factors that influence daily activity patterns. Socio-demographic and environmental factors that define time-activity subgroups also define quantifiable differences in VOC personal exposures to different sources and individual compounds in the Expolis study. Significant differences in exposures to traffic-related compounds ethylbenzene, m- and p-xylene and o-xylene were observed in relation to gender, number of children and living alone. Categorization of exposures further indicated time exposed to traffic at work and time in a car as important determinants. Increased exposures to decane, nonane and undecane were observed for males, housewives and self-employed. Categorization of exposures indicated exposure subgroups related to workshop use and living downtown. Higher exposures to 3-carene and α-pinene commonly found in household cleaning products and fragrances were associated with more children, while exposures to traffic compounds ethylbenzene, m- and p-xylene and o-xylene were reduced with more children. Considerable unexplained variation remained in categorization of exposures associated with home product use and fragrances, due to individual behavior and product choice. More targeted data collection methods in VOC exposure studies for these sources should be used. Living alone was associated with decreased exposures to 2-methyl-1-propanol and 1-butanol, and traffic-related compounds. Identification of these subgroups may help to reduce the large amount of unexplained variation in VOC exposure studies. Further they may help in assessing impacts of urban planning that result in changes in behavior of individuals, resulting in shifts in

  9. Supporting technology for the development of Controlled Ecological Life Support Systems (CELSS)

    NASA Technical Reports Server (NTRS)

    Li, Ku-Yen; Yaws, Carl L.; Simon, William E.; Mei, Harry T.

    1995-01-01

    To support the development of Controlled Ecological Life Support Systems (CELSS) in the space program, a metabolic simulator has been selected for use in a closed chamber to test functions of the CELSS. This metabolic simulator is a catalytic reactor which oxidizes the methyl acetate to produce carbon dioxide and water vapor. In this project, kinetic studies of catalytic oxidation of methyl acetate were conducted using monolithic and pellet catalysts with 0.5% (by weight) platinum (Pt) on aluminum oxide (Al2O3). The reaction was studied at a pressure of one atmosphere and at temperatures varying from 160 C to 420 C. By-products were identified at the exit of the preheater and reactor. For the kinetic study with the monolithic catalyst, a linear regression method was used to correlate the kinetic data with zero-order, first-order and Langmuir-Hinshelwood models. Results indicate that the first-order model represents the data adequately at low concentrations of methyl acetate. For higher concentrations of methyl acetate, the Langmuir-Hinshelwood model best represents the kinetic data. Both rate constant and adsorption equilibrium constants were estimated from the regression. A Taguchi orthogonal array (L(sub 9)) was used to investigate the effects of temperature, flow rate, and concentration on the catalytic oxidation of methyl acetate. For the monolithic catalyst, temperature exerts the most significant effect, followed by concentration of methyl acetate. For the pellet catalyst, reaction temperature is the most significant factor, followed by gas flow rate and methyl acetate concentration. Concentrations of either carbon dioxide or oxygen were seen to have insignificant effect on the methyl acetate conversion process. Experimental results indicate that the preheater with glass beads can accomplish thermal cracking and catalytic reaction of methyl acetate to produce acetic acid, methanol, methyl formate, and 1-propanol. The concentration of all by-products was

  10. Liquid-feed flame spray pyrolysis synthesis of oxide nanopowders for the processing of ceramic composites

    NASA Astrophysics Data System (ADS)

    Taylor, Nathan John

    In the liquid-feed flame spray pyrolysis (LF-FSP) process, alcohol solutions of metalloorganic precursors are aerosolized by O2 and combusted. The metal oxide combustion products are rapidly quenched (< 10 ms) from flame temperatures of 1500°C to temperatures < 400° C, limiting particle growth. The resulting nanopowders are typically agglomerated but unaggregated. Here, we demonstrate two processing approaches to dense materials: nanopowders with the exact composition, and mixed single metal oxide nanopowders. The effect of the initial degree of phase separation on the final microstructures was determined by sintering studies. Our first studies included the production of yttrium aluminum garnet, Y3Al5O12 (YAG), tubes which we extruded from a thermoplastic/ceramic blend. At equivalent final densities, we found finer grain sizes in the from the mixed Y2O3 and Al2 O3 nanopowders, which was attributed to densification occurring before full transformation to the YAG phase. The enhanced densification in production of pure YAG from the reactive sintering process led us to produce composites in the YAG/alpha-Al 2O3 system. Finally, a third Y2O3 stabilized ZrO2 (YSZ) phase was added to further refine grain sizes using the same two processing approaches. In a separate study, single-phase metastable Al2O3 rich spinels with the composition MO•3Al 2O3 where M = Mg, Ni, and Co were sintered to produce dense MAl2O4/alpha-Al2O3 composites. All of these studies provide a test of the bottom-up approach; that is, how the initial length scale of mixing affects the final composite microstructure. Overall, the length scale of mixing is highly dependent upon the specific oxide composites studied. This work provides a processing framework to be adopted by other researchers to further refine microstructural size. LF-FSP flame temperatures were mapped using different alcohols with different heats of combustion: methanol, ethanol, 1-propanol, and n-butanol. The effect of different

  11. Regulation of SREBPs by Sphingomyelin in Adipocytes via a Caveolin and Ras-ERK-MAPK-CREB Signaling Pathway

    PubMed Central

    Makdissy, Nehman; Popa, Iuliana; Younsi, Mohamed; Valet, Philippe; Brunaud, Laurent; Ziegler, Olivier; Quilliot, Didier

    2015-01-01

    Sterol response element binding protein (SREBP) is a key transcription factor in insulin and glucose metabolism. We previously demonstrated that elevated levels of membrane sphingomyelin (SM) were related to peroxisome proliferator–activated receptor-γ (PPARγ), which is a known target gene of SREBP-1 in adipocytes. However, the role of SM in SREBP expression in adipocytes remains unknown. In human abdominal adipose tissue from obese women with various concentrations of fasting plasma insulin, SREBP-1 proteins decreased in parallel with increases in membrane SM levels. An inverse correlation was found between the membrane SM content and the levels of SREBP-1c/ERK/Ras/PPARγ/CREB proteins. For the first time, we demonstrate the effects of SM and its signaling pathway in 3T3-F442A adipocytes. These cells were enriched or unenriched with SM in a range of concentrations similar to those observed in obese subjects by adding exogenous natural SMs (having different acyl chain lengths) or by inhibiting neutral sphingomyelinase. SM accumulated in caveolae of the plasma membrane within 24 h and then in the intracellular space. SM enrichment decreased SREBP-1 through the inhibition of extracellular signal-regulated protein kinase (ERK) but not JNK or p38 mitogen-activated protein kinase (MAPK). Ras/Raf-1/MEK1/2 and KSR proteins, which are upstream mediators of ERK, were down-regulated, whereas SREBP-2/caveolin and cholesterol were up-regulated. In SM-unmodulated adipocytes treated with DL-1-Phenyl-2-Palmitoylamino-3-morpholino-1-propanol (PPMP), where the ceramide level increased, the expression levels of SREBPs and ERK were modulated in an opposite direction relative to the SM-enriched cells. SM inhibited the insulin-induced expression of SREBP-1. Rosiglitazone, which is an anti-diabetic agent and potent activator of PPARγ, reversed the effects of SM on SREBP-1, PPARγ and CREB. Taken together, these findings provide novel insights indicating that excess membrane SM

  12. Volumetric Properties of Dilute Aqueous Solutions of 1- and 2-propanol to 50 MPa and 373.15 K

    NASA Astrophysics Data System (ADS)

    Seitz, J.; Bahramian, J.; Blackwell, R.; Inaki, T.; York, D.; Schulte, M. D.

    2014-12-01

    The need to accurately model and understand reactions among organic compounds and biomolecules in solution is necessary to develop realistic chemical models for the reactions leading to the emergence of life and metabolic processes of extremophiles under elevated temperature and pressure conditions. Unfortunately, the scarcity of experimentally determined volumetric (and other) properties for important compounds at high temperatures and pressures leads to uncertainty in the calculation of reaction properties. Experimentally determined volumetric properties of aqueous solutions at non-standard conditions provide direct tests of current estimation methods and aid in the refinement of these methods. The goal of our research is to provide a database of experimentally determined volumetric properties. In previous studies, we have examined important organic molecules and biomolecules such as adenosine, coenzyme M and D-ribose. In this study, we investigate the volumetric properties of the structural isomers 1- and 2-propanol. 1-propanol (n-propanol) is a primary alcohol (CH3CH2CH2OH) and 2-propanol (isopropanol) is the simplest example of a secondary alcohol (CH3CHOHCH3). These compounds differ slightly in structure depending on to which carbon atom the hydroxyl group is bonded and will provide a sensitive test of current estimation methods and lead to more accurate predictions of the properties of complex aqueous systems at elevated temperatures and pressures. We obtained the densities of aqueous solutions of the alchohols using an Anton Paar DMA HP vibrating tube densimeter. Pressure was measured (pressure transducer) to an accuracy of ±0.01% and temperature was measured (integrated platinum thermometer) with an accuracy of ±0.05 K. Experimental uncertainty of density measurements is less than ±0.0001 g·cm-3. The partial molar volumes at infinite dilution (V∞) for 1- and 2-propanol were calculated from the measured densities and are shown in the figure at 0

  13. Effect of dielectric friction on the perpendicular reorientation of the nitrate ion in water and organic solvents

    NASA Astrophysics Data System (ADS)

    Nakahara, Masaru; Emi, Keiji

    1993-10-01

    The perpendicular orientational correlation time τ2R has been determined for the nitrate ion in tetrabutylammonium nitrate (Bu4NNO3) solutions in such an aprotic solvent as acetonitrile (MeCN) and such protic solvents as water (H2O), methanol (MeOH), ethanol (EtOH), and 1-propanol (PrOH) as a function of concentration (c) between 0.01 and 1 M at 30 °C by measuring the 14N nuclear magnetic resonance spin-lattice relaxation times. To ensure the presence of the common limit of τ2R at infinite dilution, the countercation effect on τ2R has been investigated for the potassium ion in water and for the lithium ion in ethanol. In all cases, the rotational correlation time depends linearly on concentration (c); τ2R=τ2R0(1+αc). The reduced slope α depends on the solvent and the cation size; α increases with a decrease in the solvent polarity and the countercation size. The effect on α of the solvent polarity and the surface charge density of the countercation can be explained qualitatively well by our hydrodynamic interaction model previously presented; the anomalously large slope for the Bu4N+ ion in water indicates its promoting effect on the water structure. The limiting correlation times (τ2R0) are 1.08±0.01, 1.14±0.01, 3.38±0.03, 6.12±0.06, and 11.6±0.1 ps, respectively, in MeCN, H2O, MeOH, EtOH, and PrOH. The solvent effect on τ2R0 is much stronger than that expected from viscosity, except for water. The friction coefficient which exceeds the viscosity contribution indicates a key role of the dielectric friction (DF), as predicted by the Hubbard-Onsager DF theory for ionic rotation.

  14. Enneanuclear [Ni6Ln3] Cages: [Ln(III)3] Triangles Capping [Ni(II)6] Trigonal Prisms Including a [Ni6Dy3] Single-Molecule Magnet.

    PubMed

    Canaj, Angelos B; Tzimopoulos, Demetrios I; Siczek, Milosz; Lis, Tadeusz; Inglis, Ross; Milios, Constantinos J

    2015-07-20

    The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H3L, in Ni/Ln chemistry has led to the isolation of three new isostructural [Ni(II)6Ln(III)3] metallic cages. More specifically, the reaction of Ni(ClO4)2·6H2O, the corresponding lanthanide nitrate salt, and H3L in MeCN, under solvothermal conditions in the presence of NEt3, led to the isolation of three complexes with the formulas [Ni6Gd3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (1·5.75MeCN·2Et2O·1.5H2O), [Ni6Dy3(OH)6(HL)6(NO3)3]·2MeCN·2.7Et2O·2.4H2O (2·2MeCN·2.7Et2O·2.4H2O), and [Ni6Er3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (3·5.75MeCN·2Et2O·1.5H2O). The structure of all three clusters describes a [Ln(III)3] triangle capping a [Ni(II)6] trigonal prism. Direct current magnetic susceptibility studies in the 5-300 K range for complexes 1-3 reveal the different nature of the magnetic interactions within the clusters: dominant antiferromagnetic exchange interactions for the Dy(III) and Er(III) analogues and dominant ferromagnetic interactions for the Gd(III) example. Alternating current magnetic susceptibility measurements under zero external dc field displayed fully formed temperature- and frequency-dependent out-of-phase peaks for the [Ni(II)6Dy(III)3] analogue, establishing its single molecule magnetism behavior with Ueff = 24 K.

  15. 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.

  16. Chromatographic assessment of two hybrid monoliths prepared via epoxy-amine ring-opening polymerization and methacrylate-based free radical polymerization using methacrylate epoxy cyclosiloxane as functional monomer.

    PubMed

    Wang, Hongwei; Ou, Junjie; Lin, Hui; Liu, Zhongshan; Huang, Guang; Dong, Jing; Zou, Hanfa

    2014-11-07

    Two kinds of hybrid monolithic columns were prepared by using methacrylate epoxy cyclosiloxane (epoxy-MA) as functional monomer, containing three epoxy moieties and one methacrylate group. One column was in situ fabricated by ring-opening polymerization of epoxy-MA and 1,10-diaminodecane (DAD) using a porogenic system consisting of isopropanol (IPA), H2O and ethanol at 65°C for 12h. The other was prepared by free radical polymerization of epoxy-MA and ethylene dimethacrylate (EDMA) using 1-propanol and 1,4-butanediol as the porogenic solvents at 60°C for 12h. Two hybrid monoliths were investigated on the morphology and chromatographic assessment. Although two kinds of monolithic columns were prepared with epoxy-MA, their morphologies looked rather different. It could be found that the epoxy-MA-DAD monolith possessed higher column efficiencies (25,000-34,000plates/m) for the separation of alkylbenzenes than the epoxy-MA-EDMA monolith (12,000-13,000plates/m) in reversed-phase nano-liquid chromatography (nano-LC). Depending on the remaining epoxy or methacrylate groups on the surface of two pristine monoliths, the epoxy-MA-EDMA monolith could be easily modified with 1-octadecylamine (ODA) via ring-opening reaction, while the epoxy-MA-DAD monolith could be modified with stearyl methacrylate (SMA) via free radical reaction. The chromatographic performance for the separation of alkylbenzenes on SMA-modified epoxy-MA-DAD monolith was remarkably improved (42,000-54,000 plates/m) when compared with that on pristine epoxy-MA-DAD monolith, while it was not obviously enhanced on ODA-modified epoxy-MA-EDMA monolith when compared with that on pristine epoxy-MA-EDMA monolith. The enhancement of the column efficiency of epoxy-MA-DAD monolith after modification might be ascribed to the decreased mass-transfer resistence. The two kinds of hybrid monoliths were also applied for separations of six phenols and seven basic compounds in nano-LC.

  17. The effect of thiolated additives on the properties of wheat gluten based plastics, aqueous solutions and electrospun fibers

    NASA Astrophysics Data System (ADS)

    Dong, Jing

    Wheat gluten (WG) is a promising substitute for petroleum-based plastics due to its unique ability to form a cohesive blend with viscoelastic properties once plasticized. Previous work blending WG with thiolated poly(vinyl alcohol) (TPVA) showed that both the strength and elongation of compression molded native WG bars can be improved via thiol/disulfide interchange reactions between WG and TPVA. In this study, the morphology of WG/TPVA blends was investigated by atomic force (AFM) and transmission electron microscopy (TEM), as well as by modulated dynamic scanning calorimetry (MDSC). Consistent with our earlier results, AFM and TEM imaging clearly indicated that TPVA is much more compatible with WG compared with poly(vinyl alcohol) (PVA) although there are still two phases in the blend: one WG rich phase and another TPVA rich phase. TPVA was also blended with WG in an aqueous solvent (1/1 (v/v) water/1-propanol mixture) to improve its solubility and spinnability. Control experiments were conducted with PVA and dithiothreitol (DTT) for comparison purposes. The concentration and the thiolation level of TPVA were also varied to explore the parameter space. The interactions of thiol groups from TPVA and soluble WG were found to be important during electrospinning. The fiber diameter became more uniform and the fiber quality increased very noticeably when TPVA was included. Furthermore, the time-dependent rheology behaviors of TPVA/WG and DTT/WG electrospinning solutions were investigated by using steady shear sweeps, oscillatory frequency sweeps, SE-HPLC and free -SH content determination. A two-step mechanism of interaction was proposed for DTT/WG and TPVA/WG solutions based on current results and other earlier studies. In comparison with WG and PVA/WG solutions, the reduction and reformation of disulfide linkages in both TPVA/WG and DTT/WG solutions were believed to play a key role in determining the rheological properties and molecular weight distribution of WG

  18. Combined theoretical and experimental study of the photophysics of asulam.

    PubMed

    Giussani, Angelo; Pou-Amérigo, Rosendo; Serrano-Andrés, Luis; Freire-Corbacho, Antonio; Martínez-García, Cristina; Fernández P, Ma Isabel; Sarakha, Mohamed; Canle L, Moisés; Santaballa, J Arturo

    2013-03-14

    The photophysics of the neutral molecular form of the herbicide asulam has been described in a joint experimental and theoretical, at the CASPT2 level, study. The unique π → π* aromatic electronic transition (f, ca. 0.5) shows a weak red-shift as the polarity of the solvent is increased, whereas the fluorescence band undergoes larger red-shifts. Solvatochromic data point to higher dipole moment in the excited state than in the ground state (μ(g) < μ(e)). The observed increase in pKa in the excited state (pKa* - pKa, ca. 3) is consistent with the results of the Kamlet-Abboud-Taft and Catalán et al. multiparametric approaches. Fluorescence quantum yield varies with the solvent, higher in water (ϕ(f) = 0.16) and lower in methanol and 1-propanol (approx. 0.02). Room temperature fluorescence lifetime in aqueous solution is (1.0 ± 0.2) ns, whereas the phosphorescence lifetime in glassy EtOH at 77 K and the corresponding quantum yield are (1.1 ± 0.1) s and 0.36, respectively. The lack of mirror image symmetry between modified absorption and fluorescence spectra reflects different nuclear configurations in the absorbing and emitting states. The low value measured for the fluorescence quantum yield is justified by an efficient nonradiative decay channel, related with the presence of an easily accessible conical intersection between the initially populated singlet bright (1)(L(a) ππ*) state and the ground state (gs/ππ*)(CI). Along the main decay path of the (1)(L(a) ππ*) state the system undergoes an internal conversion process that switches part of the population from the bright (1)(L(a) ππ*) to the dark (1)(L(b) ππ*) state, which is responsible for the fluorescence. Additionally, singlet-triplet crossing regions have been found, a fact that can explain the phosphorescent emission detected. An intersystem crossing region between the phosphorescent state (3)(L(a) ππ*) and the ground state has been characterized, which contributes to the nonradiative

  19. Molecular analysis of volatile metabolites released specifically by staphylococcus aureus and pseudomonas aeruginosa

    PubMed Central

    2012-01-01

    Background The routinely used microbiological diagnosis of ventilator associated pneumonia (VAP) is time consuming and often requires invasive methods for collection of human specimens (e.g. bronchoscopy). Therefore, it is of utmost interest to develop a non-invasive method for the early detection of bacterial infection in ventilated patients, preferably allowing the identification of the specific pathogens. The present work is an attempt to identify pathogen-derived volatile biomarkers in breath that can be used for early and non- invasive diagnosis of ventilator associated pneumonia (VAP). For this purpose, in vitro experiments with bacteria most frequently found in VAP patients, i.e. Staphylococcus aureus and Pseudomonas aeruginosa, were performed to investigate the release or consumption of volatile organic compounds (VOCs). Results Headspace samples were collected and preconcentrated on multibed sorption tubes at different time points and subsequently analyzed with gas chromatography mass spectrometry (GC-MS). As many as 32 and 37 volatile metabolites were released by S. aureus and P. aeruginosa, respectively. Distinct differences in the bacteria-specific VOC profiles were found, especially with regard to aldehydes (e.g. acetaldehyde, 3-methylbutanal), which were taken up only by P. aeruginosa but released by S. aureus. Differences in concentration profiles were also found for acids (e.g. isovaleric acid), ketones (e.g. acetoin, 2-nonanone), hydrocarbons (e.g. 2-butene, 1,10-undecadiene), alcohols (e.g. 2-methyl-1-propanol, 2-butanol), esters (e.g. ethyl formate, methyl 2-methylbutyrate), volatile sulfur compounds (VSCs, e.g. dimethylsulfide) and volatile nitrogen compounds (VNCs, e.g. 3-methylpyrrole). Importantly, a significant VOC release was found already 1.5 hours after culture start, corresponding to cell numbers of ~8*106 [CFUs/ml]. Conclusions The results obtained provide strong evidence that the detection and perhaps even identification of bacteria

  20. Lipolytic activity of ricin from Ricinus sanguineus and Ricinus communis on neutral lipids.

    PubMed Central

    Lombard, S; Helmy, M E; Piéroni, G

    2001-01-01

    The present study was carried out with a view of determining ricin lipolytic activity on neutral lipids in emulsion and in a membrane-like model. Using 2,3-dimercapto-1-propanol tributyrate (BAL-TC(4)) as substrate, the lipolytic activity of ricin was found to be proportional to ricin and substrate concentrations, with an apparent K(m) (K(m,app)) of 2.4 mM, a k(cat) of 200 min(-1) and a specific activity of 1.0 unit/mg of protein. This work was extended to p-nitrophenyl (pNP) fatty acid esters containing two to twelve carbon atoms. Maximum lipolytic activity was registered on pNP decanoate (pNPC(10)), with a K(m,app) of 3.5 mM, a k(cat) of 173 min(-1) and a specific activity of 3.5 units/mg of protein. Ricin lipolytic activity is pH and galactose dependent, with a maximum at pH 7.0 in the presence of 0.2 M galactose. Using the monolayer technique with dicaprin as substrate, ricin showed a lipolytic activity proportional to the ricin concentration at 20 mN/m, which is dependent on the surface pressure of the lipid monolayer and is detectable up to 30 mN/m, a surface pressure that is of the same order of magnitude as that of natural cell membranes. The methods based on pNPC(10) and BAL-TC(4) hydrolysis are simple and reproducible; thus they can be used for routine studies of ricin lipolytic activity. Ricin from Ricinus communis and R. sanguineus were treated with diethyl p-nitrophenylphosphate, an irreversible serine esterase inhibitor, and their lipolytic activities on BAL-TC(4) and pNPC(10), and cytotoxic activity, were concurrently recorded. A reduction in lipolytic activity was accompanied by a decrease in cytotoxicity on Caco2 cells. These data support the idea that the lipolytic activity associated with ricin is relevant to a lipase whose activity is pH and galactose dependent, sensitive to diethyl p-nitrophenylphosphate, and that a lipolytic step may be involved in the process of cell poisoning by ricin. Both colorimetric tests used in this study are sensitive

  1. Phase-transfer energetics of small-molecule alcohols across the water-hexane interface: molecular dynamics simulations using charge equilibration models.

    PubMed

    Bauer, Brad A; Zhong, Yang; Meninger, David J; Davis, Joseph E; Patel, Sandeep

    2011-04-01

    We study the water-hexane interface using molecular dynamics (MD) and polarizable charge equilibration (CHEQ) force fields. Bulk densities for TIP4P-FQ water and hexane, 1.0086±0.0002 and 0.6378±0.0001 g/cm(3), demonstrate excellent agreement with experiment. Interfacial width and interfacial tension are consistent with previously reported values. The in-plane component of the dielectric permittivity (ɛ(||)) for water is shown to decrease from 81.7±0.04 to unity, transitioning longitudinally from bulk water to bulk hexane. ɛ(||) for hexane reaches a maximum in the interface, but this term represents only a small contribution to the total dielectric constant (as expected for a non-polar species). Structurally, net orientations of the molecules arise in the interfacial region such that hexane lies slightly parallel to the interface and water reorients to maximize hydrogen bonding. Interfacial potentials due to contributions of the water and hexane are calculated to be -567.9±0.13 and 198.7±0.01 mV, respectively, giving rise to a total potential in agreement with the range of values reported from previous simulations of similar systems. Potentials of mean force (PMF) calculated for methanol, ethanol, and 1-propanol for the transfer from water to hexane indicate an interfacial free energy minimum, corresponding to the amphiphilic nature of the molecules. The magnitudes of transfer free energies were further characterized from the solvation free energies of alcohols in water and hexane using thermodynamic integration. This analysis shows that solvation free energies for alcohols in hexane are 0.2-0.3 kcal/mol too unfavorable, whereas solvation of alcohols in water is approximately 1 kcal/mol too favorable. For the pure hexane-water interfacial simulations, we observe a monotonic decrease of the water dipole moment to near-vacuum values. This suggests that the electrostatic component of the desolvation free energy is not as severe for polarizable models than for

  2. The cooperative dynamics of the H-bond system in 2-propanol/water mixtures: Steric hindrance effects of nonpolar head group

    NASA Astrophysics Data System (ADS)

    Sato, Takaaki; Buchner, Richard

    2003-11-01

    We have determined the complex dielectric spectra of 2-propanol/water mixtures employing time domain reflectometry for the entire mixing range in 0.1⩽ν/GHz⩽25 at 20 °C, 25 °C, and 30 °C. At the specific concentrations, a frequency range was expanded up to 89 GHz with the help of waveguide interferometry. The excess activation free energy, ΔGE, enthalpy, ΔHE, and entropy, ΔSE, and their partial molar quantities, ΔGiE, ΔHiE, and ΔSiE [i=2-propanol (2PA) and water (W)] were derived from the relaxation time of the cooperative process, τ1. In the water-rich region, ΔHE and ΔSE exhibit conspicuous behavior with large positive values, which suggests an increase of the "time averaged" number and the strength of H-bonds. τ1 becomes considerably larger for 2-propanol/water than that for 1-propanol/water, resulting in ˜10% larger maxima of ΔH and ΔS. This indicates that the steric hindrance caused by the nonpolar group is more efficient for the branched isopropyl unit than that for the linear n-propyl moiety in preventing "disturbing fifth neighbor water molecules" from acting as new H-bond partners for a hydroxyl group of alcohols. The two pertinent maxima in ΔH2PAE and ΔS2PAE at X(molar fraction of 2-propanol)˜0.03 and ˜0.07 support the view that around X˜0.05, water molecules are pushed out of the first coordination shell of the nonpolar group into the bulk due to solute-solute association, commonly called hydrophobic interaction. In X⩾0.15, ΔH2PAE and ΔS2PAE become nearly zero, suggesting the generation of zigzag H-bonded alcohol chains similar to the pure alcohol. The analysis of the effective correlation factor, geff, revealed a strong structural perturbation effect of water in 0.5⩽X⩽1.0.

  3. Preparation of monolithic chelating adsorbent inside a syringe filter tip for solid phase microextraction of trace elements in natural water prior to their determination by ICP-MS.

    PubMed

    Rahmi, Dwinna; Takasaki, Yuka; Zhu, Yanbei; Kobayashi, Hiroharu; Konagaya, Shigeji; Haraguchi, Hiroki; Umemura, Tomonari

    2010-06-15

    A syringe-based sample pretreatment tool, named herein "tip-in chelating monolith", has been developed for simple and facile solid phase microextraction (SPME) of trace elements in natural waters. The tip-in chelating monolith was directly prepared within the confines of a commercially available syringe filter tip by a two-step process: (1) in situ polymerization of a monomer solution consisting of 22.5% glycidyl methacrylate (GMA), 7.5% ethylene glycol dimethacrylate (EDMA), 35% 1-propanol, 28% 1,4-butanediol, and 7% water and (2) its subsequent modification with 1molL(-1) of iminodiacetate solution (adjusted to pH 10) via ring-opening reaction of epoxide. The adsorption properties of the tip-in chelating monolith thus obtained were evaluated through an adsorption/desorption experiment, where the effects of sample solution pH and eluent on the SPME of trace metals and metalloids were systematically examined. Consequently, when sample solution pH was adjusted to 5.0 and 0.9mL of 2molL(-1) nitric acid was used as an eluent, good recoveries of more than 80% were obtained for 27 elements in a single-step extraction. The proposed SPME method was validated through the analysis of two river water certified reference materials (CRMs: JSAC 0301-1 and NMIJ 7201-a). After 50-fold preconcentration (from 50mL of the original river water sample to 1.0mL of final analysis solution), 22 trace elements including Ti, Fe, Co, Ni, Cu, Ga, Cd, Sn and REEs were quantitatively determined by inductively coupled plasma mass spectrometry (ICP-MS). The analytical detection limits were in the range from 0.000003microgL(-1) for Ho to 0.18microgL(-1) for Fe. Good agreement of the observed values with the certified or reference values indicates that the proposed SPME using the tip-in chelating monolith is practically applicable.

  4. Overloaded elution band profiles of ionizable compounds in reversed-phase liquid chromatography: Influence of the competition between the neutral and the ionic species

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2008-01-01

    The parameters that affect the shape of the band profiles of acido-basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pK{sub a} are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 {micro}L) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C{sub 18}-bonded packing materials, including the 5 {micro}m Xterra-C{sub 18} (121 {angstrom}), 5 {micro}m Gemini-C{sub 18} (110 {angstrom}), 5 {micro}m Luna-C{sub 18}(2) (93 {angstrom}), 3.5 {micro}m Extend-C{sub 18} (80 {angstrom}), and 2.7 {micro}m Halo-C{sub 18} (90 {angstrom}). The mobile phase was an aqueous solution of methanol buffered at a constant {sub W}{sup W}pH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3-phenyl 1-propanol, 2-phenyl butyric acid, amphetamine, aniline, benzylamine, p-toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pK{sub a} and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution.

  5. Heptanuclear lanthanide [Ln7] clusters: from blue-emitting solution-stable complexes to hybrid clusters.

    PubMed

    Canaj, Angelos B; Tsikalas, George K; Philippidis, Aggelos; Spyros, Apostolos; Milios, Constantinos J

    2014-09-07

    The use of LH3 (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) and aibH (2-amino-isobutyric acid) in 4f chemistry has led to the isolation of eight new isostructural lanthanide complexes. More specifically, the reaction of the corresponding lanthanide nitrate salt with LH3 and aibH in MeOH, under solvothermal conditions in the presence of NEt3, led to the isolation and characterization of seven complexes with the general formulae [Ln(III)7(OH)2(L')9(aib)]·4MeOH (Ln = Gd, ·4MeOH; Tb, ·4MeOH; Dy, ·4MeOH; Ho, ·4MeOH; Er, ·4MeOH; Tm, ·4MeOH; Yb, ·4MeOH L' = the dianion of the Schiff base between naphthalene aldehyde and 2-amino-isobutyric acid). Furthermore, the isostructural Y(III) analogue, cluster [Y(III)7(OH)2(L')9(aib)]·4MeOH (·4MeOH), was synthesized in a similar manner to . The structure of all eight clusters describes a distorted [M(III)6] octahedron which encapsulates a seventh M(III) ion in an off-centre fashion. Dc magnetic susceptibility studies in the 5-300 K range for complexes reveal the presence of dominant antiferromagnetic exchange interactions within the metallic clusters as evidenced by the negative Weiss constant, θ, while ac magnetic susceptibility measurements show temperature and frequency dependent out-of-phase signals for the [Dy(III)7] analogue (·4MeOH), suggesting potential single molecule magnetism character. Furthermore, for complex , simulation of its dc magnetic susceptibility data yielded very weak antiferromagnetic interactions within the metallic centres. Solid-state emission studies for all clusters display ligand-based emission, while extended 1D and 2D NMR studies for ·4MeOH reveal that the species retain their structural integrity in solution. In addition, TGA measurements for , and revealed excellent thermal stability up to 340 °C for the clusters.

  6. 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.

  7. Wet chemistry applications for low dimensional bismuth-based solids

    NASA Astrophysics Data System (ADS)

    Shen, Wei-Ning

    This dissertation investigates the relationship between nanoporous microstructures and transport properties. A liquid-phase metalorganic deposition (IMOD) method has been implemented to synthesize Bi films with nano-size pores. Typical nanoporous Bi film preparation involves a spin-coat of a solution of Bi 2-ethylhexanoate with glycerol into 2-methyl-1-propanol solvent on Si substrates followed by a pyrolysis under pure H2. MOD was also used in Bi-based films and patterns. Bi2Te 3 films were prepared by mixing Bi and Te 2-methoxyethoxides in 2-methoxyethanol. Composite films of Bi2Te3-Bi and Bi2Se 3-Bi were obtained by mixing in Bi2Te3 and Bi 2Se3 platelet powders during MOD spin-coating. Patterns of Bi and Bi2Te3 were accomplished by using MOD solutions and soft lithography methods. Nanoporous Bi films with porosity of 11--50% (thickness from 20 to 570 nm) were prepared. The nanoporous Bi films exhibited some preferred orientation, with the (003) aligned parallel to the substrate. A H2 plasma treatment was applied to the Bi film to reduce the residual carbon impurities coming from MOD precursors. The nanoporous structure of the Bi films consists of inter-connected nanoporous channels between polygonal Bi crystallites (˜36 nm). Phonon scattering was influenced more by nanopore size than by the number of pores. Calculations suggested that the phonon mean free path of nanoporous Bi films was limited to 7A and was nearly independent of temperature (100 to 300K). The thermal conductivity of nanoporous, Bi films at 300K was dramatically reduced, to 0.1 W/mK, from the 2.5 W/mK value for dense films. In contrast, the electrical conductivity of nanoporous Bi films was slightly reduced, to 800 S/cm, only a factor of 2 less than that of a dense film at 300K. The Seebeck coefficient of nanoporous; Bi films with porosity of 11--23% at 300K varied from -25 to -45 muV/K. In general, both electrical and thermal conductivities were reduced as the porosity increased, while the

  8. Porcine Sapelovirus Uses α2,3-Linked Sialic Acid on GD1a Ganglioside as a Receptor

    PubMed Central

    Kim, Deok-Song; Son, Kyu-Yeol; Koo, Kyung-Min; Kim, Ji-Yun; Alfajaro, Mia Madel; Park, Jun-Gyu; Hosmillo, Myra; Soliman, Mahmoud; Baek, Yeong-Bin; Cho, Eun-Hyo; Lee, Ju-Hwan; Kang, Mun-Il

    2016-01-01

    ABSTRACT The receptor(s) for porcine sapelovirus (PSV), which causes diarrhea, pneumonia, polioencephalomyelitis, and reproductive disorders in pigs, remains largely unknown. Given the precedent for other picornaviruses which use terminal sialic acids (SAs) as receptors, we examined the role of SAs in PSV binding and infection. Using a variety of approaches, including treating cells with a carbohydrate-destroying chemical (NaIO4), mono- or oligosaccharides (N-acetylneuraminic acid, galactose, and 6′-sialyllactose), linkage-specific sialidases (neuraminidase and sialidase S), lectins (Maakia amurensis lectin and Sambucus nigra lectin), proteases (trypsin and chymotrypsin), and glucosylceramide synthase inhibitors (dl-threo-1-phenyl-2-decanoylamino-3-morpholino-1-propanol and phospholipase C), we demonstrated that PSV could recognize α2,3-linked SA on glycolipids as a receptor. On the other hand, PSVs had no binding affinity for synthetic histo-blood group antigens (HBGAs), suggesting that PSVs could not use HBGAs as receptors. Depletion of cell surface glycolipids followed by reconstitution studies indicated that GD1a ganglioside, but not other gangliosides, could restore PSV binding and infection, further confirming α2,3-linked SA on GD1a as a PSV receptor. Our results could provide significant information on the understanding of the life cycle of sapelovirus and other picornaviruses. For the broader community in the area of pathogens and pathogenesis, these findings and insights could contribute to the development of affordable, useful, and efficient drugs for anti-sapelovirus therapy. IMPORTANCE The porcine sapelovirus (PSV) is known to cause enteritis, pneumonia, polioencephalomyelitis, and reproductive disorders in pigs. However, the receptor(s) that the PSV utilizes to enter host cells remains largely unknown. Using a variety of approaches, we showed that α2,3-linked terminal sialic acid (SA) on the cell surface GD1a ganglioside could be used for PSV

  9. A novel micellar per aqueous liquid chromatographic method for simultaneous determination of diltiazem hydrochloride, metoprolol tartrate and isosorbide mononitrate in human serum.

    PubMed

    Li, Ning; Li, Chun-lan; Lu, Ning-wei; Dong, Yu-ming

    2014-09-15

    A novel micellar per aqueous liquid chromatographic method was investigated to simultaneously determine diltiazem hydrochloride, metoprolol tartrate and isosorbide mononitrate in human serum. Separation and determination of the analytes were performed on a Pinnacle II Cyano column as the stationary phase using the mobile phase consisted of aqueous solution (4.15×10(-2) mol/L sodium dodecyl sulfate and 0.02 mol/L sodium dihydrogen phosphate) with 10% (v/v) of 1-propanol at pH 7.0. This method was validated by linearity, lower limit of quantification, extraction recovery, stability, precision, and accuracy. The main analytical parameters were linearity (r>0.9950), intra- and inter-day precisions (intra-day RSD 2.2-3.5%, and inter-day RSD 3.7-9.5%), lower limit of quantification (20 ng mL(-1) for isosorbide mononitrate, metoprolol tartrate and diltiazem hydrochloride). The extraction recovery was 63.3% (0.1 μg/mL), 65.6% (1.0 μg/mL), and 69.5% (25 μg/mL) for isosorbide mononitrate; 65.1% (0.1 μg/mL), 69.5% (1.0 μg mL) and 73.5% (2.5 μg/mL) for metoprolol tartrate; 67.1% (0.1 μg/mL), 68.8% (1.0 μg/mL) and 73.8 % (2.5 μg/mL) for diltiazem hydrochloride. The relative error of stability was <6.4% at the room temperature for 24h, <3.8% at 4 °C for 1 week, <4.6% at -20 °C for 1 month, and <6.7% for freeze/thaw cycles (n=3). The results indicated that the proposed method was rapid, sensitive, and accurate for determination of the three antianginal drugs in human serum. The possible separation mechanism of the method was also discussed, and a model of separation mechanism for the analytes was established.

  10. Phase-Transfer Energetics of Small-Molecule Alcohols Across the Water-Hexane Interface: Molecular Dynamics Simulation Using Charge Equilibration Models

    PubMed Central

    Bauer, Brad A.; Zhong, Yang; Meninger, David J.; Davis, Joseph E.; Patel, Sandeep

    2010-01-01

    We study the water-hexane interface using molecular dynamics (MD) and polarizable charge equilibration (CHEQ) force fields. Bulk densities for TIP4P-FQ water and hexane, 1.0086±0.0002 g/cm3 and 0.6378±0.0001 g/cm3, demonstrate excellent agreement with experiment. Interfacial width and interfacial tension are consistent with previously reported values. The in-plane component of the dielectric permittivity (ε∥) for water is shown to decrease from 81.7±0.04 to unity, transitioning longitudinally from bulk water to bulk hexane. ε∥ for hexane reaches a maximum in the interface, but this term represents only a small contribution to the total dielectric constant (as expected for a non-polar species). Structurally, net orientations of the molecules arise in the interfacial region such that hexane lies slightly parallel to the interface and water reorients to maximize hydrogen bonding. Interfacial potentials due to contributions of the water and hexane are calculated to be -567.9±0.13mV and 198.7±0.01mV, respectively, giving rise to a total potential in agreement with the range of values reported from previous simulations of similar systems. Potentials of mean force (PMF) calculated for methanol, ethanol, and 1-propanol for the transfer from water to hexane indicate an interfacial free energy minimum, corresponding to the amphiphilic nature of the molecules. The magnitudes of transfer free energies were further characterized from the solvation free energies of alcohols in water and hexane using thermodynamic integration. This analysis shows that solvation free energies for alcohols in hexane are 0.2-0.3 kcal/mol too unfavorable, whereas solvation of alcohols in water is approximately 1 kcal/mol too favorable. For the pure hexane-water interfacial simulations, we observe a monotonic decrease of the water dipole moment to near-vacuum values. This suggests that the electrostatic component of the desolvation free energy is not as severe for polarizable models than

  11. Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding.

    PubMed

    Boyd, Glen R; Li, Minghua; Husserl, Johana; Ocampo-Gómez, Ana M

    2006-01-10

    A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30

  12. Novel technologies for SO{sub x}/NO{sub x} removal from flue gas. [Quarterly] technical report, September 1--November 30, 1994

    SciTech Connect

    Kung, H.; Kung, M.; Spivey, J.J.; Jang, B.W.

    1994-12-31

    The goal of this project is to develop a cost-effective low temperature deNO{sub x}, catalyst to be used in the Research Triangle Institute (RTI)-Waterloo SO{sub x}/NO{sub x} process for boiler retrofit applications. The performance goal of the catalyst is to convert over 80% of the NO in the flue gas at a temperature as low as 150{degrees}C in the presence of 4 % O{sub 2} and 10 % water. In this quarter a two prong approach was used: Northwestern University concentrated their effort to better understand the reduction of NO{sub x} with alcohol over CU-ZrO{sub 2} catalyst while RTI studied the oxidation of NO to NO,. The chief problem encountered in low temperature reduction of NO was catalyst deactivation, which occurred with all alcohols tested (ethanol, 1-propanol, 2-propanol and 2-butanol). This was probably due to coke formation, as regeneration of the catalyst can be achieved by heating in 4 % oxygen. Catalysts with higher Cu loadings deactivated slower. Use of NO{sub 2} instead of NO, in the hope to reduce catalyst coking, improved N{sub 2} yield temporarily but could not stop deactivation. NO oxidation to NO{sub 2} was studied over different catalysts to support the research to improve the stability of catalytic activity. In the presence of SO{sub 2} and H{sub 2}O at 150{degrees}C, the highest NO oxidation activity was observed over a 10 % CoO/Al{sub 2}O3 catalyst. The activity of the catalyst at first increased slowly, reaching a maximum at around 6 hours on stream, and then slowly decreased. The maximum activity as well as the activity profile with time on stream were affected by the presence of SO{sub 2}. With 0.2 % SO{sub 2}, the activity for NO oxidation to NO{sub 2} reached the maximum with 60 % conversion of NO at 3 hours on stream compared with 42 % at 6 hours when 0.1 % SO{sub 2} was used. The concentrations of O{sub 2}and H{sub 2}O also affected the NO oxidation activity.

  13. Insights on Alterations to the Rumen Ecosystem by Nitrate and Nitrocompounds

    PubMed Central

    Latham, Elizabeth A.; Anderson, Robin C.; Pinchak, William E.; Nisbet, David J.

    2016-01-01

    Nitrate and certain short chain nitrocompounds and nitro-oxy compounds are being investigated as dietary supplements to reduce economic and environmental costs associated with ruminal methane emissions. Thermodynamically, nitrate is a preferred electron acceptor in the rumen that consumes electrons at the expense of methanogenesis during dissimilatory reduction to an intermediate, nitrite, which is primarily reduced to ammonia although small quantities of nitrous oxide may also be produced. Short chain nitrocompounds act as direct inhibitors of methanogenic bacteria although certain of these compounds may also consume electrons at the expense of methanogenesis and are effective inhibitors of important foodborne pathogens. Microbial and nutritional consequences of incorporating nitrate into ruminant diets typically results in increased acetate production. Unlike most other methane-inhibiting supplements, nitrate decreases or has no effect on propionate production. The type of nitrate salt added influences rates of nitrate reduction, rates of nitrite accumulation and efficacy of methane reduction, with sodium and potassium salts being more potent than calcium nitrate salts. Digestive consequences of adding nitrocompounds to ruminant diets are more variable and may in some cases increase propionate production. Concerns about the toxicity of nitrate's intermediate product, nitrite, to ruminants necessitate management, as animal poisoning may occur via methemoglobinemia. Certain of the naturally occurring nitrocompounds, such as 3-nitro-1-propionate or 3-nitro-1-propanol also cause poisoning but via inhibition of succinate dehydrogenase. Typical risk management procedures to avoid nitrite toxicity involve gradually adapting the animals to higher concentrations of nitrate and nitrite, which could possibly be used with the nitrocompounds as well. A number of organisms responsible for nitrate metabolism in the rumen have been characterized. To date a single rumen bacterium

  14. 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

  15. Gluconacetobacter medellinensis sp. nov., cellulose- and non-cellulose-producing acetic acid bacteria isolated from vinegar.

    PubMed

    Castro, Cristina; Cleenwerck, Ilse; Trcek, Janja; Zuluaga, Robin; De Vos, Paul; Caro, Gloria; Aguirre, Ricardo; Putaux, Jean-Luc; Gañán, Piedad

    2013-03-01

    The phylogenetic position of a cellulose-producing acetic acid bacterium, strain ID13488, isolated from commercially available Colombian homemade fruit vinegar, was investigated. Analyses using nearly complete 16S rRNA gene sequences, nearly complete 16S-23S rRNA gene internal transcribed spacer (ITS) sequences, as well as concatenated partial sequences of the housekeeping genes dnaK, groEL and rpoB, allocated the micro-organism to the genus Gluconacetobacter, and more precisely to the Gluconacetobacter xylinus group. Moreover, the data suggested that the micro-organism belongs to a novel species in this genus, together with LMG 1693(T), a non-cellulose-producing strain isolated from vinegar by Kondo and previously classified as a strain of Gluconacetobacter xylinus. DNA-DNA hybridizations confirmed this finding, revealing a DNA-DNA relatedness value of 81 % between strains ID13488 and LMG 1693(T), and values <70 % between strain LMG 1693(T) and the type strains of the closest phylogenetic neighbours. Additionally, the classification of strains ID13488 and LMG 1693(T) into a single novel species was supported by amplified fragment length polymorphism (AFLP) and (GTG)5-PCR DNA fingerprinting data, as well as by phenotypic data. Strains ID13488 and LMG 1693(T) could be differentiated from closely related species of the genus Gluconacetobacter by their ability to produce 2- and 5-keto-d-gluconic acid from d-glucose, their ability to produce acid from sucrose, but not from 1-propanol, and their ability to grow on 3 % ethanol in the absence of acetic acid and on ethanol, d-ribose, d-xylose, sucrose, sorbitol, d-mannitol and d-gluconate as carbon sources. The DNA G+C content of strains ID13488 and LMG 1693(T) was 58.0 and 60.7 mol%, respectively. The major ubiquinone of LMG 1693(T) was Q-10. Taken together these data indicate that strains ID13488 and LMG 1693(T) represent a novel species of the genus Gluconacetobacter for which the name Gluconacetobacter

  16. Peak shapes of acids and bases under overloaded conditions in reversed-phase liquid chromatography, with weakly buffered mobile phases of various pH: A thermodynamic interpretation

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2009-01-01

    We measured overloaded band profiles for a series of nine compounds (phenol, caffeine, 3-phenyl 1-propanol, 2-phenylbutyric acid, amphetamine, aniline, benzylamine, p-toluidine, and procainamidium chloride) on columns packed with four different C{sub 18}-bonded packing materials: XTerra-C{sub 18}, Gemini-C{sub 18}, Luna-C{sub 18}(2), and Halo-C{sub 18}, using buffered methanol-water mobile phases. The {sub W}{sup S}pH of the mobile phase was increased from 2.6 to 11.3. The buffer concentration (either phosphate, acetate, or carbonate buffers) was set constant at values below the maximum concentration of the sample in the band. The influence of the surface chemistry of the packing material on the retention and the shape of the peaks was investigated. Adsorbents having a hybrid inorganic/organic structure tend to give peaks exhibiting moderate or little tailing. The retention and the shape of the band profiles can easily be interpreted at {sub W}{sup S}pHs that are well above or well below the {sub W}{sup S}pK{sub a} of the compound studied. In contrast, the peak shapes in the intermediary pH range (i.e., close to the compound {sub W}{sup S}pK{sub a}) have rarely been studied. These shapes reveal the complexity of the competitive adsorption behavior of couples of acido-basic conjugated compounds at {sub W}{sup S}pHs that are close to their {sub W}{sup S}pK{sub a}. They also reveal the role of the buffer capacity on the resulting peak shape. With increasing {sub W}{sup S}pH, the overloaded profiles are first langmuirian (isotherm type I) at low {sub W}{sup S}pHs, they become S-shaped (isotherm type II), then anti-langmuirian (isotherm type III), S-shaped again at intermediate {sub W}{sup S}pHs, and finally return to a langmuirian shape at high {sub W}{sup S}pHs. A new general adsorption isotherm model that takes into account the dissociation equilibrium of conjugated acidic and basic species in the bulk mobile phase accounts for these transient band shapes. An

  17. The promotional effects of cesium promoter on higher alcohol synthesis from syngas over cesium-promoted Cu/ZnO/Al2O3 catalysts

    SciTech Connect

    Sun, Jie; Cai, Qiuxia; Wan, Yan; Wan, Shaolong; Wang, Li; Lin, Jingdong; Mei, Donghai; Wang, Yong

    2016-09-02

    In this study, the promotional effects of cesium promoter on higher alcohol (C2+OH) synthesis from syngas over Cs-Cu/ZnO/Al2O3 catalysts were investigated using a combined experimental and theoretical density functional theory (DFT) calculation method. In the presence of cesium, the C2+OH productivity increases from 77.1 g•kgcat-1•h-1 to 157.3 g•kgcat-1•h-1 at 583 K due to the enhancement of the initial C–C bond formation. Detailed analysis of chain growth probabilities (CGPs) confirms that initial C–C bond formation is the rate-determining step in the temperature range of 543-583 K. Addition of cesium promoter significantly increases the productivities of 2-methyl-1-propanol, while the CGPs values (C3* to 2-methyl-C3*) is almost unaffected. With the assistance of cesium promoter, the CGPs of the initial C–C bond formation step (C1* to C2*) could be increased from 0.13 to 0.25 at 583 K. DFT calculations indicate that the initial C–C bond formation is mainly contributed by the HCO+HCO coupling reaction over the ZnCu(211) model surface. In the presence of the Cs2O, the stabilities of key reaction intermediates such as HCO and H2CO are enhanced which facilitates both HCO+HCO and HCO+H2CO coupling reaction steps with lower activation barriers over the Cs2O-ZnCu(211) surface. The promotional effects of cesium on the C2+OH productivity are also benefited from the competitive CH+HCO coupling reaction over CH hydrogenation that leads to lower alkane formation. In addition, Bader charge analysis suggests that the presence of cesium ions would facilitate the nucleophilic reaction between HCO and H2CO for initial C–C bond formation. This work was supported by the National Natural Science Foundation of China (No. 91545114 and No. 91545203). We appreciate the joint PhD scholarship support from the China Scholarship Council. The authors would also like to thank the support from Collaborative Innovation Center of Chemistry for Energy Materials (2011-iChEM). DM

  18. The Production of Biodiesel from Cottonseed Oil Using Rhizopus oryzae Whole Cell Biocatalysts

    NASA Astrophysics Data System (ADS)

    Athalye, Sneha Kishor

    accumulation of 15.6 g (dry cell wt)/L. A reduction in dynamic viscosity of the reaction mixture from 47.3 centipoise to 30.6 centipoise was observed. The impact of moisture addition to the reaction mixture and use of ethanol as acylating agent on R.oryzae BSP fatty acid alkyl ester production was also tested. The presence of 10 wt % moisture in the reaction system had a significant effect (p ≤ 0.05) on the transesterification reaction with ethanol unlike methanol. Fatty acid ethyl ester concentration tripled from 39.3 to 129.1 g/L when moisture was added during transesterification .When oil to acyl acceptor ratio was increased from 1:3 and 1:6 to determine effect of excess alcohol on conversion, an ester conversion of 128.1 g/L for methanol and 129.1 g/L for ethanol were observed. Use of excess amount of acylating agent had a significant adverse effect (p ≤ 0.05) on the overall FAAE production due to deactivation of lipases on contact with large amounts of insoluble alcohol in the oil phase of the reaction. The effect of short chain alcohols on the enzymatic transesterification of cottonseed oil using freeze dried Rhizopus oryzae biomass was examined with and without water addition using methanol, ethanol, 1-Propanol and 1-Butanol at various molar ratios. 1- Butanol in the absence of water resulted in a significantly higher (p . 0.1) conversion of cottonseed oil to 12.5 % fatty acid butyl esters (FABEs). Addition of 10 % water to the reaction mixture significantly reduced (p ≤ 0.1) conversion. No significant difference (p > 0.1) between the conversions was observed for time points after 24 h for a 72 h reaction. 1- Butanol in ratios higher than 3:1 to cottonseed oil had a significant impact (p ≤ 0.1) on conversion. Increasing the amount of biomass used during the reaction lead to significantly higher conversion (p ≤ 0.1). The highest conversion of 27.9 % was observed for the transesterification reaction between cottonseed oil and 1-Butanol, in a 1:6 molar ratio, in

  19. Oxygenates vs. synthesis gas

    SciTech Connect

    Kamil Klier; Richard G. Herman; Alessandra Beretta; Maria A. Burcham; Qun Sun; Yeping Cai; Biswanath Roy

    1999-04-01

    Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether. Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double

  20. Oxy-combustion of high water content fuels

    NASA Astrophysics Data System (ADS)

    Yi, Fei

    As the issues of global warming and the energy crisis arouse extensive concern, more and more research is focused on maximizing energy efficiency and capturing CO2 in power generation. To achieve this, in this research, we propose an unconventional concept of combustion - direct combustion of high water content fuels. Due to the high water content in the fuels, they may not burn under air-fired conditions. Therefore, oxy-combustion is applied. Three applications of this concept in power generation are proposed - direct steam generation for the turbine cycle, staged oxy-combustion with zero flue gas recycle, and oxy-combustion in a low speed diesel-type engine. The proposed processes could provide alternative approaches to directly utilize fuels which intrinsically have high water content. A large amount of energy to remove the water, when the fuels are utilized in a conventional approach, is saved. The properties and difficulty in dewatering high water content fuels (e.g. bioethanol, microalgae and fine coal) are summarized. These fuels include both renewable and fossil fuels. In addition, the technique can also allow for low-cost carbon capture due to oxy-combustion. When renewable fuel is utilized, the whole process can be carbon negative. To validate and evaluate this concept, the research focused on the investigation of the flame stability and characteristics for high water content fuels. My study has demonstrated the feasibility of burning fuels that have been heavily diluted with water in a swirl-stabilized burner. Ethanol and 1-propanol were first tested as the fuels and the flame stability maps were obtained. Flame stability, as characterized by the blow-off limit -- the lowest O2 concentration when a flame could exist under a given oxidizer flow rate, was determined as a function of total oxidizer flow rate, fuel concentration and nozzle type. Furthermore, both the gas temperature contour and the overall ethanol concentration in the droplets along the