Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1998-01-01

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

NASA Technical Reports Server (NTRS)

DeMore, W.; Bayes, K.

1998-01-01

Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Monomethyl Ether *Dimer Acids Dioxane Ethane Ethylene Glycol Monophenyl Ether *Ethoxylates, Misc. Ethylene Glycol Dimethyl Ether Ethylene Glycol Monobutyl Ether Ethylene Glycol Monoethyl Ether Ethylene Glycol...

An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

NASA Astrophysics Data System (ADS)

Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

2018-01-01

Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.

FTIR cryospectroscopic and ab initio studies of desflurane-dimethyl ether H-bonded complexes.

PubMed

Melikova, S M; Rutkowski, K S; Rospenk, M

2017-09-05

The IR spectra of mixtures of desflurane and dimethyl ether are studied with the help of FTIR cryospectroscopy in liquefied Kr at T~118-158K. Comparative analysis of the experimental data and results of ab initio calculations show that either of the two C-H groups of desflurane is involved in heterodimer formation of comparable strengths. The blue frequency shift is found for stretching vibrations of those C-H donors which directly participate in H-bond formation. Additionally the complexes are stabilized by weaker contacts between hydrogen atoms of dimethyl ether and fluorine atoms of desflurane. Copyright © 2017 Elsevier B.V. All rights reserved.

On the Formation of the C2H6O Isomers Ethanol (C2H5OH) and Dimethyl Ether (CH3OCH3) in Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I.

2017-06-01

The structural isomers ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H2O/CH4) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C2H6O isomers: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical-radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C3H4), ketene (CH2CO), propene (C3H6), vinyl alcohol (CH2CHOH), acetaldehyde (CH3CHO), and methyl hydroperoxide (CH3OOH), in addition to ethane (C2H6), methanol (CH3OH), and CO2 detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

Combining activated carbon adsorption with heterogeneous photocatalytic oxidation: Lack of synergy for biologically treated greywater and tetraethylene glycol dimethyl ether

PubMed Central

Gulyas, Holger; Argáez, Ángel Santiago Oria; Kong, Fanzhuo; Jorge, Carlos Liriano; Eggers, Susanne; Otterpohl, Ralf

2013-01-01

The aim of the study was to evaluate whether the addition of activated carbon in the photocatalytic oxidation of biologically pretreated greywater and of a polar aliphatic compound gives synergy, as previously demonstrated with phenol. Photocatalytic oxidation kinetics were recorded with fivefold concentrated biologically pretreated greywater and with aqueous tetraethylene glycol dimethyl ether solutions using a UV lamp and the photocatalyst TiO2 P25 in the presence and the absence of powdered activated carbon. The synergy factor, SF, was quantified as the ratio of photocatalytic oxidation rate constant in the presence of powdered activated carbon to the rate constant without activated carbon. No synergy was observed for the greywater concentrate (SF ≈ 1). For the aliphatic compound, tetraethylene glycol dimethyl ether, addition of activated carbon actually had an inhibiting effect on photocatalysis (SF < 1), while synergy was confirmed in reference experiments using aqueous phenol solutions. The absence of synergy for the greywater concentrate can be explained by low adsorbability of its organic constituents by activated carbon. Inhibition of the photocatalytic oxidation of tetraethylene glycol dimethyl ether by addition of powdered activated carbon was attributed to shading of the photocatalyst by the activated carbon particles. It was assumed that synergy in the hybrid process was limited to aromatic organics. Regardless of the lack of synergy in the case of biologically pretreated greywater, the addition of powdered activated carbon is advantageous since, due to additional adsorptive removal of organics, photocatalytic oxidation resulted in a 60% lower organic concentration when activated carbon was present after the same UV irradiation time. PMID:24191472

Multivariable model predictive control design of reactive distillation column for Dimethyl Ether production

NASA Astrophysics Data System (ADS)

Wahid, A.; Putra, I. G. E. P.

2018-03-01

Dimethyl ether (DME) as an alternative clean energy has attracted a growing attention in the recent years. DME production via reactive distillation has potential for capital cost and energy requirement savings. However, combination of reaction and distillation on a single column makes reactive distillation process a very complex multivariable system with high non-linearity of process and strong interaction between process variables. This study investigates a multivariable model predictive control (MPC) based on two-point temperature control strategy for the DME reactive distillation column to maintain the purities of both product streams. The process model is estimated by a first order plus dead time model. The DME and water purity is maintained by controlling a stage temperature in rectifying and stripping section, respectively. The result shows that the model predictive controller performed faster responses compared to conventional PI controller that are showed by the smaller ISE values. In addition, the MPC controller is able to handle the loop interactions well.

Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

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

F Calaza; T Chen; D Mullins

2011-12-31

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tiltmore » away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.« less

Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

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

Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R

2011-01-01

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tiltmore » away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.« less

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

NASA Astrophysics Data System (ADS)

Chang, Qiang; Herbst, Eric

2016-03-01

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

40 CFR Table 9 to Subpart Ffff of... - Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2010 CFR

2010-07-01

... sulfate 77781 6. Dinitrotoluene (2,4) 121142 7. Dioxane (1,4) 123911 8. Ethylene glycol dimethyl ether 110714 9. Ethylene glycol monobutyl ether acetate 112072 10. Ethylene glycol monomethyl ether acetate...

On the Formation of the C{sub 2}H{sub 6}O Isomers Ethanol (C{sub 2}H{sub 5}OH) and Dimethyl Ether (CH{sub 3}OCH{sub 3}) in Star-forming Regions

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

Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu

The structural isomers ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H{sub 2}O/CH{sub 4}) ices to energetic electrons.more » The main goal is to understand the formation mechanisms in star-forming regions of two C{sub 2}H{sub 6}O isomers: ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical–radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C{sub 3}H{sub 4}), ketene (CH{sub 2}CO), propene (C{sub 3}H{sub 6}), vinyl alcohol (CH{sub 2}CHOH), acetaldehyde (CH{sub 3}CHO), and methyl hydroperoxide (CH{sub 3}OOH), in addition to ethane (C{sub 2}H{sub 6}), methanol (CH{sub 3}OH), and CO{sub 2} detected from infrared spectroscopy. The yield of all the confirmed species is also determined.« less

40 CFR Table 8 to Subpart Ffff of... - Soluble Hazardous Air Pollutants

Code of Federal Regulations, 2010 CFR

2010-07-01

.... Dinitrotoluene (2,4) 121142 7. Dioxane (1,4) 123911 8. Ethylene glycol dimethyl ether 110714 9. Ethylene glycol monobutyl ether acetate 112072 10. Ethylene glycol monomethyl ether acetate 110496 11. Isophorone 78591 12...

Sealed Gravitational Capillary Viscometry of Dimethyl Ether and Two Next-Generation Alternative Refrigerants

PubMed Central

Cousins, Dylan S.; Laesecke, Arno

2012-01-01

The viscosities of dimethyl ether (DME, C2H6O) and of the fluorinated propene isomers 2,3,3,3-tetrafluoroprop-1-ene (R1234yf, C3H2F4) and trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) were measured in a combined temperature range from 242 K to 350 K at saturated liquid conditions. The instrument was a sealed gravitational capillary viscometer developed at NIST for volatile liquids. Calibration and adjustment of the instrument constant were conducted with n-pentane. The repeatability of the measurements was found to be approximately 1.5 %, leading to a temperature-dependent estimated combined standard uncertainty of the experimental data between 5.7 % at 242 K for dimethyl ether and 2.6 % at 340 K for R1234yf. The measurements were supplemented by ab initio calculations of the molecular size, shape, and charge distributions of the measured compounds. The viscosity results for dimethyl ether were compared with literature data. One other data set measured with a sealed capillary viscometer and exceeding the present results by up to 7 % could be reconciled by applying the vapor buoyancy correction. Then, all data agreed within the estimated uncertainty of the present results. Viscosities for the fluorinated propene isomers deviate up to 4 % from values predicted with the NIST extended corresponding-states model. The viscosities of the two isomers do not scale with their dipole moments. While the measured viscosity of R1234ze(E) with the lower dipole moment is close to that of R134a, the refrigerant to be replaced, that of R1234yf with the higher dipole moment is up to 25 % lower. The viscosity of dimethyl ether is compared with those of water and methanol. PMID:26900526

Effect of Methyl Substitution on the N-H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies.

PubMed

Sarkar, Shubhra; Ramanathan, N; Sundararajan, K

2018-03-08

Hydrogen-bonded interactions of pyrrole with water and methanol have been studied using matrix isolation infrared spectroscopy and compared with the calculation performed on dimethyl ether. Computations carried out at MP2/aug-cc-pVDZ level of theory yielded two minima for the pyrrole-water and pyrrole-methanol complexes. The global and local minima correspond to the N-H···O and O-H···π complexes, respectively, where the N-H group of pyrrole interacts with oxygen of water/methanol and O-H of water and methanol interacts with the π cloud of pyrrole. Computations performed on the pyrrole-dimethyl ether gave only N-H···O type complex. From the experimental vibrational wavenumber shifts in the N-H stretching and N-H bending modes of pyrrole, as well as in the O-H stretching modes of water and methanol, the 1:1 N-H···O complexes were discerned. The strength of the N-H···O hydrogen bond and the corresponding shift in the N-H stretching vibrational wavenumbers increases in the order pyrrole-water < pyrrole-methanol < pyrrole-dimethyl ether, where a proton is successively replaced by a methyl group. Apart from the 1:1 complexes, higher clusters of 2:1 and 1:2 pyrrole-water and pyrrole-methanol complexes were also generated in N 2 matrix. Atoms in molecules and natural bond orbital analyses were carried out at the MP2/aug-cc-pVDZ level to understand the nature of interaction in the 1:1 pyrrole-water, pyrrole-methanol and pyrrole-dimethyl ether complexes.

Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite – a combined DFT/experimental study

DOE PAGES

Rasmussen, D. B.; Christensen, J. M.; Temel, B.; ...

2017-01-23

The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction of dimethyl ether with surface acetyl to form methyl acetatemore » was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. Here, the present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good agreement with previous experimental studies. The experimental study of the reaction kinetics was consistent with the theoretically derived mechanism and in addition revealed that the methyl acetate product inhibits the reaction – possibly by sterically hindering the attack of CO on the methyl groups in the side pockets.« less

40 CFR Table 9 to Subpart Ggg of... - Default Biorates for Soluble HAP

Code of Federal Regulations, 2010 CFR

2010-07-01

....178 Dinitrotoluene(2,4) 0.784 Dioxane(1,4) 0.393 Ethylene glycol dimethyl ether 0.364 Ethylene glycol monobutyl ether acetate 0.496 Ethylene glycol monomethyl ether acetate 0.159 Isophorone 0.598 Methanol a...

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2014-08-27

Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistrymore » of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO 2 via formic acid as a key intermediate. A second, higher-potential peak is due to complete oxidation of adsorbed CO (and other surface poisoning species) to CO 2. Assuming the catalysts remain in their metallic state during the DME electro-oxidation process, our results suggest that the onset potential of the surfaces increases in the order Cu < Ni < Os < Rh < Ir < Co < Ru < Pt < Ag < Pd < Re < Au. Using our results, we construct a theoretical phase diagram showing predicted catalyst activity based on two key reactivity descriptors, the free energies of adsorbed CO and OH. Here, we compare all results to methanol electro-oxidation to understand key mechanistic differences and their impacts on optimal catalyst design for direct DME fuel cells.« less

Plasma Assisted Combustion: Flame Regimes and Kinetic Studies

DTIC Science & Technology

2015-01-05

Kinetic model Fuel: Dimethyl ether Oxidizer= (1-x)O2 + xO3, x=0 - 0.1, p=1 atm Ozone chemistry & Dimethyl ether model ...diffusional cool flames • A heated counterflow burner integrated with vaporization system1 • n-heptane/nitrogen vs. oxygen/ ozone • Ozone generator...micro-DBD) produces 2- 5 % of ozone in oxygen stream, depending on oxygen flow rate • Speciation profiles by using a micro-probe sampling with a

Direct synthesis of ethanol from dimethyl ether and syngas over combined H-Mordenite and Cu/ZnO catalysts.

PubMed

Li, Xingang; San, Xiaoguang; Zhang, Yi; Ichii, Takashi; Meng, Ming; Tan, Yisheng; Tsubaki, Noritatsu

2010-10-25

Ethanol was directly synthesized from dimethyl ether (DME) and syngas with the combined H-Mordenite and Cu/ZnO catalysts that were separately loaded in a dual-catalyst bed reactor. Methyl acetate (MA) was formed by DME carbonylation over the H-Mordenite catalyst. Thereafter, ethanol and methanol were produced by MA hydrogenation over the Cu/ZnO catalyst. With the reactant gas containing 1.0% DME, the optimized temperature for the reaction was at 493 K to reach 100% conversion. In the products, the yield of methanol and ethanol could reach 46.3% and 42.2%, respectively, with a small amount of MA, ethyl acetate, and CO(2). This process is environmentally friendly as the main byproduct methanol can be recycled to DME by a dehydration reaction. In contrast, for the physically mixed catalysts, the low conversion of DME and high selectivity of methanol were observed.

Studies of Plasticized-Polymer Electrolytes Containing Mixed Zn(II) and Li(I)

DTIC Science & Technology

1992-06-12

iIIIII1iIIII!I 14. SUBJECT TERMS 15. tdUMnnrri . 9 poly(ethylene glycol) ( PEG ), poly(ethylene glycol dimethyl ether) (PEGDME), 16. PRICE CODE...glycol) ( PEG ) and poly(ethylene glycol dimethyl ether) (PEGDME). The addition of salts to either PEO or plasticized-PEO strongly influences the...were found to depend on salt concentration. Td varied from 385 to 3350 C as the zinc content was increased from 0 to 100%. Thus the overall thermal

High-energy metal air batteries

DOEpatents

Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

2014-07-01

Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

High-energy metal air batteries

DOEpatents

Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

2013-07-09

Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

Code of Federal Regulations, 2010 CFR

2010-07-01

... Dichlorobenzidine (3,3″-) 91941 Dichloroethane (1,2-) (Ethylene dichloride) (EDC) 107062 Dichloroethyl ether (Bis(2... Ethyl acrylate 140885 Ethylbenzene 100414 Ethyl chloride (Chloroethane) 75003 Ethylene dibromide (Dibromoethane) 106934 Ethylene glycol dimethyl ether 110714 Ethylene glycol monobutyl ether 111762 Ethylene...

New HPLC methods to quantitate terpenoid aldehydes in foliage of cotton (Gossypium)

USDA-ARS?s Scientific Manuscript database

The cotton plant (Gossypium) produces protective terpenoid aldehydes in lysigenous pigment glands. These terpenoids include hemigossypolone, hemigossypolone-6-methyl ether, gossypol, gossypol-6-methyl ether, gossypol-6,6'-dimethyl ether, heliocides H1, H2, H3 and H4, and heliocides B1, B2, B3 and B4...

DFT study on the adsorption of diethyl, ethyl methyl, and dimethyl ethers on the surface of gallium doped graphene

NASA Astrophysics Data System (ADS)

Shokuhi Rad, Ali; Sani, Emad; Binaeian, Ehsan; Peyravi, Majid; Jahanshahi, Mohsen

2017-04-01

In this study, we used density functional theory (DFT) to search on the adsorption properties of three important compounds of ether family; diethyl ether (DEE), ethyl methyl ether (EME), and dimethyl ether (DME) on the surface of Gallium doped graphene (GaG). We used three functionals (B3LYP, wb97xd, and MPW1PW91) for optimization and calculation of adsorption energy. After fully optimization, we scrutinized on the charge allocations on the adsorbed ethers as well as GaG (at the area of interaction) based on natural bond orbitals (NBO). Besides, we have calculated the amount of charge transfer upon adsorption of each analyte. We revel that GaG is an ideal adsorbent for chemisorption of all above-mentioned ethers. There is a little difference between the values of adsorption; -123.5, -120, and -118.3 kJ/mol (based on wb97xd) for DEE, EME, and DME, respectively. We found significant changes in the electronic structure of both adsorbent and adsorbate upon adsorption. Moreover, results of charge analyses confirm GaG is a p-type semiconductor.

Cryosurgical treatment of warts: dimethyl ether and propane versus liquid nitrogen - case report and review of the literature.

PubMed

Nguyen, Nicholas V; Burkhart, Craig G

2011-10-01

For years, dermatologists have relied on cryotherapy with liquid nitrogen as a safe and effective treatment for warts. More recently, several over-the-counter (OTC) wart-freezing therapies have become available. Manufacturers have substituted liquid nitrogen with dimethyl ether and propane (DMEP), and marketed these new preparations to be safe and effective alternatives to in-office cryotherapy with liquid nitrogen. However, data from in vitro studies and comparative studies in humans refute manufacturers' claims that these products reproduce in-office cryotherapy.

A Mechanistical Study on the Formation of Dimethyl Ether (CH3OCH3) and Ethanol (CH3CH2OH) in Methanol-containing Ices and Implications for the Chemistry of Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Góbi, Sándor; Abplanalp, Matthew J.; Kaiser, Ralf I.

2018-01-01

The underlying formation mechanisms of complex organic molecules (COMs)—in particular, structural isomers—in the interstellar medium (ISM) are largely elusive. Here, we report new experimental findings on the role of methanol (CH3OH) and methane (CH4) ices in the synthesis of two C2H6O isomers upon interaction with ionizing radiation: ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3). The present study reproduces the interstellar abundance ratios of both species with ethanol to dimethyl ether branching ratios of (2.33 ± 0.14):1 suggesting that methanol and methane represents the key precursor to both isomers within interstellar ices. Exploiting isotopic labeling combined with reflectron time-of-flight mass spectrometry (Re-TOF-MS) after isomer selective vacuum ultra-violet (VUV) photoionization of the neutral molecules, we also determine the formation mechanisms of both isomers via radical–radical recombination versus carbene (CH2) insertion with the former pathway being predominant. Formation routes to higher molecular weight reaction products such as ethylene glycol (HOCH2CH2OH), dimethyl peroxide (CH3OOCH3), and methoxymethanol (CH3OCH2OH) are discussed briefly as well.

Phenolic sodium sulphates of Frankenia laevis L.

PubMed

Hussein, S A M

2004-04-01

Four new phenolic anionic conjugates have been isolated from the whole plant aqueous alcohol extract of Frankenia laevis L. Their structures were established, mainly on the basis of ESI-MS, 1D and 2D NMR spectroscopic evidence, as gallic acid-3-methyl ether-5-sodium sulphate, acetophenone-4-methyl ether-2-sodium sulphate, ellagic acid-3,3'-dimethyl ether-4,4'-di-sodium sulphate and ellagic acid-3-methyl ether-4-sodium sulphate.

Development of an Optical Gas Leak Sensor for Detecting Ethylene, Dimethyl Ether and Methane

PubMed Central

Tan, Qiulin; Pei, Xiangdong; Zhu, Simin; Sun, Dong; Liu, Jun; Xue, Chenyang; Liang, Ting; Zhang, Wendong; Xiong, Jijun

2013-01-01

In this paper, we present an approach to develop an optical gas leak sensor that can be used to measure ethylene, dimethyl ether, and methane. The sensor is designed based on the principles of IR absorption spectrum detection, and comprises two crossed elliptical surfaces with a folded reflection-type optical path. We first analyze the optical path and the use of this structure to design a miniature gas sensor. The proposed sensor includes two detectors (one to acquire the reference signal and the other for the response signal), the light source, and the filter, all of which are integrated in a miniature gold-plated chamber. We also designed a signal detection device to extract the sensor signal and a microprocessor to calculate and control the entire process. The produced sensor prototype had an accuracy of ±0.05%. Experiments which simulate the transportation of hazardous chemicals demonstrated that the developed sensor exhibited a good dynamic response and adequately met technical requirements. PMID:23539025

Degradation of blending vulcanized natural rubber and nitril rubber (NR/NBR) by dimethyl ether through variation of elastomer ratio

NASA Astrophysics Data System (ADS)

Saputra, A. H.; Juneva, S.; Sari, T. I.; Cifriadi, A.

2018-04-01

Dimethyl ether can cause degradation of the rubber material seal in some applications. In order to use of natural rubber in industry, research about a blending of natural rubber (NR) and nitrile rubber (NBR) to produce rubber to meet the standard seal material application were conducted. This study will observe the degradation mechanisms that occur in the blending natural rubber and nitrile rubber (NR/NBR) by dimethyl ether. Nitrile rubber types used in this study is medium quality nitrile rubber with 33% of acrylonitrile content (NBR33). The observed parameters are percent change in mass, mechanical properties and surface morphology. This study is limited to see the effect of variation vulcanized blending ratio (NR/NBR33) against to swelling. The increase of nitrile rubber (NBR33) ratio of blending rubber vulcanized can reduce the tensile strength and elongation. The best elastomer variation was obtained after comparing with the standard feasibility material of seal is rubber vulcanized blending (NR/NBR33) with ratio 40:60 NR: NBR.

Preparation and physicochemical characterization of 5 niclosamide solvates and 1 hemisolvate.

PubMed

van Tonder, Elsa C; Mahlatji, Mabatane D; Malan, Sarel F; Liebenberg, Wilna; Caira, Mino R; Song, Mingna; de Villiers, Melgardt M

2004-02-23

The purpose of the study was to characterize the physicochemical, structural, and spectral properties of the 1:1 niclosamide and methanol, diethyl ether, dimethyl sulfoxide, N,N' dimethylformamide, and tetrahydrofuran solvates and the 2:1 niclosamide and tetraethylene glycol hemisolvate prepared by recrystallization from these organic solvents. Structural, spectral, and thermal analysis results confirmed the presence of the solvents and differences in the structural properties of these solvates. In addition, differences in the activation energy of desolvation, batch solution calorimetry, and the aqueous solubility at 25 degrees C, 24 hours, showed the stability of the solvates to be in the order: anhydrate > diethyl ether solvate > tetraethylene glycol hemisolvate > methanol solvate > dimethyl sulfoxide solvate > N,N' dimethylformamide solvate. The intrinsic and powder dissolution rates of the solvates were in the order: anhydrate > diethyl ether solvate > tetraethylene glycol hemisolvate > N,N' dimethylformamide solvate > methanol solvate > dimethyl sulfoxide solvate. Although these nonaqueous solvates had higher solubility and dissolution rates than the monohydrous forms, they were unstable in aqueous media and rapidly transformed to one of the monohydrous forms.

Synthesis and pKa determination of new enantiopure dimethyl-substituted acridino-crown ethers containing a carboxyl group: Useful candidates for enantiomeric recognition studies.

PubMed

Németh, Tamás; Dargó, Gergő; Petró, József Levente; Petrik, Zsófia; Lévai, Sándor; Krámos, Balázs; Béni, Zoltán; Nagy, József; Balogh, György Tibor; Huszthy, Péter; Tóth, Tünde

2017-09-01

New enantiopure dimethyl-substituted acridino-18-crown-6 and acridino-21-crown-7 ethers containing a carboxyl group at position 9 of the acridine ring [(S,S)-8, (S,S)-9, (R,R)-10] were synthesized. The pK a values of the new crown ethers [(S,S)-8, (S,S)-9, (R,R)-10] and of an earlier reported macrocycle [(R,R)-2] were determined by UV-pH titrations. Crown ether (S,S)-8 was attached to silica gel by covalent bonds and the enantiomeric separation ability of the newly prepared chiral stationary phase [(S,S)-CSP-12] was studied by high-performance liquid chromatography (HPLC). Homochiral preference was observed and the best separation was achieved for the enantiomers of 1-NEA. Ligands (S,S)-9 and (R,R)-10 are precursors of enantioselective sensor and selector molecules for the enantiomers of protonated primary amines, amino acids, and their derivatives. © 2017 Wiley Periodicals, Inc.

THE RELATION OF CHEMICAL STRUCTURE IN CATECHOL COMPOUNDS AND DERIVATIVES TO POISON IVY HYPERSENSITIVENESS IN MAN AS SHOWN BY THE PATCH TEST

PubMed Central

Keil, Harry; Wasserman, David; Dawson, Charles R.

1944-01-01

1. Additional evidence is presented in support of the view which postulates a close chemical and biologic relation between the active ingredients in poison ivy and Japan lac. 2. Biologic evidence, based on the use of the patch test in man, is presented in support of the view that the active ingredient in poison ivy is a catechol derivative with a long, unsaturated side-chain in the 3-position. 3. Of the catechol compounds and derivatives studied, group reactions in patients sensitive to poison ivy leaves or extract were exhibited by the following compounds: 3-pentadecyl catechol (100 per cent of 21 cases), 4-pentadecyl catechol (38 per cent of 21 cases), "urushiol" dimethyl ether (33 per cent of 33 cases), 3-pentadecenyl-1'-veratrole (21 per cent of 14 cases), 3-methyl catechol (14 per cent of 21 cases), and hydrourushiol dimethyl ether (10 per cent of 20 cases). It has been found that 3-geranyl catechol shows a practically constant group reactivity in persons sensitive to poison ivy. 4. The uniformly positive group reaction to 3-pentadecyl catechol is notable since this substance possesses a saturated side-chain, whereas the active ingredient in poison ivy is known to have an unsaturated side-chain. 5. The group reactivity was not restricted to the 3-position, for in some instances 4-pentadecyl catechol also gave group reactions which, however, were less intense and less frequent than those shown by 3-pentadecyl catechol. This indicates that in some cases a long side-chain in the 4 position may be effective in producing group specific reactions. 6. Only an occasional person showed sensitiveness to 3-methyl catechol (short side-chain), and in one instance the group reactivity appeared to be specific for the 3-position. 7. The position of the side-chain in the catechol configuration has some bearing on the degree and incidence of group reactions in persons hypersensitive to poison ivy. 8. Evidence is presented to indicate that the introduction of double bonds in the alkyl side-chain increases the incidence and intensity of group reactions. 9. Methylating the hydroxyl groups in the catechol configuration diminishes strongly the incidence of group reactivity but does not eliminate it entirely in persons hypersensitive to poison ivy. Thus, "urushiol" dimethyl ether (3-pentadecadienyl veratrole) gave group reactions in 33 per cent of 33 persons. 10. Methylating the hydroxyl groups as well as saturating the double bonds in the alkyl side-chain still further diminishes the group reactions but an occasional person hypersensitive to poison ivy may still show positive reaction to such a substance as 3-pentadecyl veratrole (hydrourushiol dimethyl ether). In this respect our results are not in full agreement with those recorded by Toyama who stated that hydrourushiol dimethyl ether is entirely harmless. 11. The significance of the group reactivity displayed by certain veratrole compounds is discussed, and several possible explanations of their behavior are advanced. 12. The group reactions discussed in this paper relate only to various catechol and veratrole compounds. Preliminary studies by us indicate that this sensitiveness extends to other phenolic derivatives. 13. Among the veratrole compounds showing positive reactions, the order of frequency and intensity was: (1) "urushiol" dimethyl ether (average of two double bonds); (2) S-pentadecenyl-1'-veratrole (one double bond); (3) hydrourushiol dimethyl ether (saturated side-chain). It may be noted that 4-pentadecyl veratrole was inactive. PMID:19871415

THE RELATION OF CHEMICAL STRUCTURE IN CATECHOL COMPOUNDS AND DERIVATIVES TO POISON IVY HYPERSENSITIVENESS IN MAN AS SHOWN BY THE PATCH TEST.

PubMed

Keil, H; Wasserman, D; Dawson, C R

1944-10-01

1. Additional evidence is presented in support of the view which postulates a close chemical and biologic relation between the active ingredients in poison ivy and Japan lac. 2. Biologic evidence, based on the use of the patch test in man, is presented in support of the view that the active ingredient in poison ivy is a catechol derivative with a long, unsaturated side-chain in the 3-position. 3. Of the catechol compounds and derivatives studied, group reactions in patients sensitive to poison ivy leaves or extract were exhibited by the following compounds: 3-pentadecyl catechol (100 per cent of 21 cases), 4-pentadecyl catechol (38 per cent of 21 cases), "urushiol" dimethyl ether (33 per cent of 33 cases), 3-pentadecenyl-1'-veratrole (21 per cent of 14 cases), 3-methyl catechol (14 per cent of 21 cases), and hydrourushiol dimethyl ether (10 per cent of 20 cases). It has been found that 3-geranyl catechol shows a practically constant group reactivity in persons sensitive to poison ivy. 4. The uniformly positive group reaction to 3-pentadecyl catechol is notable since this substance possesses a saturated side-chain, whereas the active ingredient in poison ivy is known to have an unsaturated side-chain. 5. The group reactivity was not restricted to the 3-position, for in some instances 4-pentadecyl catechol also gave group reactions which, however, were less intense and less frequent than those shown by 3-pentadecyl catechol. This indicates that in some cases a long side-chain in the 4 position may be effective in producing group specific reactions. 6. Only an occasional person showed sensitiveness to 3-methyl catechol (short side-chain), and in one instance the group reactivity appeared to be specific for the 3-position. 7. The position of the side-chain in the catechol configuration has some bearing on the degree and incidence of group reactions in persons hypersensitive to poison ivy. 8. Evidence is presented to indicate that the introduction of double bonds in the alkyl side-chain increases the incidence and intensity of group reactions. 9. Methylating the hydroxyl groups in the catechol configuration diminishes strongly the incidence of group reactivity but does not eliminate it entirely in persons hypersensitive to poison ivy. Thus, "urushiol" dimethyl ether (3-pentadecadienyl veratrole) gave group reactions in 33 per cent of 33 persons. 10. Methylating the hydroxyl groups as well as saturating the double bonds in the alkyl side-chain still further diminishes the group reactions but an occasional person hypersensitive to poison ivy may still show positive reaction to such a substance as 3-pentadecyl veratrole (hydrourushiol dimethyl ether). In this respect our results are not in full agreement with those recorded by Toyama who stated that hydrourushiol dimethyl ether is entirely harmless. 11. The significance of the group reactivity displayed by certain veratrole compounds is discussed, and several possible explanations of their behavior are advanced. 12. The group reactions discussed in this paper relate only to various catechol and veratrole compounds. Preliminary studies by us indicate that this sensitiveness extends to other phenolic derivatives. 13. Among the veratrole compounds showing positive reactions, the order of frequency and intensity was: (1) "urushiol" dimethyl ether (average of two double bonds); (2) S-pentadecenyl-1'-veratrole (one double bond); (3) hydrourushiol dimethyl ether (saturated side-chain). It may be noted that 4-pentadecyl veratrole was inactive.

The Microwave Spectrum of Partially Deuterated Species of Dimethyl Ether

NASA Astrophysics Data System (ADS)

Lauvergnat, D.; Margulès, L.; Motiyenko, R. A.; Guillemin, J.-C.; Coudert, L. H.

2011-06-01

Dimethyl ether is a molecule of astrophysical interest spectroscopically well characterized. It is one of the simplest molecules with two methyl groups undergoing large amplitude internal rotations. Due to deuterium enrichment in the interstellar medium, one can reasonably expect that partially deuterated species of dimethyl ether might be detected. However, there are no spectroscopic results about the microwave spectrum of such species. A theoretical calculation of the rotation-torsion energy levels of the partially deuterated species of dimethyl ether has been undertaken aided by ab initio calculations. The approach accounts for the complicated torsion-rotation interactions displayed by this molecule and for the fact that deuteration leads to changes of the bidimensional internal rotation effective potential energy surface. Due to zero-point energy contributions from the 19 small amplitude vibrational modes, this surface no longer displays G36 symmetry. Rotation-torsion energy levels are computed treating the two angles of internal rotation as active coordinates and evaluating Hamiltonian matrix elements with the help of Gaussian quadrature. It is hoped that the present results will allow us to understand the microwave spectrum of the mono deuterated species CH_2DOCH_3 which has been recorded in Lille with the new sub millimeter wave spectrometer (150--950 GHz) based on harmonic generation of solid-state sources. [2] Snyder, Buhl, and Schwartz, Astrophys. J. Letters 191 (1974) L79. [3] Endres, Drouin, Pearson, Müller, Lewen, Schlemmer, and Giesen, A&A 504 (2009) 635. [4] Solomon and Woolf, Astrophys. J. Letters 180 (1973) L89. [5] Lauvergnat and Nauts, J. Chem. Phys. 116 (2002) 8560; and Light and Bačić, J. Chem. Phys. 87 (1987) 4008.

Effects of Fuel Temperature on Injection Process and Combustion of Dimethyl Ether Engine.

PubMed

Guangxin, Gao; Zhulin, Yuan; Apeng, Zhou; Shenghua, Liu; Yanju, Wei

2013-12-01

To investigate the effects of fuel temperature on the injection process in the fuel-injection pipe and the combustion characteristics of compression ignition (CI) engine, tests on a four stroke, direct injection dimethyl ether (DME) engine were conducted. Experimental results show that as the fuel temperature increases from 20 to 40 °C, the sound speed is decreased by 12.2%, the peak line pressure at pump and nozzle sides are decreased by 7.2% and 5.6%, respectively. Meanwhile, the injection timing is retarded by 2.2 °CA and the injection duration is extended by 0.8 °CA. Accordingly, the ignition delay and the combustion duration are extended by 0.7 °CA and 4.0 °CA, respectively. The cylinder peak pressure is decreased by 5.4%. As a result, the effective thermal efficiency is decreased, especially for temperature above 40 °C. Before beginning an experiment, the fuel properties of DME, including the density, the bulk modulus, and the sound speed were calculated by "ThermoData." The calculated result of sound speed is consistent with the experimental results.

Fourier Transform Microwave Spectroscopic Studies of Dimethyl Ether and Ethylene Flames

NASA Astrophysics Data System (ADS)

Obenchain, Daniel A.; Wullenkord, Julia; Kohse-Höinghaus, Katharina; Grabow, Jens-Uwe; Hansen, Nils

2017-06-01

Microwave spectroscopy has been a proven technique for the detection of short-lived molecules produced from a variety of molecular sources. With the goal of observing more reactive intermediates produced in combustion reactions, the products of a home-built flat flame burner were measured on a coaxially oriented beam resonator arrangement (COBRA) Fourier transform microwave spectrometer. The products are coupled into a molecular beam using a fast-mixing nozzle styled after the work of Gutowsky and co-workers. Probing the flame at various positions, the relative abundance of products can be observed as a function of flame depth. One dimensional intensity profiles are available for formaldehyde, ketene, acetaldehyde, and dimethyl ether, where either a dimethyl ether fuel or an ethylene fuel was burned in the presence of oxygen. The current arrangement allows only for stable species produced in the flame to be observed in the molecular beam. This combination of species source and detection shows promise for future work in observing new, short-lived, combustion intermediates. J.-U. Grabow, W. Stahl, H. Dreizler, Rev. Sci. Instrum. 67, 4072, 1996 T. Emilsson, T. D. Klots, R. S. Ruoff, H.S. Gutowsky, J. Chem. Phys. 93, 6971, 1990

Scientific bases of biomass processing into basic component of aviation fuel

NASA Astrophysics Data System (ADS)

Kachalov, V. V.; Lavrenov, V. A.; Lishchiner, I. I.; Malova, O. V.; Tarasov, A. L.; Zaichenko, V. M.

2016-11-01

A combination of feedstock pyrolysis and the cracking of the volatile pyrolysis products on the charcoal at 1000 °C allows to obtain a tarless synthesis gas which contains 90 vol% or more of carbon monoxide and hydrogen in approximately equal proportions. Basic component of aviation fuel was synthesized in a two-stage process from gas obtained by pyrolytic processing of biomass. Methanol and dimethyl ether can be efficiently produced in a two-layer loading of methanolic catalyst and γ-Al2O3. The total conversion of CO per pass was 38.2% using for the synthesis of oxygenates a synthesis gas with adverse ratio of H2/CO = 0.96. Conversion of CO to CH3OH was 15.3% and the conversion of CO to dimethyl ether was 20.9%. A high yield of basic component per oxygenates mass (44.6%) was obtained during conversion. The high selectivity of the synthesis process for liquid hydrocarbons was observed. An optimal recipe of aviation fuel B-92 based on a synthesized basic component was developed. The prototype of aviation fuel meets the requirements for B-92 when straight fractions of 50-100 °C (up to 35 wt%), isooctane (up to 10 wt%) and ethyl fluid (2.0 g/kg calculated as tetraethyl lead) is added to the basic component.

High-activity PtRuPd/C catalyst for direct dimethyl ether fuel cells.

PubMed

Li, Qing; Wen, Xiaodong; Wu, Gang; Chung, Hoon T; Gao, Rui; Zelenay, Piotr

2015-06-22

Dimethyl ether (DME) has been considered as a promising alternative fuel for direct-feed fuel cells but lack of an efficient DME oxidation electrocatalyst has remained the challenge for the commercialization of the direct DME fuel cell. The commonly studied binary PtRu catalyst shows much lower activity in DME than methanol oxidation. In this work, guided by density functional theory (DFT) calculation, a ternary carbon-supported PtRuPd catalyst was designed and synthesized for DME electrooxidation. DFT calculations indicated that Pd in the ternary PtRuPd catalyst is capable of significantly decreasing the activation energy of the CO and CH bond scission during the oxidation process. As evidenced by both electrochemical measurements in an aqueous electrolyte and polymer-electrolyte fuel cell testing, the ternary catalyst shows much higher activity (two-fold enhancement at 0.5 V in fuel cells) than the state-of-the-art binary Pt50 Ru50 /C catalyst (HiSPEC 12100). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on systems based on coal and natural gas for producing dimethyl ether

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

Zhou, L.; Hu, S.Y.; Chen, D.J.

2009-04-15

China is a coal-dependent country and will remain so for a long time. Dimethyl ether (DME), a potential substitute for liquid fuel, is a kind of clean diesel motor fuel. The production of DME from coal is meaningful and is studied in this article. Considering the C/H ratios of coal and natural gas (NG), the cofeed (coal and NG) system (CFS), which does not contain the water gas shift process, is studied. It can reduce CO{sub 2} emission and increase the conversion rate of carbon, producing more DME. The CFS is simulated and compared with the coal-based and NG-based systemsmore » with different recycling ratios. The part of the exhaust gas that is not recycled is burned, producing electricity. On the basis of the simulation results, the thermal efficiency, economic index, and CO{sub 2} emission ratio are calculated separately. The CFS with a 100% recycling ratio has the best comprehensive evaluation index, while the energy, economy, and environment were considered at the same time.« less

Extraction of Fucoxanthin from Raw Macroalgae excluding Drying and Cell Wall Disruption by Liquefied Dimethyl Ether

PubMed Central

Kanda, Hideki; Kamo, Yuichi; Machmudah, Siti; Wahyudiono; Goto, Motonobu

2014-01-01

Macroalgae are one of potential sources for carotenoids, such as fucoxanthin, which are consumed by humans and animals. This carotenoid has been applied in both the pharmaceutical and food industries. In this study, extraction of fucoxanthin from wet brown seaweed Undaria pinnatifida (water content was 93.2%) was carried out with a simple method using liquefied dimethyl ether (DME) as an extractant in semi-continuous flow-type system. The extraction temperature and absolute pressure were 25 °C and 0.59 MPa, respectively. The liquefied DME was passed through the extractor that filled by U. pinnatifida at different time intervals. The time of experiment was only 43 min. The amount of fucoxanthin could approach to 390 μg/g dry of wet U. pinnatifida when the amount of DME used was 286 g. Compared with ethanol Soxhlet and supercritical CO2 extraction, which includes drying and cell disruption, the result was quite high. Thus, DME extraction process appears to be a good method for fucoxanthin recovery from U. pinnatifida with improved yields. PMID:24796299

Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

DOE PAGES

Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

2014-10-01

In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to amore » constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.« less

Efficacy of pinosylvins against white-rot and brown-rot fungi

Treesearch

Catherine C. Celimene; Jessie A. Micales; Leslie Ferge; Raymond A. Young

1999-01-01

Three stilbenes, pinosylvin (PS), pinosylvin monomethyl ether (PSM) and pinosylvin dimethyl ether (PSD), were extracted from white spruce (Picea glauca), jack pine (Pinus banksiana), and red pine (Pinus resinosa) pine cones, and their structures were confirmed by spectroscopic and chromatographic (HPLC, GC/MS, NMR and FTIR) analysis. PS, PSM, PSD or a 1:1:1 mixture of...

40 CFR Appendix J to Part 122 - NPDES Permit Testing Requirements for Publicly Owned Treatment Works (§ 122.21(j))

Code of Federal Regulations, 2012 CFR

2012-07-01

...-ethylhexyl) phthalate 4-bromophenyl phenyl ether Butyl benzyl phthalate 2-chloronaphthalene 4-chlorophenyl phenyl ether Chrysene Di-n-butyl phthalate Di-n-octyl phthalate Dibenzo(a,h)anthracene 1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 3,3-dichlorobenzidine Diethyl phthalate Dimethyl phthalate...

Infrared spectra of complex organic molecules in astronomically relevant ice matrices. I. Acetaldehyde, ethanol, and dimethyl ether

NASA Astrophysics Data System (ADS)

Terwisscha van Scheltinga, J.; Ligterink, N. F. W.; Boogert, A. C. A.; van Dishoeck, E. F.; Linnartz, H.

2018-03-01

Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking. Aim. This work provides infrared reference spectra of acetaldehyde (CH3CHO), ethanol (CH3CH2OH), and dimethyl ether (CH3OCH3) recorded in a variety of ice environments and for astronomically relevant temperatures, as needed to guide or interpret astronomical observations, specifically for upcoming James Webb Space Telescope observations. Methods: Fourier transform transmission spectroscopy (500-4000 cm-1/20-2.5 μm, 1.0 cm-1 resolution) was used to investigate solid acetaldehyde, ethanol and dimethyl ether, pure or mixed with water, CO, methanol, or CO:methanol. These species were deposited on a cryogenically cooled infrared transmissive window at 15 K. A heating ramp was applied, during which IR spectra were recorded until all ice constituents were thermally desorbed. Results: We present a large number of reference spectra that can be compared with astronomical data. Accurate band positions and band widths are provided for the studied ice mixtures and temperatures. Special efforts have been put into those bands of each molecule that are best suited for identification. For acetaldehyde the 7.427 and 5.803 μm bands are recommended, for ethanol the 11.36 and 7.240 μm bands are good candidates, and for dimethyl ether bands at 9.141 and 8.011 μm can be used. All spectra are publicly available in the Leiden Database for Ice.

Thrust Evaluation of an Arcjet Thruster Using Dimethyl Ether as a Propellant

NASA Astrophysics Data System (ADS)

Kakami, Akira; Beppu, Shinji; Maiguma, Muneyuki; Tachibana, Takeshi

This paper describes the performance of an arcjet thruster using dimethyl ether (DME) as a propellant. DME, an ether compound, has adequate characteristics for space propulsion systems; DME is storable in a liquid state without a high pressure or cryogenic device and requires no sophisticated temperature management. DME is gasified and liquefied simply by adjusting temperature, whereas hydrazine, a conventional propellant, requires an iridium-based particulate catalyst for its gasification. In this study, thrust of the designed kW-class DME arcjet thruster is measured with a torsional thrust stand. Thrust measurements show that thrust is increased with propellant mass flow rate, and that thrust using DME propellant is higher than when using nitrogen. The prototype DME arcjet thruster yields a specific impulse of 330 s, a thruster efficiency of 0.14, and a thrust of 0.19 N at 60-mg/s DME mass flow rate at 25-A discharge current. The corresponding discharge power and specific power are 2.3 kW and 39 MJ/kg.

Exploring low-temperature dehydrogenation at ionic Cu sites in beta zeolite to enable alkane recycle in dimethyl ether homologation

DOE PAGES

Farberow, Carrie A.; Cheah, Singfoong; Kim, Seonah; ...

2017-04-24

Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Bronsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. Furthermore, these results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C 5+) hydrocarbon yield.

Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: synthesis of (-)-sugiresinol dimethyl ether.

PubMed

Evans, P Andrew; Leahy, David K

2003-07-30

The transition metal-catalyzed allylic alkylation represents a fundamentally important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a regioselective and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical allylic alcohol derivatives using copper(I) enolates to prepare beta-substituted ketones. This protocol represents a convenient asymmetric Claisen rearrangement surrogate in which alpha-substituted enolates permit the introduction of an additional stereogenic center. The synthetic utility of this transformation was highlighted in the construction of a trans-1,2-disubstituted cyclohexene and the total synthesis of (-)-sugiresinol dimethyl ether. Finally, we anticipate that copper(I) enolates may prove useful nucleophiles in related metal-catalyzed reactions.

CH3OCH3 in Orion-KL: a striking similarity with HCOOCH3

NASA Astrophysics Data System (ADS)

Brouillet, N.; Despois, D.; Baudry, A.; Peng, T.-C.; Favre, C.; Wootten, A.; Remijan, A. J.; Wilson, T. L.; Combes, F.; Wlodarczak, G.

2013-02-01

Context. Orion-KL is a remarkable, nearby star-forming region where a recent explosive event has generated shocks that could have released complex molecules from the grain mantles. Aims: A comparison of the distribution of the different complex molecules will help in understanding their formation and constraining the chemical models. Methods: We used several data sets from the Plateau de Bure Interferometer to map the dimethyl ether emission with different arcsec spatial resolutions and different energy levels (from Eup = 18 to 330 K) to compare with our previous methyl formate maps. Results: Our data show remarkable similarity between the dimethyl ether (CH3OCH3) and the methyl formate (HCOOCH3) distributions even on a small scale (1.8″ × 0.8″ or ~500 AU). This long suspected similarity, seen from both observational and theoretical arguments, is demonstrated with unprecedented confidence, with a correlation coefficient of maps ~0.8. Conclusions: A common precursor is the simplest explanation of our correlation. Comparisons with previous laboratory work and chemical models suggest the major role of grain surface chemistry and a recent release, probably with little processing, of mantle molecules by shocks. In this case the CH3O radical produced from methanol ice would be the common precursor (whereas ethanol, C2H5OH, is produced from the radical CH2OH). The alternative gas phase scheme, where protonated methanol CH3OH+2 is the common precursor to produce methyl formate and dimethyl ether through reactions with HCOOH and CH3OH, is also compatible with our data. Our observations cannot yet definitely allow a choice between the different chemical processes, but the tight correlation between the distributions of HCOOCH3 and CH3OCH3 strongly contrasts with the different behavior we observe for the distributions of ethanol and formic acid. This provides a very significant constraint on models. Based on observations carried out with the IRAM Plateau de Bure Interferometer. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).

Chemistry within Molecular van der Waals Clusters

DTIC Science & Technology

1990-07-18

and Discussion 1) Stabilizing an Unstable Reagent within a Cluster a) 1, 1- Difluoroethane Clusters 2) Providing New Chemical Pathways a) Ammonia...1- difluoroethane clusters 24, the generation of (CH3 OCH 3 )nH3 O+ & (CH3 OCH 3 )nCH3 OH2 + ions from dimethyl ether dusters25 ,26, the generation of...Stabilizing an Unstable Reagent within a Cluster a) 1.1- Difluoroethane Clusters 24 The dominant reactive process which occurs within the majority of cluster

Selective inhibition of ammonium oxidation and nitrification-linked N2O formation by methyl fluoride and dimethyl ether

USGS Publications Warehouse

Miller, L.G.; Coutlakis, M.D.; Oremland, R.S.; Ward, B.B.

1993-01-01

Methyl fluoride (CH3F) and dimethyl ether (DME) inhibited nitrification in washed-cell suspensions of Nitrosomonas europaea and in a variety of oxygenated soils and sediments. Headspace additions of CH3F (10% [vol/vol]) and DME (25% [vol/vol]) fully inhibited NO2- and N2O production from NH4+ in incubations of N. europaea, while lower concentrations of these gases resulted in partial inhibition. Oxidation of hydroxylamine (NH2OH) by N. europaea and oxidation of NO2- by a Nitrobacter sp. were unaffected by CH3F or DME. In nitrifying soils, CH3F and DME inhibited N2O production. In field experiments with surface flux chambers and intact cores, CH3F reduced the release of N2O from soils to the atmosphere by 20- to 30-fold. Inhibition by CH3F also resulted in decreased NO3- + NO2- levels and increased NH4+ levels in soils. CH3F did not affect patterns of dissimilatory nitrate reduction to ammonia in cell suspensions of a nitrate- respiring bacterium, nor did it affect N2O metabolism in denitrifying soils. CH3F and DME will be useful in discriminating N2O production via nitrification and denitrification when both processes occur and in decoupling these processes by blocking NO2- and NO3- production.

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

Su, Liang; Ferrandon, Magali; Barton, John L.

The identification and development of conductive electrolytes with high concentrations of redox active species is key to realizing energy-dense nonaqueous flow batteries. Herein, we explore the use of ether solvents (1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (DEGDME), and tetraethylene glycol dimethyl ether (TEGDME)) as the basis for redox electrolytes containing a lithium ion supporting salt (LiBF4 or LiTFSI) and 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) as an active material. An automated high-throughput platform is employed to screen various electrolyte compositions by measuring solution conductivity and solute solubility as a function of solvent and salt type, component concentration, and temperature. Subsequently, the electrochemicalmore » and transport properties of select redox electrolytes are characterized by cyclic voltammetry using glassy carbon disk electrodes and by linear sweep voltammetry using carbon fiber ultramicroelectrodes. In general, improvements in electrolyte conductivity and solute solubility are observed with ether-based formulations as compared to previously reported propylene carbonate (PC)-based formulations. In particular, the addition of DOL to a DME-based electrolyte increases the conductivity and decreases the temperature for solubilization at high LiTFSI and DBBB concentrations. The redox behavior of DBBB remains consistent across the range of concentrations tested while the diffusion coefficient scales with changes in solution viscosity.« less

76 FR 63282 - Foreign-Trade Zone 140-Flint, Michigan; Application for Subzone; Dow Corning Corporation (Silicon...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-12

..., allylglycol, allyl glycidyl ether, methyl ethyl ketone, diacetone alcohol, octanoic acid, undecylenic acid, monoplex dos, ethyl silicate, sparc base, dimethylethanolamine, vinyltriacetoxysilane, dimethyl me...

Antiprotozoal, antimycobacterial, and anti-inflammatory evaluation of Cnidoscolus chayamansa (Mc Vaugh) extract and the isolated compounds.

PubMed

Pérez-González, Mariana Z; Gutiérrez-Rebolledo, Gabriel A; Yépez-Mulia, Lilián; Rojas-Tomé, Irma S; Luna-Herrera, Julieta; Jiménez-Arellanes, María A

2017-05-01

Cnidoscolus chayamansa is a medicinal and edible plant known as Chaya, is commonly used as an anti-inflammatory, antiprotozoal, antibacterial agent and as a remedy for respiratory illness, gastrointestinal disorders, and vaginal infections related with the inflammation process. In this paper, we describe the plant's phytochemical analysis and biological activities (antimycobacterial, antibacterial, antiprotozoal, and anti-inflammatory properties) of the CHCl 3 :MeOH (1:1) leaves extract and isolated compounds, as well as the acute and sub-acute toxic effects. Chemical identification of isolated compounds was performed by 1 H- and 13 C NMR spectra data. In vitro antibacterial and antimycobacterial activities were determined by disc diffusion and MABA assays, respectively; antiprotozoal test by means of the sub-culture test. Topical and systemic anti-inflammatory effects were tested by TPA and carrageenan assay on BALB/c mice. Moretenol, moretenyl acetate, kaempferol-3,7-dimethyl ether, and 5-hydroxy-7-3',4'-trimethoxyflavanone were the main compounds isolated. The CHCl 3 :MeOH extract showed antiprotozoal (IC 50 ≤65.29μg/mL), antimycobacterial (MIC≤50μg/mL), and anti-inflammatory activities (ED 50 =1.66mg/ear and 467.73mg/kg), but was inactive against the bacterial strains tested. The LD 50 for extract was >2g/kg. In the sub-acute toxicity test, the extract was administered at 1g/kg for 28days and did not cause lethality or any alteration in hematological and biochemical parameters; in addition, liver, kidney, and spleen histological analysis exhibited no structural changes. Moretenol and moretenyl acetate showed MIC=25μg/mL against Mycobacterium tuberculosis H37Rv and against four monoresistant strains of M. tuberculosis H37Rv. Both compounds exhibited moderate activity against Entamoeba histolytica and Giardia lamblia (IC 50 ≤71.70μg/mL). Kaempferol-3,7-dimethyl ether and 5-hydroxy-7-3',4'-trimethoxy-flavanone were more active than the extract against E. histolytica and G. lamblia, showing IC 50 ≤27.43μg/mL. As topical anti-inflammatory agents, moretenol and kaempferol-3,7-dimethyl ether were the most active compounds inhibiting the edema in 30.52 and 26.67%, respectively. Moretenol and moretenyl acetate showed significant antimycobacterial and antiprotozoal activities; in addition, important antiprotozoal effect was detected with kaempferol-3,7-dimethyl ether and 5-hydroxy-7-3',4'-trimethoxyflavanone. The extract and the terpenoids possess good anti-inflammatory activity. The extract did not produce lethality or adverse effects in acute and sub-acute tests. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Proceedings of the 1995 SAE alternative fuels conference. P-294

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

NONE

1995-12-31

This volume contains 32 papers and five panel discussions related to the fuel substitution of trucks, automobiles, buses, cargo handling equipment, diesel passenger cars, and pickup trucks. Fuels discussed include liquefied natural gas, natural gas, ethanol fuels, methanol fuels, dimethyl ether, methyl esters from various sources (rape oil, used cooking oils, soya, and canola oils), hydrogen fuels, and biodiesel. Other topics include fuel cell powered vehicles, infrastructure requirements for fuel substitution, and economics. Papers have been processed separately for inclusion on the data base.

Synthesis and characteristics of polyarylene ether sulfones

NASA Technical Reports Server (NTRS)

Viswanathan, R.; Johnson, B. C.; Ward, T. C.; Mcgrath, J. E.

1981-01-01

A method utilizing potassium carbonate/dimethyl acetamide, as base and solvent respectively, was used for the synthesis of several homopolymers and copolymers derived from various bisphenols. It is demonstrated that this method deviates from simple second order kinetics; this deviation being due to the heterogeneous nature of the reaction. Also, it is shown that a liquid induced crystallization process can improve the solvent resistance of these polymers. Finally, a Monte Carlo simulation of the triad distribution of monomers in nonequilibrium copolycondensation is discussed.

Dimethyl Ether Between 214.6 and 265.3 Ghz: the Complete, Temperature Resolved Spectrum

NASA Astrophysics Data System (ADS)

McMillan, James P.; Neese, Christopher F.; De Lucia, Frank C.

2017-06-01

We have studied dimethyl ether, one of the so-called 'astronomical weeds', in the 214.6-265.3 GHz band. We have experimentally gathered a set of intensity calibrated, complete, and temperature resolved spectra from across the temperature range of 238-391 K. Using our previously reported method of analysis, the point by point method, we are capable of generating the complete spectrum at astronomically significant temperatures. Many lines, of nontrivial intensity, which were previously not included in the available astrophysical catalogs have been found. Lower state energies and line strengths have been found for a number of lines which are not currently present in the catalogs. The extent to which this may be useful in making assignments will be discussed. J. McMillan, S. Fortman, C. Neese, F. DeLucia, ApJ. 795, 56 (2014)

Ab initio calculations for the spectral analysis of dimethyl ether (CH_3OCH_3) and their isotopologues

NASA Astrophysics Data System (ADS)

Senent, M. L.; Villa, M.; Dominguez-Gomez, R.; Alvarez-Bajo, O.; Carvajal, M.

2011-05-01

Dimethyl ether is a complex interstellar molecule with two internal rotors, which has a high abundance in the star-forming regions. This point, jointed with the recent development of the last-generation observatories operating at the sub-mm and mm wavelengths, has motivated a new laboratory spectral recording in this frequency range. In spite of that, the rotational spectra was only analysed in depth within its vibrational ground state and a new spectral analysis within the fundamental torsional states is in progress. These analysis were carried out with ERHAM, a global model that takes into account the large amplitude motions owing to the two equivalent internal CH3 tops. Nevertheless, their torsional modes in principle interact with the bending COC mode and an appropiate torsional-bending description would be needed in order to analyse the rotational spectra within higher excited states. In this work, a new analysis of the COC bending and the CH3 torsional degrees of freedom has been carried out by means of ab initio calculations. A new and more accurate three-dimensional Potential Energy Surface (PES), is obtained using the CCSD(T) level of theory. This approach has also been applied to other isotopologues of interest, as 13C-dimethyl ether and the monodeuterated species. The purpose of this study is to help in the assignment of new spectral lines of these species and hence to contribute in the spectral cleaning of the astronomical observations to the interstellar medium.

Cannabidiol-2',6'-dimethyl ether, a cannabidiol derivative, is a highly potent and selective 15-lipoxygenase inhibitor.

PubMed

Takeda, Shuso; Usami, Noriyuki; Yamamoto, Ikuo; Watanabe, Kazuhito

2009-08-01

The inhibitory effect of nordihydroguaiaretic acid (NDGA) (a nonselective lipoxygenase (LOX) inhibitor)-mediated 15-LOX inhibition has been reported to be affected by modification of its catechol ring, such as methylation of the hydroxyl group. Cannabidiol (CBD), one of the major components of marijuana, is known to inhibit LOX activity. Based on the phenomenon observed in NDGA, we investigated whether or not methylation of CBD affects its inhibitory potential against 15-LOX, because CBD contains a resorcinol ring, which is an isomer of catechol. Although CBD inhibited 15-LOX activity with an IC(50) value (50% inhibition concentration) of 2.56 microM, its monomethylated and dimethylated derivatives, CBD-2'-monomethyl ether and CBD-2',6'-dimethyl ether (CBDD), inhibited 15-LOX activity more strongly than CBD. The number of methyl groups in the resorcinol moiety of CBD (as a prototype) appears to be a key determinant for potency and selectivity in inhibition of 15-LOX. The IC(50) value of 15-LOX inhibition by CBDD is 0.28 microM, and the inhibition selectivity for 15-LOX (i.e., the 5-LOX/15-LOX ratio of IC(50) values) is more than 700. Among LOX isoforms, 15-LOX is known to be able to oxygenate cholesterol esters in the low-density lipoprotein (LDL) particle (i.e., the formation of oxidized LDL). Thus, 15-LOX is suggested to be involved in development of atherosclerosis, and CBDD may be a useful prototype for producing medicines for atherosclerosis.

O-methylation of natural phenolic compounds based on green chemistry using dimethyl carbonate

NASA Astrophysics Data System (ADS)

Prakoso, N. I.; Pangestu, P. H.; Wahyuningsih, T. D.

2016-02-01

The alkyl aryl ether compounds, of which methyl eugenol and veratraldehyde are the simplest intermediates can be synthesized by reacting eugenol and vanillin with the green reagent dimethyl carbonate (DMC). The reaction was carried out under mild of temperature and pressure. Excellent yields and selective products were obtained (95-96%) after a few hours. In the end of the reaction, the catalysts (base and Phase Transfer Catalyst) can be recovered and regenerated.

Analyzing the flavor compounds in Chinese traditional fermented shrimp pastes by HS-SPME-GC/MS and electronic nose

NASA Astrophysics Data System (ADS)

Fan, Yan; Yin, Li'ang; Xue, Yong; Li, Zhaojie; Hou, Hu; Xue, Changhu

2017-04-01

Shrimp paste is a type of condiments with high nutritional value. However, the flavors of shrimp paste, particularly the non-uniformity flavors, have limited its application in food processing. In order to identify the characteristic flavor compounds in Chinese traditional shrimp pastes, five kinds of typical commercial products were evaluated in this study. The differences in the volatile composition of the five products were investigated. Solid phase micro-extraction method was employed to extract the volatile compounds. GC-MS and electronic nose were applied to identify the compounds, and the data were analyzed using principal component analysis (PCA). A total of 62 volatile compounds were identified, including 8 alcohols, 7 aldehydes, 3 ketones, 7 ethers, 7 acids, 3 esters, 6 hydrocarbons, 12 pyrazines, 2 phenols, and 7 other compounds. The typical volatile compounds contributing to the flavor of shrimp paste were found as follows: dimethyl disulfide, dimethyl tetrasulfide, dimethyl trisulfide, 2, 3, 5-trimethyl-6-ethyl pyrazine, ethyl-2, 5-dimethyl-pyrazine, phenol and indole. Propanoic acid, butanoic acid, furans, and 2-hydroxy-3-pentanone caused unpleasant odors, such as pungent and rancid odors. Principal component analysis showed that the content of volatile compounds varied depending on the processing conditions and shrimp species. These results indicated that the combinations of multiple analysis and identification methods could make up the limitations of a single method, enhance the accuracy of identification, and provide useful information for sensory research and product development.

Poly(ether ester) Ionomers as Water-Soluble Polymers for Material Extrusion Additive Manufacturing Processes.

PubMed

Pekkanen, Allison M; Zawaski, Callie; Stevenson, André T; Dickerman, Ross; Whittington, Abby R; Williams, Christopher B; Long, Timothy E

2017-04-12

Water-soluble polymers as sacrificial supports for additive manufacturing (AM) facilitate complex features in printed objects. Few water-soluble polymers beyond poly(vinyl alcohol) enable material extrusion AM. In this work, charged poly(ether ester)s with tailored rheological and mechanical properties serve as novel materials for extrusion-based AM at low temperatures. Melt transesterification of poly(ethylene glycol) (PEG, 8k) and dimethyl 5-sulfoisophthalate afforded poly(ether ester)s of sufficient molecular weight to impart mechanical integrity. Quantitative ion exchange provided a library of poly(ether ester)s with varying counterions, including both monovalent and divalent cations. Dynamic mechanical and tensile analysis revealed an insignificant difference in mechanical properties for these polymers below the melting temperature, suggesting an insignificant change in final part properties. Rheological analysis, however, revealed the advantageous effect of divalent countercations (Ca 2+ , Mg 2+ , and Zn 2+ ) in the melt state and exhibited an increase in viscosity of two orders of magnitude. Furthermore, time-temperature superposition identified an elevation in modulus, melt viscosity, and flow activation energy, suggesting intramolecular interactions between polymer chains and a higher apparent molecular weight. In particular, extrusion of poly(PEG 8k -co-CaSIP) revealed vast opportunities for extrusion AM of well-defined parts. The unique melt rheological properties highlighted these poly(ether ester) ionomers as ideal candidates for low-temperature material extrusion additive manufacturing of water-soluble parts.

Coordination geometries of solvated lanthanide(II) ions: Molecular structures of the cationic species [(DIME)[sub 3]Ln][sup 2+] (DIME = diethylene glycol dimethyl ether; Ln[sup 2+] = Sm, Yb), [(DIME)[sub 2]Yb(CH[sub 3]CN)[sub 2

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

White, J.P. III; Deng, H.; Boyd, E.P.

1994-04-13

The first lanthanide(II) cationic species with coordination numbers 7,8, and 9 have been structurally characterized. Mercury amalgams of the elemental lanthanides (Ln(Hg) where Ln = Sm, Eu, Yb) cleanly reduce Mn[sub 2](CO)[sub 10] and Co[sub 2](CO)[sub 8] in polydentate ethers to [Mn(CO)[sub 5

Quantum Chemical and Physicochemical Studies of Oximes (Prophylactics against and Reactivators of Phosphorylated AChE).

DTIC Science & Technology

1984-10-25

crystal structure of nicotinic acid ,. and we used the ether bridge from the crystal structure of dimethyl ether. We are investigating various rotamers...observations were made: - The titration curve (after the subtraction of the blank curve) shows only one titrable group, i.e. the oxime moiety. - The...subtraction of the blank curve, shows two titrable groups, i.e. the two oxime moieties. The results are as follows: Temperature Conditions PKa pK2

40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

Code of Federal Regulations, 2012 CFR

2012-07-01

... glycol dimethyl ether 111966 Diethyl sulfate 64675 Dimethylaniline (N,N-) 121697 Dimethylhydrazine (1,1... 67721 Hexane 110543 Isophorone 78591 Methanol 67561 Methyl bromide (Bromomethane) 74839 Methyl chloride...

Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

DOE PAGES

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; ...

2015-10-28

This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

Influence of Solvent on the Drug-Loading Process of Amphiphilic Nanogel Star Polymers.

PubMed

Carr, Amber C; Piunova, Victoria A; Maarof, Hasmerya; Rice, Julia E; Swope, William C

2018-05-31

We present an all-atom molecular dynamics study of the effect of a range of organic solvents (dichloromethane, diethyl ether, toluene, methanol, dimethyl sulfoxide, and tetrahydrofuran) on the conformations of a nanogel star polymeric nanoparticle with solvophobic and solvophilic structural elements. These nanoparticles are of particular interest for drug delivery applications. As drug loading generally takes place in an organic solvent, this work serves to provide insight into the factors controlling the early steps of that process. Our work suggests that nanoparticle conformational structure is highly sensitive to the choice of solvent, providing avenues for further study as well as predictions for both computational and experimental explorations of the drug-loading process. Our findings suggest that when used in the drug-loading process, dichloromethane, tetrahydrofuran, and toluene allow for a more extensive and increased drug-loading into the interior of nanogel star polymers of the composition studied here. In contrast, methanol is more likely to support shallow or surface loading and, consequently, faster drug release rates. Finally, diethyl ether should not work in a formulation process since none of the regions of the nanogel star polymer appear to be sufficiently solvated by it.

Carbon dioxide recycling

EPA Science Inventory

The recycling of carbon dioxide to methanol and dimethyl ether is seen to offer a substantial route to renewable and environmentally carbon neutral fuels. One of the authors has championed the “Methanol Economy" in articles and a book. By recycling ambient CO2, the authors argue ...

Spontaneous Generation of Chirality in Simple Diaryl Ethers.

PubMed

Lennartson, Anders; Hedström, Anna; Håkansson, Mikael

2015-07-01

We studied the spontaneous formation of chiral crystals of four diaryl ethers, 3-phenoxybenzaldehyde, 1; 1,3-dimethyl-2-phenoxybenzene, 2; di(4-aminophenyl) ether, 3; and di(p-tolyl) ether, 4. Compounds 1, 3, and 4 form conformationally chiral molecules in the solid state, while the chirality of 2 arises from the formation of supramolecular helices. Compound 1 is a liquid at ambient temperature, but 2-4 are crystalline, and solid-state CD-spectroscopy showed that they could be obtained as optically active bulk samples. It should be noted that the optical activity arise upon crystallization, and no optically active precursors were used. Indeed, even commercial samples of 3 and 4 were found to be optically active, giving evidence for the ease at which total spontaneous resolution may occur in certain systems. © 2015 Wiley Periodicals, Inc.

40 CFR Appendix - Tables to Part 132

Code of Federal Regulations, 2012 CFR

2012-07-01

...-Bromophenyl phenyl ether Butyl benzyl phthalate Cadmium Carbon tetrachloride; tetrachloromethane Chlorobenzene...) phthalate Diazinon 1,2:5,6-Dibenzanthracene; dibenz[a,h]anthracene Dibutyl phthalate; di-n-butyl phthalate 1...-dichloropropylene Diethyl phthalate 2,4-Dimethylphenol; 2,4-xylenol Dimethyl phthalate 4,6-Dinitro-o-cresol; 2...

Direct transformation of silyl enol ethers into functionalized allenes.

PubMed

Langer, P; Döring, M; Seyferth, D; Görls, H

2001-02-02

The first elimination reactions of silyl enol ethers to lithiated allenes are reported. These reactions allow a direct transformation of readily available silyl enol ethers into functionalized allenes. The action of three to four equivalents of lithium diisopropylamide (LDA) on silyl enol ethers results in the formation of lithiated allenes by initial allylic lithiation, subsequent elimination of a lithium silanolate, and finally, lithiation of the allene thus formed. Starting with amide-derived silyl imino ethers, lithiated ketenimines are obtained. A variety of reactions of the lithiated allenes with electrophiles (chlorosilanes, trimethylchlorostannane, dimethyl sulfate and ethanol) were carried out. Elimination of silanolate is observed only for substrates that contain the hindered SiMe2tBu or Si(iPr)3 moiety, but not for the SiMe3 group. The reaction of 1,1-dilithio-3,3-diphenylallene with ketones provides a convenient access to novel 1,1-di(hydroxymethyl)allenes which undergo a domino Nazarov-Friedel-Crafts reaction upon treatment with p-toluenesulfonic acid.

Models for liquid-liquid partition in the system dimethyl sulfoxide-organic solvent and their use for estimating descriptors for organic compounds.

PubMed

Karunasekara, Thushara; Poole, Colin F

2011-07-15

Partition coefficients for varied compounds were determined for the organic solvent-dimethyl sulfoxide biphasic partition system where the organic solvent is n-heptane or isopentyl ether. These partition coefficient databases are analyzed using the solvation parameter model facilitating a quantitative comparison of the dimethyl sulfoxide-based partition systems with other totally organic partition systems. Dimethyl sulfoxide is a moderately cohesive solvent, reasonably dipolar/polarizable and strongly hydrogen-bond basic. Although generally considered to be non-hydrogen-bond acidic, analysis of the partition coefficient database strongly supports reclassification as a weak hydrogen-bond acid in agreement with recent literature. The system constants for the n-heptane-dimethyl sulfoxide biphasic system provide an explanation of the mechanism for the selective isolation of polycyclic aromatic compounds from mixtures containing low-polarity hydrocarbons based on the capability of the polar interactions (dipolarity/polarizability and hydrogen-bonding) to overcome the opposing cohesive forces in dimethyl sulfoxide that are absent for the interactions with hydrocarbons of low polarity. In addition, dimethyl sulfoxide-organic solvent systems afford a complementary approach to other totally organic biphasic partition systems for descriptor measurements of compounds virtually insoluble in water. Copyright © 2011 Elsevier B.V. All rights reserved.

β-Sitosterol and flavonoids isolated from Bauhinia malabarica found during screening for Wnt signaling inhibitory activity.

PubMed

Park, Hyun Young; Toume, Kazufumi; Arai, Midori A; Koyano, Takashi; Kowithayakorn, Thaworn; Ishibashi, Masami

2014-01-01

Screening with a cell-based luciferase assay was conducted to identify bioactive natural products which inhibit Wnt signaling activity-guided separation of an MeOH extract of Bauhinia malabarica (Caesalpiniaceae) leaves yielded five compounds, which were identified as β-sitosterol (1), quercetin (2), 6,8-C-dimethyl kaempferol-3-O-rhamnopyranoside (3), hyperin (4), and 6,8-C-dimethyl kaempferol-3-methyl ether (5). The tested compounds 1, 3, and 5 exhibited Wnt signaling inhibitory activity, with IC50 values of 0.77, 0.74, and 16.6 μM, respectively.

Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO.

PubMed

Boronat, Mercedes; Martínez-Sánchez, Cristina; Law, David; Corma, Avelino

2008-12-03

The mechanism of methanol carbonylation at different positions of zeolite MOR is investigated by quantum-chemical methods in order to discover which are the active sites that can selectively catalyze the desired reaction. It is shown that when methanol carbonylation competes with hydrocarbon formation, the first reaction occurs preferentially within 8MR channels. However, the unique selectivity for the carbonylation of methanol and dimethyl ether in mordenite is not only due to the size of the 8MR channel: neither process occurs equally at the two T3-O31 and T3-O33 positions. We show that only the T3-O33 positions are selective and that this selectivity is due to the unusual orientation of the methoxy group in relation to the 8MR channel (parallel to the cylinder axis). Only in this situation does the transition state for the attack of CO fit perfectly in the 8MR channel, while the reaction with methanol or DME is sterically impeded. This result explains why T3-O31, while also located in the 8MR channel of mordenite, is not as selective as the T3-O33 position and why ferrierite, although it contains 8MR channels, is less selective than mordenite. The competing effect of water is explained at the molecular level, and the molecular microkinetic reaction model has been established.

Emission reduction potential of using gas-to-liquid and dimethyl ether fuels on a turbocharged diesel engine.

PubMed

Xinling, Li; Zhen, Huang

2009-03-15

A study of engine performance characteristics and both of regulated (CO, HC, NO(x), and smoke) and unregulated (ultrafine particle number, mass concentrations and size distribution) emissions for a turbocharged diesel engine fueled with conventional diesel, gas-to-liquid (GTL) and dimethyl ether (DME) fuels respectively at different engine loads and speeds have been carried out. The results indicated that fuel components significantly affected the engine performance and regulated/unregulated emissions. GTL exhibited almost the same power and torque output as diesel, while improved fuel economy. GTL significantly reduced regulated emissions with average reductions of 21.2% in CO, 15.7% in HC, 15.6% in NO(x) and 22.1% in smoke in comparison to diesel, as well as average reductions in unregulated emissions of total ultrafine particle number (N(tot)) and mass (M(tot)) emissions by 85.3% and 43.9%. DME can significantly increase torque and power, compared with the original diesel engine, as well as significantly reduced regulated emissions of 40.1% in HC, 48.2% in NO(x) and smoke free throughout all the engine conditions. However, N(tot) for DME is close to that for diesel. The reason is that the accumulation mode particle number emissions for DME are very low due to the characteristics of oxygen content and no C-C bond, which promotes the processes of nucleation and condensation of the semi-volatile compounds in the exhaust gas, as a result, a lot of nucleation mode particles produce.

Formation and Recondensation of Complex Organic Molecules During Protostellar Luminosity Outbursts

NASA Technical Reports Server (NTRS)

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

2016-01-01

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

NASA Astrophysics Data System (ADS)

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

2016-04-01

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

Elemental sulfur identified in urine of cheetah, Acinonyx jubatus.

PubMed

Burger, Ben V; Visser, Runine; Moses, Alvira; Le Roux, Maritha

2006-06-01

The urine of the cheetah, Acinonyx jubatus, is almost odorless, and probably for this reason, it has not attracted much attention from scientists. Using gas chromatography-mass spectrometry, we identified 27 and 37 constituents in the headspace vapor of the urine of male and female cheetah, respectively. These constituents, composed of hydrocarbons, short-chain ethers, aldehydes, saturated and unsaturated cyclic and acyclic ketones, 2-acetylfuran, dimethyl disulfide, dimethyl sulfone, phenol, myristic acid (tetradecanoic acid), urea, and elemental sulfur, are all present in the headspace vapor in very small quantities; dimethyl disulfide is present in such a low concentration that it cannot be detected by the human nose. This is only the second example of elemental sulfur being secreted or excreted by an animal. It is hypothesized that the conversion of sulfur-containing compounds in the cheetah's diet to elemental sulfur and to practically odorless dimethyl sulfone enables this carnivore to operate as if "invisible" to the olfactory world of its predators as well as its prey, which would increase its chances of survival.

40 CFR 721.3550 - Dipropylene glycol dimethyl ether.

Code of Federal Regulations, 2010 CFR

2010-07-01

... described in paragraph (a)(2) of this section. This class 2 substance is exempt from the notification...′-oxybis[1-methoxy- (CAS No. 189354-80-1), which is one of the possible products of the manufacturing... as specified in § 721.63 (a)(1), (a)(2)(i), and (a)(3). (ii) Industrial, commercial, and consumer...

Application of a constant hole volume Sanchez-Lacombe equation of state to mixtures relevant to polymeric foaming.

PubMed

von Konigslow, Kier; Park, Chul B; Thompson, Russell B

2018-06-06

A variant of the Sanchez-Lacombe equation of state is applied to several polymers, blowing agents, and saturated mixtures of interest to the polymer foaming industry. These are low-density polyethylene-carbon dioxide and polylactide-carbon dioxide saturated mixtures as well as polystyrene-carbon dioxide-dimethyl ether and polystyrene-carbon dioxide-nitrogen ternary saturated mixtures. Good agreement is achieved between theoretically predicted and experimentally determined solubilities, both for binary and ternary mixtures. Acceptable agreement with swelling ratios is found with no free parameters. Up-to-date pure component Sanchez-Lacombe characteristic parameters are provided for carbon dioxide, dimethyl ether, low-density polyethylene, nitrogen, polylactide, linear and branched polypropylene, and polystyrene. Pure fluid low-density polyethylene and nitrogen parameters exhibit more moderate success while still providing acceptable quantitative estimations. Mixture estimations are found to have more moderate success where pure components are not as well represented. The Sanchez-Lacombe equation of state is found to correctly predict the anomalous reversal of solubility temperature dependence for low critical point fluids through the observation of this behaviour in polystyrene nitrogen mixtures.

On the temperature dependence of flammability limits of gases.

PubMed

Kondo, Shigeo; Takizawa, Kenji; Takahashi, Akifumi; Tokuhashi, Kazuaki

2011-03-15

Flammability limits of several combustible gases were measured at temperatures from 5 to 100 °C in a 12-l spherical flask basically following ASHRAE method. The measurements were done for methane, propane, isobutane, ethylene, propylene, dimethyl ether, methyl formate, 1,1-difluoroethane, ammonia, and carbon monoxide. As the temperature rises, the lower flammability limits are gradually shifted down and the upper limits are shifted up. Both the limits shift almost linearly to temperature within the range examined. The linear temperature dependence of the lower flammability limits is explained well using a limiting flame temperature concept at the lower concentration limit (LFL)--'White's rule'. The geometric mean of the flammability limits has been found to be relatively constant for many compounds over the temperature range studied (5-100 °C). Based on this fact, the temperature dependence of the upper flammability limit (UFL) can be predicted reasonably using the temperature coefficient calculated for the LFL. However, some compounds such as ethylene and dimethyl ether, in particular, have a more complex temperature dependence. Copyright © 2011 Elsevier B.V. All rights reserved.

Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2

NASA Astrophysics Data System (ADS)

Bennett, David A.; Cargnello, Matteo; Diroll, Benjamin T.; Murray, Christopher B.; Vohs, John M.

2016-12-01

Structure-activity relationships and the influence of particle size and shape on the partial- and photo-oxidation of methanol on nanocrystalline anatase TiO2 were investigated using temperature-programmed desorption. The study employed two distinct nanoparticle morphologies: truncated bipyramids exposing primarily {101} facets, and flatter platelets exposing primarily {001} surfaces, whose nominal sizes ranged from 10 to 25 nm. The platelets were found to be more active for thermally-driven reactions, such as coupling of methoxide groups to produce dimethyl ether, and deoxygenation to produce methane. A dependence of the reactivity of {001} facets for the coupling of methoxide groups to produce dimethyl ether on facet size was also observed. In contrast to the thermally-driven reactions, the bipyramidal nanoparticles were observed to be more active for a range of photochemical reactions, including oxidation and coupling to produce methyl formate, and photo-decomposition of surface methoxide species. This study also shows how well-defined nanocrystals can be used to help bridge the materials gap between studies of single crystal model catalysts and their high surface area industrial analogs.

System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers

NASA Astrophysics Data System (ADS)

Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N.; Economou, Ioannis G.; Maginn, Edward J.

2016-08-01

Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

DOEpatents

Ramprasad, D.; Waller, F.J.

1999-04-06

This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1999-01-01

This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

Ether-based nonflammable electrolyte for room temperature sodium battery

NASA Astrophysics Data System (ADS)

Feng, Jinkui; Zhang, Zhen; Li, Lifei; Yang, Jian; Xiong, Shenglin; Qian, Yitai

2015-06-01

Safety problem is one of the key points that hinder the development of room temperature sodium batteries. In this paper, four well-known nonflammable organic compounds, Trimethyl Phosphate (TMP), Tri(2,2,2-trifluoroethyl) phosphite (TFEP), Dimethyl Methylphosphonate (DMMP), Methyl nonafluorobuyl Ether (MFE), are investigated as nonflammable solvents in sodium batteries for the first time. Among them, MFE is stable towards sodium metal at room temperature. The electrochemical properties and electrode compatibility of MFE based electrolyte are investigated. Both Prussian blue cathode and carbon nanotube anode show good electrochemical performance retention in this electrolyte. The results suggest that MFE is a promising option as nonflammable electrolyte additive for sodium batteries.

FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

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

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

2016-04-10

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The modelmore » calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.« less

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

75 FR 4288 - Oxirane, 2-Methyl-, Polymer with Oxirane, Dimethyl Ether; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-27

... a finite tolerance is not necessary to ensure that there is a reasonable certainty that no harm will... composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in 40 CFR 723.250(d...

Assessment of Current and Future Air Pollutant Emission Reduction Technologies for Marine Diesel Engines

DTIC Science & Technology

2014-02-01

33 6.3.1 Biodiesel ...6.3 Alternative Fuels There is some consideration of alternatives to liquid fossil oil fuels for the marine industry. Three of these are biodiesel ...Liquefied Natural Gas and Methanol – Dimethyl Ether. 6.3.1 Biodiesel An extensive review across many transportation sectors of the emissions of

Dimethyl ether electro-oxidation on platinum surfaces

DOE PAGES

Roling, Luke T.; Herron, Jeffrey A.; Budiman, Winny; ...

2016-02-27

A first-principles density functional theory study was performed in this paper to elucidate the mechanism of dimethyl ether electro-oxidation on three low-index platinum surfaces (Pt(111), Pt(100), and Pt(211)). The goal of this study is to provide a fundamental explanation for the high activity observed experimentally on Pt(100) compared to Pt(111) and stepped surfaces. We determine that the enhanced activity of Pt(100) stems from more facile C–O bond breaking kinetics, as well as from easier removal of CO as a surface poison through activation of water. In general, the C–O bond (in CH xOCH y) becomes easier to break as dimethylmore » ether is dehydrogenated to a greater extent. In contrast, dehydrogenation becomes more difficult as more hydrogen atoms are removed. We perform two analyses of probable reaction pathways, which both identify CHOC and CO as the key reaction intermediates on these Pt surfaces. We show that the reaction mechanism on each surface is dependent on the cell operating potential, as increasing the potential facilitates C–H bond scission, in turn promoting the formation of intermediates for which C–O scission is more facile. We additionally demonstrate that CO oxidation determines the high overpotential required for electro-oxidation on Pt surfaces. Finally, at practical operating potentials (~0.60 V RHE), we determine that C–O bond breaking is most likely the most difficult step on all three Pt surfaces studied.« less

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes

PubMed Central

2017-01-01

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions. PMID:28656757

Role of solvents on the oxygen reduction and evolution of rechargeable Li-O2 battery

NASA Astrophysics Data System (ADS)

Christy, Maria; Arul, Anupriya; Zahoor, Awan; Moon, Kwang Uk; Oh, Mi Young; Stephan, A. Manuel; Nahm, Kee Suk

2017-02-01

The choice of electrolyte solvent is expected to play a key role in influencing the lithium-oxygen battery performance. The electrochemical performances of three electrolytes composed of lithium bis (trifluoromethane sulfonyl) imide (LiTFSI) salt and different solvents namely, ethylene carbonate/propylene carbonate (EC/PC), tetra ethylene glycol dimethyl ether (TEGDME) and dimethyl sulfoxide (DMSO) are investigated by assembling lithium oxygen cells. The electrolyte composition significantly varied the specific capacity of the battery. The choice of electrolyte also influences the overpotential, cycle life, and rechargeability of the battery. Electrochemical impedance spectra, cyclic voltammetry, and chronoamperometry were utilized to determine the reversible reactions associated with the air cathode.

Mathematical Modeling and Optimization of Gaseous Fuel Processing as a Basic Technology for Long-distance Energy Transportation: The Use of Methanol and Dimethyl Ether as Energy Carriers.

NASA Astrophysics Data System (ADS)

Tyurina, E. A.; Mednikov, A. S.

2017-11-01

The paper presents the results of studies on the perspective technologies of natural gas conversion to synthetic liquid fuel (SLF) at energy-technology installations for combined production of SLF and electricity based on their detailed mathematical models. The technologies of the long-distance transport of energy of natural gas from large fields to final consumers are compared in terms of their efficiency. This work was carried out at Melentiev Energy Systems Institute of Siberian Branch of the Russian Academy of Sciences and supported by Russian Science Foundation via grant No 16-19-10174

Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state

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

Morini, Filippo; Deleuze, Michael Simon, E-mail: michael.deleuze@uhasselt.be; Watanabe, Noboru

The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b{sub 1}, 6a{sub 1}, 4b{sub 2}, and 1a{sub 2} orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point outmore » in particular the most appreciable role which is played by a few specific molecular vibrations of A{sub 1}, B{sub 1}, and B{sub 2} symmetries, which correspond to C–H stretching and H–C–H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.« less

Dimethyl ether (DME) as an alternative fuel

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.; Greene, Howard L.

With ever growing concerns on environmental pollution, energy security, and future oil supplies, the global community is seeking non-petroleum based alternative fuels, along with more advanced energy technologies (e.g., fuel cells) to increase the efficiency of energy use. The most promising alternative fuel will be the fuel that has the greatest impact on society. The major impact areas include well-to-wheel greenhouse gas emissions, non-petroleum feed stocks, well-to-wheel efficiencies, fuel versatility, infrastructure, availability, economics, and safety. Compared to some of the other leading alternative fuel candidates (i.e., methane, methanol, ethanol, and Fischer-Tropsch fuels), dimethyl ether appears to have the largest potential impact on society, and should be considered as the fuel of choice for eliminating the dependency on petroleum. DME can be used as a clean high-efficiency compression ignition fuel with reduced NO x, SO x, and particulate matter, it can be efficiently reformed to hydrogen at low temperatures, and does not have large issues with toxicity, production, infrastructure, and transportation as do various other fuels. The literature relevant to DME use is reviewed and summarized to demonstrate the viability of DME as an alternative fuel.

System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO{sub 2}, n-alkanes, and poly(ethylene glycol) dimethyl ethers

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

Moultos, Othonas A.; Economou, Ioannis G.; Zhang, Yong

Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO{sub 2}, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH{sub 3}O–(CH{sub 2}CH{sub 2}O){sub n}–CH{sub 3} with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. Themore » magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.« less

Relevant Features of a Triethylene Glycol Dimethyl Ether-Based Electrolyte for Application in Lithium Battery.

PubMed

Carbone, Lorenzo; Di Lecce, Daniele; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steve; Hassoun, Jusef

2017-05-24

Triethylene glycol dimethyl ether (TREGDME) dissolving lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) is studied as a suitable electrolyte medium for lithium battery. Thermal and rheological characteristics, transport properties of the dissolved species, and the electrochemical behavior in lithium cell represent the most relevant investigated properties of the new electrolyte. The self-diffusion coefficients, the lithium transference numbers, the ionic conductivity, and the ion association degree of the solution are determined by pulse field gradient nuclear magnetic resonance and electrochemical impedance spectroscopy. The study sheds light on the determinant role of the lithium nitrate (LiNO 3 ) addition for allowing cell operation by improving the electrode/electrolyte interfaces and widening the voltage stability window. Accordingly, an electrochemical activation procedure of the Li/LiFePO 4 cell using the upgraded electrolyte leads to the formation of stable interfaces at the electrodes surface as clearly evidenced by cyclic voltammetry, impedance spectroscopy, and ex situ scanning electron microscopy. Therefore, the lithium battery employing the TREGDME-LiCF 3 SO 3 -LiNO 3 solution shows a stable galvanostatic cycling, a high efficiency, and a notable rate capability upon the electrochemical conditions adopted herein.

Rotational Investigation of the Adducts of Formic Acid with Alcohols, Ethers and Esters

NASA Astrophysics Data System (ADS)

Evangelisti, Luca; Spada, Lorenzo; Li, Weixing; Caminati, Walther

2016-06-01

Mixtures of formic acid with methyl alcohol, with isopropyl alcohol, with tert-butyl alcohol, with dimethylether and with isopropylformiate have been supersonically expanded as pulsed jets. The obtained cool plumes have been analyzed by Fourier transform microwave spectroscopy. It has been possible to assign the rotational spectra of the 1:1 adducts of formic acid with tert-butyl alcohol, with dimethyl ether and with isopropylformiate. The conformational shapes and geometries of these adducts, as well as the topologies of their itermolecular hydrogen bonds will be presented. An explanation is given of the failure of the assignments of the rotational spectra of the adducts of formic acid with methyl alcohol and isopropyl alcohol.

Dimethyl Sulfide-Dimethyl Ether and Ethylene Oxide-Ethylene Sulfide Complexes Investigated by Fourier Transform Microwave Spectroscopy and AB Initio Calculation

NASA Astrophysics Data System (ADS)

Kawashima, Yoshiyuki; Tatamitani, Yoshio; Mase, Takayuki; Hirota, Eizi

2015-06-01

The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type transitions were assigned for the normal, 34S, and three 13C species of the DMS-DME and a-type and b-type rotational transitions for the normal, 34S, and two 13C species of the EO-ES. The observed transitions were analyzed by using an S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)---O and one S---H-C(DME) hydrogen bonds. The barrier height V3 to internal rotation of the "free" methyl group in the DME was determined to be 915.4 (23) wn, which is smaller than that of the DME monomer, 951.72 (70) wn, and larger than that of the DME dimer, 785.4 (52) wn. For the EO-ES complex the observed data were interpreted in the terms of an antiparallel Cs geometry with the EO bound to the ES by two C-H(ES)---O and two S---H-C(EO) hydrogen bonds. We have applied a natural bond orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ΔEσσ*), which were closely correlated with the binding energy EB, as found for other related complexes. Y. Niide and M. Hayashi, J. Mol. Spectrosc. 220, 65-79 (2003). Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, J. Am. Chem. Soc. 124, 2739-2743 (2002).

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 11, January 1--March 31, 1997

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

NONE

1997-06-11

During this quarter, the third draft of the Topical Report on Process Economics Studies was issued for review. A recommendation to continue with design verification testing on the coproduction of methanol and dimethyl ether (DME) was made. A liquid phase dimethyl ether (LPDME) catalyst system with reasonable long-term activity and stability is being developed, and a decision to proceed with a proof-of-concept test run at the LaPorte Alternative Fuels Development Unit (AFDU) is pending the release of a memo from Air Products on the catalyst targets and corresponding economics for a commercially successful LPDME catalyst. The off-site product-use test planmore » is to be updated in June of 1997. During this quarter, Air Products and Acurex Environmental Corporation continued developing the listing of product-use test participants who are involved in fuel cell, transportation, and stationary power plant applications. Start-up activities (Task 3.1) began during the reporting period, and coal-derived synthesis gas (syngas) was introduced to the demonstration unit. The recycle compressor was tested successfully on syngas at line pressure of 700 psig, and the reactor loop reached 220 C for carbonyl burnout. Iron carbonyl in the balanced gas feed remained below the 10 ppbv detection limit for all samples but one. Within the reactor loop, iron carbonyl levels peaked out near 200 ppbv after about 40 hours on-stream, before decreasing to between 10--20 ppbv at 160 hours on -stream. Nickel carbonyl measurements reached a peak of about 60 ppbv, and decreased at all sampling locations to below the 10 ppbv detection limit by 70 hours on-stream. Catalyst activation of the nine 2,250 lb batches required for the initial catalyst charge began and concluded. All batches met or slightly exceeded the theoretical maximum uptake of 2.82 SCF of reducing gas/lb catalyst.« less

Conversion of Dimethyl Ether to Branched Hydrocarbons Over Cu/BEA: the Roles of Lewis Acidic and Metallic Sites in H2 Incorporation

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

Hensley, Jesse E.; Schaidle, Joshua A.; Ruddy, Daniel A.

2017-04-26

Conversion of biomass to fuels remains as one of the most promising approach to support our energy needs. It has been previously shown that the gasification of non-edible cellulosic biomass can be used to derive fuels like methanol and dimethyl ether (DME). However, the use of methanol and DME is limited due to the fact that they have low energy densities, poor lubricity and lower viscosity when compared to long-chain hydrocarbons. Increasing the blending percentage can also lead to undesired amounts of oxygenated molecules in the transportation fuel infrastructure, which restrict their applicability as jet or diesel fuels. Consequently, themore » petroleum-derived hydrocarbons remain as the main constituent of the middle-distillate based fuels. One way to increase the share of biofuels in middle-distillates is to use methanol/DME as building blocks for producing renewable, energy-dense hydrocarbons. One way to achieve this is by catalytically converting the DME and methanol to light olefins, followed by oligomerization to higher molecular weight premium alkanes, which can directly be used as kerosene/diesel fuels. Here, we report the catalytic dimerization of biomass-derived deoxygenated olefins into transportation fuel-range hydrocarbons under liquid-phase stirred-batch conditions. Specifically, the effect of operating conditions, such as reaction temperature, solvent-type, reaction duration and olefin-structure, on the conversion, selectivity and kinetics of dimerization of triptene (2,3,3-trimethyl-1-butene) were investigated. Triptene, as previously reported, is one of the major products of DME-homologation reaction over a BEA zeolite4. We show that triptene can be converted to high quality middle-distillates using a commercially available ion-exchange acid resin, Amberlyst-35 (dry) by the process of catalytic dimerization.« less

Persubstituted p-benzoquinone monoxime alkyl ethers and their molecular structure

NASA Astrophysics Data System (ADS)

Slaschinin, D. G.; Alemasov, Y. A.; Ilushkin, D. I.; Sokolenko, W. A.; Tovbis, M. S.; Kirik, S. D.

2012-05-01

Theoretical and experimental approaches were applied for the investigation of the reactivity of persubstituted 4-nitrosophenols in the reaction with alkyl iodides, in particular the potassium salt of 2,6-di(alkoxycarbonyl)-3,5-dimethyl-4-nitrosophenol. Hartre-Fock calculations showed that the anion negative charge was located mostly on the oxygen of hydroxyl group, while estimation of the total energy of the alkylated products pointed out the benefit of alkylation on the oxygen atom of the nitroso group yielding p-benzoquinone monoxime alkyl ethers. Methylation and ethylation of persubstituted nitrosophenols were carried out. The products obtained were investigated using X-ray diffraction, 1Н NMR spectroscopy and mass spectrometry. The crystal structure of the methyl ether of 2,6-di(alkoxycarbonyl)-3,5-dimethyl-1,4-benzoquinone-1-oxime (С15H19NO6) (I) was determined by the X-ray powder diffraction technique. The unit cell parameters were: a = 7.3322(6) Å, b = 10.5039(12) Å, c = 21.1520(20) Å, β = 93.742(6)°, V = 1625.58(2) Å3Z = 4, Sp.Gr. P21/c. The structure modeling was made in direct space by the Monte-Carlo approach using rigid and soft restrictions. The structure refinement was completed by the Rietveld method. It was established that the alkylation occurred on the oxygen atom of the nitroso group. The molecules (I) in the crystal structure were packed in columns along the axis a with pairwise convergence in a column up to the distance of 3.63 Å due to a 180° turn of every second molecule around the column axis. In the molecular structure the methyloxime group was oriented in the benzene plane and had π-conjugation with the ring. The ethoxycarbonyl groups were turned nearly perpendicular to the ring. Other compounds obtained had the structure of the alkyl ethers of 1.4-benzoquinone-1-oxime, which was proved by 1Н NMR spectroscopy and mass-spectrometry.

Poly(aryl ethers) and related polysiloxane copolymer molecular coatings: Preparation and radiation degradation

NASA Technical Reports Server (NTRS)

Mcgrath, J. E.

1982-01-01

The radiation degradation of poly(arylene ether sulfones) and related materials is studied. These basic studies are important both as a means to developing stronger, more stable matrix resins for composite materials, as well as to improve the data base in regard to chemical structure-physical property relationships. Thirty homo and copolymers were synthesized, at least partially characterized and, in several cases suitable film casting techniques were developed. Four samples were chosen for initial radiation degradation. Poly(dimethyl siloxane) soft bocks/segments can preferentially migrate to the surface of copolymer films. Since siloxanes are utilized as thermal control coatings, this form of 'molecular' coating is of interest. The chemistry for preparing such copolymers with any of the polymers described was demonstrated.

Fuel Surrogate Physical Property Effects on Direct Injection Spray and Ignition Behavior

DTIC Science & Technology

2015-09-01

of fuel density and the energy required to vaporize the liquid fuel. Genzale et al. [11] compared diesel and biodiesel sprays under conditions...relevant to late-cycle post-injection conditions and showed ~15 % longer liquid penetration length for biodiesel . Kook and Pickett [12] tested various...emissions, and spray characteristics to the properties of alternative diesel fuels, such as dimethyl ether (DME), biodiesel , and jet fuel, which are

Development of GREET Catalyst Module

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

Wang, Zhichao; Benavides, Pahola T.; Dunn, Jennifer B.

2015-09-01

In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al 2O3, and Pt/ γ-Al 2O 3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

PubMed Central

Kim, Moon Suk; Lee, Sang Bong

2014-01-01

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively. PMID:28788147

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers.

PubMed

Kim, Moon Suk; Lee, Sang Bong

2014-07-31

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF₆). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO > GME > GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

Repellent activity of estrogenic compounds toward zoospores of the phytopathogenic fungus Aphanomyces cochlioides.

PubMed

Islam, M T; Tahara, S

2001-01-01

Screening chemical compounds, we found that a xenoestrogen, bisphenol A, showed potent repellent activity against the zoospores of Aphanomyces cochlioides. Based on this finding, we tested a number of androgenic and estrogenic compounds (e.g. testosterone, progesterone, estradiols, diethylstilbestrol, estrone, estriol, pregnenolone, dienestrol etc.) on the motility behavior of A. cochlioides zoospores. Interestingly, most of the estrogenic compounds exhibited potent repellent activity (1 microg/ml or less by the "particle method") toward the motile zoospores of A. cochlioides. We derivatized some of the estrogens and discussed the relationship between the structure of active molecules and their repellent activity. Apparently, aromatization of the A ring with a free hydroxyl group at C-3 position of a steroidal structure is necessary for higher repellent activity. Interestingly, methylation of diethylstilbestrol (DES) yielded completely different activity i.e. both mono- and di-methyl ethers of DES showed attractant activity. Moreover, the attracted zoospores were encysted and then germinated in the presence of di-methyl ether of DES. The potential usefulness of this repellent test is discussed for the detection of estrogenic activity of naturally occurring compounds, and the possible role of phytoestrogens in host/parasite interactions. So far, this will be the first report of repellent activity of estrogenic compounds toward trivial fungal zoospores.

A Pulsed Plasma Thruster Using Dimethyl Ether as Propellant

NASA Astrophysics Data System (ADS)

Masui, Souichi; Okada, Terumasa; Kitatomi, Makoto; Kakami, Akira; Tachibana, Takeshi

The pulsed plasma thruster (PPT), has attracted attention again as a micro-thruster because of its compactness, light weight, and comparatively low power consumption. On the other hand, the propellant utilization efficiency of a conventinal Teflon PPT is relatively low among electric propulsion devices because a propellant that originates from late-time ablation produces negligible thrust. The liquid propellant PPT (LP-PPT), in which water or ethanol is fed with an injector, was proposed to overcome these difficulties. Thrust measurements show that a LP-PPT provides higher specific impulses than a conventional PPT. However, water requires temperature management for propellant storage due to its relatively high freezing point. Moreover, even if ethanol, which has a sufficiently low freezing point, is used as propellant, a pressurant is necessary, as well as water, because the vapor pressures are insufficient for self-pressurization. In this study, we propose to use dimethyl ether (DME) as the propellant. DME, which has a freezing point of 131 K at 1 atm and a vapor pressure of 6 atm at 298 K, can be stored in tanks as a liquid, and requires no feeding pressurant. We designed a DME pulsed plasma thruster to evaluate performance. Thrust measurement yielded a specific impulse of 430 s for a coaxial type at a capacitor-stored energy of 13 J.

Ternary PtRuPd/C catalyst for high-performance, low-temperature direct dimethyl ether fuel cells

DOE PAGES

Dumont, Joseph Henry; Martinez, Ulises; Chung, Hoon T.; ...

2016-08-19

Here, dimethyl ether (DME) is a promising alternative fuel option for direct-feed low-temperature fuel cells. Until recently, DME had not received the same attention as alcohol fuels, such as methanol or ethanol, despite its notable advantages. These advantages include a high theoretical open-cell voltage (1.18 V at 25 °C) that is similar to that of methanol (1.21 V), much lower toxicity than methanol, and no need for the carbon–carbon bond scission that is needed in ethanol oxidation. DME is biodegradable, has a higher energy content than methanol (8.2 vs. 6.1 kWh kg –1), and, like methanol, can be synthesized frommore » recycled carbon dioxide. Although the performance of direct DME fuel cells (DDMEFCs) has progressed over the past few years, DDMEFCs have not been viewed as fully viable. In this work, we report much improved performance from the ternary Pt 55Ru 35Pd 10/C anode catalyst, allowing DDMEFCs to compete directly with direct methanol fuel cells (DMFCs). We also report results involving binary Pt alloys as reference catalysts and an in situ infrared electrochemical study to better understand the mechanism of DME electro-oxidation on ternary PtRuPd/C catalysts.« less

Partial oxidation of dimethyl ether using the structured catalyst Rh/Al2O3/Al prepared through the anodic oxidation of aluminum.

PubMed

Yu, B Y; Lee, K H; Kim, K; Byun, D J; Ha, H P; Byun, J Y

2011-07-01

The partial oxidation of dimethyl ether (DME) was investigated using the structured catalyst Rh/Al2O3/Al. The porous Al2O3 layer was synthesized on the aluminum plate through anodic oxidation in an oxalic-acid solution. It was observed that about 20 nm nanopores were well developed in the Al2O3 layer. The thickness of Al2O3 layer can be adjusted by controlling the anodizing time and current density. After pore-widening and hot-water treatment, the Al2O3/Al plate was calcined at 500 degrees C for 3 h. The obtained delta-Al2O3 had a specific surface area of 160 m2/g, making it fit to be used as a catalyst support. A microchannel reactor was designed and fabricated to evaluate the catalytic activity of Rh/Al2O3/Al in the partial oxidation of DME. The structured catalyst showed an 86% maximum hydrogen yield at 450 degrees C. On the other hand, the maximum syngas yield by a pack-bed-type catalyst could be attained by using a more than fivefold Rh amount compared to that used in the structured Rh/Al2O3/Al catalyst.

Cannabidiol-2',6'-dimethyl ether as an effective protector of 15-lipoxygenase-mediated low-density lipoprotein oxidation in vitro.

PubMed

Takeda, Shuso; Hirayama, Akari; Urata, Shino; Mano, Nobutaka; Fukagawa, Keiko; Imamura, Midori; Irii, Ayumi; Kitajima, Satomi; Masuyama, Tomoko; Nomiyama, Mai; Tatei, Sachiko; Tomita, Saari; Kudo, Taichi; Noguchi, Momoko; Yamaguchi, Yasuhiro; Okamoto, Yoshiko; Amamoto, Toshiaki; Fukunishi, Yoshifumi; Watanabe, Kazuhito; Omiecinski, Curtis John; Aramaki, Hironori

2011-01-01

15-Lipoxygenase (15-LOX) is one of the key enzymes responsible for the formation of oxidized low-density lipoprotein (ox-LDL), a major causal factor for atherosclerosis. Both enzymatic (15-LOX) and non-enzymatic (Cu(2+)) mechanisms have been proposed for the production of ox-LDL. We have recently reported that cannabidiol-2',6'-dimethyl ether (CBDD) is a selective and potent inhibitor of 15-LOX-catalyzed linoleic acid oxygenation (Takeda et al., Drug Metab. Dispos., 37, 1733-1737 (2009)). In the LDL, linoleic acid is present as cholesteryl linoleate, the major fatty acid esterified to cholesterol, and is susceptible to oxidative modification by 15-LOX or Cu(2+). In this investigation, we examined the efficacy of CBDD on i) 15-LOX-catalyzed oxygenation of cholesteryl linoleate, and ii) ox-LDL formation catalyzed by 15-LOX versus Cu(2+)-mediated non-enzymatic generation of this important mediator. The results obtained demonstrate that CBDD is a potent and selective inhibitor of ox-LDL formation generated by the 15-LOX pathway. These studies establish CBDD as both an important experimental tool for characterizing 15-LOX-mediated ox-LDL formation, and as a potentially useful therapeutic agent for treatment of atherosclerosis.

Cannabidiol-2′,6′-dimethyl Ether as an Effective Protector of 15-Lipoxygenase-Mediated Low-Density Lipoprotein Oxidation in Vitro

PubMed Central

Takeda, Shuso; Hirayama, Akari; Urata, Shino; Mano, Nobutaka; Fukagawa, Keiko; Imamura, Midori; Irii, Ayumi; Kitajima, Satomi; Masuyama, Tomoko; Nomiyama, Mai; Tatei, Sachiko; Tomita, Saari; Kudo, Taichi; Noguchi, Momoko; Yamaguchi, Yasuhiro; Okamoto, Yoshiko; Amamoto, Toshiaki; Fukunishi, Yoshifumi; Watanabe, Kazuhito; Omiecinski, Curtis John; Aramaki, Hironori

2014-01-01

15-Lipoxygenase (15-LOX) is one of the key enzymes responsible for the formation of oxidized low-density lipoprotein (ox-LDL), a major causal factor for atherosclerosis. Both enzymatic (15-LOX) and non-enzymatic (Cu2+) mechanisms have been proposed for the production of ox-LDL. We have recently reported that cannabidiol-2′,6′-dimethyl ether (CBDD) is a selective and potent inhibitor of 15-LOX-catalyzed linoleic acid oxygenation (Takeda et al., Drug Metab. Dispos., 37, 1733–1737 (2009)). In the LDL, linoleic acid is present as cholesteryl linoleate, the major fatty acid esterified to cholesterol, and is susceptible to oxidative modification by 15-LOX or Cu2+. In this investigation, we examined the efficacy of CBDD on i) 15-LOX-catalyzed oxygenation of cholesteryl linoleate, and ii) ox-LDL formation catalyzed by 15-LOX versus Cu2+-mediated non-enzymatic generation of this important mediator. The results obtained demonstrate that CBDD is a potent and selective inhibitor of ox-LDL formation generated by the 15-LOX pathway. These studies establish CBDD as both an important experimental tool for characterizing 15-LOX-mediated ox-LDL formation, and as a potentially useful therapeutic agent for treatment of atherosclerosis. PMID:21804214

Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether.

PubMed

Moshammer, Kai; Jasper, Ahren W; Popolan-Vaida, Denisia M; Wang, Zhandong; Bhavani Shankar, Vijai Shankar; Ruwe, Lena; Taatjes, Craig A; Dagaut, Philippe; Hansen, Nils

2016-10-04

This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015 , 119 , 7361 - 7374 ] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450-1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH 2 OCH 2 O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H 2 O 2 , HCOOH, CH 3 OCHO, and CH 3 OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

Conceptual Design of Low-Temperature Hydrogen Production and High-Efficiency Nuclear Reactor Technology

NASA Astrophysics Data System (ADS)

Fukushima, Kimichika; Ogawa, Takashi

Hydrogen, a potential alternative energy source, is produced commercially by methane (or LPG) steam reforming, a process that requires high temperatures, which are produced by burning fossil fuels. However, as this process generates large amounts of CO2, replacement of the combustion heat source with a nuclear heat source for 773-1173K processes has been proposed in order to eliminate these CO2 emissions. In this paper, a novel method of nuclear hydrogen production by reforming dimethyl ether (DME) with steam at about 573K is proposed. From a thermodynamic equilibrium analysis of DME steam reforming, the authors identified conditions that provide high hydrogen production fraction at low pressure and temperatures of about 523-573K. By setting this low-temperature hydrogen production process upstream from a turbine and nuclear reactor at about 573K, the total energy utilization efficiency according to equilibrium mass and heat balance analysis is about 50%, and it is 75%for a fast breeder reactor (FBR), where turbine is upstream of the reformer.

Life cycle assessment of biomethane use in Argentina.

PubMed

Morero, Betzabet; Groppelli, Eduardo; Campanella, Enrique A

2015-04-01

Renewable substitutes for natural gas, such as biogas, require adequate treatment to remove impurities. This paper presents the life cycle and environmental impact of upgrading biogas using absorption-desorption process with three different solvents: water, diglycolamine and polyethylene glycol dimethyl ether. The results showed that water produces a minor impact in most of the considered categories, and an economic analysis showed that water is the most feasible solvent for obtaining the lowest payback period. This analysis includes three different sources for biogas production and two end uses for biomethane. The use of different wastes as sources results in different environmental impacts depending on the type of energy used in the anaerobic digestion. The same situation occurs when considering the use of biomethane as a domestic fuel or for power generation. Using energy from biogas to replace conventional energy sources in production and upgrading biogas significantly reduce the environmental impacts of processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Instruments for preparation of heterogeneous catalysts by an impregnation method

NASA Astrophysics Data System (ADS)

Yamada, Yusuke; Akita, Tomoki; Ueda, Atsushi; Shioyama, Hiroshi; Kobayashi, Tetsuhiko

2005-06-01

Instruments for the preparation of heterogeneous catalysts in powder form have been developed. The instruments consist of powder dispensing robot and an automated liquid handling machine equipped with an ultrasonic and a vortex mixer. The combination of these two instruments achieves the catalyst preparation by incipient wetness and ion exchange methods. The catalyst library prepared with these instruments were tested for dimethyl ether steam reforming and characterized by transmission electron microscopy observations.

40 CFR Appendix A to Part 355 - The List of Extremely Hazardous Substances and Their Threshold Planning Quantities

Code of Federal Regulations, 2011 CFR

2011-07-01

... Trifluoride Compound With Methyl Ether (1:1) 1,000 1,000 28772-56-7 Bromadiolone 100 100/10,000 7726-95-6...-1 Dimethyl sulfate 100 500 75-78-5 Dimethyldichlorosilane d 500 500 57-14-7 Dimethylhydrazine 10 1... 100 100 65-30-5 Nicotine Sulfate 100 100/10,000 7697-37-2 Nitric Acid 1,000 1,000 10102-43-9 Nitric...

40 CFR Appendix A to Part 355 - The List of Extremely Hazardous Substances and Their Threshold Planning Quantities

Code of Federal Regulations, 2010 CFR

2010-07-01

... Trifluoride Compound With Methyl Ether (1:1) 1,000 1,000 28772-56-7 Bromadiolone 100 100/10,000 7726-95-6...-1 Dimethyl sulfate 100 500 75-78-5 Dimethyldichlorosilane d 500 500 57-14-7 Dimethylhydrazine 10 1... 100 100 65-30-5 Nicotine Sulfate 100 100/10,000 7697-37-2 Nitric Acid 1,000 1,000 10102-43-9 Nitric...

Photosynthesis Involvement in the Mechanism of Action of Diphenyl Ether Herbicides 1

PubMed Central

Ensminger, Michael P.; Hess, F. Dan

1985-01-01

Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1′-dimethyl-4,4′-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity. PMID:16664206

Photosynthesis involvement in the mechanism of action of diphenyl ether herbicides.

PubMed

Ensminger, M P; Hess, F D

1985-05-01

Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1'-dimethyl-4,4'-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity.

Methanolobus taylorii sp nov, a new methylotropic, estuarine methanogen

USGS Publications Warehouse

Oremland, Ronald S.; Boone, David R.

1994-01-01

Strain GS-16T (T = type strain) is a methylotrophic methanogen that was isolated from estuarine sediments from San Francisco Bay (4) and has been deposited in the Oregon Collection of Methanogens (Oregon Graduate Institute, Portland) as strain OCM 5ST. This strain was isolated by using dimethyl sulfide as the catabolic substrate (4), but it can also grow on methylamines (13) and methanethiol (8, 9) and grew when it was inoculated into MSHA medium (6) supplemented with 20 mM methanol as the sole catabolic substrate. Strain GS-16T cells form methane from methylmercury (12) and dimethylselenide (16), although they cannot grow on these substrates, and form traces of ethane from diethyl sulfide (15). Methanogenesis from trimethylamine is inhibited by methyl fluoride (11) and methyl bromide (14), but not by dimethyl ether (1 1).

Characterisation of two-stage ignition in diesel engine-relevant thermochemical conditions using direct numerical simulation

DOE PAGES

Krisman, Alex; Hawkes, Evatt R.; Talei, Mohsen; ...

2016-08-30

With the goal of providing a more detailed fundamental understanding of ignition processes in diesel engines, this study reports analysis of a direct numerical simulation (DNS) database. In the DNS, a pseudo turbulent mixing layer of dimethyl ether (DME) at 400 K and air at 900 K is simulated at a pressure of 40 atmospheres. At these conditions, DME exhibits a two-stage ignition and resides within the negative temperature coefficient (NTC) regime of ignition delay times, similar to diesel fuel. The analysis reveals a complex ignition process with several novel features. Autoignition occurs as a distributed, two-stage event. The high-temperaturemore » stage of ignition establishes edge flames that have a hybrid premixed/autoignition flame structure similar to that previously observed for lifted laminar flames at similar thermochemical conditions. In conclusion, a combustion mode analysis based on key radical species illustrates the multi-stage and multi-mode nature of the ignition process and highlights the substantial modelling challenge presented by diesel combustion.« less

Experimental investigation into the oxidation reactivity and nanostructure of particulate matter from diesel engine fuelled with diesel/polyoxymethylene dimethyl ethers blends

PubMed Central

Yang, Hao; Li, Xinghu; Wang, Yan; Mu, Mingfei; Li, Xuehao; Kou, Guiyue

2016-01-01

This paper focuses on oxidation reactivity and nanostructural characteristics of particulate matter (PM) emitted from diesel engine fuelled with different volume proportions of diesel/polyoxymethylene dimethyl ethers (PODEn) blends (P0, P10 and P20). PM was collected using a metal filter from the exhaust manifold. The collected PM samples were characterized using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The TGA results indicated that the PM produced by P20 had the highest moisture and volatility contents and the fastest oxidation rate of solid carbon followed by P10 and P0 derived PM. SEM analysis showed that PM generated from P20 was looser with a lower mean value than PM emitted from P10 and P0. Quantitative analysis of high-resolution TEM images presented that fringe length was reduced along with increased separation distance and tortuosity with an increase in PODEn concentration. These trends improved the oxidation reactivity. According to Raman spectroscopy data, the intensity, full width at half-maximum and intensity ratio of the bands also changed demonstrating that PM nanostructure disorder was correlated with a faster oxidation rate. The results show the use of PODEn affects the oxidation reactivity and nanostructure of PM that is easier to oxidize. PMID:27876872

Experimental investigation into the oxidation reactivity and nanostructure of particulate matter from diesel engine fuelled with diesel/polyoxymethylene dimethyl ethers blends

NASA Astrophysics Data System (ADS)

Yang, Hao; Li, Xinghu; Wang, Yan; Mu, Mingfei; Li, Xuehao; Kou, Guiyue

2016-11-01

This paper focuses on oxidation reactivity and nanostructural characteristics of particulate matter (PM) emitted from diesel engine fuelled with different volume proportions of diesel/polyoxymethylene dimethyl ethers (PODEn) blends (P0, P10 and P20). PM was collected using a metal filter from the exhaust manifold. The collected PM samples were characterized using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The TGA results indicated that the PM produced by P20 had the highest moisture and volatility contents and the fastest oxidation rate of solid carbon followed by P10 and P0 derived PM. SEM analysis showed that PM generated from P20 was looser with a lower mean value than PM emitted from P10 and P0. Quantitative analysis of high-resolution TEM images presented that fringe length was reduced along with increased separation distance and tortuosity with an increase in PODEn concentration. These trends improved the oxidation reactivity. According to Raman spectroscopy data, the intensity, full width at half-maximum and intensity ratio of the bands also changed demonstrating that PM nanostructure disorder was correlated with a faster oxidation rate. The results show the use of PODEn affects the oxidation reactivity and nanostructure of PM that is easier to oxidize.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Chemical complexity induced by efficient ice evaporation in the Barnard 5 molecular cloud

NASA Astrophysics Data System (ADS)

Taquet, V.; Wirström, E. S.; Charnley, S. B.; Faure, A.; López-Sepulcre, A.; Persson, C. M.

2017-10-01

Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. Here we present the detection of the complex organic molecules (COMs) acetaldehyde (CH3CHO) and methyl formate (CH3OCHO), as well as formic acid (HCOOH) and ketene (CH2CO), and the tentative detection of di-methyl ether (CH3OCH3) towards the "methanol hotspot" of Barnard 5 located between two dense cores using the single dish OSO 20 m, IRAM 30 m, and NRO 45 m telescopes. The high energy cis-conformer of formic acid is detected, suggesting that formic acid is mostly formed at the surface of interstellar grains and then evaporated. The detection of multiple transitions for each species allows us to constrain their abundances through LTE and non-LTE methods. All the considered COMs show similar abundances between 1 and 10% relative to methanol depending on the assumed excitation temperature. The non-detection of glycolaldehyde, an isomer of methyl formate, with a [glycolaldehyde]/[methyl formate] abundance ratio lower than 6%, favours gas phase formation pathways triggered by methanol evaporation. According to their excitation temperatures derived in massive hot cores, formic acid, ketene, and acetaldehyde have been designated as "lukewarm" COMs whereas methyl formate and di-methyl ether were defined as "warm" species. Comparison with previous observations of other types of sources confirms that lukewarm and warm COMs show similar abundances in low-density cold gas whereas the warm COMs tend to be more abundant than the lukewarm species in warm protostellar cores. This abundance evolution suggests either that warm COMs are indeed mostly formed in protostellar environments and/or that lukewarm COMs are efficiently depleted by increased hydrogenation efficiency around protostars.

Electrochemical oxidation of hydrolyzed poly oxymethylene-dimethyl ether by PtRu catalysts on Nb-doped SnO(2-δ) supports for direct oxidation fuel cells.

PubMed

Kakinuma, Katsuyoshi; Kim, In-Tae; Senoo, Yuichi; Yano, Hiroshi; Watanabe, Masahiro; Uchida, Makoto

2014-12-24

We synthesized Pt and PtRu catalysts supported on Nb-doped SnO(2-δ) (Pt/Sn0.99Nb0.01O(2-δ), PtRu/Sn0.99Nb0.01O(2-δ)) for direct oxidation fuel cells (DOFCs) using poly oxymethylene-dimethyl ether (POMMn, n = 2, 3) as a fuel. The onset potential for the oxidation of simulated fuels of POMMn (methanol-formaldehyde mixtures; n = 2, 3) for Pt/Sn0.99Nb0.01O(2-δ) and PtRu/Sn0.99Nb0.01O(2-δ) was less than 0.3 V vs RHE, which was much lower than those of two commercial catalysts (PtRu black and Pt2Ru3/carbon black). In particular, the onset potential of the oxidation reaction of simulated fuels of POMMn (n = 2, 3) for PtRu/Sn0.99Nb0.01O(2-δ) sintered at 800 °C in nitrogen atmosphere was less than 0.1 V vs RHE and is thus considered to be a promising anode catalyst for DOFCs. The mass activity (MA) of PtRu/Sn0.99Nb0.01O(2-δ) sintered at 800 °C was more than five times larger than those of the commercial catalysts in the measurement temperature range from 25 to 80 °C. Even though the MA for the methanol oxidation reaction was of the same order as those of the commercial catalysts, the MA for the formaldehyde oxidation reaction was more than five times larger than those of the commercial catalysts. Sn from the Sn0.99Nb0.01O(2-δ) support was found to have diffused into the Pt catalyst during the sintering process. The Sn on the top surface of the Pt catalyst accelerated the oxidation of carbon monoxide by a bifunctional mechanism, similar to that for Pt-Ru catalysts.

(1RS,4SR)-3-Dichloro­methyl­ene-1,4-dimethyl-2-oxabicyclo­[2.2.2]oct-5-ene

PubMed Central

Tyrrell, Andrew J.; Feast, George C.; Robertson, Jeremy

2008-01-01

X-ray crystallography was used to confirm the structure of the enantio-enriched title compound, C10H12Cl2O, a bicylic enol ether. A bridged boat-like structure is adopted and the dichloro­methyl­ene C atom is positioned significantly removed from the core bicyclic unit. In the crystal structure, mol­ecules pack to form sheets approximately perpendicular to the a and c axes. PMID:21202895

Mutagenic Potential of: 4-Nitrophenyl Dimethyl Phosphinate (TA007) using the Sex-Linked Recessive Lethal Test in Drosophila melanogaster.

DTIC Science & Technology

1984-10-01

Drosophila Stock Center, Bowling Green State University, Bowling Green, Ohio. Diet The diet was the standard medium consisting of cornmeal , unsulfured mol...isses, yeast, and nutrient agar used for colony rearing of D. melanogaster. A materials list and instructions for its preparation are contained in LAIR...SOP-OP-STX-5 Drosophila Media Preparation. Restraint Ether anesthesia was used for restraint of flies being collected for mating and for general

Infrared Spectroscopy of the Mass 31 Cation: Protonated Formaldehyde VS. The Triplet Methoxy Cation

NASA Astrophysics Data System (ADS)

Mosley, J. D.; Cheng, T. C.; Duncan, M. A.

2012-06-01

The m/z=31 cation is produced by ionization and fragmentation of methanol, ethanol, dimethyl ether, etc. Two structures have been proposed, protonated formaldehyde (^1CH_2OH^+) and the triplet methoxy cation (^3CH_3O^+). The infrared spectrum of the mass 31 cation is obtained using infrared photodissociation spectroscopy with Ar tagging. The spectrum reveals the presence of two stable isomers, protonated formaldehyde (^1CH_2OH^+) and the triplet methoxy cation (^3CH_3O^+). The triplet methoxy cation has been studied extensively and is predicted to interconvert to protonated formaldehyde through an essentially barrierless process on a timescale much faster than our experiment (>100 μs). The presence of two structural isomers is verified by comparison of spectra from different precursors and spectra of different temperature ions from the same precursor.

Bis[μ-N-(tert-butyl­dimethyl­silyl)-N-(pyridin-2-ylmeth­yl)amido]­bis­[methyl­cobalt(II)

PubMed Central

Malassa, Astrid; Agthe, Christine; Görls, Helmar; Westerhausen, Matthias

2012-01-01

The green title complex, [Co2(CH3)2(C12H21N2Si)2], was obtained from bis­{[μ-N-tert-butyl­dimethyl­silyl-N-(pyridin-2-ylmeth­yl)amido]­chloridocobalt(II)} and methyl­lithium in diethyl ether at 195 K via a metathesis reaction. The dimeric cobalt(II) complex exhibits a crystallographic center of inversion in the middle of the Co2N2 ring (average Co—N = 2.050 Å). The CoII atom shows a distorted tetra­hedral coordination sphere. The exocyclic Co—N bond length to the pyridyl group shows a similar value of 2.045 (4) Å. The exocyclic methyl group has a rather long Co—C bond length of 2.019 (5) Å. PMID:22969464

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

Underwood, R.P.

As part of the DOE-sponsored contract Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas'' experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al[sub 2]O[sub 3] methanol synthesis catalyst, developed in Air Products' laboratories, has the highest performance in terms of rate and selectivity for C[sub 2+]-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

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

Underwood, R.P.

As part of the DOE-sponsored contract ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas`` experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst, developed in Air Products` laboratories, has the highest performance in terms of rate and selectivity for C{sub 2+}-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

Analysis of organic volatile flavor compounds in fermented stinky tofu using SPME with different fiber coatings.

PubMed

Liu, Yuping; Miao, Zhiwei; Guan, Wei; Sun, Baoguo

2012-03-26

The organic volatile flavor compounds in fermented stinky tofu (FST) were studied using SPME-GC/MS. A total of 39 volatile compounds were identified, including nine esters, seven alcohols, five alkenes, four sulfides, three heterocycles, three carboxylic acids, three ketones, two aldehydes, one phenol, one amine and one ether. These compounds were determined by MS, and conformed by comparison of the retention times of the separated constituents with those of authentic samples and by comparison of retention indexes (RIs) of separated constituents with the RIs reported in the literature. The predominant volatile compound in FST was indole, followed by dimethyl trisulfide, phenol, dimethyl disulfide and dimethyl tetrasulfide. In order to find a better extraction time, the extraction times was optimized for each type of SPME fiber; the results show that the best extraction time for Carboxen/PDMS is 60 min, for PDMS/DVB 30 min, for DVB/CAR/PDMS 60 min and for PDMS 75 min. Of the four fibers used in this work, Carboxen/PDMS is found to be the most suitable to extract the organic volatile flavor compounds in fermented stinky tofu.

Determination of low ppm levels of dimethyl sulfate in an aqueous soluble API intermediate using liquid-liquid extraction and GC-MS.

PubMed

Zheng, Jie; Pritts, Wayne A; Zhang, Shuhong; Wittenberger, Steve

2009-12-05

Dimethyl sulfate (DMS) is an alkylating reagent commonly used in organic syntheses and pharmaceutical manufacturing processes. Due to its potential carcinogenicity, the level of DMS in the API process needs to be carefully monitored. However, in-process testing for DMS is challenging because of its reactivity and polarity as well as complex matrix effects. In this short communication, we report a GC-MS method for determination of DMS in an API intermediate that is a methyl sulfate salt. To overcome the complex matrix interference, DMS and an internal standard, d6-DMS, were extracted from the matrix with methyl tert-butyl ether. GC separation was conducted on a DB-624 column (30 m long, 0.32 mm ID, 1.8 microm film thickness). MS detection was performed on a single-quad Agilent MSD equipped with an electron impact source while the MSD signal was acquired in selected ion monitoring mode. This GC/MS method showed a linear response for DMS equivalent from 1.0 to 60 ppm. The practical quantitation limit for DMS was 1.0 ppm and the practical detection limit was 0.3 ppm. The relative standard derivation for analyte response was found as 0.1% for six injections of a working standard equivalent to 18.6 ppm of DMS. The spike recovery was ranged from 102.1 to 108.5% for a sample of API intermediate spiked with 8.0 ppm of DMS. In summary, the GC/MS method showed adequate specificity, linearity, sensitivity, repeatability and accuracy for determination of DMS in the API intermediate. This method has been successfully applied to study the efficiency of removing DMS from the process.

A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

NASA Astrophysics Data System (ADS)

Rao, B. Narasimha; Suvarna, R. Padma

2016-05-01

Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

Interaction of platelets, fibrinogen and endothelial cells with plasma deposited PEO-like films

NASA Astrophysics Data System (ADS)

Yang, Zhilu; Wang, Jin; Li, Xin; Tu, Qiufen; Sun, Hong; Huang, Nan

2012-02-01

For blood-contacting biomedical implants like retrievable vena cava filters, surface-based diagnostic devices or in vivo sensors, limiting thrombosis and cell adhesion is paramount, due to a decrease even failure in performance. Plasma deposited PEO-like films were investigated as surface modifications. In this work, mixed gas composed of tetraethylene glycol dimethyl ether (tetraglyme) vapor and oxygen was used as precursor. It was revealed that plasma polymerization under high ratio of oxygen/tetraglyme led to deposition of the films that had high content of ether groups. This kind of PEO-like films had good stability in phosphate buffer solution. In vitro hemocompatibility and endothelial cell (EC) adhesion revealed low platelet adhesion, platelet activation, fibrinogen adhesion, EC adhesion and proliferation on such plasma deposited PEO-like films. This made it a potential candidate for the applications in anti-fouling surfaces of blood-contacting biomedical devices.

Optimized Structures and Proton Affinities of Fluorinated Dimethyl Ethers: An Ab Initio Study

NASA Technical Reports Server (NTRS)

Orgel, Victoria B.; Ball, David W.; Zehe, Michael J.

1996-01-01

Ab initio methods have been used to investigate the proton affinity and the geometry changes upon protonation for the molecules (CH3)2O, (CH2F)2O, (CHF2)2O, and (CF3)2O. Geometry optimizations were performed at the MP2/3-2 I G level, and the resulting geometries were used for single-point energy MP2/6-31G calculations. The proton affinity calculated for (CH3)2O was 7 Kjoule/mole from the experimental value, within the desired variance of +/- 8Kjoule/mole for G2 theory, suggesting that the methodology used in this study is adequate for energy difference considerations. For (CF3)20, the calculated proton affinity of 602 Kjoule/mole suggests that perfluorinated ether molecules do not act as Lewis bases under normal circumstances; e.g. degradation of commercial lubricants in tribological applications.

Flow field and scalar measurements in a series of turbulent partially-premixed dimethyl ether/air jet flames

DOE PAGES

Coriton, Bruno; Im, Seong -Kyun; Gamba, Mirko; ...

2017-03-12

Here, we present a series of benchmark flames consisting of six partially-premixed piloted dimethyl ether (DME)/air jet flames. These flames provide an opportunity to understand turbulence-flame interactions for oxygenated fuels and to develop predictive models for these interactions using a canonical burner geometry. The development of accurate models for DME/air flames would establish a foundation for studies of more complex oxygenated fuels. The flames are stabilized on a piloted jet burner similar to that of the partially-premixed methane/air jet flames that have been studied extensively within the context of the TNF Workshop. This series of six jet flames spans jetmore » exit Reynolds numbers, ReD, from 29,300 to 73,300 and stoichiometric mixture fractions, ξ st, from 0.35 to 0.60. Flame conditions range from very low probability of localized extinction to a high probability of localized extinction and subsequent re-ignition. Measurements in the flames are compared at downstream locations from 5 to 25 diameters above the nozzle exit. Mean and fluctuating velocity components are measured using stereo particle image velocimetry (SPIV). Simultaneous laser-induced fluorescence (LIF) imaging of OH and CH 2O provides insights into the distribution of these intermediate species in partially-premixed DME/air flames. OH LIF imaging is also combined with SPIV to investigate the strain rate field across the reaction zone.« less

Flow field and scalar measurements in a series of turbulent partially-premixed dimethyl ether/air jet flames

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

Coriton, Bruno; Im, Seong -Kyun; Gamba, Mirko

Here, we present a series of benchmark flames consisting of six partially-premixed piloted dimethyl ether (DME)/air jet flames. These flames provide an opportunity to understand turbulence-flame interactions for oxygenated fuels and to develop predictive models for these interactions using a canonical burner geometry. The development of accurate models for DME/air flames would establish a foundation for studies of more complex oxygenated fuels. The flames are stabilized on a piloted jet burner similar to that of the partially-premixed methane/air jet flames that have been studied extensively within the context of the TNF Workshop. This series of six jet flames spans jetmore » exit Reynolds numbers, ReD, from 29,300 to 73,300 and stoichiometric mixture fractions, ξ st, from 0.35 to 0.60. Flame conditions range from very low probability of localized extinction to a high probability of localized extinction and subsequent re-ignition. Measurements in the flames are compared at downstream locations from 5 to 25 diameters above the nozzle exit. Mean and fluctuating velocity components are measured using stereo particle image velocimetry (SPIV). Simultaneous laser-induced fluorescence (LIF) imaging of OH and CH 2O provides insights into the distribution of these intermediate species in partially-premixed DME/air flames. OH LIF imaging is also combined with SPIV to investigate the strain rate field across the reaction zone.« less

Microbial desalination cell with sulfonated sodium poly(ether ether ketone) as cation exchange membranes for enhancing power generation and salt reduction.

PubMed

Moruno, Francisco Lopez; Rubio, Juan E; Atanassov, Plamen; Cerrato, José M; Arges, Christopher G; Santoro, Carlo

2018-06-01

Microbial desalination cell (MDC) is a bioelectrochemical system capable of oxidizing organics, generating electricity, while reducing the salinity content of brine streams. As it is designed, anion and cation exchange membranes play an important role on the selective removal of ions from the desalination chamber. In this work, sulfonated sodium (Na + ) poly(ether ether ketone) (SPEEK) cation exchange membranes (CEM) were tested in combination with quaternary ammonium chloride poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membrane (AEM). Non-patterned and patterned (varying topographical features) CEMs were investigated and assessed in this work. The results were contrasted against a commercially available CEM. This work used real seawater from the Pacific Ocean in the desalination chamber. The results displayed a high desalination rate and power generation for all the membranes, with a maximum of 78.6±2.0% in salinity reduction and 235±7mWm -2 in power generation for the MDCs with the SPEEK CEM. Desalination rate and power generation achieved are higher with synthesized SPEEK membranes when compared with an available commercial CEM. An optimized combination of these types of membranes substantially improves the performances of MDC, making the system more suitable for real applications. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

The generation of singlet oxygen (o(2)) by the nitrodiphenyl ether herbicide oxyfluorfen is independent of photosynthesis.

PubMed

Haworth, P; Hess, F D

1988-03-01

The mechanism of action of the p-nitrodiphenyl ether herbicides has remained ambiguous because of conflicting reports in the literature. The diphenyl ether herbicide oxyfluorfen causes a light induced consumption of oxygen which resembles the electron acceptor reaction of paraquat. However, this reaction is not linked to the transport of electrons through photosystem I. This conclusion is based on the observation that the rate of oxygen consumption, in the presence of oxyfluorfen, does not demonstrate a first order rate dependence on light intensity. Using the bleaching of N,N-dimethyl p-nitrosoaniline as a specific detector of singlet oxygen, we demonstrate that oxyfluorfen is a potent generator of this toxic radical. The production of singlet oxygen occurs in the presence of inhibitors of photosynthetic electron transport (oxyfluorfen at 10(-4) molar and paraquat) and also under temperature conditions (3 degrees C) which prevent electron transport. This light induced reaction results in oxygen consumption and is the primary cause of lethality for oxyfluorfen. The production of singlet oxygen occurs rapidly and at low herbicide concentrations (10(-9) molar). The reaction occurs without photosynthetic electron transport but does require an intact thylakoid membrane.

The Generation of Singlet Oxygen (1O2) by the Nitrodiphenyl Ether Herbicide Oxyfluorfen Is Independent of Photosynthesis

PubMed Central

Haworth, Phil; Hess, F. Dan

1988-01-01

The mechanism of action of the p-nitrodiphenyl ether herbicides has remained ambiguous because of conflicting reports in the literature. The diphenyl ether herbicide oxyfluorfen causes a light induced consumption of oxygen which resembles the electron acceptor reaction of paraquat. However, this reaction is not linked to the transport of electrons through photosystem I. This conclusion is based on the observation that the rate of oxygen consumption, in the presence of oxyfluorfen, does not demonstrate a first order rate dependence on light intensity. Using the bleaching of N,N-dimethyl p-nitrosoaniline as a specific detector of singlet oxygen, we demonstrate that oxyfluorfen is a potent generator of this toxic radical. The production of singlet oxygen occurs in the presence of inhibitors of photosynthetic electron transport (oxyfluorfen at 10−4 molar and paraquat) and also under temperature conditions (3°C) which prevent electron transport. This light induced reaction results in oxygen consumption and is the primary cause of lethality for oxyfluorfen. The production of singlet oxygen occurs rapidly and at low herbicide concentrations (10−9 molar). The reaction occurs without photosynthetic electron transport but does require an intact thylakoid membrane. PMID:16665968

High Performance of Perovskite Solar Cells via Catalytic Treatment in Two-Step Process: The Case of Solvent Engineering.

PubMed

Li, Wenzhe; Fan, Jiandong; Li, Jiangwei; Niu, Guangda; Mai, Yaohua; Wang, Liduo

2016-11-09

Currently, the potential mechanism of the solvent-assisted crystallization for mixed cations perovskite thin film (FA x MA 1-x PbI 3 ) prepared via two-step solution-process still remains obscure. Here, we clarified the molecular-competing-reacted process of NH 2 CH═NH 2 I (FAI) and CH 3 NH 3 I (MAI) with PbI 2 (DMSO) x complex in dimethyl sulfoxide (DMSO) and diethyl ether (DE) catalytic solvent system in the sequential two-step solution-process. The microscopic dynamics was characterized via the characterizations of in situ photoluminescence spectra. In addition, we found that the thermal stability of the perovskite films suffered from the residual solvent with high boiling point, for example, DMSO. The further DE treatment could promote the volatility process of DMSO and accelerate the crystallization process of perovskite films. The highest PCE over 19% with slight hysteresis effect was eventually obtained with a reproducible FA 0.88 MA 0.12 PbI 3 solar cell, which displayed a constant power output within 100 s upon light soaking and stable PCE output within 30 d in the thermal stability test.

Melting of superheated molecular crystals

NASA Astrophysics Data System (ADS)

Cubeta, Ulyana; Bhattacharya, Deepanjan; Sadtchenko, Vlad

2017-07-01

Melting dynamics of micrometer scale, polycrystalline samples of isobutane, dimethyl ether, methyl benzene, and 2-propanol were investigated by fast scanning calorimetry. When films are superheated with rates in excess of 105 K s-1, the melting process follows zero-order, Arrhenius-like kinetics until approximately half of the sample has transformed. Such kinetics strongly imply that melting progresses into the bulk via a rapidly moving solid-liquid interface that is likely to originate at the sample's surface. Remarkably, the apparent activation energies for the phase transformation are large; all exceed the enthalpy of vaporization of each compound and some exceed it by an order of magnitude. In fact, we find that the crystalline melting kinetics are comparable to the kinetics of dielectric α-relaxation in deeply supercooled liquids. Based on these observations, we conclude that the rate of non-isothermal melting for superheated, low-molecular-weight crystals is limited by constituent diffusion into an abnormally dense, glass-like, non-crystalline phase.

Renewable Gasoline, Solvents, and Fuel Additives from 2,3-Butanediol.

PubMed

Harvey, Benjamin G; Merriman, Walter W; Quintana, Roxanne L

2016-07-21

2,3-Butanediol (2,3-BD) is a renewable alcohol that can be prepared in high yield from biomass sugars. 2,3-BD was selectively dehydrated in a solvent-free process to a complex mixture of 2-ethyl-2,4,5-trimethyl-1,3-dioxolanes and 4,5-dimethyl-2isopropyl dioxolanes with the heterogeneous acid catalyst Amberlyst-15. The purified dioxolane mixture exhibited an anti-knock index of 90.5, comparable to high octane gasoline, and a volumetric net heat of combustion 34 % higher than ethanol. The solubility of the dioxolane mixture in water was only 0.8 g per 100 mL, nearly an order of magnitude lower than the common gasoline oxygenate methyl tert-butyl ether. The dioxolane mixture has potential applications as a sustainable gasoline blending component, diesel oxygenate, and industrial solvent. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Not Available

Phillips Petroleum Co. is poised to license its high conversion process to produce fuel ethers for blending in reformulated gasolines. The technology has been proven in a Phillips semiworks at Bartlesville, Okla. The process can produce methyl tertiary butyl ether, ethyl tertiary butyl ether, tertiary amyl methyl ether, or tertiary amyl ethyl ether with typical refinery process equipment and techniques. Phillips said it can achieve conversion levels of 92-99%, depending on the ether. The ether produced is determined by which hydrocarbon fraction is used for feedstock and which alcohol is chosen for reaction. The process is described.

In situ reinforced polymers using low molecular weight compounds

NASA Astrophysics Data System (ADS)

Yordem, Onur Sinan

2011-12-01

The primary objective of this research is to generate reinforcing domains in situ during the processing of polymers by using phase separation techniques. Low molecular weight compounds were mixed with polymers where the process viscosity is reduced at process temperatures and mechanical properties are improved once the material system is cooled or reacted. Thermally induced phase separation and thermotropic phase transformation of low molar mass compounds were used in isotactic polypropylene (iPP) and poly(ether ether ketone) (PEEK) resins. Reaction induced phase separation was utilized in thermosets to generate anisotropic reinforcements. A new strategy to increase fracture toughness of materials was introduced. Simultaneously, enhancement in stiffness and reduction in process viscosity were also attained. Materials with improved rheological and mechanical properties were prepared by using thermotropic phase transformations of metal soaps in polymers (calcium stearate/iPP). Morphology and thermal properties were studied using WAXS, DSC and SEM. Mechanical and rheological investigation showed significant reduction in process viscosity and substantial improvement in fracture toughness were attained. Effects of molecular architecture of metal soaps were investigated in PEEK (calcium stearate/PEEK and sodium stearate/PEEK). The selected compounds reduced the process viscosity due to the high temperature co-continuous morphology of metal soaps. Unlike the iPP system that incorporates spherical particles, interaction between PEEK and metal soaps resulted in two discrete and co-continuous phases of PEEK and the metal stearates. DMA and melt rheology exhibited that sodium stearate/PEEK composites are stiffer. Effective moduli of secondary metal stearate phase were calculated using different composite theories, which suggested bicontinuous morphology to the metal soaps in PEEK. Use of low molecular weight crystallizable solvents was investigated in reactive systems. Formation of anisotropic reinforcements was evaluated using dimethyl sulfone (DMS) as the crystallizable diluent and diglycidyl ether of bisphenol-A (DGEBA)/m-phenylene diamine (mPDA) material system as the epoxy thermoset. Miscible blends of DMS and DGEBA/mPDA form homogenous mixtures that undergo polymerization induced phase separation, once the DGEBA oligomers react with mPDA. The effect of the competition between the crystallization and phase separation of DMS resulted in nano-wires to micro-scale fiber-like crystals that were generated by adjusting the reaction temperature and DMS concentration.

Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons.

PubMed

Olah, George A; Goeppert, Alain; Prakash, G K Surya

2009-01-16

Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. In contrast, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products can be achieved via its capture and subsequent reductive hydrogenative conversion. The present Perspective reviews this new approach and our research in the field over the last 15 years. Carbon recycling represents a significant aspect of our proposed Methanol Economy. Any available energy source (alternative energies such as solar, wind, geothermal, and atomic energy) can be used for the production of needed hydrogen and chemical conversion of CO(2). Improved new methods for the efficient reductive conversion of CO(2) to methanol and/or DME that we have developed include bireforming with methane and ways of catalytic or electrochemical conversions. Liquid methanol is preferable to highly volatile and potentially explosive hydrogen for energy storage and transportation. Together with the derived DME, they are excellent transportation fuels for internal combustion engines (ICE) and fuel cells as well as convenient starting materials for synthetic hydrocarbons and their varied products. Carbon dioxide thus can be chemically transformed from a detrimental greenhouse gas causing global warming into a valuable, renewable and inexhaustible carbon source of the future allowing environmentally neutral use of carbon fuels and derived hydrocarbon products.

Ether- and Ester-Bound iso-Diabolic Acid and Other Lipids in Members of Acidobacteria Subdivision 4

PubMed Central

Rijpstra, W. Irene C.; Hopmans, Ellen C.; Foesel, Bärbel U.; Wüst, Pia K.; Overmann, Jörg; Tank, Marcus; Bryant, Donald A.; Dunfield, Peter F.; Houghton, Karen; Stott, Matthew B.

2014-01-01

Recently, iso-diabolic acid (13,16-dimethyl octacosanedioic acid) has been identified as a major membrane-spanning lipid of subdivisions 1 and 3 of the Acidobacteria, a highly diverse phylum within the Bacteria. This finding pointed to the Acidobacteria as a potential source for the bacterial glycerol dialkyl glycerol tetraethers that occur ubiquitously in peat, soil, lakes, and hot springs. Here, we examined the lipid composition of seven phylogenetically divergent strains of subdivision 4 of the Acidobacteria, a bacterial group that is commonly encountered in soil. Acid hydrolysis of total cell material released iso-diabolic acid derivatives in substantial quantities (11 to 48% of all fatty acids). In contrast to subdivisions 1 and 3 of the Acidobacteria, 6 out of the 7 species of subdivision 4 (excepting “Candidatus Chloracidobacterium thermophilum”) contained iso-diabolic acid ether bound to a glycerol in larger fractional abundance than iso-diabolic acid itself. This is in agreement with the analysis of intact polar lipids (IPLs) by high-performance liquid chromatography-mass spectrometry (HPLC-MS), which showed the dominance of mixed ether-ester glycerides. iso-Diabolic acid-containing IPLs were not identified, because these IPLs are not released with a Bligh-Dyer extraction, as observed before when studying lipid compositions of subdivisions 1 and 3 of the Acidobacteria. The presence of ether bonds in the membrane lipids does not seem to be an adaptation to temperature, because the five mesophilic isolates contained a larger amount of ether lipids than the thermophile “Ca. Chloracidobacterium thermophilum.” Furthermore, experiments with Pyrinomonas methylaliphatogenes did not reveal a major influence of growth temperature over the 50 to 69°C range. PMID:24928878

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

DOE PAGES

Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi; ...

2015-10-26

This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs +). SANS profiles obtained for the complex of ace-DB20C6 and Cs + (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs + coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that themore » SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs + is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs + above the center of the crown ether ring of ace-DB20C6.« less

Small-angle neutron scattering study of specific interaction and coordination structure formed by mono-acetyl-substituted dibenzo-20-crown-6-ether and cesium ions

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

Motokawa, Ryuhei; Kobayashi, Tohru; Endo, Hitoshi

This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl-substituted dibenzo-20-crown-6-ether (ace-DB20C6) with cesium ions (Cs +). SANS profiles obtained for the complex of ace-DB20C6 and Cs + (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs + coordination resulted in a more compact structure than the free ace-DB20C6. The data were fitted well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on density functional theory calculation was used. Furthermore, we conclude that themore » SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs + is formed with an ace-DB20C6/Cs molar ratio of 1/1 and (2) the two benzene rings of ace-DB20C6 fold around Cs + above the center of the crown ether ring of ace-DB20C6.« less

Characterization of double oxide system Cu-Cr-O supported on γ-Al2O3

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Kolev, H.; Krstić, J.; Dimitrov, D.; Ivanov, K.; Loncarević, D.; Jovanović, D.; Mitov, I.

2009-09-01

Series of alumina supported chromium-copper catalysts were prepared by co-impregnation method. The samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. Dispersion and porosity was also obtained. The experimental and catalytic test results have drawn a conclusion that an interaction between copper and chromium ions takes place. This interaction is responsible for the enhanced catalytic activity of studied catalysts in reaction of total oxidation of industrial formaldehyde production exhaust gas, which contains CO, dimethyl ether and methanol as main components.

Extended Le Chatelier's formula for carbon dioxide dilution effect on flammability limits.

PubMed

Kondo, Shigeo; Takizawa, Kenji; Takahashi, Akifumi; Tokuhashi, Kazuaki

2006-11-02

Carbon dioxide dilution effect on the flammability limits was measured for various flammable gases. The obtained values were analyzed using the extended Le Chatelier's formula developed in a previous study. As a result, it has been found that the flammability limits of methane, propane, propylene, methyl formate, and 1,1-difluoroethane are adequately explained by the extended Le Chatelier's formula using a common set of parameter values. Ethylene, dimethyl ether, and ammonia behave differently from these compounds. The present result is very consistent with what was obtained in the case of nitrogen dilution.

Molecular Engineering of Liquid Crystalline Polymers by Living Polymerization. 10. Influence of Molecular Weight on the Phase Transitions of Poly(Omega-((4-Cyano-4’-Biphenyl)oxy)alkyl Vinyl Ethers)s with Nonyl and Decanyl Alkyl Groups

DTIC Science & Technology

1990-10-16

washed with concentrated sulfuric acid , then with water, dried over anhydrous magnesium sulfate, refluxed over calcium hydride and freshly distilled...oxide, filtered, and fractionally distilled under reduced pressure. Trifluoromethane sulfonic acid (triflic acid , 98%, Aldrich) w s distilled under...flask. Then the flask was filled with argon, cooled to 0°C and the methylene chloride, dimethyl sulfide and triflic acid were added via a syringe. The

Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters.

PubMed

West, Adam H C; Yoder, Bruce L; Luckhaus, David; Saak, Clara-Magdalena; Doppelbauer, Maximilian; Signorell, Ruth

2015-04-16

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem to be mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes but decrease slightly with increasing cluster size.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

A Review: Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

NASA Technical Reports Server (NTRS)

McCoy, LaShelle E.

2013-01-01

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing. and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and carbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes.

Simultaneous small-angle neutron scattering and Fourier transform infrared spectroscopic measurements on cocrystals of syndiotactic polystyrene with polyethylene glycol dimethyl ethers.

PubMed

Kaneko, Fumitoshi; Seto, Naoki; Sato, Shuma; Radulescu, Aurel; Schiavone, Maria Maddalena; Allgaier, Jürgen; Ute, Koichi

2016-10-01

Syndiotactic polystyrene (sPS) is a crystalline polymer which has a unique property; it is able to form cocrystals with a wide range of chemical compounds, in which the guest molecules are confined in the vacancies of the host sPS crystalline region. Recently, it has been found that even polyethylene glycol oligomers with a molecular weight of more than several hundreds can be introduced into the sPS crystalline region. It is quite important to know how such a long-chain molecule is stored in the host sPS lattice. To tackle this issue, a new simultaneous measurement method combing small-angle neutron scattering and Fourier transform infrared spectroscopy (SANS/FTIR), which has been recently developed by the authors, was applied to an sPS cocrystal with polyethylene glycol dimethyl ether with a molecular weight of 500 (PEGDME500). The temperature-dependent changes of the SANS profile and FTIR spectrum were followed from room temperature up to 413 K for a one-dimensionally oriented SANS/PEGDME500 cocrystal sample. The intensity of the reflections due to the stacking of crystalline lamellae showed a significant temperature dependence. The two-dimensional pattern in the high Q region of SANS also changed depending on temperature. The combined information obtained by SANS and FTIR suggested that PEGDME500 molecules are distributed in both the crystalline and amorphous regions in the low-temperature region close to room temperature, but they are predominantly included in the amorphous region in the high-temperature region. It was also suggested by the two-dimensional SANS profile that PEGDME500 molecules in the crystalline region have an elongated structure along the thickness direction of the crystalline lamellae.

Simultaneous small-angle neutron scattering and Fourier transform infrared spectroscopic measurements on cocrystals of syndiotactic polystyrene with polyethylene glycol dimethyl ethers1

PubMed Central

Kaneko, Fumitoshi; Seto, Naoki; Sato, Shuma; Radulescu, Aurel; Schiavone, Maria Maddalena; Allgaier, Jürgen; Ute, Koichi

2016-01-01

Syndiotactic polystyrene (sPS) is a crystalline polymer which has a unique property; it is able to form cocrystals with a wide range of chemical compounds, in which the guest molecules are confined in the vacancies of the host sPS crystalline region. Recently, it has been found that even polyethylene glycol oligomers with a molecular weight of more than several hundreds can be introduced into the sPS crystalline region. It is quite important to know how such a long-chain molecule is stored in the host sPS lattice. To tackle this issue, a new simultaneous measurement method combing small-angle neutron scattering and Fourier transform infrared spectroscopy (SANS/FTIR), which has been recently developed by the authors, was applied to an sPS cocrystal with polyethylene glycol dimethyl ether with a molecular weight of 500 (PEGDME500). The temperature-dependent changes of the SANS profile and FTIR spectrum were followed from room temperature up to 413 K for a one-dimensionally oriented SANS/PEGDME500 cocrystal sample. The intensity of the reflections due to the stacking of crystalline lamellae showed a significant temperature dependence. The two-dimensional pattern in the high Q region of SANS also changed depending on temperature. The combined information obtained by SANS and FTIR suggested that PEGDME500 molecules are distributed in both the crystalline and amorphous regions in the low-temperature region close to room temperature, but they are predominantly included in the amorphous region in the high-temperature region. It was also suggested by the two-dimensional SANS profile that PEGDME500 molecules in the crystalline region have an elongated structure along the thickness direction of the crystalline lamellae. PMID:27738412

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

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

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

2014-08-10

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

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

NASA Astrophysics Data System (ADS)

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

2014-08-01

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

Influence of low-temperature combustion and dimethyl ether-diesel blends on performance, combustion, and emission characteristics of common rail diesel engine: a CFD study.

PubMed

Lamani, Venkatesh Tavareppa; Yadav, Ajay Kumar; Narayanappa, Kumar Gottekere

2017-06-01

Due to presence of more oxygen, absence of carbon-carbon (C-C) bond in chemical structure, and high cetane number of dimethyl ether (DME), pollution from DME operated engine is less compared to diesel engine. Hence, the DME can be a promising alternative fuel for diesel engine. The present study emphasizes the effect of various exhaust gas recirculation (EGR) rates (0-20%) and DME/Diesel blends (0-20%) on combustion characteristics and exhaust emissions of common rail direct injection (CRDI) engine using three-dimensional computational fluid dynamics (CFD) simulation. Extended coherent flame model-3 zone (ECFM-3Z) is implemented to carry out combustion analysis, and k-ξ-f model is employed for turbulence modeling. Results show that in-cylinder pressure marginally decreases with employing EGR compared to without EGR case. As EGR rate increases, nitrogen oxide (NO) formation decreases, whereas soot increases marginally. Due to better combustion characteristics of DME, indicated thermal efficiency (ITE) increases with the increases in DME/diesel blend ratio. Adverse effect of EGR on efficiency for blends is less compared to neat diesel, because the anoxygenated region created due to EGR is compensated by extra oxygen present in DME. The trade-off among NO, soot, carbon monoxide (CO) formation, and efficiency is studied by normalizing the parameters. Optimum operating condition is found at 10% EGR rate and 20% DME/diesel blend. The maximum indicated thermal efficiency was observed for DME/diesel ratio of 20% in the present range of study. Obtained results are validated with published experimental data and found good agreement.

On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2015-09-24

The electro-oxidation of dimethyl ether (DME) was investigated using periodic, self-consistent density functional theory (DFT) calculations on the (111) and (100) facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. The goal of this study is to understand the experimentally observed structure sensitivity of this reaction on Pt, and to predict trends in structure sensitivity of this reaction across the other seven metals studied. The main conclusion is that the enhanced activity of Pt(100) originates from more facile C–O bond breaking and removal of surface poisoning species, including CO and CH. When comparing C–O bondmore » breaking energetics, we do not find a universal trend where these elementary steps are always more exergonic on the (100) facet. However, we find that, at a given potential, DME can be dehydrogenated (prior to breaking the C–O bond) to a greater extent on the (100) facet. Additionally, we find that the reaction energy for C–O bond breaking in CHxOCHy-type species becomes increasingly exergonic as the species becomes increasingly dehydrogenated. Together, the more facile dehydrogenation on the (100) facets provides more favorable routes to C–O bond activation. Though we calculate a lower onset potential on Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) than their respective (111) facets, the calculated onset potential for Ni(100), Ir(100), and Rh(100) are actually higher than for their respective (111) facets. Lastly, by constructing theoretical volcano plots, we conclude that Au(100), Ag(100), Cu(100), Pt(100), and Pd(100) should be more active than their respective (111) facets, while Ni(100), Rh(100), and Ir(100) will show the opposite trend.« less

Surface hydrophobicity and acidity effect on alumina catalyst in catalytic methanol dehydration reaction

PubMed Central

Osman, Ahmed I; Thompson, Jillian; Halawy, Samih A; Mohamed, Mohamed A

2017-01-01

Abstract BACKGROUND Methanol to dimethyl ether (MTD) is considered one of the main routes for the production of clean bio‐fuel. The effect of copper loading on the catalytic performance of different phases of alumina that formed by calcination at two different temperatures was examined for the dehydration of methanol to dimethyl ether (DME). RESULTS A range of Cu loadings of (1, 2, 4, 6, 10 and 15% Cu wt/wt) on Al2O3 calcined at 350 and 550 °C were prepared and characterized by TGA, XRD, BET, NH3‐TPD, TEM, H2‐TPR, SEM, EDX, XPS and DRIFT‐Pyridine techniques. The prepared catalysts were used in a fixed bed reactor under reaction conditions in which the temperature ranged from 180–300 °C with weight hourly space velocity (WHSV) = 12.1 h‐1. It was observed that all catalysts calcined at 550 °C (γ‐Al2O3 support phase) exhibited higher activity than those calcined at 350 °C (γ‐AlOOH), and this is due to the phase support change. Furthermore, the optimum Cu loading was found to be 6% Cu/γ‐Al2O3 with this catalyst also showing a high degree of stability under steady state conditions and this is attributed to the enhancement in surface acidity and hydrophobicity. CONCLUSION The addition of copper to the support improved the catalyst properties and activity. For all the copper modified catalysts, the optimum catalyst with high degree of activity and stability was 6% copper loaded on gamma alumina. © 2017 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. PMID:29200585

Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

DOEpatents

Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

1999-01-01

A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

DOEpatents

Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

1999-03-30

A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-24

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

In-Situ Immobilization of Ni Complex on Amine-Grafted SiO₂ for Ethylene Polymerization.

PubMed

Lee, Sang Yun; Ko, Young Soo

2018-02-01

The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1993-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Lewis super-acid catalyzed cyclizations: a new route to fragrance compounds.

PubMed

Coulombel, Lydie; Grau, Fanny; Weïwer, Michel; Favier, Isabelle; Chaminade, Xavier; Heumann, Andreas; Bayón, J Carles; Aguirre, Pedro A; Duñach, Elisabet

2008-06-01

This review deals with the application of Lewis super acids such as Al(III), In(III), and Sn(IV) triflates and triflimidates as catalysts in the synthesis of fragrance materials. Novel catalytic reactions involving C-C and C-heteroatom bond-forming reactions, as well as cycloisomerization processes are presented. In particular, Sn(IV) and Al(III) triflates were employed as catalysts in the selective cyclization of unsaturated alcohols to cyclic ethers, as well as in the cyclization of unsaturated carboxylic acids to lactones. The addition of thiols and thioacids to non-activated olefins, both in intra- and intermolecular versions, was efficiently catalyzed by In(III) derivatives. Sn(IV) Triflimidates catalyzed the cycloisomerization of highly substituted 1,6-dienes to gem-dimethyl-substituted cyclohexanes bearing an isopropylidene substituent. The hydroformylation of these unsaturated substrates, catalyzed by a Rh(I) complex with a bulky phosphite ligand, selectively afforded the corresponding linear aldehydes. The olfactory evaluation of selected heterocycles, carbocycles, and aldehydes synthesized is also discussed.

Absorption degree analysis on biogas separation with ionic liquid systems.

PubMed

Zhang, Xin; Zhang, Suojiang; Bao, Di; Huang, Ying; Zhang, Xiangping

2015-01-01

For biogas upgrading, present work mainly focuses on either thermodynamics or mass transfer properties. A systematical study on these two aspects is important for developing a new biogas separation process. In this work, a new criterion "absorption degree", which combines both thermodynamics and mass transfer properties, was proposed for the first time to comprehensively evaluate the absorption performance. Henry's law constants of CO2 and CH4 in ionic liquids-polyethylene glycol dimethyl ethers mixtures were investigated. The liquid-side mass transfer coefficients (kL) were determined. The results indicate that IL-NHD mixtures exhibit not only a high CO2/CH4 selectivity, but also a fast kL for CO2 absorption. The [bmim][NO3]+NHD mixtures present a high absorption degree value for CO2 but a low value for CH4. For presenting a highest relative absorption degree value, the 50wt% [bmim][NO3]+50wt% NHD mixture is recommended for biogas upgrading. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

DOEpatents

Hofmann, Michael A.

2006-11-14

The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

Process for making propenyl ethers and photopolymerizable compositions containing them

DOEpatents

Crivello, James V.

1996-01-01

Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

Gibbs energies of transferring triglycine from water into H2O-DMSO solvent

NASA Astrophysics Data System (ADS)

Usacheva, T. R.; Kuz'mina, K. I.; Lan, Pham Thi; Kuz'mina, I. A.; Sharnin, V. A.

2014-08-01

The Gibbs energies of transferring triglycine (3Gly, glycyl-glycyl-glycine) from water into mixtures of water with dimethyl sulfoxide (χDMSO = 0.05, 0.10, and 0.15 mole fractions) at 298.15 K are determined from the interphase distribution. An increased dimethyl sulfoxide (DMSO) concentration in the solvent slightly raises the positive values of Δtr G ○(3Gly), possibly indicating the formation of more stable 3Gly-H2O solvated complexes than ones of 3Gly-DMSO. It is shown that the change in the Gibbs energy of transfer of 3Gly is determined by the enthalpy component. The relationship of 3Gly and 18-crown-6 ether (18C6) solvation's contributions to the change in the Gibbs energy of [3Gly18C6] molecular complex formation in H2O-DMSO solvents is analyzed, and the key role of 3Gly solvation's contribution to the change in the stability of [3Gly18C6] upon moving from H2O to mixtures with DMSO is revealed.

An Immunoassay for Monitoring Environmental and Human Exposure to the Polybrominated Diphenyl Ether BDE-47

PubMed Central

Ahn, Ki Chang; Gee, Shirley J.; Tsai, Hsing-Ju; Bennett, Deborah; Nishioka, Marcia G.; Blum, Arlene; Fishman, Elana; Hammock, Bruce D.

2012-01-01

We developed a selective competitive enzyme-linked immunosorbent assay (ELISA) to monitor environmental and human exposure to polybrominated diphenyl ether BDE-47 that is used as a flame retardant. 2,2’,4,4’-Tetrabromodiphenyl ether (BDE-47) a dominant PBDE congener of toxicological concern, was the target analyte. To achieve effective hapten presentation on the carrier protein for antibody production, immunizing haptens with a rigid double-bonded hydrocarbon linker introduced at different positions on the target molecule were synthesized as well as coating haptens that mimic a characteristic fragment of the molecule. Rabbit antisera produced against each immunizing antigen were screened against competitive hapten coating antigens. Under optimized competitive indirect ELISA conditions, the linear detection range in the assay buffer that includes 50% dimethyl sulfoxide was 0.35 - 8.50 μg/L with an IC50 value of 1.75 μg/L for BDE-47. Little or no cross-reactivity (< 6%) was observed to related PBDE congeners containing the BDE-47 moiety and other halogenated compounds. Using a magnetic particle-based competitive direct ELISA increased the sensitivity by 10-fold over the indirect ELISA. The ELISA provided quantitative results when performed on small volume/weight samples such as dust, furniture foam, and blood/serum following sample preparation, suggesting a convenient screening tool. PMID:19921894

Process for making propenyl ethers and photopolymerizable compositions containing them

DOEpatents

Crivello, J.V.

1996-01-23

Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} (V) wherein n is an integer from one to six and A is selected from cyclic ethers, polyether, and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

[Inhibition effects of Houttuynia cordata Thunb. on Microcystis aeruginosa].

PubMed

Liu, Lu; Li, Cheng; Xia, Wentong; Yang, Xiaohui; Zhang, Tingting

2014-05-01

To research the inhibitory effect of Houttuynia cordata Thunb. on Microcystis aeruginosa. M. aeruginosat were treated respectively by H. cordata leaching solution or H. cordata extracts. H. cordata leaching solution extracted by water and the H. cordata extracts extracted by organic solvent (acetone, ethyl acetate, petroleum ether and ethanol, respectively). The inhibition ratios were calculated according to the M. aeruginosa densities, and the allelochemicals of the extract that had the best inhibitiory effect on M. aeruginosa were identified by GC-MS analysis. It was proved that leaching solution of H. cordata and four crude extracts had good inhibitory effect on M. aeruginosa. The inhibitory effects of the four crude extracts were the fraction extracted by ethyl acetate, the fraction extracted by ethanol, the fraction extracted by acetone and the fraction extracted by petroleum ether form strong to weak in turn. Then, the allelochemicals of the fraction extracted by ethyl acetate were indentified, mainly including acetonyldimethylcarbinol, 2,2-dimethyl-3-hexanone, 6-chlorohexanoic and 4-cyanophenyl ester. H. cordata has strong inhibitory effect on water-blooming cyanobacteria and the potential to develop into an ecological M. aeruginosa inhibiting agent.

Preparation and characterization of polymer blend based on sulfonated poly (ether ether ketone) and polyetherimide (SPEEK/PEI) as proton exchange membranes for fuel cells

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

Hashim, Nordiana; Ali, Ab Malik Marwan; Lepit, Ajis

2015-08-28

Blends of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios using N-methyl-2-pyrrolidone (NMP) as solvent by the solution cast technique. The degree of sulfonation (DS) of the sulfonated PEEK was determined from deuterated dimethyl sulfoxide (DMSO-d{sub 6}) solution of the purified polymer using {sup 1}H NMR method. The properties studied in the present investigation includes conductivity, water uptake, thermal stability and structure analysis of pure SPEEK as well as SPEEK-PEI polymer blend membranes. The experimental results show that the conductivity of the membranes increased with increase in temperature from 30 to 80°C,more » except for that of pure SPEEK membrane which increased with temperature from 30 to 60°C while its conductivity decreased with increasing temperature from 60 to 80°C. The conductivity of 70wt.%SPEEK-30wt.%PEI blend membrane at 80% relative humidity (RH) is found to be 1.361 × 10{sup −3} Scm{sup −1} at 30°C and 3.383 × 10{sup −3} Scm{sup −1} at 80°C respectively. It was also found that water uptake and thermal stability of the membranes slightly improved upon blending with PEI. Structure analysis was carried out using Fourier Transform Infrared (FTIR) spectroscopy which revealed considerable interactions between sulfonic acid group of SPEEK and imide groups of PEI. Modification of SPEEK by blending with PEI shows good potential for improving the electrical and physical properties of proton exchange membranes.« less

Polymer blends based on epoxy resin and polyphenylene ether as a matrix material for high-performance composites

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

Venderbosch, R.W.; Nelissen, J.G.L.; Peijs, A.A.J.M.

1993-12-31

The application of poly(2,6-dimethyl-1,4-phenylene ether), PPE, as a matrix material for continuous carbon fiber reinforced composites was studied. PPE is an amorphous thermoplastic exhibiting a high glass transition temperature (220 C) and outstanding mechanical properties with respect to e.g. toughness. However, due to the limited thermal stability at temperatures above T{sub g}, PPE can be regarded as an intractable polymer. Consequently, the introduction of PPE in a composite structure via a melt impregnation route is not feasible. In this investigation a solution impregnation route, using epoxy resin as a reactive solvent, was developed. During impregnation epoxy resin acts as amore » solvent which results in enhanced flow and a reduced processing temperature enabling the preparation of high quality composites, avoiding any degradation. Upon curing of the neat system, phase separation and phase inversion occurs resulting in a continuous PPE matrix filled with glassy epoxy spheres. As a result of this morphology the mechanical and thermal properties of the final material are mainly dominated by the PPE component. In composite applications, a strong influence of the polarity of the carbon fiber surface on the resulting matrix morphology was found. Upon curing, phase separation is initiated at the fiber surface resulting in an epoxy `interlayer` at the fiber surface. This phenomenon can provide a high level of interfacial adhesion. A preliminary investigation of the resulting composite materials revealed outstanding mechanical properties with respect to e.g. interlaminar toughness and strength.« less

Propenyl ether monomers for photopolymerization

DOEpatents

Crivello, J.V.

1996-10-22

Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of the above formula together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

Propenyl ether monomers for photopolymerization

DOEpatents

Crivello, James V.

1996-01-01

Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

Process for the preparation of protected dihydroxypropyl trialkylammonium salts and derivatives thereof

DOEpatents

Hollingsworth, Rawle I.; Wang, Guijun

2000-01-01

A process for the preparation of protected dihydroxypropyl trialkylammonium salts, particularly in chiral form is described. In particular, a process for the preparation of (2,2-dimethyl-1,3-dioxolan-4-ylmethyl)trialkylammonium salts, particularly in chiral form is described. Furthermore, a process is described wherein the (2,2-dimethyl-1,3-dioxolan-4ylmethyl)trialkylammonium salts is a 2,2-dimethyl-1,3-dioxolan-4-ylmethyl trimethylammonium salt, preferably in chiral form. The protected dihydroxypropyl trialkylammonium salts lead to L-carnitine (9) when in chiral form (5).

Mechanistic differences between methanol and dimethyl ether carbonylation in side pockets and large channels of mordenite.

PubMed

Boronat, Mercedes; Martínez, Cristina; Corma, Avelino

2011-02-21

The activity and selectivity towards carbonylation presented by Brønsted acid sites located inside the 8MR pockets or in the main 12MR channels of mordenite is studied by means of quantum-chemical calculations, and the mechanistic differences between methanol and DME carbonylation are investigated. The selectivity towards carbonylation is higher inside the 8MR pockets, where the competitive formation of DME and hydrocarbons that finally leads to catalyst deactivation is sterically impeded. Moreover, inclusion of dispersion interactions in the calculations leads to agreement between the calculated activation barriers for the rate determining step and the experimentally observed higher reactivity of methoxy groups located inside the 8MR channels.

Effect of Ce2O3, La2O3 and ZnO additives on the oxygenates conversion into liquid hydrocarbons

NASA Astrophysics Data System (ADS)

Kachalov, V. V.; Lavrenov, V. A.; Lishchiner, I. I.; Malova, O. V.; Tarasov, A. L.; Zaichenko, V. M.

2018-01-01

A selective modifying effect of cerium, magnesium and zinc oxide additives on the activity and the selectivity of a pentasil group zeolite catalyst in the reaction of conversion of oxygenates (methanol and dimethyl ether) to liquid hydrocarbons was found. It was found that zinc oxide contributes to the stable operation of the zeolite catalyst in the conversion of oxygenates in the synthesis gas stream and leads to the production of gasolines with low durene content (not more than 6.1 wt%). The obtained results demonstrate the rationale for producing hydrocarbons from synthesis gas without the stage of oxygenate separation with their subsequent conversion to synthetic gasoline.

Secondary metabolites from Penicillium pinophilum SD-272, a marine sediment-derived fungus.

PubMed

Wang, Ming-Hui; Li, Xiao-Ming; Li, Chun-Shun; Ji, Nai-Yun; Wang, Bin-Gui

2013-06-21

Two new secondary metabolites, namely, pinodiketopiperazine A (1) and 6,7-dihydroxy-3-methoxy-3-methylphthalide (2), along with alternariol 2,4-dimethyl ether (3) and L-5-oxoproline methyl ester (4), which were isolated from a natural source for the first time but have been previously synthesized, were characterized from the marine sediment-derived fungus Penicillium pinophilum SD-272. In addition, six known metabolites (5-10) were also identified. Their structures were elucidated by analysis of the NMR and mass spectroscopic data. The absolute configuration of compound 1 was determined by experimental and calculated ECD spectra. Compound 2 displayed potent brine shrimp (Artemia salina) lethality with LD₅₀ 11.2 μM.

Electron impact dissociation of amorphous cis-methyl acetate ice analogs

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Mukherjee, R.; Subramanian, K. P.; Banerjee, S. B.

2014-08-01

We have carried out, for the first time, electron irradiation on methyl acetate (CH3COOCH3) ices grown, under astrochemical condition, at 85 K and the chemical changes were probed by FTIR spectroscopy in the mid-IR region (4000-500 cm-1). Carbon dioxide (CO2), carbon monoxide (CO) molecules were found to be the major products indicating a competing dissociation pathway along with the by-products ethane (C2H6) and dimethyl ether (CH3OCH3), respectively. CH3OH (methyl alcohol) formation showed the possibility of acetate to alcohol conversion by keV electron irradiation. In addition irradiation induced aggregation of CH3COOCH3 molecules is also proposed.

Molecular dynamics simulation of the ionic liquid N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2007-10-11

Thermodynamics, structure, and dynamics of an ionic liquid based on a quaternary ammonium salt with ether side chain, namely, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, MOENM2E TFSI, are investigated by molecular dynamics (MD) simulations. Average density and configurational energy of simulated MOENM2E TFSI are interpreted with models that take into account empirical ionic volumes. A throughout comparison of the equilibrium structure of MOENM2E TFSI with previous results for the more common ionic liquids based on imidazolium cations is provided. Several time correlation functions are used to reveal the microscopic dynamics of MOENM2E TFSI. Structural relaxation is discussed by the calculation of simultaneous space-time correlation functions. Temperature effects on transport coefficients (diffusion, conductivity, and viscosity) are investigated. The ratio between the actual conductivity and the estimate from ionic diffusion by the Nernst-Einstein equation indicates that correlated motion of neighboring ions in MOENM2E TFSI is similar to imidazolium ionic liquids. In line with experiment, Walden plot of conductivity and viscosity indicates that simulated MOENM2E TFSI should be classified as a poor ionic liquid.

Volatile sulphur compounds in UHT milk.

PubMed

Al-Attabi, Z; D'Arcy, B R; Deeth, H C

2009-01-01

Several volatile sulphur compounds have been detected in raw and processed milk. These are hydrogen sulphide, methanethiol, carbonyl sulphide, dimethyl sulphide, carbon disulphide, dimethyl disulphide, dimethyl trisulphide, dimethyl sulphoxide, and dimethyl sulphone. Many of these increase in milk during heat processing and are associated with the cooked flavor of heat-treated milks, particularly UHT and sterilized milk. Several researchers have attempted to explain the origin of these volatiles in both raw and processed milk, and how to reduce the associated cooked flavor that has a negative impact on consumer acceptability of processed milk. These compounds are difficult to detect and analyze due to their high volatility, sensitivity to oxidation and heat, and in some cases, their very low concentrations. However, methods of detection and quantification have improved in recent years. Pre-concentration methods such as solid phase microextraction (SPME) together with gas chromatography equipped with sulphur-selective detectors now enable low concentrations of these compounds to be analyzed. In this review, methods of extraction and analyzes of these volatile sulphur compounds are compared, and their occurrence in milk is reviewed.

Synthesis, characterization and properties of carbon nanotubes microspheres from pyrolysis of polypropylene and maleated polypropylene

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

Zhang, Junhao, E-mail: jhzhang6@mail.ustc.edu.cn; Department of Chemistry, University of Science and Technology of China, Heifei, Anhui 230026; Du, Jin

Microspheres assembled from carbon nanotubes (MCNTs), with the diameters ranging from 5.5 to 7.5 {mu}m, were synthesized by means of pyrolysis of polypropylene and maleated polypropylene in an autoclave. The characterization of structure and morphology was carried out by X-ray diffractometer (XRD), field-emission scanning electron microscopy (FESEM), (high resolution) transmission electron microscope [(HR)TEM)], selected-area electron diffraction (SAED) and Raman spectrum. As a typical morphology, the possible growth process of MCNTs was also investigated and discussed. The results of nitrogen adsorption-desorption indicate that the Brunauer-Emett-Teller (BET) surface area (140.6 m{sup 2}/g) of the MCNTs obtained at 600 {sup o}C is aboutmore » twice as that (74.5 m{sup 2}/g) of carbon nanotubes obtained at 700 {sup o}C. The results of catalytic experiment show that MCNTs based catalyst has higher catalytic activity than the carbon nanotubes based catalyst for the preparation of methanol and dimethoxy-ethane by oxidation of dimethyl ether.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

NASA Technical Reports Server (NTRS)

McCoy, LaShelle E.

2012-01-01

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified .. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and cbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes. Issues such as carbon sequestration and subsequent carbon balance of the closed system and identifying ideal process methods to achieve the highest quality products, whilst being energy friendly, will also be addressed.

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

Tan, Eric; Talmadge, M.; Dutta, Abhijit

The U.S. Department of Energy (DOE) promotes research for enabling cost-competitive liquid fuels production from lignocellulosic biomass feedstocks. The research is geared to advance the state of technology (SOT) of biomass feedstock supply and logistics, conversion, and overall system sustainability. As part of their involvement in this program, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) investigate the economics of conversion pathways through the development of conceptual biorefinery process models. This report describes in detail one potential conversion process for the production of high octane gasoline blendstock via indirect liquefaction (IDL). The steps involve themore » conversion of biomass to syngas via indirect gasification followed by gas cleanup and catalytic syngas conversion to a methanol intermediate; methanol is then further catalytically converted to high octane hydrocarbons. The conversion process model leverages technologies previously advanced by research funded by the Bioenergy Technologies Office (BETO) and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via tar and hydrocarbons reforming was one of the key technology advancements as part of that research. The process described in this report evaluates a new technology area with downstream utilization of clean biomass-syngas for the production of high octane hydrocarbon products through a methanol intermediate, i.e., dehydration of methanol to dimethyl ether (DME) which subsequently undergoes homologation to high octane hydrocarbon products.« less

Correlation between urinary methoxyacetic acid and exposure of ethylene glycol dimethyl ether in a lithium battery plant.

PubMed

Yokota, Kozo; Ueno, Hiroshi; Ikeda, Naoko; Johyama, Yasushi; Michitsuji, Hiromi; Yamada, Seiji

2007-10-01

To examine the correlation between airborne ethylene glycol dimethyl ether (EGdiME) exposures and the urinary methoxyacetic acid (MAA) and to approach the issue of a permissible exposure limit for EGdiME. The survey was conducted on Thursday. Workers occupationally exposed to EGdiME, as well as nonexposed controls, were studied in combination with one of the authors, who was coincidentally exposed to EGdiME while carrying out the study. Air levels of EGdiME were determined by personal sampling on passive gas tubes. Urine was collected from nine control subjects and ten workers immediately before and after the shift, and from one of the authors at intervals during 12 h. The analyses of EGdiME in air and MAA in urine were performed by gas chromatography with flame ionization detection. The time-weighted average (TWA) air levels of EGdiME ranged from 0.7 to 10.5 ppm during 8 h work shifts. The urinary levels of MAA in one of the authors increased continuously during exposure and after the end of exposure. The levels of urinary MAA in the exposed workers were significantly higher than those in the control subjects. On the other hand, the postshift values were higher than the preshift values in the exposed workers, but the difference was not significant. A linear correlation was found between the TWA air levels of EGdiME and creatinine-adjusted MAA levels in urine collected at the end of the shift (r = 0.933; P < 0.0001). According to our equation, a linear extrapolation to the biological limit value recommended by Shih et al. (1999) of 40 mg MAA/g crea indicated an average inhalation exposure to EGdiME over the workweek of 12 ppm. These results indicate that the determination of MAA in urine is suitable for use in the biological monitoring of EGdiME exposure.

Probing the antagonistic effect of toluene as a component in surrogate fuel models at low temperatures and high pressures. A case study of toluene/dimethyl ether mixtures

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

Zhang, Yingjia; Somers, Kieran P.; Mehl, Marco

There is a dearth of experimental data which examine the fundamental low-temperature ignition (T < 900 K) behavior of toluene resulting in a lack of data for the construction, validation, and interpretation of chemical kinetic models for commercial fuels. In order to gain a better understanding of its combustion chemistry, dimethyl ether (DME) has been used as a radical initiator to induce ignition in this highly knock resistant aromatic, and its influence on the combustion of toluene ignition was studied in both shock tube and rapid compression machines as a function of temperature (624–1459 K), pressure (20–40 atm), equivalence ratiomore » (0.5–2.0), and blending ratio (100% toluene, 76% toluene (76T/24D), 58% toluene (58T/42D), 26% toluene (26T/74D) and 100% DME). We use several literature chemical kinetic models to interpret our experimental results. For mixtures containing high concentrations of toluene at low-temperatures none of these are capable of reproducing experiment. This then implies an incomplete understanding of the low-temperature oxidation pathways which control its ignition in our experimental reactors, and by extension, in spark- (SI) and compression-ignition (CI) engines, and an updated detailed chemical kinetic model is presented for engineering applications. Model analyses indicate that although the initial fate of the fuel is dominated by single-step H-atom abstraction reactions from both the benzylic and phenylic sites, the subsequent fate of the allylic and vinylic radicals formed is much more complex. Further experimental and theoretical endeavors are required to gain a holistic qualitative and quantitative chemical kinetics based understanding of the combustion of pure toluene, toluene blends, and commercial fuels containing other aromatic components, at temperatures of relevance to SI and CI engines.« less

Probing the antagonistic effect of toluene as a component in surrogate fuel models at low temperatures and high pressures. A case study of toluene/dimethyl ether mixtures

DOE PAGES

Zhang, Yingjia; Somers, Kieran P.; Mehl, Marco; ...

2016-07-12

There is a dearth of experimental data which examine the fundamental low-temperature ignition (T < 900 K) behavior of toluene resulting in a lack of data for the construction, validation, and interpretation of chemical kinetic models for commercial fuels. In order to gain a better understanding of its combustion chemistry, dimethyl ether (DME) has been used as a radical initiator to induce ignition in this highly knock resistant aromatic, and its influence on the combustion of toluene ignition was studied in both shock tube and rapid compression machines as a function of temperature (624–1459 K), pressure (20–40 atm), equivalence ratiomore » (0.5–2.0), and blending ratio (100% toluene, 76% toluene (76T/24D), 58% toluene (58T/42D), 26% toluene (26T/74D) and 100% DME). We use several literature chemical kinetic models to interpret our experimental results. For mixtures containing high concentrations of toluene at low-temperatures none of these are capable of reproducing experiment. This then implies an incomplete understanding of the low-temperature oxidation pathways which control its ignition in our experimental reactors, and by extension, in spark- (SI) and compression-ignition (CI) engines, and an updated detailed chemical kinetic model is presented for engineering applications. Model analyses indicate that although the initial fate of the fuel is dominated by single-step H-atom abstraction reactions from both the benzylic and phenylic sites, the subsequent fate of the allylic and vinylic radicals formed is much more complex. Further experimental and theoretical endeavors are required to gain a holistic qualitative and quantitative chemical kinetics based understanding of the combustion of pure toluene, toluene blends, and commercial fuels containing other aromatic components, at temperatures of relevance to SI and CI engines.« less

Experimental and Modeling Investigation of the Low-Temperature Oxidation of Dimethyl Ether.

PubMed

Rodriguez, Anne; Frottier, Ophélie; Herbinet, Olivier; Fournet, René; Bounaceur, Roda; Fittschen, Christa; Battin-Leclerc, Frédérique

2015-07-16

The oxidation of dimethyl ether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K; equivalence ratios of 0.25, 1, and 2; residence time of 2 s; pressure of 106.7 kPa (close to the atmospheric pressure); and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring-down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde, which is one of the major products from DME oxidation, as well as that of hydrogen peroxide, which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bars on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine, and flame data from literature. The kinetic analysis of the model enabled the highlighting of some specificities of the oxidation chemistry of DME: (1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H atom abstraction) with oxygen yielding an olefin + HO2·; (2) the low-temperature reactivity is driven by the relative importance of the second addition to O2 (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting effect.

Performance Characteristics of a DME Propellant Arcjet Thruster

NASA Astrophysics Data System (ADS)

Kakami, Akira; Beeppu, Shinji; Maiguma, Muneyuki; Tachibana, Takeshi

This paper describes the influence of cathode configuration on performance of an arcjet thruster using dimethyl ether (DME) propellant. DME, an ether compound, has suitable characteristics for a space propulsion system; DME is storable in a liquid state without being kept under a high pressure, and requires no sophisticated temperature management such as a cryogenic device. DME can be gasified and liquefied simply by adjusting temperature whereas hydrazine, a conventional propellant, requires an iridium-based particulate catalyst for its gasification. In this study, thrust of a 1-kW class DME arcjet thruster is measured at a discharge current of 13 A, DME mass flow rates ranging 15 to 60 mg/s under three cathode configurations: flat-tip rods of 2 and 4 mm in diam. and 4-mm-diam. rod having a cavity of 2 mm in diameter. Thrust measurements show that thrust is increased with propellant mass flow rate. Among the tested cathodes, the flat-tip rod of 4 mm in diam. with 55 mg/s DME flow rate yielded the highest performance: specific impulse of 330 s, thrust of 0.18 N, discharge power of 1400 W and specific power of 25 MJ/kg.

Synthesis and biological studies of positron-emitting radiopharmaceuticals

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

Dischino, D.D.

The development and clinical evaluation of two-positron emitting radiopharmaceuticals designed to image myelin in humans is reported. Carbon-11-labeled benzyl methyl ether was synthesized by the reaction of carbon-11-labeled methanol and benzyl chloride in dimethyl sulfoxide containing powdered potassium hydroxide in a radiochemical yield of 43% and a synthesis and purification time of 40 minutes. Carbon-11-labeled diphenylmethanol was synthesized by the reaction of carbon-11-labeled carbon dioxide and phenyllithium followed by the reduction of the carbon-11-labeled intermediate to diphenylmethanol via lithium aluminum hydride in a radiochemical yield of 71% and a synthesis and purification time of 38 minutes. Carbon-11-labeled benzyl methyl ethermore » and diphenylmethanol were each evaluated as myelin imaging agents in three patients with multiple sclerosis via positron-emission tomography. In two out of three patients studied with carbon-11-labeled benzyl methyl ether, the distribution of activity in the brain was not consistent with local lipid content. A new synthesis of carbon-11-labeled-DL-phenylalanine labeled in the benzylic position and the synthesis of fluorine-18-labeled 1-(2-nitro-1-imidazolyl)-3-fluoro-2-propanol, a potential in vivo marker of hypoxic tissue, are reported.« less

Co-processing as a tool to improve aqueous dispersibility of cellulose ethers.

PubMed

Sharma, Payal; Modi, Sameer R; Bansal, Arvind K

2015-01-01

Cellulose ethers are important materials with numerous applications in pharmaceutical industry. They are widely employed as stabilizers and viscosity enhancers for dispersed systems, binders in granulation process and as film formers for tablets. These polymers, however, exhibit challenge during preparation of their aqueous dispersions. Rapid hydration of their surfaces causes formation of a gel that prevents water from reaching the inner core of the particle. Moreover, the surfaces of these particles become sticky, thus leading to agglomeration, eventually reducing their dispersion kinetics. Numerous procedures have been tested to improve dispersibility of cellulose ethers. These include the use of cross-linking agents, alteration in the synthesis process, adjustment of water content of cellulose ether, modification by attaching hydrophobic substituents and co-processing using various excipients. Among these, co-processing has provided the most encouraging results. This review focuses on the molecular mechanisms responsible for the poor dispersibility of cellulose ethers and the role of co-processing technologies in overcoming the challenge. An attempt has been made to highlight various co-processing techniques and specific role of excipients used for co-processing.

Diastereoisomers of 2-benzyl-2, 3-dihydro-2-(1H-inden-2-yl)-1H-inden-1-ol: potential anti-inflammatory agents.

PubMed

Sheridan, Helen; Walsh, John J; Cogan, Carina; Jordan, Michael; McCabe, Tom; Passante, Egle; Frankish, Neil H

2009-10-15

The synthesis and biological activity of the novel diastereoisomers of 2-benzyl-2,3-dihydro-2-(1H-inden-2-yl)-1H-inden-1-ol is reported. The 2,2-coupled indane dimers were synthesised by coupling of the silyl enol ether of 1-indanone with the dimethyl ketal of 2-indanone. The coupled product was directly alkylated to give the racemic ketone which was reduced to the diastereoisomeric alcohols. The alcohols were separated and their relative stereochemistry was established by X-ray crystallography. These molecules demonstrate significant anti-inflammatory activity in vivo and in vitro and may represent a new class of anti-inflammatory agent.

Kinetic and equilibrium lithium acidities of arenes: theory and experiment.

PubMed

Streitwieser, Andrew; Shah, Kamesh; Reyes, Julius R; Zhang, Xingyue; Davis, Nicole R; Wu, Eric C

2010-08-26

Kinetic acidities of arenes, ArH, measured some time ago by hydrogen isotope exchange kinetics with lithium cyclohexylamide (LiCHA) in cyclohexylamine (CHA) show a wide range of reactivities that involve several electronic mechanisms. These experimental reactivities give an excellent Brønsted correlation with equilibrium lithium ion pair acidities (pK(Li)) derived as shown recently from computations of ArLi.2E (E = dimethyl ether). The various electronic mechanisms are well modeled by ab initio HF calculations with modest basis sets. Additional calculations using NH(3) as a model for CHA further characterize the TS of the exchange reactions. The slopes of Brønsted correlations of ion pair systems can vary depending on the nature of the ion pairs.

A ToF-SIMS and XPS study of protein adsorption and cell attachment across PEG-like plasma polymer films with lateral compositional gradients

NASA Astrophysics Data System (ADS)

Menzies, Donna J.; Jasieniak, Marek; Griesser, Hans J.; Forsythe, John S.; Johnson, Graham; McFarland, Gail A.; Muir, Benjamin W.

2012-12-01

In this work we report a detailed X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) study of poly(ethylene glycol) PEG-like chemical gradients deposited via plasma enhanced chemical vapour deposition (PECVD) at two different load powers using diethylene glycol dimethyl ether (DG) as a monomer. Principal component analysis (PCA) was applied to the ToF-SIMS data both before and after protein adsorption on the plasma polymer thin films. Results of the PCA loadings indicated a higher content of hydrocarbon fragments across the higher load power gradient, which adsorbed higher amounts of proteins. Gradients deposited at a lower load power retained a higher degree of monomer like functionality as did the central region directly underneath the knife edge electrode. Analysis of the adsorption of serum proteins (human serum albumin and fetal bovine serum) was monitored across the gradient films and increased with decreasing ether (PEG-like) film chemistries. The effect of protein incubation time on the levels adsorbed fetal bovine serum on the plasma polymer films was critical, with significantly more protein adsorbing after 24 hour incubation times on both gradient films. The attachment of HeLa cells on the gradients appeared to be dictated not only by the surface chemistry, but also by the adsorption of serum proteins. XPS analysis revealed that at surface ether concentrations of less than 70% in the gradient films, significant increases in protein and cell attachment were observed.

Relative Sustainability of Natural Gas Assisted High-Octane Gasoline Blendstock Production from Biomass

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

Tan, Eric C; Zhang, Yi Min; Cai, Hao

Biomass-derived hydrocarbon fuel technologies are being developed and pursued for better economy, environment, and society benefits underpinning the sustainability of transportation energy. Increasing availability and affordability of natural gas (NG) in the US can play an important role in assisting renewable fuel technology development, primarily in terms of economic feasibility. When a biorefinery is co-processing NG with biomass, the current low cost of NG coupled with the higher NG carbon conversion efficiency potentially allow for cost competitiveness of the fuel while achieving a minimum GHG emission reduction of 50 percent or higher compared to petroleum fuel. This study evaluates themore » relative sustainability of the production of high-octane gasoline blendstock via indirect liquefaction (IDL) of biomass (and with NG co-feed) through methanol/dimethyl ether intermediates. The sustainability metrics considered in this study include minimum fuel selling price (MFSP), carbon conversion efficiency, life cycle GHG emissions, life cycle water consumption, fossil energy return on investment (EROI), GHG emission avoidance cost, and job creation. Co-processing NG can evidently improve the MFSP. Evaluation of the relative sustainability can shed light on the biomass-NG synergistic impacts and sustainability trade-offs associated with the IDL as high-octane gasoline blendstock production.« less

URANIUM PURIFICATION PROCESS

DOEpatents

Winters, C.E.

1957-11-12

A method for the preparation of a diethyl ether solution of uranyl nitrate is described. Previously the preparation of such ether solutions has been difficult and expensive, since crystalline uranyl nitrate hexahydrate dissolves very slowly in ether. An improved method for effecting such dissolution has been found, and it comprises adding molten uranyl nitrate hexahydrate at a temperature of 65 to 105 deg C to the ether while maintaining the temperature of the ether solvent below its boiling point.

Alkyl Aryl Ether Bond Formation with PhenoFluor**

PubMed Central

Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

2015-01-01

An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

Infrared spectra of some acetone—magnesium adducts

NASA Astrophysics Data System (ADS)

Hisatsune, I. C.

Co-deposition of atomic magnesium with excess acetone at liquid-nitrogen temperature produces an unstable charge-transfer complex with a characteristic carbonyl infrared band at 1595 cm -1 and stable acetone adducts in which the metal atom bridges the carbonyl bond (π-complex) or coordinates to the oxygen atom (σ-complex). Infrared spectra of these complexes with (CH 3) 2CO and (CD 3) 2CO have been obtained. Corroborations for these adducts were obtained from infrared studies of acetone matrices with atomic copper and acetaldehyde matrices with atomic magnesium and with atomic copper. Infrared spectra of an acetone adduct and a dimethyl ether adduct of the Grignard reagent CH 3MgI have also been obtained. Hydrolysis of a σ-adduct gives acetone but isopropyl alcohol is obtained from hydrolysis of the π-adduct.

Antimutagenic activity of extracts of leaves of four common edible vegetable plants in Nigeria (west Africa).

PubMed

Obaseiki-Ebor, E E; Odukoya, K; Telikepalli, H; Mitscher, L A; Shankel, D M

1993-06-01

Organic solvent extracts of leaves of 4 common edible vegetable plants--Bryophyllum pinnatum, Dialium guincense, Ocimum gratissimum and Vernonia amygdalina--had inhibitory activity for His- to His+ reverse-mutations induced by ethyl methanesulfonate acting on Salmonella typhimurium TA100. The concentrated ethyl acetate, methanol and petroleum ether extracts were heat-stable when dissolved in dimethyl sulfoxide. The Bryophyllum ethyl acetate extract was fractionated into alkaloidal/water-soluble, acids, polar lipid and non-polar lipid fractions. The polar and non-polar lipid fractions inhibited reversion mutations induced by ethyl methanesulfonate acting on TA100 or TA102, and were also active against reversions induced by 4-nitro-O-phenylenediamine and 2-aminofluorene in TA98. The alkaloidal/water-soluble and the acid fractions had no appreciable antimutagenic activities.

4-{2-[2-(4-Formyl-phen-oxy)eth-oxy]eth-oxy}benzaldehyde.

PubMed

Ma, Zhen; Cao, Yiqun

2011-06-01

The title compound, C(18)H(18)O(5), was obtained by the reaction of 4-hy-droxy-benzaldehyde with bis-(2,2-dichloro-eth-yl) ether in dimethyl-formamide. In the crystal, the mol-ecule lies on a twofold rotation axis that passes through the central O atom of the aliphatic chain, thus leading to one half-mol-ecule being present per asymmetric unit. The carbonyl, aryl and O-CH(2)-CH(2) groups are almost coplanar, with an r.m.s. deviation of 0.030 Å. The aromatic rings are approximately perpendicular to each other, forming a dihedral angle of 78.31 sh;H⋯O hydrogen bonds and C-H⋯π inter-actions help to consolidate the three-dimensional network.

Analysis of hydroquinone and some of its ethers by using capillary electrochromatography.

PubMed

Desiderio, C; Ossicini, L; Fanali, S

2000-07-28

Capillary electrochromatography (CEC) was used for the analysis of relevant compounds in cosmetic preparation. Hydroquinone (HQ) and some of its ethers (methyl-, dimethyl-, benzyl-, phenyl-, propyl-HQ derivatives) were analyzed by using an octadecylsilica (ODS) stationary phase packed in fused-silica capillary (100 microm I.D.; 30 cm and 21.5 cm total and effective lengths, respectively). 20 mM Ammonium acetate pH 6-acetonitrile (50-70%) were the mobile phases used for the experiments. The acetonitrile (ACN) content strongly influenced the resolution of the studied compounds as well as the efficiency and the retention factor. Baseline resolution for the studied analytes was achieved at both the lowest and the highest percentage of ACN, the last one providing the shortest analysis time. Mobile phase containing 70% of ACN was therefore used for the analysis of an extract of skin-toning cream declared to contain HQ. Good repeatability of both retention times, peak areas and peak areas ratio (Asample/Ainternational standard) was found. The calibration graphs were linear in the concentration range studied (5-90 microg/ml) with correlation coefficients between 0.9975 and 09991. The analysis of the cosmetic preparation revealed the presence of HQ (1.72%, w/w) and of two additional peaks (not identified).

Our Galactic Neighbor Hosts Complex Organic Molecules

NASA Astrophysics Data System (ADS)

Hensley, Kerry

2018-03-01

For the first time, data from the Atacama Large Millimeter/submillimeter Array (ALMA) reveal the presence of methyl formate and dimethyl ether in a star-forming region outside our galaxy. This discovery has important implications for the formation and survival of complex organic compounds importantfor the formation of life in low-metallicity galaxies bothyoung and old.No Simple Picture of Complex Molecule FormationALMA, pictured here with the Magellanic Clouds above, has observed organic molecules in our Milky Way Galaxy and beyond. [ESO/C. Malin]Complex organic molecules (those with at least six atoms, one or more of which must be carbon) are the precursors to the building blocks of life. Knowing how and where complex organic molecules can form is a key part of understanding how life came to be on Earth and how it might arise elsewhere in the universe. From exoplanet atmospheres to interstellar space, complex organic molecules are ubiquitous in the Milky Way.In our galaxy, complex organic molecules are often found in the intense environments of hot cores clumps of dense molecular gas surrounding the sites of star formation. However, its not yet fully understood how the complex organic molecules found in hot cores come to be. One possibility is that the compounds condense onto cold dust grains long before the young stars begin heating their natal shrouds. Alternatively, they might assemble themselves from the hot, dense gas surrounding the blazing protostars.Composite infrared and optical image of the N 113 star-forming region in the LMC. The ALMA coverage is indicated by the gray line. Click to enlarge. [Sewio et al. 2018]Detecting Complexity, a Galaxy AwayUsing ALMA, a team of researchers led by Marta Sewio (NASA Goddard Space Flight Center) recently detected two complex organic molecules methyl formate and dimethyl ether for the first time in our neighboring galaxy, the Large Magellanic Cloud (LMC). Previous searches for organic molecules in the LMC detected small amounts of methanol, the parentmolecule of the two newly-discovered compounds. By revealing the spectral signatures of dimethyl ether and methyl formate, Sewio and collaboratorsfurther prove thatorganic chemistry is hard at work in hot cores in the LMC.This discovery is momentous because dwarf galaxies like theLMC tend to have a lower abundance of the heavy elements that make up complex organic molecules most importantly, oxygen, carbon, and nitrogen. Beyond lacking the raw materials necessary to create complex molecules, the gas of low-metallicity galaxies does a poorer job preventing the penetration of high-energy photons. The impinging photons warm dust grains, resulting in a lower probability of forming and maintaining complex organic molecules. Despite this, organic molecules appear to beable todevelop and persist which has exciting implications for organic chemistry in low-metallicity environments.ALMA observation of emission by methyl formate in a hot core in the LMC.[Adapted from Sewio et al. 2018]A Lens into the PastIn the early universe, before the budding galaxies have had time to upcycle their abundant hydrogen into heavier elements, organic chemistry is thought to proceed slowly or not at all. The discovery of complex organic molecules in a nearby low-metallicity galaxy upends this theory and propels us toward a better understanding of the organic chemistry in the early universe.CitationMarta Sewio et al 2018ApJL853L19. doi:10.3847/2041-8213/aaa079

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

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

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Analysis of lignans in Magnoliae Flos by turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry.

PubMed

Zhou, Xuan; Chen, Cen; Ye, Xiaolan; Song, Fenyun; Fan, Guorong; Wu, Fuhai

2016-04-01

In this study, a method coupling turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry was developed for analyzing the lignans in Magnoliae Flos. By the online pretreatment of turbulent flow chromatography solid-phase extraction, the impurities removal and analytes concentration were automatically processed, and the lignans were separated rapidly and well. Seven lignans of Magnoliae Flos including epieudesmin, magnolin, 1-irioresinol-B-dimethyl ether, epi-magnolin, fargesin aschantin, and demethoxyaschantin were identified by comparing their retention behavior, UV spectra, and mass spectra with those of reference substances or literature data. The developed method was validated, and the good results showed that the method was not only automatic and rapid, but also accurate and reliable. The turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry method holds a high potential to become an effective method for the quality control of lignans in Magnoliae Flos and a useful tool for the analysis of other complex mixtures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sterol Alkyl Ethers in Immature Callovian (Middle Jurassic) Sediments of Pas de Calais and Normandy (France): Environmental Constraints on their Potential Origins.

NASA Astrophysics Data System (ADS)

Kenig, F. P. H.

2017-12-01

Steryl alkyl ethers (SAEs), steroids with C8-C12 alkyl ether substituent at C3have only been reported in a limited number of studies since their first identification in modern diatomaceous ooze (Boon and de Leeuw, 1979 Mar. Chem. 7, 117-132). These compounds were identified in Holocene to Eocene sediments, but only once in the Cretaceous, in the Valanginian sediments of Shasky Rise (Brassell, 2009; Palaeo Palaeo Palaeo 282, 45-57). The origin of these compounds remains unclear, though they have been proposed to be associated with diatoms and biologically productive environments and cold water. Here we report the occurrence of SAEs in Callovian (Middle Jurassic), thermally immature sediments of the Marnes d'Argences near Caen (Normandy, France) and near Le Wast (Pas de Calais, France), extanding their geological occurrence by 28 million years. These marls contain C36 to C41 SAEs with C9 or C10 alkyl moieties. The steroid moieties (C27 to C31) are saturated, unsaturated (at C5 or C22), or di-unsaturated (at C5 and C22). Some of the samples collected near Le Wast contain only 4-methyl substituted C27, C28 and C29 steroid moieties as well as steroid moieties typical of dinoflagellates such 4,23,24-trimethylsteroids saturated and unsaturated at C22, and diatoms such as 4-desmethyl-23,24-dimethyl-steroid. The origin of SAEs will be discussed in view of their novel identification in Jurassic sediments and considering the environment of deposition of the Marnes d'Argences and comparison with their stratigraphic equivalent in England (Oxford Clay) and Eastern France where none of these compounds were observed.

Mechanisms underlying the relaxant effect of Galetin 3,6- dimethyl ether, from Piptadenia stipulacea (Benth.) Ducke, on guinea-pig trachea.

PubMed

Macêdo, Cibério Landim; Vasconcelos, Luiz Henrique César; Correia, Ana Carolina de Carvalho; Martins, Italo Rossi Roseno; Lira, Daysianne Pereira de; Santos, Bárbara Viviana de Oliveira; Silva, Bagnólia Araújo da

2014-01-01

Galetin 3,6-dimethyl ether (FGAL), a flavonoid from the aerial parts of Piptadenia stipulacea (Benth.) Ducke, was found to exert a relaxant effect on carbachol (CCh)-pre-contracted guinea-pig trachea. Based on cumulative concentration-response curves to CCh, FGAL antagonized muscarinic receptors pseudo-irreversibly and noncompetitively, since it inhibited and shifted these curves towards higher concentrations in a nonparallel manner. In addition, FGAL was more potent in relaxing contractions induced by 18 mM as compared to 60 mM KCl (pD2 = 5:50 ±0:36 and 4.80 ±0.07, respectively), indicating the participation of K+ channels. In the presence of 10 mM tetraethylammonium (TEA+) chloride, a nonselective K+ channel blocker, the relaxant potency of FGAL was reduced (from pD2 = 5:12 ±0:07 to 4.87 ±0.02). Among several selective blockers of K+ channel subtypes, only apamin, an SKCa (small-conductance Ca2+-activated K+ channels) blocker, attenuated the relaxant potency of FGAL (pD2 = 4:85±0:06), suggesting SKCa activation. FGAL was equipotent in relaxing trachea contracted by 60 mM KCl (pD2 =4:80 ±0:07) or 10-6 M CCh (pD2 = 5:02 ±0:07), suggesting CaV (voltage-gated calcium channel), but not ROCs (receptor-operated calcium channels) participation. Furthermore, aminophylline-induced relaxation (pD2 = 4:12 ±0:06) was potentiated around 4-fold (pD2 = 4:80 ±0:44) in the presence of FGAL. Moreover, forskolininduced relaxation (pD2 = 6:51 ±0:06) was potentiated around 2.5-fold (pD2 = 6:90 ±0:05) by FGAL. Conversely, sodium nitroprusside-induced relaxation was unaffected, indicating that the AC/cAMP/PKA pathway, but not the NO pathway, may be modulated by the flavonoid. These results suggest that, in guinea-pig trachea, FGAL induces relaxation by pseudo-irreversible noncompetitive antagonism on muscarinic receptors, modulation of K+ and Ca2+ channels, as well as activation of the AC/cAMP/PKA pathway.

Dimethyl phthalate

Integrated Risk Information System (IRIS)

Dimethyl phthalate ; CASRN 131 - 11 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogeni

Tunable Crystallization and Nucleation of Planar CH3NH3PbI3 through Solvent-Modified Interdiffusion.

PubMed

Yao, Zhibo; Jones, Timothy W; Grigore, Mihaela; Duffy, Noel W; Anderson, Kenrick F; Dunbar, Ricky B; Feron, Krishna; Hao, Feng; Lin, Hong; Wilson, Gregory J

2018-05-02

A smooth and compact light absorption perovskite layer is a highly desirable prerequisite for efficient planar perovskite solar cells. However, the rapid reaction between CH 3 NH 3 I methylammonium iodide (MAI) and PbI 2 often leads to an inconsistent CH 3 NH 3 PbI 3 crystal nucleation and growth rate along the film depth during the two-step sequential deposition process. Herein, a facile solvent additive strategy is reported to retard the crystallization kinetics of perovskite formation and accelerate the MAI diffusion across the PbI 2 layer. It was found that the ultrasmooth perovskite thin film with narrow crystallite size variation can be achieved by introducing favorable solvent additives into the MAI solution. The effects of dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, chlorobenzene, and diethyl ether additives on the morphological properties and cross-sectional crystallite size distribution were investigated using atomic force microscopy, X-ray diffraction, and scanning electron microscopy. Furthermore, the light absorption and band structure of the as-prepared CH 3 NH 3 PbI 3 films were investigated and correlated with the photovoltaic performance of the equivalent solar cell devices. Details of perovskite nucleation and crystal growth processes are presented, which opens new avenues for the fabrication of more efficient planar solar cell devices with these ultrasmooth perovskite layers.

Postextraction Separation, On-Board Storage, and Catalytic Conversion of Methane in Natural Gas: A Review.

PubMed

Saha, Dipendu; Grappe, Hippolyte A; Chakraborty, Amlan; Orkoulas, Gerassimos

2016-10-12

In today's perspective, natural gas has gained considerable attention, due to its low emission, indigenous availability, and improvement in the extraction technology. Upon extraction, it undergoes several purification protocols including dehydration, sweetening, and inert rejection. Although purification is a commercially established technology, several drawbacks of the current process provide an essential impetus for developing newer separation protocols, most importantly, adsorption and membrane separation. This Review summarizes the needs of natural gas separation, gives an overview of the current technology, and provides a detailed discussion of the progress in research on separation and purification of natural gas including the benefits and drawbacks of each of the processes. The transportation sector is another growing sector of natural gas utilization, and it requires an efficient and safe on-board storage system. Compressed natural gas (CNG) and liquefied natural gas (LNG) are the most common forms in which natural gas can be stored. Adsorbed natural gas (ANG) is an alternate storage system of natural gas, which is advantageous as compared to CNG and LNG in terms of safety and also in terms of temperature and pressure requirements. This Review provides a detailed discussion on ANG along with computation predictions. The catalytic conversion of methane to different useful chemicals including syngas, methanol, formaldehyde, dimethyl ether, heavier hydrocarbons, aromatics, and hydrogen is also reviewed. Finally, direct utilization of methane onto fuel cells is also discussed.

One-Pot Preparation of Dimethyl Isosorbide from d-Sorbitol via Dimethyl Carbonate Chemistry.

PubMed

Aricò, F; Aldoshin, A S; Tundo, P

2017-01-10

Direct synthesis of dimethyl isosorbide (DMI) from d-sorbitol via dimethyl carbonate (DMC) chemistry is herein first reported. High yield of DMI was achieved using the nitrogen superbase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst and performing the reaction in a stainless steel autoclave by increasing the temperature from 90 to 200 °C. In this procedure, DMC features its full capacity acting in the different steps of the process as carboxymethylating, leaving-group (cyclization), and methylating agent; DMC is also employed as the reaction media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dimethyl terephthalate (DMT)

Integrated Risk Information System (IRIS)

Dimethyl terephthalate ( DMT ) ; CASRN 120 - 61 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for No

Dimethyl sulfate

Integrated Risk Information System (IRIS)

Dimethyl sulfate ; CASRN 77 - 78 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

Kinetic and thermodynamic selectivity of intermolecular C-H activation at [Tp'Rh(PMe3)]. How does the ancillary ligand affect the metal-carbon bond strength?

PubMed

Jiao, Yunzhe; Morris, James; Brennessel, William W; Jones, William D

2013-10-30

Tp'Rh(PMe3)(CH3)H was synthesized as a precursor to produce the coordinatively unsaturated fragment [Tp'Rh(PMe3)], which reacts with benzene, mesitylene, 3,3-dimethyl-1-butene, 2-methoxy-2-methylpropane, 2-butyne, acetone, pentane, cyclopentane, trifluoroethane, fluoromethane, dimethyl ether, and difluoromethane at ambient temperature to give only one product in almost quantitative yield in each case. All of the complexes Tp'Rh(PMe3)(R)H were characterized by NMR spectroscopy, and their halogenated derivatives were fully characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The active species [Tp'Rh(PMe3)] was also able to activate the alkynyl C-H bond of terminal alkynes to give activation products of the type Tp'Rh(PMe3)(C≡CR)H (R = t-Bu, SiMe3, hexyl, CF3, Ph, p-MeOC6H4, and p-CF3C6H4). The measured relative rhodium-carbon bond strengths display two linear correlations with the corresponding carbon-hydrogen bond strengths, giving a slope of 1.54 for α-unsubstituted hydrocarbons and a slope of 1.71 for substrates with α-substitution. Similar trends of energy correlations were established by DFT calculated metal-carbon bond strengths for the same groups of substrates.

Kinetics of the gas-phase reaction between ozone and three unsaturated oxygenated compounds: Ethyl 3,3-dimethyl acrylate, 2-methyl-2-pentenal and 6-methyl-5-hepten-2-one at atmospheric pressure

NASA Astrophysics Data System (ADS)

Gaona Colmán, Elizabeth; Blanco, María B.; Barnes, Ian; Teruel, Mariano A.

2015-05-01

Rate coefficients for the gas-phase reactions of O3 molecules with three unsaturated oxygenated compounds have been determined using the relative kinetic technique in an environmental chamber with FTIR detection of the reactants at (298 ± 2) K in 760 Torr total pressure of synthetic air. The following rate coefficients (in units of 10-17 cm3 molecule-1 s-1) were determined: ethyl 3,3-dimethyl acrylate (0.82 ± 0.19), 2-methyl-2-pentenal (0.71 ± 0.16) and 6-methyl-5-hepten-2-one (26 ± 7). The different reactivity of the unsaturated oxygenated compounds toward O3 is discussed in terms of their chemical structure. In addition, a correlation between the reactivity of structurally different unsaturated compounds (alkenes and unsaturated oxygenated VOCs, such as ethers, esters, aldehydes, ketones and alcohols) toward O3 molecules and the HOMO (Highest Occupied Molecular Orbital) of the compounds is presented. Using the kinetic parameters determined in this work, residence times of these unsaturated compounds in the atmosphere with respect to reaction with O3 have been calculated. In urban and rural areas the main sink of 6-methyl-5-hepten-2-one is reaction with O3 molecules with a residence time in the order of few minutes.

Total Synthesis of Purported Cephalosporolides H and I, Penisporolide B, and Their Stereoisomers.

PubMed

Wang, Jian; Tong, Rongbiao

2016-05-20

Development of a unified, bioinspired synthetic strategy to access four possible diastereomers of unique 2,2-dimethyl-[5,5]-spiroacetal-cis-fused-γ-lactone (Me2SAFL) is reported, featuring pyridinium chlorochromate (PCC)-promoted oxidative ring expansion of β-hydroxy cyclic ethers and dehydrative ring-contraction rearrangement of 10-membered lactones. Synthetic utility of this strategy was demonstrated by total syntheses of 12 Me2SAFLs, corresponding to the purported cephalosporolide H (CesH), cephalosporolide I (CesI), and penisporolide B (PenB) and their possible diastereomers. Comprehensive NMR data analysis suggested that the tricyclic Me2SAFL core of CesH, CesI, and PenB should be revised to the same relative (3R*, 4R*, 6S*, 9R*) configuration and that the side chains required an unknown constitutional structure revision.

Carma 1 CM Line Survey of Orion-Kl

NASA Astrophysics Data System (ADS)

Friedel, Douglas; Looney, Leslie; Corby, Joanna F.; Remijan, Anthony

2015-06-01

We have conducted the first 1 cm (27-35 GHz) line survey of the Orion-KL region by an array. With a primary beam of ˜4.5 arcminutes, the survey looks at a region ˜166,000 AU (0.56 pc) across. The data have a resolution of ˜6 arcseconds on the sky and 97.6 kHz(1.07-0.84 km/s) in frequency. This region of frequency space is much less crowded than at 3mm or 1mm frequencies and contains the fundamental transitions of several complex molecular species, allowing us to probe the largest extent of the molecular emission. We present the initial results, and comparison to 3mm results, from several species including, dimethyl ether [(CH_3)_2O], ethyl cyanide [C_2H_5CN], acetone [(CH_3)_2CO], SO, and SO_2.

A Nonaqueous Potassium-Based Battery-Supercapacitor Hybrid Device.

PubMed

Fan, Ling; Lin, Kairui; Wang, Jue; Ma, Ruifang; Lu, Bingan

2018-05-01

A low cost nonaqueous potassium-based battery-supercapacitor hybrid device (BSH) is successfully established for the first time with soft carbon as the anode, commercialized activated carbon as the cathode, and potassium bis(fluoro-slufonyl)imide in dimethyl ether as the electrolyte. This BSH reconciles the advantages of potassium ion batteries and supercapacitors, achieving a high energy density of 120 W h kg -1 , a high power density of 599 W kg -1 , a long cycle life of 1500 cycles, and an ultrafast charge/slow discharge performance (energy density and power density are calculated based on the total mass of active materials in the anode and cathode). This work demonstrates a great potential of applying the nonaqueous BSH for low cost electric energy storage systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics ofmore » conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to DME, which is subsequently converted via homologation reactions to high-octane, gasoline-range hydrocarbon products.« less

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

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit

This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

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

Gao, Yue; Zhao, Yuming; Li, Yuguang C.

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Identification of potent odorants in different cultivars of snake fruit [Salacca zalacca (Gaert.) Voss] using gas chromatography-olfactometry.

PubMed

Wijaya, C H; Ulrich, D; Lestari, R; Schippel, K; Ebert, G

2005-03-09

Three cultivars of snake fruits, Pondoh Hitam, Pondoh Super, and Gading, were freshly extracted using liquid-liquid extraction. The aroma compounds of the three samples were analyzed by GC-MS and GC-olfactometry using the nasal impact frequency (NIF) method. A total of 24 odor-active compounds were associated with the aroma of snake fruit. Methyl 3-methylpentanoate was regarded as the character impact odorant of typical snake fruit aroma. 2-Methylbutanoic acid, 3-methylpentanoic acid, and an unknown odorant with very high intensity were found to be responsible for the snake fruit's sweaty odor. Other odorants including methyl 3-methyl-2-butenoate (overripe fruity, ethereal), methyl 3-methyl-2-pentenoate (ethereal, strong green, woody), and 2,5-dimethyl-4-hydroxy-3[2]-furanone (caramel, sweet, cotton candy-like) contribute to the overall aroma of snake fruit. Methyl dihydrojasmonate and isoeugenol, which also have odor impact, were identified for the first time as snake fruit volatiles. The main differences between the aroma of Pondoh and Gading cultivars could be attributed to the olfactory attributes (metallic, chemical, rubbery, strong green, and woody), which were perceived by most of the panelists in the Pondoh samples but were not detected in the Gading samples. This work is a prerequisite for effective selection of salak genotypes with optimal aroma profiles for high consumer acceptance.

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE PAGES

Gao, Yue; Zhao, Yuming; Li, Yuguang C.; ...

2017-10-06

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Catalyst system and process for benzyl ether fragmentation and coal liquefaction

DOEpatents

Zoeller, Joseph Robert

1998-04-28

Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

Sorbents for High Temperature Removal of Arsenic from Coal-Derived Synthesis Gas

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

Alptekin, G.O.; Copeland, R.; Dubovik, M.

2002-09-20

Gasification technologies convert coal and other heavy feedstocks into synthesis gas feed streams that can be used in the production of a wide variety of chemicals, ranging from hydrogen through methanol, ammonia, acetic anhydride, dimethyl ether (DME), methyl tertiary butyl ether (MTBE), high molecular weight liquid hydrocarbons and waxes. Syngas can also be burned directly as a fuel in advanced power cycles to generate electricity with very high efficiency. However, the coal-derived synthesis gas contains a myriad of trace contaminants that may poison the catalysts that are used in the downstream manufacturing processes and may also be regulated in powermore » plant emissions. Particularly, the catalysts used in the conversion of synthesis gas to methanol and other liquid fuels (Fischer-Tropsch liquids) have been found to be very sensitive to the low levels of poisons, especially arsenic, that are present in the synthesis gas from coal. TDA Research, Inc. (TDA) is developing an expendable high capacity, low-cost chemical absorbent to remove arsenic from coal-derived syngas. Unlike most of the commercially available sorbents that physically adsorb arsenic, TDA's sorbent operates at elevated temperatures and removes the arsenic through chemical reaction. The arsenic content in the coal gas stream is reduced to ppb levels with the sorbent by capturing and stabilizing the arsenic gas (As4) and arsenic hydrides (referred to as arsine, AsH3) in the solid state. To demonstrate the concept of high temperature arsenic removal from coal-derived syngas, we carried out bench-scale experiments to test the absorption capacity of a variety of sorbent formulations under representative conditions. Using on-line analysis techniques, we monitored the pre- and post-breakthrough arsine concentrations over different sorbent samples. Some of these samples exhibited pre-breakthrough arsine absorption capacity over 40% wt. (capacity is defined as lb of arsenic absorbed/lb of sorbent), while maintaining an arsine outlet concentration at less than 10 ppb.« less

Biaxial deformation behaviour of poly-ether-ether-ketone

NASA Astrophysics Data System (ADS)

Turner, Josh; Menary, Gary; Martin, Peter

2018-05-01

The biaxial tensile properties of thin poly-ether-ether-ketone (PEEK) films are presented. Investigation into the biaxial mechanical behaviour of PEEK films will provide a preliminary insight into the anticipated stress/strain response, and potential suitability, to the possible fabrication of thin walled parts through stretch blow moulding and thermoforming processes - with the multi-axial state of strain imposed onto the heated thermoplastic sheet representative of the expected strain history experienced during these material forming processes. Following identification of the prospective forming temperature window, the biaxial mechanical behaviour of the material is characterized under differing modes of deformation, at a nominal strain rate of 1 s-1. The temperature dependence is outlined within - with an appreciable increase in flow behaviour correlated with specimen temperature exceeding its glass transition temperature (Tg).

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

PubMed

Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

2017-08-01

Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

4,4\\'-Methylene bis(N,N\\'-dimethyl)aniline

Integrated Risk Information System (IRIS)

4,4 ' - Methylene bis ( N , N ' - dimethyl ) aniline ; CASRN 101 - 61 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Haz

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

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

2015-04-01

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

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

NASA Astrophysics Data System (ADS)

Vasyunin, A. I.; Herbst, Eric

2013-05-01

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

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

NASA Astrophysics Data System (ADS)

Li, Lijie; Cocker, David R.

2018-05-01

Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA formation.

Development of a stereoselective and scalable process for the preparation of a methylcyclobutanol-pyridyl ether.

PubMed

Kuethe, Jeffrey T; Basu, Kallol; Orr, Robert K; Ashley, Eric; Poirier, Marc; Tan, Lushi

2018-02-15

The evolution of a scalable process for the preparation of methylcyclobutanol-pyridyl ether 1 is described. Key aspects of this development including careful control of the stereochemistry, elimination of chromatography, and application to kilogram-scale synthesis are addressed. Copyright © 2017 Elsevier Ltd. All rights reserved.

77 FR 50613 - Didecyl Dimethyl Ammonium Carbonate and Didecyl Dimethyl Ammonium Bicarbonate; Exemption From the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-22

... used as sanitizers on appliances, beverage bottling, counter tops, food packaging, refrigerators..., countertops, and in food/beverage processing facilities. The assessment calculated the Daily Dietary Dose (DDD... estimates from exposure to treated food packaging and beverage bottles are also below the Agency's LOC...

Cross-dehydrogenative coupling and oxidative-amination reactions of ethers and alcohols with aromatics and heteroaromatics

PubMed Central

Vuram, Prasanna K.

2017-01-01

Cross-dehydrogenative coupling (CDC) is a process in which, typically, a C–C bond is formed at the expense of two C–H bonds, either catalyzed by metals or other organic compounds, or via uncatalyzed processes. In this perspective, we present various modes of C–H bond-activation at sp3 centers adjacent to ether oxygen atoms, followed by C–C bond formation with aromatic systems as well as with heteroaromatic systems. C–N bond-formation with NH-containing heteroaromatics, leading to hemiaminal ethers, is also an event that can occur analogously to C–C bond formation, but at the expense of C–H and N–H bonds. A large variety of hemiaminal ether-forming reactions have recently appeared in the literature and this perspective also includes this complementary chemistry. In addition, the participation of C–H bonds in alcohols in such processes is also described. Facile access to a wide range of compounds can be attained through these processes, rendering such reactions useful for synthetic applications via Csp3 bond activations. PMID:28970941

Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

PubMed

Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

2017-11-13

A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Revisiting the Formation and Tunable Dissociation of a [2]Pseudorotaxane Formed by Slippage Approach

PubMed Central

Leung, Ken Cham-Fai; Lau, Kwun-Ngai; Wong, Wing-Yan

2015-01-01

A new [2]pseudorotaxane DB24C8⊃1-H·PF6 with dibenzo[24]crown-8 (DB24C8) crown ether-dibenzylammonium (1-H·PF6) binding which was formed by slippage approach at different solvents and temperature, had been isolated and characterized by NMR spectroscopy and mass spectrometry. The [2]pseudorotaxane DB24C8⊃1-H·PF6 was stable at room temperature. The dissociation rate of [2]pseudorotaxane DB24C8⊃1-H·PF6 could be tuned by using different stimuli such as triethylamine (TEA)/diisopropylethylamine (DIPEA) and dimethyl sulfoxide (DMSO). In particular, the dissociation of [2]pseudorotaxane DB24C8⊃1-H·PF6 by an excess of TEA/DIPEA base mixture possessed a long and sustained, complete dissociation over 60 days. Other stimuli by DMSO possessed a relatively fast dissociation over 24 h. PMID:25872145

Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

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

Jones, Andrew J.; Iglesia, Enrique

Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy-mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpy–entropy trade-offs merely reflect the intervening role of temperature in activation free energies and the prevalence of moremore » complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H-bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.« less

Characterization of the key aroma compounds in beef extract using aroma extract dilution analysis.

PubMed

Takakura, Yukiko; Sakamoto, Tomohiro; Hirai, Sachi; Masuzawa, Takuya; Wakabayashi, Hidehiko; Nishimura, Toshihide

2014-05-01

Aroma extract dilution analysis (AEDA) of an ether extract prepared from beef extract (BE) and subsequent identification experiments led to the determination of seven aroma-active compounds in the flavor dilution (FD) factor range of 32-128. Omission experiments to select the most aroma-active compounds from the seven aroma compounds suggested that 2,3,5-trimethyl pyrazine, 1-octen-3-ol, 3-methylbutanoic acid, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone were the main active compounds contributing to the aroma of BE. Aroma recombination, addition, and omission experiments of the four aroma compounds in taste-reconstituted BE showed that each compound had an individual aroma profile. A comparison of the overall aroma between this recombination mixture and BE showed a high similarity, suggesting that the key aroma compounds had been identified successfully. Copyright © 2014 Elsevier Ltd. All rights reserved.

4-{2-[2-(4-Formyl­phen­oxy)eth­oxy]eth­oxy}benzaldehyde

PubMed Central

Ma, Zhen; Cao, Yiqun

2011-01-01

The title compound, C18H18O5, was obtained by the reaction of 4-hy­droxy­benzaldehyde with bis­(2,2-dichloro­eth­yl) ether in dimethyl­formamide. In the crystal, the mol­ecule lies on a twofold rotation axis that passes through the central O atom of the aliphatic chain, thus leading to one half-mol­ecule being present per asymmetric unit. The carbonyl, aryl and O—CH2—CH2 groups are almost coplanar, with an r.m.s. deviation of 0.030 Å. The aromatic rings are approximately perpendicular to each other, forming a dihedral angle of 78.31 sh;H⋯O hydrogen bonds and C—H⋯π inter­actions help to consolidate the three-dimensional network. PMID:21754870

Mechanism of radiosensitization by porphyrins.

PubMed

Luksiene, Zivile; Labeikyte, Danute; Juodka, Benediktas; Moan, Johan

2006-01-01

According to our previous data, hematoporphyrin dimethyl ether (HPde) at concentrations useful for photodynamic therapy can radiosensitize aggressive Ehrlich ascite carcinoma (EAT) to 2Gy irradiation inducing total tumour growth inhibition. The aim of this study was to further investigate the possible mechanism of radiosensitization of EAT by dicarboxylic porphyrin-HPde. Our results reveal that HPde is inducing several rearrangements in the EAT cells: 1.2 x 10-6 M of the photosensitizer diminishes the number of cells in mitosis by a factor of 3, increases the number of cells in the S phase of the cell cycle, modifies the activities of antioxidant enzymes glutation S-transferase (GST) and DT-diaphorase (DTD), and eventually induces slight apoptosis. Moreover, it was shown that HPde is a ligand of peripheral benzodiazepine receptor (PBR). Named "house keeper," PBR is usually responsible for all these perturbations, which, in our case, act in concert with the following ionizing radiation, producing the interaction of two antiproliferative/destructive factors.

[Study on three kinds of gasoline oxygenates-induced DNA damage in mice fibroblasts].

PubMed

Song, Chonglin; Zhang, Zhifu; Chen, Xue; Zhang, Yanfeng; Wang, Chunhua; Liu, Keming

2002-10-01

To study DNA damage of three kinds of gasoline oxygenates. Single cell gel electrophoresis assay(Comet assay) was used to detect the damage effects of three gasoline oxygenates[methyl tertiary butyl ether(MTBE), ethanol anhydrous(EA) and dimethyl carbonate(DMC)] on DNA in L-929 mice fibroblasts. In certain concentation(37.500-150.000 mg/ml), MTBE could directly cause DNA damage of L-929 mice fibroblasts. There was obvious dose-effect relationship, i.e. when the concentration of MTBE was increased from 9.375 to 150.000 mg/ml, the comet rate also increased from 4% to 85%, and the length of comet tail changed correspondingly. The results of EA and DMC were negative. Under the condition of this experiment(150.000 mg/ml), MTBE could directly cause DNA damage while the effect of EA and DMC on DNA damage was not found.

Consider the DME alternative for diesel engines

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

Fleisch, T.H.; Meurer, P.C.

1996-07-01

Engine tests demonstrate that dimethyl ether (DME, CH{sub 3}OCH{sub 3}) can provide an alternative approach toward efficient, ultra-clean and quiet compression ignition (CI) engines. From a combustion point of view, DME is an attractive alternative fuel for CI engines, primarily for commercial applications in urban areas, where ultra-low emissions will be required in the future. DME can resolve the classical diesel emission problem of smoke emissions, which are completely eliminated. With a properly developed DME injection and combustion system, NO{sub x} emissions can be reduced to 40% of Euro II or U.S. 1998 limits, and can meet the future ULEVmore » standards of California. Simultaneously, the combustion noise is reduced by as much as 15 dB(A) below diesel levels. In addition, the classical diesel advantages such as high thermal efficiency, compression ignition, engine robustness, etc., are retained.« less

Acetylene-chromene terminated resins as high temperature thermosets

NASA Technical Reports Server (NTRS)

Godschalx, J. P.; Inbasekaran, M. N.; Bartos, B. R.; Scheck, D. M.; Laman, S. A.

1990-01-01

A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

DOEpatents

Smith, L.A. Jr.; Jones, E.M. Jr.; Hearn, D.

1984-05-08

Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

DOEpatents

Smith, Jr., Lawrence A.; Jones, Jr., Edward M.; Hearn, Dennis

1984-01-01

Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150.degree. to 250.degree. F. at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C.sub.3 to C.sub.6 and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom.

Integrated membrane and microbial fuel cell technologies for enabling energy-efficient effluent Re-use in power plants.

PubMed

Shrestha, Namita; Chilkoor, Govinda; Xia, Lichao; Alvarado, Catalina; Kilduff, James E; Keating, John J; Belfort, Georges; Gadhamshetty, Venkataramana

2017-06-15

Municipal wastewater is an attractive alternative to freshwater sources to meet the cooling water needs of thermal power plants. Here we offer an energy-efficient integrated microbial fuel cell (MFC)/ultrafiltration (UF) process to purify primary clarifier effluent from a municipal wastewater treatment plant for use as cooling water. The microbial fuel cell was shown to significantly reduce chemical oxygen demand (COD) in the primary settled wastewater effluent upstream of the UF module, while eliminating the energy demand required to deliver dissolved oxygen in conventional aerobic treatment. We investigated surface modification of the UF membranes to control fouling. Two promising hydrophilic monomers were identified in a high-throughput search: zwitterion (2-(Methacryloyloxy)-ethyl-dimethyl-(3-sulfopropyl ammoniumhydroxide, abbreviated BET SO 3 - ), and amine (2-(Methacryloyloxy) ethyl trimethylammonium chloride, abbreviated N(CH 3 ) 3 + ). Monomers were grafted using UV-induced polymerization on commercial poly (ether sulfone) membranes. Filtration of MFC effluent by membranes modified with BET SO 3 - and N(CH 3 ) 3 + exhibited a lower rate of resistance increase and lower energy consumption than the commercially available membrane. The MFC/UF process produced high quality cooling water that meets the Electrical Power Research Institute (EPRI) recommendations for COD, a suite of metals (Fe, Al, Cu, Zn, Si, Mn, S, Ca and Mg), and offered extremely low corrosion rates (<0.05 mm/yr). A series of AC and DC diagnostic tests were used to evaluate the MFC performance. Copyright © 2017 Elsevier Ltd. All rights reserved.

Halogen bonding from a hard and soft acids and bases perspective: investigation by using density functional theory reactivity indices.

PubMed

Pinter, Balazs; Nagels, Nick; Herrebout, Wouter A; De Proft, Frank

2013-01-07

Halogen bonds between the trifluoromethyl halides CF(3)Cl, CF(3)Br and CF(3)I, and dimethyl ether, dimethyl sulfide, trimethylamine and trimethyl phosphine were investigated using Pearson's hard and soft acids and bases (HSAB) concept with conceptual DFT reactivity indices, the Ziegler-Rauk-type energy-decomposition analysis, the natural orbital for chemical valence (NOCV) framework and the non-covalent interaction (NCI) index. It is found that the relative importance of electrostatic and orbital (charge transfer) interactions varies as a function of both the donor and acceptor molecules. Hard and soft interactions were distinguished and characterised by atomic charges, electrophilicity and local softness indices. Dual-descriptor plots indicate an orbital σ hole on the halogen similar to the electrostatic σ hole manifested in the molecular electrostatic potential. The predicted high halogen-bond-acceptor affinity of N-heterocyclic carbenes was evidenced in the highest complexation energy for the hitherto unknown CF(3) I·NHC complex. The dominant NOCV orbital represents an electron-density deformation according to a n→σ*-type interaction. The characteristic signal found in the reduced density gradient versus electron-density diagram corresponds to the non-covalent interaction between contact atoms in the NCI plots, which is the manifestation of halogen bonding within the NCI theory. The unexpected C-X bond strengthening observed in several cases was rationalised within the molecular orbital framework. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An ab initio/Rice-Ramsperger-Kassel-Marcus study of the hydrogen-abstraction reactions of methyl ethers, H(3)COCH(3-x)(CH(3))(x), x = 0-2, by OH; mechanism and kinetics.

PubMed

Zhou, Chong-Wen; Simmie, John M; Curran, Henry J

2010-07-14

A theoretical study of the mechanism and kinetics of the H-abstraction reaction from dimethyl (DME), ethylmethyl (EME) and iso-propylmethyl (IPME) ethers by the OH radical has been carried out using the high-level methods CCSD(T)/CBS, G3 and G3MP2BH&H. The computationally less-expensive methods of G3 and G3MP2BH&H yield results for DME within 0.2-0.6 and 0.7-0.9 kcal mol(-1), respectively, of the coupled cluster, CCSD(T), values extrapolated to the basis set limit. So the G3 and G3MP2BH&H methods can be confidently used for the reactions of the higher ethers. A distinction is made between the two different kinds of H-atoms, classified as in/out-of the symmetry plane, and it is found that abstraction from the out-of-plane H-atoms proceeds through a stepwise mechanism involving the formation of a reactant complex in the entrance channel and product complex in the exit channel. The in-plane H-atom abstractions take place through a more direct mechanism and are less competitive. Rate constants of the three reactions have been calculated in the temperature range of 500-3000 K using the Variflex code, based on the weak collision, master equation/microcanonical variational RRKM theory including tunneling corrections. The computed total rate constants (cm(3) mol(-1) s(-1)) have been fitted as follows: k(DME) = 2.74 xT(3.94) exp (1534.2/T), k(EME) = 20.93 xT(3.61) exp (2060.1/T) and k(IPME) = 0.55 xT(3.93) exp (2826.1/T). Expressions of the group rate constants for the three different carbon sites are also provided.

Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters.

PubMed

Ishikawa, Akio; Neurock, Matthew; Iglesia, Enrique

2007-10-31

The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt cluster size, because small clusters, with more coordinatively unsaturated surface atoms, bind oxygen atoms more strongly than larger clusters and exhibit lower steady-state vacancy concentrations and a consequently smaller number of adsorbed DME intermediates involved in kinetically relevant steps. These effects of cluster size and metal-oxygen bond energies on reactivity are ubiquitous in oxidation reactions requiring vacancies on surfaces nearly saturated with intermediates derived from O2.

Tribromodiphenyl ether

Integrated Risk Information System (IRIS)

Tribromodiphenyl ether ; CASRN 49690 - 94 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarci

Octabromodiphenyl ether

Integrated Risk Information System (IRIS)

Octabromodiphenyl ether ; CASRN 32536 - 52 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

Nonabromodiphenyl ether

Integrated Risk Information System (IRIS)

Nonabromodiphenyl ether ; CASRN 63936 - 56 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

Hexabromodiphenyl ether

Integrated Risk Information System (IRIS)

Hexabromodiphenyl ether ; CASRN 36483 - 60 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

Pentabromodiphenyl ether

Integrated Risk Information System (IRIS)

Pentabromodiphenyl ether ; CASRN 32534 - 81 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

Tetrabromodiphenyl ether

Integrated Risk Information System (IRIS)

Tetrabromodiphenyl ether ; CASRN 40088 - 47 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

Mobil cuts the alcohol out of oxygenate production

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

Wood, A.

1992-04-15

Mobil Corp. has unveiled a new etherification technology that can produce fuel oxygenated based only on olefinic refinery streams and water. The process has the potential to allow refiners to produce oxygenates without having to rely on an external supply of alcohols such as methanol or ethanol. Mobil has developed the technology around a new oxygenate, disopropyl ether (DIPE), based on propylene. However, the process has also been tested using mixed propylene/C{sub 4} and straight C{sub 4} streams, says Michael J. McNally, manager of Mobil`s Motor Gasoline Group (Paulsboro, NJ), producing ethers analogous to methyl tert-butyl ether (MTBE).

RECOVERY OF URANIUM FROM PITCHBLENDE

DOEpatents

Ruehle, A.E.

1958-06-24

The decontamination of uranium from molybdenum is described. When acid solutions containing uranyl nitrate are contacted with ether for the purpose of extracting the uranium values, complex molybdenum compounds are coextracted with the uranium and also again back-extracted from the ether with the uranium. This invention provides a process for extracting uranium in which coextraction of molybdenum is avoided. It has been found that polyhydric alcohols form complexes with molybdenum which are preferentially water-soluble are taken up by the ether extractant to only a very minor degree. The preferred embodiment of the process uses mannitol, sorbitol or a mixture of the two as the complexing agent.

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 hydrogen sulphide was suspected. Acetophenone emissions originated from the wood chips. Olfactory measurements need to be correlated to gaseous emissions for a more accurate odour emission evaluation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Arginine (Di)methylated Human Leukocyte Antigen Class I Peptides Are Favorably Presented by HLA-B*07.

PubMed

Marino, Fabio; Mommen, Geert P M; Jeko, Anita; Meiring, Hugo D; van Gaans-van den Brink, Jacqueline A M; Scheltema, Richard A; van Els, Cécile A C M; Heck, Albert J R

2017-01-06

Alterations in protein post-translational modification (PTM) are recognized hallmarks of diseases. These modifications potentially provide a unique source of disease-related human leukocyte antigen (HLA) class I-presented peptides that can elicit specific immune responses. While phosphorylated HLA peptides have already received attention, arginine methylated HLA class I peptide presentation has not been characterized in detail. In a human B-cell line we detected 149 HLA class I peptides harboring mono- and/or dimethylated arginine residues by mass spectrometry. A striking preference was observed in the presentation of arginine (di)methylated peptides for HLA-B*07 molecules, likely because the binding motifs of this allele resemble consensus sequences recognized by arginine methyl-transferases. Moreover, HLA-B*07-bound peptides preferentially harbored dimethylated groups at the P3 position, thus consecutively to the proline anchor residue. Such a proline-arginine sequence has been associated with the arginine methyl-transferases CARM1 and PRMT5. Making use of the specific neutral losses in fragmentation spectra, we found most of the peptides to be asymmetrically dimethylated, most likely by CARM1. These data expand our knowledge of the processing and presentation of arginine (di)methylated HLA class I peptides and demonstrate that these types of modified peptides can be presented for recognition by T-cells. HLA class I peptides with mono- and dimethylated arginine residues may therefore offer a novel target for immunotherapy.

Intramolecular allyl transfer reaction from allyl ether to aldehyde groups: experimental and theoretical studies.

PubMed

Franco, Delphine; Wenger, Karine; Antonczak, Serge; Cabrol-Bass, Daniel; Duñach, Elisabet; Rocamora, Mercè; Gomez, Montserrat; Muller, Guillermo

2002-02-02

The intramolecular transfer of the allyl group of functionalized allyl aryl ethers to an aldehyde group in the presence of Ni0 complexes was studied from chemical, electrochemical and theoretical points of view. The chemical reaction involves the addition of Ni0 to the allyl ether followed by stoichiometric allylation. The electrochemical process is catalytic in nickel and involves the reduction of intermediate eta3-allylnickel(II) complexes.

Responses of the L51781Y tk/sup +//tk/sup -/ mouse lymphoma cell forward mutation assay: III. 72 coded chemicals

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

McGregor, D.B.; Brown, A.; Cattanach, P.

Seventy-two chemicals were tested for their mutagenic potential in the L51781Y tk/sup +///sup -/ mouse lymphoma cell forward mutation assay, using procedures based upon those described previously. Cultures were exposed to the chemicals for 4 hr, then cultured for 2 days before planting in soft agar with or without trifluorothymidine (TFT), 3 ..mu..g/ml. The chemicals were tested at least twice. Significant responses were obtained with allyl isothiocyanate, p-benzoquinone dioxime, benzyl acetate, 2-biphenylamine HCl, bis(2-chloro-1-methylethyl)ether, cadmium chloride, chlordane, chlorobenzene, chlorobenzilate, 2-chloroethanol, chlorothalonil, cytarabine x HCl, p,p'-DDE, diazinon, 2,6-dichloro-p-phenylenediamine, N,N-diethylthiourea, diglycidylresorcinol ether, 2,4-dimethoxy aniline x HCl, disperse yellow 3, endosulfan, 1,2-epoxyhexadecane, ethylmore » acrylate, ethyl benzene, ethylene thiourea, F D and C yellow Number 6, furan, heptachlor, isophorone, mercuric chloride, 4,4'-methylenedianiline x 2 HCl, methyl viologen, nickel sulfate x 6H/sub 2/O, 4,4'-oxydianiline, pentachloroethane, piperonyl butoxide, propyl gallate, quinoline, rotenone, 2,4,5,6-tetrachloro-4-nitro-anisole, 1,1,1,2-tetrachloroethane, trichlorfon, 2,4,6-trichlorophenol, 2,4,5-trimethoxybenzaldehyde, 1,1,3-trimethyl-2-thiourea, 1-vinyl-3-cyclopetene dioxide, vinyl toluene, and ziram. The assay was incapable of providing a clear indication of whether some chemicals were mutagens; these benzyl alcohol, 1,4-dichlorobenzene, phenol, succinic acid-2,2-dimethyl hydrazide, and toluene.« less

Binding specificity of the juvenile hormone carrier protein from the hemolymph of the tobacco hornworm Manduca sexta Johannson (Lepidoptera: Sphingidae).

PubMed

Peterson, R C; Reich, M F; Dunn, P E; Law, J H; Katzenellnbogen, J A

1977-05-17

A series of analogues of insect juvenile hormone (four geometric isomers of methyl epoxyfarnesenate, several para-substituted epoxygeranyl phenyl ethers, and epoxyfarnesol and its acetate and haloacetate derivatives) was prepared to investigate the binding specificity of the hemolymph juvenile hormone binding protein from the tobacco hornworm Manduct sexta. The relative binding affinities were determined by a competition assay against radiolabeled methyl (E,E)-3,11-dimethyl-7-ethyl-cis-10,11-epoxytrideca-2,6-dienoate (JH I). The ratio of dissociation constants was estimated by plotting competitor data according to a linear transformation of the dissociation equations describing competition of two ligands for a binding protein. The importance of the geometry of the sesquiterpene hydrocarbon chain is indicated by the fact that the binding affinity is decreased as Z (cis) double bonds are substituted for E (trans) double bonds in the methyl epoxyfarnesenate series; the unepoxidized analogues do not bind. A carboxylic ester function is important although its orientation can be reversed, as indicated by the good binding of epoxyfarnesyl acetate. In the monoterpene series, methyl epoxygeranoate shows no affinity for the binding protein, but substitution of a phenyl or p-carbomethoxyphenyl ether for the ester function imparts a low, but significant affinity. These data taken together with earlier results indicate that the binding site for juvenile hormone in the hemolymph binding protein is characterized by a sterically defined hydrophobic region with polar sites that recognize the epoxide and the ester functions.

Phytochemical composition, protective and therapeutic effect on gastric ulcer and α-amylase inhibitory activity of Achillea biebersteinii Afan.

PubMed

Abd-Alla, Howaida I; Shalaby, Nagwa M M; Hamed, Manal A; El-Rigal, Nagy Saba; Al-Ghamdi, Samira N; Bouajila, Jalloul

2016-01-01

Three sesquiterpene lactones [two germacranolides (micranthin and sintenin) and one guaianolide (4β,10α-dihydroxy-5β,7β,8βH-guaia-1,11(13)dien-12,8α-olide)] and four derivatives of 3-methoxy flavones (santin, quercetagetin-3,6,3'-trimethyl ether, quercetagetin-3,6-dimethyl ether, and 5,7 dihydroxy 3,3',4'-trimethoxy flavone) were isolated from the ethyl acetate extract (EAE) of the aerial parts of Achillea biebersteinii Afan. (Asteraceae). Evaluation of protective and therapeutic effects of EAE against ethanol-induced gastric ulcer in rats was carried. Antiulcer activity evaluation was done through measuring ulcer indices, stomach acidity, gastric volume and lesion counts. Oxidative stress markers; malondialdehyde, glutathione and superoxide dismutase were also estimated. The work was extended to determine the histopathological assessment of the stomach. Gastric ulcer exhibited a significant elevation of the ulcer index and oxidative stress markers. The extract attenuated these increments and recorded protective and therapeutic effects against gastric ulcer. Hyperglycaemia increases the mucosal susceptibility to ulcerogenic stimuli and predisposes gastric ulceration. In vitro α-amylase inhibitory assay was applied to evaluate the post prandial antihyperglycaemia activity. The result showing that the EAE has the ability to reduce starch-induced postprandial glycaemic excursions by virtue of potent intestinal α-amylase inhibitory activity. These findings demonstrated the remarkable potential of A. biebersteinii as valuable source of antiulcer agent with post prandial hyperglycaemia lowering effect.

Oxidation mechanism of diethyl ether: a complex process for a simple molecule.

PubMed

Di Tommaso, Stefania; Rotureau, Patricia; Crescenzi, Orlando; Adamo, Carlo

2011-08-28

A large number of organic compounds, such as ethers, spontaneously form unstable peroxides through a self-propagating process of autoxidation (peroxidation). Although the hazards of organic peroxides are well known, the oxidation mechanisms of peroxidizable compounds like ethers reported in the literature are vague and often based on old experiments, carried out in very different conditions (e.g. atmospheric, combustion). With the aim to (partially) fill the lack of information, in this paper we present an extensive Density Functional Theory (DFT) study of autoxidation reaction of diethyl ether (DEE), a chemical that is largely used as solvent in laboratories, and which is considered to be responsible for various accidents. The aim of the work is to investigate the most probable reaction paths involved in the autoxidation process and to identify all potential hazardous intermediates, such as peroxides. Beyond the determination of a complex oxidation mechanism for such a simple molecule, our results suggest that the two main reaction channels open in solution are the direct decomposition (β-scission) of DEE radical issued of the initiation step and the isomerization of the peroxy radical formed upon oxygen attack (DEEOO˙). A simple kinetic evaluation of these two competing reaction channels hints that radical isomerization may play an unexpectedly important role in the global DEE oxidation process. Finally industrial hazards could be related to the hydroperoxide formation and accumulation during the chain propagation step. The resulting information may contribute to the understanding of the accidental risks associated with the use of diethyl ether.

Ethyl ether

Integrated Risk Information System (IRIS)

Ethyl ether ; CASRN 60 - 29 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

p-Bromodiphenyl ether

Integrated Risk Information System (IRIS)

p - Bromodiphenyl ether ; CASRN 101 - 55 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcin

Evaluation of sub-chronic toxic effects of petroleum ether, a laboratory solvent in Sprague-Dawley rats

PubMed Central

Parasuraman, Subramani; Sujithra, Jeyabalan; Syamittra, Balakrishnan; Yeng, Wong Yeng; Ping, Wu Yet; Muralidharan, Selvadurai; Raj, Palanimuthu Vasanth; Dhanaraj, Sokkalingam Arumugam

2014-01-01

Background: In general, organic solvents are inhibiting many physiological enzymes and alter the behavioural functions, but the available scientific knowledge on laboratory solvent induced organ specific toxins are very limited. Hence, the present study was planned to determine the sub-chronic toxic effects of petroleum ether (boiling point 40–60°C), a laboratory solvent in Sprague-Dawley (SD) rats. Materials and Methods: The SD rats were divided into three different groups viz., control, low exposure petroleum ether (250 mg/kg; i.p.) and high exposure petroleum ether (500 mg/kg; i.p.) administered group. The animals were exposed with petroleum ether once daily for 2 weeks. Prior to the experiment and end of the experiment animals behaviour, locomotor and memory levels were monitored. Before initiating the study animals were trained for 2 weeks for its learning process and its memory levels were evaluated. Body weight (BW) analysis, locomotor activity, anxiogenic effect (elevated plus maze) and learning and memory (Morris water navigation task) were monitored at regular intervals. On 14th day of the experiment, few ml of blood sample was collected from all the experimental animals for estimation of biochemical parameters. At the end of the experiment, all the animals were sacrificed, and brain, liver, heart, and kidney were collected for biochemical and histopathological analysis. Results: In rats, petroleum ether significantly altered the behavioural functions; reduced the locomotor activity, grip strength, learning and memory process; inhibited the regular body weight growth and caused anxiogenic effects. Dose-dependent organ specific toxicity with petroleum ether treated group was observed in brain, heart, lung, liver, and kidney. Extrapyramidal effects that include piloerection and cannibalism were also observed with petroleum ether administered group. These results suggested that the petroleum ether showed a significant decrease in central nervous system (CNS) activity, and it has dose-dependent toxicity on all vital organs. Conclusion: The dose-dependent CNS and organ specific toxicity was observed with sub-chronic administration of petroleum ether in SD rats. PMID:25316988

Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

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

Hanson, Susan K; Gordon, John C; Thorn, David L

2009-01-01

The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress hasmore » been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), and 1,2-diphenyl-2-methoxyethanol (C) (Figure 1). Reaction of (dipic)V{sup V}(O)O{sup i}Pr (1a) or (dipic)V{sup v}(O)OEt (lb) with A, B, or C in acetonitrile yielded new vanadium(V) complexes where the alcohol-ether ligand was bound in a chelating fashion. From the reaction of 1b with pinacol monomethyl ether (A) in acetonitrile solution, (dipic)V{sup v}(O)(pinOMe) (2) (PinOMe = 2,3-dimethyl-3-methoxy-2-butanoxide) was isolated in 61 % yield. Reaction of 1b with 2-phenoxyethanol (B) in acetonitrile gave the new complex (dipic)V{sup v}(O)(OPE) (3) (OPE = 2-phenoxyethoxide), which was isolated in 76% yield. In a similar fashion, 1a reacted with 1,2-diphenyl-2-methoxyethanol (C) to give (dipic)V(O)(DPME) (4) (DPME = 1,2-diphenyl-2-methoxyethoxide), which was isolated in 39% yield. Complexes 2, 3, and 4 were characterized by {sup 1}H NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Compared to the previously reported vanadium(V) pinacolate complex (dipic)V(O)(pinOH) the X-ray structure of complex 2 reveals a slightly shorter V = O bond, 1.573(2) {angstrom} vs 1.588(2) {angstrom} for the pinOH structure. Complexes 3 and 4 display similar vanadium oxo bond distances of 1.568(2) {angstrom} and 1.576(2) {angstrom}, respectively. All three complexes show longer bonds to the ether-oxygen trans to the oxo (2.388(2) {angstrom} for 2, 2.547(2) {angstrom} for 3, and 2.438(2) {angstrom} for 4) than to the hydroxy-oxygen in the pinOH structure (2.252(2) {angstrom}).« less

Bis(chloroethyl)ether (BCEE)

Integrated Risk Information System (IRIS)

Bis ( chloroethyl ) ether ( BCEE ) ; CASRN 111 - 44 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

Propylene glycol monomethyl ether (PGME)

Integrated Risk Information System (IRIS)

Propylene glycol monomethyl ether ( PGME ) ; CASRN 107 - 98 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

Bis(chloromethyl)ether (BCME)

Integrated Risk Information System (IRIS)

Bis ( chloromethyl ) ether ( BCME ) ; CASRN 542 - 88 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

Chloromethyl methyl ether (CMME)

Integrated Risk Information System (IRIS)

Chloromethyl methyl ether ( CMME ) ; CASRN 107 - 30 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

Triethylene glycol monobutyl ether

Integrated Risk Information System (IRIS)

Triethylene glycol monobutyl ether ; CASRN 143 - 22 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

p,p\\'-Dibromodiphenyl ether

Integrated Risk Information System (IRIS)

p , p ' - Dibromodiphenyl ether ; CASRN 2050 - 47 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

Triethylene glycol monoethyl ether

Integrated Risk Information System (IRIS)

Triethylene glycol monoethyl ether ; CASRN 112 - 50 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

Propylene glycol monoethyl ether

Integrated Risk Information System (IRIS)

Propylene glycol monoethyl ether ; CASRN 52125 - 53 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

Bis(2-chloro-1-methylethyl) ether

Integrated Risk Information System (IRIS)

Bis ( 2 - chloro - 1 - methylethyl ) ether ; CASRN 108 - 60 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

Ethylene glycol monobutyl ether (EGBE) (2-Butoxyethanol)

Integrated Risk Information System (IRIS)

Ethylene glycol monobutyl ether ( EGBE ) ( 2 - Butoxyethanol ) ; CASRN 111 - 76 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I (

Methyl tert-butyl ether (MTBE)

Integrated Risk Information System (IRIS)

Methyl tert - butyl ether ( MTBE ) ; CASRN 1634 - 04 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

Up-regulation of Jun/AP-1 during differentiation of N1E-115 neuroblastoma cells.

PubMed

de Groot, R P; Kruijer, W

1991-12-01

Neuroblastoma cell lines isolated from neuroblastoma tumors can be induced to differentiate into neuronal cell types by treatment with chemical agents, such as dimethyl sulfoxide and retinoic acid. The molecular mechanisms underlying this differentiation process, however, are completely obscure. In this paper, we show that neuronal differentiation of mouse N1E-115 neuroblastoma cells by dimethyl sulfoxide is accompanied by a prolonged rise in c-jun, junB, and junD expression and AP-1 activity. Multiple sequence elements in the Jun promoters are involved in this process. Furthermore, we show that c-jun and junD, but not junB, are expressed at high levels in the neuronal cell types obtained after dimethyl sulfoxide treatment. These results suggest an important role for c-jun and junD in neuronal differentiation of N1E-115 cells.

SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Clark, H.M.; Duffey, D.

1958-06-17

A process is described for extracting uranium from uranium ore, wherein the uranium is substantially free from molybdenum contamination. In a solvent extraction process for recovering uranium, uranium and molybdenum ions are extracted from the ore with ether under high acidity conditions. The ether phase is then stripped with water at a lower controiled acidity, resaturated with salting materials such as sodium nitrate, and reextracted with the separation of the molybdenum from the uranium without interference from other metals that have been previously extracted.

Hydrodebromination of decabromodiphenyl ether (BDE-209) in cooking experiments with salmon fillet.

PubMed

Bendig, Paul; Blumenstein, Marina; Hägele, Florian; Vetter, Walter

2012-08-29

Polybrominated diphenyl ethers (PBDEs) are environmental contaminants regularly detected in biota and food. Seafood has been identified as the major dietary source for human uptake. Fish is predominantly consumed after cooking, and this process may alter the actual human intake of contaminants. This study thus aimed to investigate the fate of PBDEs in this cooking process. Heating of fish fortified with 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) at typical cooking conditions (200 °C, in plant oil) resulted in a decrease of its concentration in favor of the formation of lower brominated congeners. After 15 min, ∼25% of BDE-209 was transformed into nona- to octabrominated congeners. The major transformation route was BDE-209 → BDE-206 → BDE-196 and BDE-199. Low amounts of heptabrominated congeners as well as one hexabromodibenzofuran and a heptabromodibenzofuran isomer were also detected. However, penta- and tetrabrominated diphenyl ethers were not observed, and heating of BDE-47 did not produce new transformation products.

A simple approach for making a viable, safe, and high-performances lithium-sulfur battery

NASA Astrophysics Data System (ADS)

Carbone, Lorenzo; Coneglian, Thomas; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steve; Hassoun, Jusef

2018-02-01

We report an electrolyte with low flammability, based on diethylene glycol dimethyl ether (DEGDME) dissolving lithium bis-trifluoromethane sulfonimidate (LiTFSI), and lithium nitrate (LiNO3) for high-performances lithium/sulfur battery. Self-diffusion coefficients, conductivity, and lithium transport number of the electrolyte are obtained by nuclear magnetic resonance and electrochemical impedance spectroscopy. Interface stability, lithium stripping/deposition ability, and the electrochemical stability window of the electrolyte are determined by voltammetry and impedance spectroscopy. The tests suggest conductivity higher than 10-2 S cm-1, lithium transport number of about 0.5, electrochemical stability extending from 0 V to 4.6 V, and excellent compatibility with lithium metal. A composite cathode using sulfur and multi walled carbon nanotubes (MWCNTs) is characterized in terms of structure and morphology by X-ray diffraction and scanning electron microscopy. The study shows spherical flakes in which the carbon nanotubes protect the crystalline sulfur from excessive dissolution, and create the optimal host for allowing the proper cell operation. The Li/S cell reveals highly reversible process during charge/discharge cycles, fast kinetic, and lithium diffusion coefficient in the sulfur electrode ranging from 10-12 to 10-10 cm2 s-1. The cell evidences a coulombic efficiency approaching 100%, capacity from 1300 mAh g-1 to 900 mAh g-1 and practical energy density higher than 400 Wh kg-1.

Combined Sustainability Assessment and Techno-Economic Analysis for the Production of Biomass-Derived High-Octane Gasoline Blendstock

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

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit

Conversion technologies for biomass to liquid hydrocarbon fuels are being actively developed. Converting biomass into advanced hydrocarbon fuels requires detailed assessments to help prioritize research; techno-economic analysis (TEA) is a long established tool used to assess feasibility and progress. TEA provides information needed to make informed judgments about the viability of any given conceptual conversion process; it is particularly useful to identify technical barriers and measure progress toward overcoming those barriers. Expansion of the cellulosic biofuels industry at the scale needed to meet the Renewable Fuel Standard goals is also expected to have environmental impacts. Hence, the success of themore » biofuels industry depends not only on economic viability, but also on environmental sustainability. A biorefinery process that is economically feasible but suffers from key sustainability drawbacks is not likely to represent a long-term solution to replace fossil-derived fuels. Overarching concerns like environmental sustainability need to be addressed for biofuels production. Combined TEA and environmental sustainability assessment of emerging pathways helps facilitate biorefinery designs that are both economically feasible and minimally impactful to the environment. This study focuses on environmental sustainability assessment and techno-economic analysis for the production of high-octane gasoline blendstock via gasification and methanol/dimethyl ether intermediates. Results from the conceptual process design with economic analysis, along with the quantification and assessment of the environmental sustainability, are presented and discussed. Sustainability metrics associated with the production of high-octane gasoline include carbon conversion efficiency, consumptive water use, life-cycle greenhouse gas emissions, fossil energy consumption, energy return on investment and net energy value.« less

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{sup trademark}) process. Third quarterly report, 1996

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

NONE

The Liquid Phase Methanol (LPMEOH)(TM) demonstration project at King sport, Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L. P. (the Partnership). A demonstration unit producing 80,000 gallons per day (260 TPD) of methanol is being designed and constructed at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. The Partnership will own and operate the facility for the four year demonstration period. This project is sponsored under the DOE`s Clean Coal Technology Program, and its primary objective is to `demonstrate the production ofmore » methanol using the LPMEOH(TM) Process in conjunction with an integrated coal gasification facility.` The project will also demonstrate the suitability of the methanol produced for use as a chemical feedstock or as a low-sulfur dioxide, low-nitrogen oxides alternative fuel in stationary and transportation applications. The project may also demonstrate the production of dimethyl ether (DME) as a mixed coproduct with methanol, if laboratory- and pilot-scale research and market verification studies show promising results. If implemented, the DME would be produced during the last six months of the four year demonstration period. The LPMEOH(TM) process is the product of a cooperative development effort by Air Products and the DOE in a program that started in 1981. It was successfully piloted at a 10-TPD rate in the DOE-owned experimental unit at Air Products` LaPorte, Texas, site. This demonstration project is the culmination of that extensive cooperative development effort.« less

Process to convert biomass and refuse derived fuel to ethers and/or alcohols

DOEpatents

Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

1996-01-01

A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

The failure of poly (ether ether ketone) in high speed contacts

NASA Astrophysics Data System (ADS)

Briscoe, B. J.; Stuart, B. H.; Sebastian, S.; Tweedale, P. J.

1993-04-01

The paper describes an experimental study, with an associated analysis incorporating supplementary data, of the anti-boundary lubricating action of an alkane-aliphatic carboxylic acid lubricant system in a poly (ether ether ketone)-mild steel contact. The experiments involve progressively increasing the load in a contact formed between a polymer plate and a rotating steel shaft and estimating the frictional work dissipated. Scuffing is identified when a rapid increase in frictional work is noted at a characteristic normal load. It is shown that the additive induces premature scuffing. Subsidiary data is provided using Raman spectroscopy and hardness probes, and confirms that certain additives such as decanoic acid and dodecylamine will induce surface plasticization in poly (ether ether ketone). The trends in the frictional data have been interpreted using the adhesive model of friction in conjunction with temperature-dependent interfacial theology and bulk mechanical property data. It is proposed that the scuffing process is induced prematurely as a consequence of excessive additive-induced subsurface plasticization. Restricted surface plasticization in this system provides an enhanced self-lubricating capacity.

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

NASA Technical Reports Server (NTRS)

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

1975-01-01

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

Conversion of Dexon (p-Dimethylaminobenzenediazo Sodium Sulfonate) to N,N-Dimethyl-p-Phenylenediamine by Pseudomonas fragi Bk9

PubMed Central

Karanth, N. G. K.; Bhat, S. G.; Vaidyanathan, C. S.; Vasantharajan, V. N.

1974-01-01

The metabolism of the fungicide Dexon (p-dimethylaminobenzenediazo sodium sulfonate) by a soil bacterium is reported for the first time. The organism which is capable of using Dexon only by a co-metabolic process was obtained by enrichment culture and was identified as Pseudomonas fragi. The first metabolic product of Dexon was identified as N,N-dimethyl-p-phenylenediamine. The presence of an enzyme, p-dimethylaminobenzenediazo sodium sulfonate reductase, capable of reducing Dexon to N,N-dimethyl-p-phenylenediamine has been demonstrated in the cell-free extracts of the organism. The enzyme is found to be in the soluble fraction and requires dithiothreitol as a reductant. PMID:4809909

Multicomponent synthesis of 4,4-dimethyl sterol analogues and their effect on eukaryotic cells.

PubMed

Alonso, Fernando; Cirigliano, Adriana M; Dávola, María Eugenia; Cabrera, Gabriela M; García Liñares, Guadalupe E; Labriola, Carlos; Barquero, Andrea A; Ramírez, Javier A

2014-06-01

Most sterols, such as cholesterol and ergosterol, become functional only after the removal of the two methyl groups at C-4 from their biosynthetic precursors. Nevertheless, some findings suggest that 4,4-dimethyl sterols might be involved in specific physiological processes. In this paper we present the synthesis of a collection of analogues of 4,4-dimethyl sterols with a diamide side chain and a preliminary analysis of their in vitro activity on selected biological systems. The key step for the synthesis involves an Ugi condensation, a versatile multicomponent reaction. Some of the new compounds showed antifungal and cytotoxic activity. Copyright © 2014 Elsevier Inc. All rights reserved.

2,2\\',4,4\\',5,5\\'-Hexabromodiphenyl ether (BDE-153)

Integrated Risk Information System (IRIS)

2,2 ' , 4,4 ' , 5,5 ' - Hexabromodiphenyl ether ( BDE - 153 ) ; CASRN 68631 - 49 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I (

REMOVAL OF METHYL T-BUTYL ETHER (MTBE) FROM WATER BY PERVAPORATION: BENCH-SCALE AND PILOT SCALE EVALUATIONS

EPA Science Inventory

The ability of pervaporation to remove methyl t-butyl ether (MTBE) from water was evaluated at bench- and pilot-scales. Process parameters studied included flow rate, temperature, MTBE concentration, membrane module type, and permeate pressure. Pervaporation performance was ass...

IRIS Toxicological Review of Ethylene Glycol Mono-Butyl Ether (Egbe) (Interagency Science Discussion Draft)

EPA Science Inventory

EPA released the draft report, Toxicological Review for Ethylene Glycol Mono-Butyl Ether , that was distributed to Federal agencies and White House Offices for comment during the Science Discussion step of the IRIS Assessment Development Process. Comments received from ot...

Molecular dynamics simulations of polyethers and a quaternary ammonium ionic liquid as CO2 absorbers

NASA Astrophysics Data System (ADS)

Cardoso, Piercarlo Fortunato; Fernandez, Juan S. L. C.; Lepre, Luiz Fernando; Ando, Rômulo Augusto; Costa Gomes, Margarida F.; Siqueira, Leonardo J. A.

2018-04-01

The properties of mixtures of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], with poly(ethyleneglycol) dimethyl ether, PEO, were described as a function of PEO chain size by molecular dynamics simulations. Both PEO chain size and mixture composition revealed to play a significant role in determining the structure and the dynamics of the fluids. The remarkably higher viscosity observed for mixtures composed by 0.25 mole fraction of PEO was attributed to the increase in the gauche population of OCCO dihedral of the polyether of longer chains. The negative solvation enthalpy (ΔsolH < 0) and entropy (ΔsolS < 0) revealed a favorable CO2 absorption by the neat and mixture systems. The CO2 absorption was higher in neat PEO, particularly considering longer chains. The gas solubility in the mixtures presented intermediate values in comparison to the neat PEO and neat ionic liquid. The CO2 solutions had their structures discussed in the light of the calculated radial and spatial distribution functions.

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

The study on the application of low polymerization degree PODE2

NASA Astrophysics Data System (ADS)

Xue, Zhenzhen; Shang, Hongyan; Zhang, Zailong; Cui, Chuntao; Zhao, Shidong

2017-05-01

Polyoxymethylene dimethyl ethers (PODEn) are a kind of excellent diesel blending components. Due to the low flash point of PODE2, it is not appropriate to be used as diesel blending component, so in this paper, the application of PODE2 have been studied. It seems that PODE2 is a kind of excellent green rubber solvent oil without sulfur and aromatic. Moreover, the application of PODE2 as gasoline blending component is investigated and it is found that the Research Octane Number(RON) of gasoline product and the RON of four different gasoline components(including hydrofining gasoline, hydrocracking light naphtha, catalytic reforming gasoline and mixed gasoline with 80vol% hydrofining gasoline and 20vol% catalytic reforming gasoline) is all slightly decreased to some extent respectively, which indicates that there is no apparently synergistic effect between PODE2 and the gasoline components, but PODE2 can effectively reduce the sulfur content, olefin content, aromatic content and can suppress the vapor pressure of gasoline.

Spectroscopic analysis of radiation-generated changes in tensile properties of a polyetherimide film

NASA Technical Reports Server (NTRS)

Long, E. R., Jr.; Long, S. A. T.

1985-01-01

The effects of electron radiation on Ultem, a polyetherimide were studied for doses from 2 x 10 to the 9th power to 6 x 10 to the 9th power rad. Specimens were studied for tensile property testing and for electron paramagnetic resonance and infrared spectroscopic measurements of molecular structure. A Faraday cup design and a method for remote temperature measurement were developed. The spectroscopic data show that radiation caused dehydrogenation of methyl groups, rupture of main-chain ether linkage, and opening of imide rings, all to form radicals and indicate that the so-formed atomic hydrogen attached to phenyl radicals, but not to phenoxyl radicals, which would have formed hydroxyls. The observed decays of the radiation-generated phenoxyl, gem-dimethyl, and carbonyl radicals were interpreted as a combining of the radicals to form crosslinking. This crosslinking is the probable cause of the major reduction in the elongation of the tensile specimens after irradiation. Subsequent classical solubility tests indicate that the irradiation caused massive crosslinking.

Characterization of a developmental toxicity dose-response model.

PubMed Central

Faustman, E M; Wellington, D G; Smith, W P; Kimmel, C A

1989-01-01

The Rai and Van Ryzin dose-response model proposed for teratology experiments has been characterized for its appropriateness and applicability in modeling the dichotomous response data from developmental toxicity studies. Modifications were made in the initial probability statements to reflect more accurately biological events underlying developmental toxicity. Data sets used for the evaluation were obtained from the National Toxicology Program and U.S. EPA laboratories. The studies included developmental evaluations of ethylene glycol, diethylhexyl phthalate, di- and triethylene glycol dimethyl ethers, and nitrofen in rats, mice, or rabbits. Graphic examination and statistical evaluation demonstrate that this model is sensitive to the data when compared to directly measured experimental outcomes. The model was used to interpolate to low-risk dose levels, and comparisons were made between the values obtained and the no-observed-adverse-effect levels (NOAELs) divided by an uncertainty factor. Our investigation suggests that the Rai and Van Ryzin model is sensitive to the developmental toxicity end points, prenatal deaths, and malformations, and appears to model closely their relationship to dose. PMID:2707204

Molecular dynamics simulations of polyethers and a quaternary ammonium ionic liquid as CO2 absorbers.

PubMed

Cardoso, Piercarlo Fortunato; Fernandez, Juan S L C; Lepre, Luiz Fernando; Ando, Rômulo Augusto; Costa Gomes, Margarida F; Siqueira, Leonardo J A

2018-04-07

The properties of mixtures of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N 4111 ][NTf 2 ], with poly(ethyleneglycol) dimethyl ether, PEO, were described as a function of PEO chain size by molecular dynamics simulations. Both PEO chain size and mixture composition revealed to play a significant role in determining the structure and the dynamics of the fluids. The remarkably higher viscosity observed for mixtures composed by 0.25 mole fraction of PEO was attributed to the increase in the gauche population of OCCO dihedral of the polyether of longer chains. The negative solvation enthalpy (Δ sol H < 0) and entropy (Δ sol S < 0) revealed a favorable CO 2 absorption by the neat and mixture systems. The CO 2 absorption was higher in neat PEO, particularly considering longer chains. The gas solubility in the mixtures presented intermediate values in comparison to the neat PEO and neat ionic liquid. The CO 2 solutions had their structures discussed in the light of the calculated radial and spatial distribution functions.

Modeling of correlated data with informative cluster sizes: An evaluation of joint modeling and within-cluster resampling approaches.

PubMed

Zhang, Bo; Liu, Wei; Zhang, Zhiwei; Qu, Yanping; Chen, Zhen; Albert, Paul S

2017-08-01

Joint modeling and within-cluster resampling are two approaches that are used for analyzing correlated data with informative cluster sizes. Motivated by a developmental toxicity study, we examined the performances and validity of these two approaches in testing covariate effects in generalized linear mixed-effects models. We show that the joint modeling approach is robust to the misspecification of cluster size models in terms of Type I and Type II errors when the corresponding covariates are not included in the random effects structure; otherwise, statistical tests may be affected. We also evaluate the performance of the within-cluster resampling procedure and thoroughly investigate the validity of it in modeling correlated data with informative cluster sizes. We show that within-cluster resampling is a valid alternative to joint modeling for cluster-specific covariates, but it is invalid for time-dependent covariates. The two methods are applied to a developmental toxicity study that investigated the effect of exposure to diethylene glycol dimethyl ether.

Evaluation of mosquito larvicidal activity of fruit extracts of Acacia auriculiformis against the Japanese encephalitis vector Culex vishnui.

PubMed

Barik, Mousumi; Rawani, Anjali; Laskar, Subrata; Chandra, Goutam

2018-02-19

The larvicidal potentiality of crude and ethyl acetate extracts of fruits of Acacia auriculiformis was investigated against all the larval instars of JE vector Culex vishnui. The crude extracts showed good results against all the larval instars with highest mortality at 0.09%. Highest mortality was found at 300 ppm of ethyl acetate extract. Lowest LC 50 value was obtained at 72 h for third instar larvae. Non target organisms tested, showed no to very less mortality to ethyl acetate solvent extract. Presence of N-H stretching, a C=O stretching, C=C and C-N stretching vibrations of secondary amide or amine group were confirmed from IR analysis. GC-MS analysis revealed the presence of three compounds namely Ethane 2-chloro-1,1-dimethoxy, Acetic acid, 1-methyl ether ester and [4-[1-[3,5-Dimethyl-4[(trimethylsilyl)oxy)phenyl]-1,3-dimethylbutyl)-2,6dimethylphenoxy)(trimethyl) silane, responsible for mosquito larval death.

An Investigation of Flow in Nozzle Hole of Dimethyl Ether

NASA Astrophysics Data System (ADS)

Kato, M.; Yokota, T.; Weber, J.; Gill, D.

2015-12-01

For over twenty years, DME has shown itself to be a most promising fuel for diesel combustion. DME is produced by simple synthesis of such common sources as coal, natural gas, biomass, and waste feedstock. DME is a flammable, thermally-stable liquid similar to liquefied petroleum gas (LPG) and can be handled like LPG. However, the physical properties of DME such as its low viscosity, lubricity and bulk modulus have negative effects for the fuel injection system, which have both limited the achievable injection pressures to about 500 bar and DME's introduction into the market. To overcome some of these effects, a common rail fuel injection system was adapted to operate with DME and produce injection pressures of up to 1000 bar. To understand the effect of the high injection pressure, tests were carried out using 2D optically accessed nozzles. This allowed the impact of the high vapour pressure of DME on the onset of cavitation in the nozzle hole to be assessed and improve the flow characteristics.

Atomistic simulation of CO2 solubility in poly(ethylene oxide) oligomers

NASA Astrophysics Data System (ADS)

Hong, Bingbing; Panagiotopoulos, Athanassios Z.

2014-06-01

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henry's constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henry's constant. Dependence of the calculated Henry's constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length.

Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

NASA Astrophysics Data System (ADS)

Hu, Wen-Juan; Xie, Fen-Yan; Chen, Qiang; Weng, Jing

2008-10-01

We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C-O-C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C-O-C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.

DFT conformational studies of the HI-6 molecule

NASA Astrophysics Data System (ADS)

Silva, Gustavo R.; Borges, Itamar; Figueroa-Villar, Jose D.

A systematic study of the oxime HI-6 [1-(2-hydroxyiminomethyl-1-pyridinium)-1-(4-carboxy-aminopyridinium)dimethyl ether] hydrochloride, which is one of the most promising antidotes against soman intoxication, was carried out using density functional theory with the B3LYP (Becke, Lee, Yang, and Parr) method and the 6-31+G*, 6-31+G*, and 6-31+G** basis sets. Rotational barriers, equilibrium geometries, and charge distributions were calculated in order to investigate the role of the side chain for the larger oximes used as antidotes in the treatment of neurotoxic organophosphate poisoning. Also reported is the comparison between HI-6 and pralidoxime (2-PAM), a smaller oxime previously studied in our research group. It is shown that conformation minima for the protonated E isomer do not depend on the size of the side chain; on the other hand, this effect has a pronounced influence on the protonated Z isomer. For the unprotonated isomers, other effects, such as electrostatic interactions and resonance, should be taken into account in their conformational analysis.

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

NASA Astrophysics Data System (ADS)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li-air battery. Towards this end, using either tetrabutylammonium hexafluorophosphate (TBAPF6) or lithium hexafluorophosphate (LiPF6) electrolyte solutions in four different solvents, namely, dimethyl sulfoxide (DMSO), acetonitrile (MeCN), dimethoxyethane (DME), and tetraethylene glycol dimethyl ether (TEGDME), possessing a range of properties, we have determined that the solvent and the supporting electrolyte cations in the solution act in concert to influence the nature of reduction products and their rechargeability. In solutions containing TBA +, O2 reduction is a highly reversible one-electron process involving the O2/O2- couple in all of the electrolytes examined with little effect on the nature of the solvent. On the other hand, in Li+-containing electrolytes relevant to the Li-air battery, O2 reduction proceeds in a stepwise fashion to form O2-, O22- and O2- as products. These reactions in presence of Li+ are irreversible or quasi-reversible electrochemical processes and the solvents have significant influence on the kinetics, and reversibility or lack thereof, of the different reduction products. Reversible reduction of O2 to long-lived superoxide in a Li+-conducting electrolyte in DMSO has been shown for the first time here. Chapter 5 is the culmination of the thesis where the practical application of the work is demonstrated. We designed electrolytes that facilitate Li-Air rechargeability, by applying the knowledge gained from chapters 2-4. A rechargeable Li-air cell utilizing an electrolyte composed of a solution of LiPF6 in tetraethylene glycol dimethyl ether, CH3O(CH2CH 2O)4CH3 was designed, built and its performance studied. It was shown that the cell yields high capacity and can be recharged in spite the absence of catalyst in the carbon cathode. The application of X-ray diffraction to identify these products formed in a porous carbon electrode is shown here for the first time. The rechargeability of the cell was investigated by repeated charge/discharge cycling of the cell, and the factors limiting the cycle life of the cell were studied using AC impedance spectra of the cells as a function of cycle number. In conclusion, the work carried out in this research has shown that the O2 electrochemistry in organic electrolytes is substantially different from that in aqueous electrolytes. Our work has uncovered the key roles the ion conducting salts and the organic solvents play in determining the nature of the reduction products and their reversibility. The results presented here for the first time provide a rational approach to the design and selection of organic electrolyte solutions for use in the rechargeable Li-air battery. (Abstract shortened by UMI.)

A New Octadecenoic Acid Derivative from Caesalpinia gilliesii Flowers with Potent Hepatoprotective Activity

PubMed Central

Osman, Samir M.; El-Haddad, Alaadin E.; El-Raey, Mohamed A.; Abd El-Khalik, Soad M.; Koheil, Mahmoud A.; Wink, Michael

2016-01-01

Background: Caesalpinia gilliesii Hook is an ornamental shrub with showy yellow flowers. It was used in folk medicine due to its contents of different classes of secondary metabolites. In our previous study, dichloromethane extract of C. gilliesii flowers showed a good antioxidant activity. Aim of the Study: Isolation and identification of bioactive hepatoprotective compounds from C. gilliesii flowers dichloromethane fraction. Materials and Methods: The hepatoprotective activity of dichloromethane fraction and isolated compounds were studied in CCl4-intoxicated rat liver slices by measuring liver injury markers (alanine aminotransferase, aspartate aminotransferase and glutathione [GSH]). All compounds were structurally elucidated on the basis of electron ionization-mass spectrometry, one- and two-dimensional nuclear magnetic resonance. Results: A new 12,13,16-trihydroxy-14(Z)-octadecenoic acid was identified in addition to the known β-sitosterol-3-O-butyl, daucosterol, isorhamnetin, isorhamnetin-3-O-rhamnoside, luteolin-7,4’-dimethyl ether, genistein-5-methyl ether, luteolin-7-O-rhamnoside, isovanillic acid, and p-methoxybenzoic acid. Dichloromethane fraction and isorhamnetin were able to significantly protect the liver against intoxication. Moreover, the dichloromethane fraction and the isolated phytosterols induced GSH above the normal level. Conclusion: The hepatoprotective activity of C. gilliesii may be attributed to its high content of phytosterols and phenolic compounds. SUMMARY Bioactive Hepatoprotective phytosterols and phenolics from chloroform extract of Caesalpinia gilliesii Abbreviations used: ALT: Alanine Aminotransferase; AST: Aspartate aminotransferase; GSH: Glutathione; SC50: Scavenging Capacity 50 (SC 50); COSY: Correlation spectroscopy; NMR: Nuclear Magnetic Resonance; CC: Column chromatography; EI-MS: Electron-impact mass spectrometry; HSQC: Heteronuclear single-quantum correlation. PMID:27563221

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

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

Blazy, V., E-mail: vincent.blazy@irstea.fr; Guardia, A. de, E-mail: amaury.de-guardia@irstea.fr; Benoist, J.C

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, compostingmore » 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 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{sup 5} to 10{sup 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 hydrogen sulphide was suspected. Acetophenone emissions originated from the wood chips. Olfactory measurements need to be correlated to gaseous emissions for a more accurate odour emission evaluation.« less

Metal-Organic Frameworks of Pyrazolate Derivatives: Synthesis and Applications for Chemical Sensing, Gas Separation, and Catalysis

NASA Astrophysics Data System (ADS)

Kivi, Charlie Eric William

In this work we examine the structure and applications of metal-organic frameworks (MOFs) synthesized from pyrazolate derivatives. In total, six pyrazolate ligands were examined: 4-(4-(3,5-dimethyl-1H-pyrazol-4-yl)phenyl)pyridine (HL), 1,1'-methylenebis(3,5-dimethyl-1H-pyrazolyl-4-carboxylic acid) (H2BPM), triethyl-1,1',1''-methanetriyltris(3,5-dimethyl-1H-pyrazole-4-carboxylate) (TPM-1), triethyl-4,4',4''-(methanetriyltris[3,5-dimethyl-1H-pyrazole-1,4-diyl])tribenzoate (TPM-2), 1,1',1'',1'''-(propane-1,1,3,3-tetrayl)tetrakis(3,5-dimethyl-1H-pyrazole-4-carboxylic acid) (H4TPP), tetraethyl-1,1',1'',1'''-(1,4-phenylenebis[methanetriyl]) tetrakis(3,5-dimethyl-1H-pyrazole-4-carboxylate)pyridinephenylpyrazole ( TPX). These ligands were used to synthesize a variety of MOFs that were subsequently investigated for luminescent sensing, gas storage, and catalytic performance. In Chapter 2, three MOFs synthesized from the reaction of HL and CuX (X = Br, I) were investigated. These materials were found to form MOFs which contained the luminescent trinuclear Cu(I) pyrazolate unit. Only CuBr and HL alone resulted in a MOF of sufficient purity and stability to permit evaluation as a luminescent sensor. Experiments with various volatile organic compounds revealed turn-on (luminescence enhancement) behaviour for ethyl acetate, pentane, and benzene and turn-off (luminescence quenching) behaviour for diethyl ether and chloroform for this material. In Chapters 3 and 4, ten MOFs are described. These were synthesized from H2BPM and metal-acetate salts. Chapter 3 encompassed two MOFs: [Ni(BPM)]n·xDMSO and [Cd(BPM)]n·xDMSO. These MOFs are isostructural, microporous materials. Evacuation of the pores led to collapse of the [Cd(BPM)]n·xDMSO material but [Ni(BPM)]n·xDMSO proved to be permanently porous. Further investigations revealed [Ni(BPM)] n·xDMSO selectively adsorbed methane over nitrogen indicating it may serve as a porous material for coal mine methane capture. Chapter 4 investigated the many other structures H2BPM can assume in the presence of manganese, cobalt, iron, copper, and europium. Cobalt in particular proved highly tunable with 4 separate structures being synthesized such as [Co2(BPM)2(H2 O)4(Bpy)0.5]n·2DMF·2(H 2O). This was achieved through varying the synthetic conditions. [Co 2(BPM)2(H2O)4(Bpy) 0.5]n·2DMF·2(H2O)and [Eu( BPM)(OAc)]n were further investigated for the oxidation of olefins and luminescence respectively. In Chapter 5, metal complexes Mo(TPM-1)(CO)3, Mo(TPM-2)(CO)3, Pd2(H4TPP )Cl4, and Pd2(TPX)Cl4 were synthesized. The catalytic performance of Mo(TPM-1)(CO) 3 was evaluated and found to be effective for the oxidation of olefins. MOF synthesis was attempted with all four compounds but was ultimately unsuccessful. Although one MOF was produced from Mo(TPM-1)(CO)3, large scale synthesis was not possible preventing full investigation of its properties.

Process to convert biomass and refuse derived fuel to ethers and/or alcohols

DOEpatents

Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

1996-04-02

A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

Treatability of phenol-production wastewater: Rate constant and pathway of dimethyl phenyl carbinol oxidation by hydroxyl radicals.

PubMed

Boonrattanakij, Nonglak; Joysampao, Atsawin; Pobsuktanasub, Tuksinaiya; Anotai, Jin; Ruangchainikom, Chalermchai

2017-12-15

Phenol-production wastewater is difficult to treat biologically by aerobic processes to meet the effluent standard COD of 120 mg L -1 because it contains several highly refractory aromatic pollutants, particularly dimethyl phenyl carbinol. Pretreatment revealed that dimethyl phenyl carbinol was slowly oxidized by molecular ozone; however, it readily reacted with hydroxyl radicals to yield acetophenone as a primary product. Acetophenone was further oxidized, first through five different pathways to form benzoic acid, phenyl glyoxalic acid, 4-4'-diacetyl biphenyl, and several hydroxylated aromatic compounds, and later to aliphatic carboxylic acids via ring cleavage. Regardless of system configuration (homogeneous vs heterogeneous), operating mode (batch vs continuous), and chemical concentration, the average intrinsic rate constants were 1.05 × 10 10 and 9.29 × 10 9  M -1  s -1 for dimethyl phenyl carbinol and acetophenone, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

The 2007 water crisis in Wuxi, China: analysis of the origin.

PubMed

Zhang, Xiao-jian; Chen, Chao; Ding, Jian-qing; Hou, Aixin; Li, Yong; Niu, Zhang-bin; Su, Xiao-yan; Xu, Yan-juan; Laws, Edward A

2010-10-15

An odorous tap water crisis that affected two million residents for several days occurred in Wuxi, China in the summer of 2007. Volatile sulfide chemicals including methyl thiols, dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide were the dominant odorous contaminants in Lake Taihu and in tap water during the crisis. These contaminants originated from the decomposition of a massive cyanobacterial bloom that was triggered by illegal industrial discharges and inadequately regulated domestic pollution. A specific emergency drinking water treatment process was quickly developed using a combination of potassium permanganate oxidation and powdered activated carbon adsorption. The emergency treatment process removed the odor from the tap water and solved the crisis successfully in several days. This experience underscores the suggestion that a combination of stresses associated with eutrophication and industrial and domestic wastewater discharges can push an aquatic system to the tipping point with consequences far more severe than would occur if the system were subjected to each stress separately. 2010 Elsevier B.V. All rights reserved.

THE SEARCH FOR A COMPLEX MOLECULE IN A SELECTED HOT CORE REGION: A RIGOROUS ATTEMPT TO CONFIRM TRANS-ETHYL METHYL ETHER TOWARD W51 e1/e2

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

Carroll, P. Brandon; McGuire, Brett A.; Blake, Geoffrey A.

2015-01-20

An extensive search has been conducted to confirm transitions of trans-ethyl methyl ether (tEME, C{sub 2}H{sub 5}OCH{sub 3}), toward the high-mass star forming region W51 e1/e2 using the 12 m Telescope of the Arizona Radio Observatory at wavelengths from 2 mm and 3 mm. In short, we cannot confirm the detection of tEME toward W51 e1/e2 and our results call into question the initial identification of this species by Fuchs et al. Additionally, re-evaluation of the data from the original detection indicates that tEME is not present toward W51 e1/e2 in the abundance reported by Fuchs and colleagues. Typical peak-to-peak noise levels for themore » present observations of W51 e1/e2 were between 10 and 30 mK, yielding an upper limit of the tEME column density of ≤1.5 × 10{sup 15} cm{sup –2}. This would make tEME at least a factor of two times less abundant than dimethyl ether (CH{sub 3}OCH{sub 3}) toward W51 e1/e2. We also performed an extensive search for this species toward the high-mass star forming region Sgr B2(N-LMH) with the National Radio Astronomy Observatory 100 m Green Bank Telescope. No transitions of tEME were detected and we were able to set an upper limit to the tEME column density of ≤4 × 10{sup 14} cm{sup –2} toward this source. Thus, we are able to show that tEME is not a new molecular component of the interstellar medium and that an exacting assessment must be carried out when assigning transitions of new molecular species to astronomical spectra to support the identification of large organic interstellar molecules.« less

Elastic electron scattering by ethyl vinyl ether

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

Khakoo, M. A.; Hong, L.; Kim, B.

2010-02-15

We report measured and calculated results for elastic scattering of low-energy electrons by ethyl vinyl ether (ethoxyethene), a prototype system for studying indirect dissociative attachment processes that may play a role in DNA damage. The integral cross section displays the expected {pi}{sup *} shape resonance. The agreement between the calculated and measured cross sections is generally good.

A review of liquid lubricant thermal/oxidative degradation

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.

1983-01-01

The fundamental processes occurring during the thermal and oxidative degradation of hydrocarbons are reviewed. Particular emphasis is given to various classes of liquid lubricants such as mineral oils, esters, polyphenyl ethers, C-ethers, and fluorinated polyethers. Experimental techniques for determining thermal and oxidative stabilities of lubricants are discussed. The role of inhibitors and catalysis is also covered.

Inhibition of microbiological sulfide oxidation by methanethiol and dimethyl polysulfides at natron-alkaline conditions.

PubMed

van den Bosch, Pim L F; de Graaff, Marco; Fortuny-Picornell, Marc; van Leerdam, Robin C; Janssen, Albert J H

2009-06-01

To avoid problems related to the discharge of sulfidic spent caustics, a biotechnological process is developed for the treatment of gases containing both hydrogen sulfide and methanethiol. The process operates at natron-alkaline conditions (>1 mol L(-1) of sodium- and potassium carbonates and a pH of 8.5-10) to enable the treatment of gases with a high partial CO(2) pressure. In the process, methanethiol reacts with biologically produced sulfur particles to form a complex mixture predominantly consisting of inorganic polysulfides, dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). The effect of these organic sulfur compounds on the biological oxidation of sulfide to elemental sulfur was studied with natron-alkaliphilic bacteria belonging to the genus Thioalkalivibrio. Biological oxidation rates were reduced by 50% at 0.05 mM methanethiol, while for DMDS and DMTS, this was estimated to occur at 1.5 and 1.0 mM, respectively. The inhibiting effect of methanethiol on biological sulfide oxidation diminished due to its reaction with biologically produced sulfur particles. This reaction increases the feasibility of biotechnological treatment of gases containing both hydrogen sulfide and methanethiol at natron-alkaline conditions.

Synthesis and anti-microbial activity of some 1- substituted amino-4,6-dimethyl-2-oxo-pyridine-3-carbonitrile derivatives.

PubMed

Khidre, Rizk E; Abu-Hashem, Ameen A; El-Shazly, Mohamed

2011-10-01

A new series of 1- substituted amino-4,6-dimethyl-2-oxo-pyridine-3-carbonitrile such as hydrazide hydrazones 3a-h; ethane-1,2-diaminopyridine 6; phthalimidopyridines 8a,b; hydrazides 10a,b; urea 11a and thiourea 11b were synthesized in a good to excellent yield in step efficient process, using 1-amino-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (1) as a key intermediate. The antibacterial and antifungal activities of the synthesized compounds were evaluated. The obtained data indicated that the majority of the tested compounds exhibited both antibacterial and antifungal activities, particularly compounds 8a and 8b showed a comparable effect to a well known antibacterial and antifungal agents. Published by Elsevier Masson SAS.

Study of emissions for a compression ignition engine fueled with a mix of DME and diesel

NASA Astrophysics Data System (ADS)

Jurchiş, Bogdan; Nicolae, Burnete; Călin, Iclodean; Nicolae Vlad, Burnete

2017-10-01

Currently, there is a growing demand for diesel engines, primarily due to the relatively low fuel consumption compared to spark-ignition engines. However, these engines have a great disadvantage in terms of pollution because they produce solid particles that ultimately form particulate matter (PM), which has harmful effects on human health and also on the environment. The toxic emissions from the diesel engine exhaust, like particulate matter (PM) and NOx, generated by the combustion of fossil fuels, lead to the necessity to develop green fuels which on one hand should be obtained from regenerative resources and on the other hand less polluting. In this paper, the authors focused on the amount of emissions produced by a diesel engine when running with a fuel mixture consisting of diesel and DME. Dimethyl ether (DME) is developed mainly by converting natural gas or biomass to synthesis gas (syngas). It is an extremely attractive resource for the future used in the transport industry, given that it can be obtained at low costs from renewable resources. Using DME mixed with diesel for the combustion process, besides the fact that it produces less smoke, the emission levels of particulate matter is reduced compared to diesel and in some situations, NOx emissions may decrease. DME has a high enough cetane number to perform well as a compression-ignition fuel but due to the poor lubrication and viscosity, it is difficult to be used as the main fuel for combustion

Novel melt-processable poly(ether ether ketone)(PEEK)/inorganic fullerene-like WS(2) nanoparticles for critical applications.

PubMed

Naffakh, Mohammed; Díez-Pascual, Ana M; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2010-09-09

The combination of high-performance thermoplastic poly(ether ether ketone) (PEEK) with inorganic fullerene-like tungsten disulfide (IF-WS(2)) nanoparticles offers an attractive way to combine the merits of organic and inorganic materials into novel polymer nanocomposite materials. Here, we report the processing of novel PEEK/IF-WS(2) nanocomposites, which overcome the nanoparticle agglomerate formation and provide PEEK-particle interactions. The IF-WS(2) nanoparticles do not require exfoliation or modification, making it possible to obtain stronger, lighter materials without the complexity and processing cost associated with these treatments. The nanocomposites were fabricated by melt blending, after a predispersion step based on ball milling and mechanical treatments in organic solvent, which leads to the dispersion of individually IF-WS(2) nanoparticles in the PEEK matrix as confirmed by scanning electron microscopy. In order to determine the performance of the PEEK/IF-WS(2) nanocomposites for potential critical applications, particularly for the aircraft industry, we have extensively investigated these materials with a wide range of structural, thermal, and mechanical techniques using time-resolved synchrotron X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, dynamic-mechanical analysis, and tensile and impact tests as well as thermal measurements. Modulus, tensile strengh, thermal stability, and thermal conductivity of PEEK exhibited remarkable improvement with the addition of IF-WS(2).

The smallest quaternary ammonium salts with ether groups for high-performance electrochemical double layer capacitors† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02755a Click here for additional data file.

PubMed Central

Han, Taihee; Park, Min-Sik; Kim, Jeonghun; Kim, Jung Ho

2016-01-01

Electrochemical double layer capacitors (EDLCs) are energy storage devices that have been used for a wide range of electronic applications. In particular, the electrolyte is one of the important components, directly related to the capacitance and stability. Herein, we first report a series of the smallest quaternary ammonium salts (QASs), with ether groups on tails and tetrafluoroborate (BF4) as an anion, for use in EDLCs. To find the optimal structure, various QASs with different sized head groups and ether-containing tail groups were systematically compared. Comparing two nearly identical structures with and without ether groups, QASs with oxygen atoms showed improved capacitance, proving that ions with oxygen atoms move more easily than their counterparts at lower electric fields. Moreover, the ether containing QASs showed low activation energy values of conductivities, leading to smaller IR drops during the charge and discharge processes, resulting in an overall higher capacitance. PMID:28959391

Low-energy (<20 eV) and high-energy (1000 eV) electron-induced methanol radiolysis of astrochemical interest

NASA Astrophysics Data System (ADS)

Sullivan, Kristal K.; Boamah, Mavis D.; Shulenberger, Katie E.; Chapman, Sitara; Atkinson, Karen E.; Boyer, Michael C.; Arumainayagam, Christopher R.

2016-07-01

We report the first infrared study of the low-energy (<20 eV) electron-induced reactions of condensed methanol. Our goal is to simulate processes which occur when high-energy cosmic rays interact with interstellar and cometary ices, where methanol, a precursor of several prebiotic species, is relatively abundant. The interactions of high-energy radiation, such as cosmic rays (Emax ˜ 1020 eV), with matter produce large numbers of low-energy secondary electrons, which are known to initiate radiolysis reactions in the condensed phase. Using temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS), we have investigated low-energy (5-20 eV) and high-energy (˜1000 eV) electron-induced reactions in condensed methanol (CH3OH). IRAS has the benefit that it does not require thermal processing prior to product detection. Using IRAS, we have found evidence for the formation of ethylene glycol (HOCH2CH2OH), formaldehyde (CH2O), dimethyl ether (CH3OCH3), methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and the hydroxyl methyl radical (·CH2OH) upon both low-energy and high-energy electron irradiation of condensed methanol at ˜85 K. Additionally, TPD results, presented herein, are similar for methanol films irradiated with both 1000 eV and 20 eV electrons. These IRAS and TPD findings are qualitatively consistent with the hypothesis that high-energy condensed phase radiolysis is mediated by low-energy electron-induced reactions. Moreover, methoxymethanol (CH3OCH2OH) could serve as a tracer molecule for electron-induced reactions in the interstellar medium. The results of experiments such as ours may provide a fundamental understanding of how complex organic molecules are synthesized in cosmic ices.

Capillary break-up, gelation and extensional rheology of hydrophobically modified cellulose ethers

NASA Astrophysics Data System (ADS)

Sharma, Vivek; Haward, Simon; Pessinet, Olivia; Soderlund, Asa; Threlfall-Holmes, Phil; McKinley, Gareth

2012-02-01

Cellulose derivatives containing associating hydrophobic groups along their hydrophilic polysaccharide backbone are used extensively in the formulations for inks, water-borne paints, food, nasal sprays, cosmetics, insecticides, fertilizers and bio-assays to control the rheology and processing behavior of multi-component dispersions. These complex dispersions are processed and used over a broad range of shear and extensional rates. The presence of hydrophobic stickers influences the linear and nonlinear rheology of cellulose ether solutions. In this talk, we systematically contrast the difference in the shear and extensional rheology of a cellulose ether: ethy-hydroxyethyl-cellulose (EHEC) and its hydrophobically-modified analog (HMEHEC) using microfluidic shear rheometry at deformation rates up to 10^6 inverse seconds, cross-slot flow extensional rheometry and capillary break-up during jetting as a rheometric technique. Additionally, we provide a constitutive model based on fractional calculus to describe the physical gelation in HMEHEC solutions.

Anti-knock quality of sugar derived levulinic esters and cyclic ethers

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

Tian, Miao; McCormick, Robert L.; Luecke, Jon

Here, the objective of this paper is to investigate the anti-knock quality of sugar-derived levulinic esters (methyl levulinate (ML) and ethyl levulinate (EL)) and cyclic ethers (furfuryl ethyl ether (FEE) and ethyl tetrahydrofurfuryl ether (ETE)). To this end, combustion experiments were carried out in both an engine and a constant volume autoignition device. The results from both apparati demonstrate that ML, EL and FEE have superior anti-knock quality than the reference Euro95 gasoline. ETE, conversely, performed markedly worse than the reference fuel on both setups and might therefore be a more appropriate fuel for compression ignition engines. The main reasonmore » of the distinctions in anti-knock quality can be found in the molecular structure of the neat biofuels. ML and EL are levulinic esters, with a ketone (C=O) functionality and an ester (C(=O)-O) group on the carbon chain. They can readily produce stable intermediates during the auto-ignition process, thereby slowing down the overall reaction rate. The unsaturated cyclic ether (FEE) has very strong ring C-H bonds. However, the saturated cyclic ether (ETE) has weak ring C-H bonds, which facilitate more readily ring opening reactions. Long side chains on the cyclic ethers further accelerate the reaction rate. Importantly for future research, our results suggest that IQT and engine experiments are interchangeable setups with respect to qualitative anti-knock quality evaluation of novel compounds.« less

Anti-knock quality of sugar derived levulinic esters and cyclic ethers

DOE PAGES

Tian, Miao; McCormick, Robert L.; Luecke, Jon; ...

2017-04-22

Here, the objective of this paper is to investigate the anti-knock quality of sugar-derived levulinic esters (methyl levulinate (ML) and ethyl levulinate (EL)) and cyclic ethers (furfuryl ethyl ether (FEE) and ethyl tetrahydrofurfuryl ether (ETE)). To this end, combustion experiments were carried out in both an engine and a constant volume autoignition device. The results from both apparati demonstrate that ML, EL and FEE have superior anti-knock quality than the reference Euro95 gasoline. ETE, conversely, performed markedly worse than the reference fuel on both setups and might therefore be a more appropriate fuel for compression ignition engines. The main reasonmore » of the distinctions in anti-knock quality can be found in the molecular structure of the neat biofuels. ML and EL are levulinic esters, with a ketone (C=O) functionality and an ester (C(=O)-O) group on the carbon chain. They can readily produce stable intermediates during the auto-ignition process, thereby slowing down the overall reaction rate. The unsaturated cyclic ether (FEE) has very strong ring C-H bonds. However, the saturated cyclic ether (ETE) has weak ring C-H bonds, which facilitate more readily ring opening reactions. Long side chains on the cyclic ethers further accelerate the reaction rate. Importantly for future research, our results suggest that IQT and engine experiments are interchangeable setups with respect to qualitative anti-knock quality evaluation of novel compounds.« less

Simultaneous quantification of flavonoids in blood plasma by a high-performance liquid chromatography method after oral administration of Blumea balsamifera leaf extracts in rats.

PubMed

Nessa, Fazilatun; Ismail, Zhari; Mohamed, Nornisah; Karupiah, Sundram

2013-03-01

The leaves of Blumea balsamifera are used as a folk medicine in kidney stone diseases in South-East Asia. Phytochemical investigation revealed leaves contained a number of flavonoids. In view of these, the present work was aimed to quantify and preliminary pharmacokinetic investigation of five flavonoids viz. dihydroquercetin-7,4¢-dimethyl ether (I), dihydroquercetin-4¢-methyl ether (II), 5,7,3¢,5¢-tetrahydroxyflavanone (III), blumeatin (IV) and quercetin (V) in rat plasma following oral administration (0.5g/Kg) of B. balsamifera leaf extract in rats. Quantification was achieved by using a validated, reproducible high-performance liquid chromatographic method. The mean recoveries of I, II, III, IV and V were 90.6, 93.4, 93.5, 91.2 and 90.3% respectively. The limit of quantification was 25 ng/mL for I and IV, 10 ng/mL for II and III and 100 ng/mL for V respectively. The within day and day-to-day precision for all the compounds were < 10%. The validated HPLC method herein was applied for pharmacokinetic studies and the main pharmacokinetic parameters were: t1/2 (hr) 5.8, 4.3, 2.9, 5.7 and 7.3, Cmax (ng/mL) 594.9, 1542.9 1659.9, 208.9 and 3040.4; Tmax (hr) 4.7, 1.0, 1.0, 3.5 and 2.3; AUC0-oo (ng hr/mL) 5040, 5893, 9260, 1064 and 27233 for I, II, III, IV and V respectively. The developed method was suitable for pharmacokinetic studies and this preliminary study also revealed significant absorption after oral dosing in rats.

Selective Cleavage of the Aryl Ether Bonds in Lignin for Depolymerization by Acidic Lithium Bromide Molten Salt Hydrate under Mild Conditions.

PubMed

Yang, Xiaohui; Li, Ning; Lin, Xuliang; Pan, Xuejun; Zhou, Yonghong

2016-11-09

The present study demonstrates that the concentrated lithium bromide (LiBr) solution with acid as catalyst was able to selectively cleave the β-O-4 aryl ether bond and lead to lignin depolymerization under mild conditions (e.g., in 60% LiBr with 0.3 M HCl at 110 °C for 2 h). Four industrial lignins from different pulping and biorefining processes, including softwood kraft lignin (SKL), hardwood kraft lignin (HKL), softwood ethanol organosolv lignin (EOL), and acid corncob lignin (ACL), were treated in the LiBr solution. The molecular weight, functional group, and interunit linkages of the lignins were characterized using GPC, FTIR, and NMR. The results indicated that the β-O-4 aryl ether bonds of the lignins were selectively cleaved, and both LiBr and HCl played crucial roles in catalyzing the cleavage of the ether bonds.

Toxicological evaluation of the natural products and some semisynthetic derivatives of Heterotheca inuloides Cass (Asteraceae).

PubMed

Rodríguez-Chávez, José Luis; Coballase-Urrutia, Elvia; Sicilia-Argumedo, Gloria; Ramírez-Apan, Teresa; Delgado, Guillermo

2015-12-04

Heterotheca ineuloides Cass (Asteraceae), popularly known as árnica mexicana, is widely used in Mexican traditional medicine to treat bruises, dermatological problems, rheumatic pains, and other disorders as cancer. The major constituents in H. inuloides are cadinane type sesquiterpenes, flavonoids and phytosterols. Compounds with a cadinane skeleton have been proved to possess cytotoxic activity against human-tumor cell lines and brine shrimp, and display toxic effects in different animal species. Although this plant has been widely used, there is little available information on the safety and toxicity especially of pure compounds. Evaluate the potential toxicity of the natural products isolated from H. inuloides and some semisynthetic derivatives. The toxic aspects of the following natural products isolated from dried flowers of H. inuloides: 7-hydroxy-3,4-dihydrocadalene (1), 7-hydroxycadalene (2), 3,7-dihydroxy-3(4H)-isocadalen-4-one (3), (1R,4R)-1-hydroxy-4H-1,2,3,4- tetrahydrocadalen-15-oic acid (4), D-chiro-inositol (5), quercetin (6), quercetin-3,7,3'-trimethyl ether (7), quercetin-3,7,3',4'-tetramethyl ether (8), eriodictyol-7,4'-dimethyl ether (9), α-spinasterol (10), caryolan-1,9β-diol (11) and 7-(3,3-dimethylallyloxy)-coumarin (12) as well as the toxic aspects of the semisynthetic compounds 7-acetoxy-3,4-dihydrocadalene (13), 7-benzoxy-3,4-dihydrocadalene (14), 7-acetoxycadalene (15), 7-benzoxycadalene (16), quercetin pentaacetate (17), 7-hydroxycalamenene (18), 3,8-dimethyl-5-(1-methylethyl)-1,2-naphthoquinone (19), and 4-isopropyl-1,6-dimethylbenzo[c]oxepine-7,9-dione (20). Toxic activities of compounds were determined by sulforhodamine B (SRB) assay, Artemia salina assay, RAW264.7 macrophage cells. Additionally, the acute toxicity in mouse of compound 1, the major natural sesquiterpene isolated from the acetone extract, was evaluated. The best cytotoxicity activity was observed for mansonone C (19) on K562 cell line with IC50 1.45 ± 0.14 μM, for 7-hydroxycadalene (2) on HCT-15 cell line with IC50 18.89 ± 1.2 μM, and for quercetin pentaacetate (17) on MCF-7 cell line with IC50 22.57 ± 2.4 μM. Sesquiterpenes mansonone C (19) and 7-hydroxy-3,4-dihydrocadalene (1) caused the strongest deleterious effects against A. salina with IC50 39.4 ± 1.07, and 45.47 ± 1.74 μM, respectively. The number of viable RAW 264.7 cells was reduced with sesquiterpenes 1 and 2 by more than 90%. In addition, the acute study of 1 revealed no lethal effects at 300 mg/kg body weight, however, a reduction in the body weight of mice, morphological changes in the tissues of the liver and kidney and toxic signs were observed at very high doses (2000 mg/kg). The results provided evidence for the cytotoxicity of Mexican arnica (H. inuloides) metabolites and may be correlated with one of the popular uses of this plant, in traditional Mexican medicine, as anticancer remedy. Among the active compounds contained in the acetone extract, the cytotoxic activity is mainly ascribable to cadinene type sesquiterpenes. In addition, evidence of acute toxicity suggests that 7-hydroxy-3,4-dihydrocadalene (1) may lead to toxicity at very high doses. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Purifying contaminated water

DOEpatents

Daughton, Christian G.

1983-01-01

Process for removing biorefractory compounds from contaminated water (e.g., oil shale retort waste-water) by contacting same with fragmented raw oil shale. Biorefractory removal is enhanced by preactivating the oil shale with at least one member of the group of carboxylic, acids, alcohols, aldehydes, ketones, ethers, amines, amides, sulfoxides, mixed ether-esters and nitriles. Further purification is obtained by stripping, followed by biodegradation and removal of the cells.

Nitrogen Molecule-Dimethyl Sulfide Complex Investigated by Fourier Transform Microwave Spectroscopy and AB Initio Calculation

NASA Astrophysics Data System (ADS)

Kawashima, Yoshiyuki; Iwano, Sakae; Hirota, Eizi

2016-06-01

This paper presents an extension of the preceding talk on the FTMW spectroscopy of N_2-ES (ethylene sulfide), namely the results on N_2-DMS (dimethyl sulfide). We have previously investigated two N_2 complexes: N_2-DME (dimethyl ether), for which we reported a prelimanary result, and N_2-EO (ethylene oxide). We have observed the ground-state rotational spectrum of the N_2-DMS complex, i.e. c-type transitions in the frequency region from 5 to 24 GHz, which we assigned to the normal, 15N_2-DMS, and 15NN-DMS species of the N_2-DMS. We have found both the ortho and para states for the 14N_2-DMS and 15N_2-DMS species. In the case of the 15N_2-DMS, some transitions with Ka = 2 and 3 were observed slightly split by the internal rotation of the two methyl tops of the DMS. The observed spectra of the 15N_2-DMS were analyzed by using the XIAM program. In the case of the para state of the 15N_2-DMS, three rotational and five centrifugal distortion constants with the V3 barrier to the methyl group internal rotation, whereas, in the case of the ortho state of the 15N_2-DMS, two more centrifugal distortion constants, ΦJK and ΦKJ, were needed to reproduce the observed spectra. For the N_2-DMS complex, we concluded that the N_2 moiety was located in a plane perpendicular to the C-S-C plane and bisecting the CSC angle of the DMS. We have carried out ab initio molecular orbital calculations at the level of MP2 with basis sets 6-311++G(d, p), aug-cc-pVDZ, and aug-cc-pVTZ, to complement the information on the intracomplex motions obtained from the observed rotational spectra. We have applied a natural bond orbital (NBO) analysis to the N_2-DMS and N_2-ES to calculate the stabilization energy CT (=Δ Eσσ*), which was closely correlated with the binding energy EB, as found for other related complexes. Y. Kawashima, Y. Tatamitani, Y. Morita, and E. Hirota, 61st International Symposium on Molecular Spectroscopy, TE10 (2006) Y. Kawashima and E. Hirota, J. Phys. Chem. A 2013 117, 13855

Properties of the Flight Model Gas Electron Multiplier for the GEMS Mission

NASA Technical Reports Server (NTRS)

Takeuchi, Yoko; Kitaguchi, Takao; Hayato, Asami; Tamagawa, Toru; Iwakiri, Wataru; Asami, Fumi; Yoshikawa, Akifumi; Kaneko, Kenta; Enoto, Teruaki; Black, Kevin;

Greenhouse gas emissions for refrigerant choices in room air conditioner units.

PubMed

Galka, Michael D; Lownsbury, James M; Blowers, Paul

2012-12-04

In this work, potential replacement refrigerants for window-mounted room air conditioners (RACs) in the U.S. have been evaluated using a greenhouse gas (GHG) emissions analysis. CO(2)-equivalent emissions for several hydrofluoroethers (HFEs) and other potential replacements were compared to the most widely used refrigerants today. Included in this comparison are pure refrigerants that make up a number of hydrofluorocarbon (HFC) mixtures, pure hydrocarbons, and historically used refrigerants such as propane and ammonia. GHG emissions from direct and indirect sources were considered in this thermodynamic analysis. Propylene, dimethyl ether, ammonia, R-152a, propane, and HFE-152a all performed effectively in a 1 ton window unit and produced slightly lower emissions than the currently used R-22 and R-134a. The results suggest that regulation of HFCs in this application would have some effect on reducing emissions since end-of-life emissions remain at 55% of total refrigerant charge despite EPA regulations that mandate 80% recovery. Even so, offsite emissions due to energy generation dominate over direct GHG emissions and all the refrigerants perform similarly in totals of indirect GHG emissions.

Assessment of Novel Routes of Biomethane Utilization in a Life Cycle Perspective

PubMed Central

Moghaddam, Elham Ahmadi; Ahlgren, Serina; Nordberg, Åke

2016-01-01

Biomethane, as a replacement for natural gas, reduces the use of fossil-based sources and supports the intended change from fossil to bio-based industry. The study assessed different biomethane utilization routes for production of methanol, dimethyl ether (DME), and ammonia, as fuel or platform chemicals and combined heat and power (CHP). Energy efficiency and environmental impacts of the different pathways was studied in a life cycle perspective covering the technical system from biomass production to the end product. Among the routes studied, CHP had the highest energy balance and least environmental impact. DME and methanol performed competently in energy balance and environmental impacts in comparison with the ammonia route. DME had the highest total energy output, as fuel, heat, and steam, among the different routes studied. Substituting the bio-based routes for fossil-based alternatives would give a considerable reduction in environmental impacts such as global warming potential and acidification potential for all routes studied, especially CHP, DME, and methanol. Eutrophication potential was mainly a result of biomass and biomethane production, with marginal differences between the different routes. PMID:28066762

Applications of the Simple Multi-Fluid Model to Correlations of the Vapor-Liquid Equilibrium of Refrigerant Mixtures Containing Carbon Dioxide

NASA Astrophysics Data System (ADS)

Akasaka, Ryo

This study presents a simple multi-fluid model for Helmholtz energy equations of state. The model contains only three parameters, whereas rigorous multi-fluid models developed for several industrially important mixtures usually have more than 10 parameters and coefficients. Therefore, the model can be applied to mixtures where experimental data is limited. Vapor-liquid equilibrium (VLE) of the following seven mixtures have been successfully correlated with the model: CO2 + difluoromethane (R-32), CO2 + trifluoromethane (R-23), CO2 + fluoromethane (R-41), CO2 + 1,1,1,2- tetrafluoroethane (R-134a), CO2 + pentafluoroethane (R-125), CO2 + 1,1-difluoroethane (R-152a), and CO2 + dimethyl ether (DME). The best currently available equations of state for the pure refrigerants were used for the correlations. For all mixtures, average deviations in calculated bubble-point pressures from experimental values are within 2%. The simple multi-fluid model will be helpful for design and simulations of heat pumps and refrigeration systems using the mixtures as working fluid.

Radical scavenging ability of some compounds isolated from Piper cubeba towards free radicals.

PubMed

Aboul-Enein, Hassan Y; Kładna, Aleksandra; Kruk, Irena

2011-01-01

The purpose of this study was to identify the antioxidant activity of 16 compounds isolated from Piper cubeba (CNCs) through the extent of their capacities to scavenge free radicals, hydroxyl radical (HO(•)), superoxide anion radical O•(2)(-) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•)), in different systems. Electron paramagnetic resonance (EPR) and 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, as the spin trap, and chemiluminescence techniques were applied. Using the Fenton-like reaction [Fe(II) + H(2)O(2)], CNCs were found to inhibit DMPO-OH radical formation ranging from 5 to 57% at 1.25 mmol L(-1) concentration. The examined CNCs also showed a high DPPH antiradical activity (ranging from 15 to 99% at 5 mmol L(-1) concentration). Furthermore, the results indicated that seven of the 16 tested compounds may catalyse the conversion of superoxide radicals generated in the potassium superoxide/18-crown-6 ether system, thus showing superoxide dismutase-like activity. The data obtained suggest that radical scavenging properties of CNCs might have potential application in many plant medicines. Copyright © 2010 John Wiley & Sons, Ltd.

High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes.

PubMed

Chen, Shuru; Zheng, Jianming; Mei, Donghai; Han, Kee Sung; Engelhard, Mark H; Zhao, Wengao; Xu, Wu; Liu, Jun; Zhang, Ji-Guang

2018-03-25

Rechargeable lithium-metal batteries (LMBs) are regarded as the "holy grail" of energy-storage systems, but the electrolytes that are highly stable with both a lithium-metal anode and high-voltage cathodes still remain a great challenge. Here a novel "localized high-concentration electrolyte" (HCE; 1.2 m lithium bis(fluorosulfonyl)imide in a mixture of dimethyl carbonate/bis(2,2,2-trifluoroethyl) ether (1:2 by mol)) is reported that enables dendrite-free cycling of lithium-metal anodes with high Coulombic efficiency (99.5%) and excellent capacity retention (>80% after 700 cycles) of Li||LiNi 1/3 Mn 1/3 Co 1/3 O 2 batteries. Unlike the HCEs reported before, the electrolyte reported in this work exhibits low concentration, low cost, low viscosity, improved conductivity, and good wettability that make LMBs closer to practical applications. The fundamental concept of "localized HCEs" developed in this work can also be applied to other battery systems, sensors, supercapacitors, and other electrochemical systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A conservative, thermodynamically consistent numerical approach for low Mach number combustion. Part I: Single-level integration

NASA Astrophysics Data System (ADS)

Nonaka, Andrew; Day, Marcus S.; Bell, John B.

2018-01-01

We present a numerical approach for low Mach number combustion that conserves both mass and energy while remaining on the equation of state to a desired tolerance. We present both unconfined and confined cases, where in the latter the ambient pressure changes over time. Our overall scheme is a projection method for the velocity coupled to a multi-implicit spectral deferred corrections (SDC) approach to integrate the mass and energy equations. The iterative nature of SDC methods allows us to incorporate a series of pressure discrepancy corrections naturally that lead to additional mass and energy influx/outflux in each finite volume cell in order to satisfy the equation of state. The method is second order, and satisfies the equation of state to a desired tolerance with increasing iterations. Motivated by experimental results, we test our algorithm on hydrogen flames with detailed kinetics. We examine the morphology of thermodiffusively unstable cylindrical premixed flames in high-pressure environments for confined and unconfined cases. We also demonstrate that our algorithm maintains the equation of state for premixed methane flames and non-premixed dimethyl ether jet flames.

Development of many-body polarizable force fields for Li-battery applications: 2. LiTFSI-doped Oligoether, polyether, and carbonate-based electrolytes.

PubMed

Borodin, Oleg; Smith, Grant D

2006-03-30

A quantum chemistry study of Li(+) interactions with ethers, carbonates, alkanes, and a trifluoromethanesulfonylimide anion (TFSI(-)) was performed at the MP2, B3LYP, and HF levels using the aug-cc-pvDz basis set for solvents and TFSI(-) anion, and [8s4p3d/5s3p2d]-type basis set for Li. A classical many-polarizable force field was developed for the LiTFSI salt interacting with ethylene carbonate (EC), gamma-butyrolactone (GBL), dimethyl carbonate (DMC), acetone, oligoethers, n-alkanes, and perfluoroalkanes. Molecular dynamics (MD) simulations were performed for EC/LiTFSI, PC/LiTFSI, GBL/LiTFSI, DMC/LiTFSI, 1,2-dimethoxyethane/LiTFSI, pentaglyme/LiTFSI, and poly(ethylene oxide) (MW = 2380)/LiTFSI electrolytes at temperatures from 298 to 423 K and salt concentrations from 0.3 to 5 M. The ion and solvent self-diffusion coefficients, electrolyte conductivity, electrolyte density, LiTFSI apparent molar volumes, and structure of the Li(+) cation environment predicted by MD simulations were found in good agreement with experimental data.

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

PubMed

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

2017-08-02

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

Volumetric Properties, Viscosities, and Refractive Indices of the Binary Systems 1-Butanol + PEG 200, + PEG 400, and + TEGDME

NASA Astrophysics Data System (ADS)

Živković, N.; Šerbanović, S.; Kijevčanin, M.; Živković, E.

2013-06-01

Densities, viscosities, and refractive indices of three binary systems consisting of 1-butanol with polyethylene glycols of different molecular weights (PEG 200 and PEG 400) or tetraethylene glycol dimethyl ether (TEGDME) were measured at ten temperatures (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, 323.15, 328.15, and 333.15) K and atmospheric pressure. Densities of the selected binary mixtures were measured with an Anton Paar DMA 5000 digital vibrating U-tube densimeter, refractive indices were measured with an automatic Anton Paar RXA-156 refractometer, while for viscosity measurements, a digital Stabinger SVM 3000/G2 viscometer was used. From these data, excess molar volumes were calculated and fitted to the Redlich-Kister equation. The obtained results have been analyzed in terms of specific molecular interactions and mixing behavior between mixture components, as well as the influence of temperature on them. Viscosity data were also correlated by Grunberg-Nissan, Eyring-UNIQUAC, three-body McAlister, and Eyring-NRTL models.

Nanodispersed Suspensions of Zeolite Catalysts for Converting Dimethyl Ether into Olefins

NASA Astrophysics Data System (ADS)

Kolesnichenko, N. V.; Yashina, O. V.; Ezhova, N. N.; Bondarenko, G. N.; Khadzhiev, S. N.

2018-01-01

Nanodispersed suspensions that are effective in DME conversion and stable in the reaction zone in a three-phase system (slurry reactor) are obtained from MFI zeolite commercial samples (TsVM, IK-17-1, and CBV) in liquid media via ultrasonic treatment (UST). It is found that the dispersion medium, in which ultrasound affects zeolite commercial sample, has a large influence on particle size in the suspension. UST in the aqueous medium produces zeolite nanoparticles smaller than 50 nm, while larger particles of MFI zeolite samples form in silicone or hydrocarbon oils. Spectral and adsorption data show that when zeolites undergo UST in an aqueous medium, the acid sites are redistributed on the zeolite surface and the specific surface area of the mesopores increases. Preliminary UST in aqueous media of zeolite commercial samples (TsVM, IK-17-1, and CBV) affects the catalytic properties of MFI zeolite nanodispersed suspensions. The selectivity of samples when paraffins and olefins form is largely due to superacid sites consisting of OH groups of hydroxonium ion H3O+.

Effect of Osmolytes on the Conformational Behavior of a Macromolecule in a Cytoplasm-like Crowded Environment: A Femtosecond Mid-IR Pump-Probe Spectroscopy Study.

PubMed

Kundu, Achintya; Verma, Pramod Kumar; Cho, Minhaeng

2018-02-15

Osmolytes found endogenously in almost all living beings play an important role in regulating cell volume under harsh environment. Here, to address the longstanding questions about the underlying mechanism of osmolyte effects, we use femtosecond mid-IR pump-probe spectroscopy with two different IR probes that are the OD stretching mode of HDO and the azido stretching mode of azido-derivatized poly(ethylene glycol) dimethyl ether (PEGDME). Our experimental results show that protecting osmolytes bind strongly with water molecules and dehydrate polymer surface, which results in promoting intramolecular interactions of the polymer. By contrast, urea behaves like water molecules without significantly disrupting water H-bonding network and favors extended and random-coil segments of the polymer chain by directly participating in solvation of the polymer. Our findings highlight the importance of direct interaction between urea and macromolecule, while protecting osmolytes indirectly affect the macromolecule through enhancing the water-osmolyte interaction in a crowded environment, which is the case that is often encountered in real biological systems.

Platelet adhesive resistance of segmented polyurethane film surface-grafted with vinyl benzyl sulfo monomer of ammonium zwitterions.

PubMed

Zhang, Jun; Yuan, Jiang; Yuan, Youling; Zang, Xiaopeng; Shen, Jian; Lin, Sicong

2003-10-01

Platelet from human plasma adhered on the segmented poly(ether urethane) (SPEU) film grafted with N,N-dimethyl-N-(p-vinylbenyl)-N-(3-sulfopropyl) ammonium (DMVSA) was studied. SPEU films were hydroxylated by potassium peroxosulfate (KPS) and then grafted with DMVSA using ceric ammonium nitrate (CAN) as initiator. The mixing time of hydroxylated SPEU/CAN and the monomer concentration effect on graft polymerization yield were determined by ATR-FTIR. Surface analysis of the grafted films by ATR-FTIR and ESCA confirmed that DMVSA was successfully grafted onto the SPEU film surface. The grafted film possessed a relatively hydrophilic surface, as revealed by water contact angle measurement. The improved blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion study and scanning electron microscopy, using original SPEU and hydroxylated SPEU films as the controls. The results showed that platelet attachment was decreased greatly on the segmented polyurethane films grafted with DMVSA. This kind of new biomaterials grafted with sulfo ammonium zwitterionic monomers might have potential for biomedical applications.

Graphene oxide as sensitive layer in Love-wave surface acoustic wave sensors for the detection of chemical warfare agent simulants.

PubMed

Sayago, Isabel; Matatagui, Daniel; Fernández, María Jesús; Fontecha, José Luis; Jurewicz, Izabela; Garriga, Rosa; Muñoz, Edgar

2016-02-01

A Love-wave device with graphene oxide (GO) as sensitive layer has been developed for the detection of chemical warfare agent (CWA) simulants. Sensitive films were fabricated by airbrushing GO dispersions onto Love-wave devices. The resulting Love-wave sensors detected very low CWA simulant concentrations in synthetic air at room temperature (as low as 0.2 ppm for dimethyl-methylphosphonate, DMMP, a simulant of sarin nerve gas, and 0.75 ppm for dipropylene glycol monomethyl ether, DPGME, a simulant of nitrogen mustard). High responses to DMMP and DPGME were obtained with sensitivities of 3087 and 760 Hz/ppm respectively. Very low limit of detection (LOD) values (9 and 40 ppb for DMMP and DPGME, respectively) were calculated from the achieved experimental data. The sensor exhibited outstanding sensitivity, good linearity and repeatability to all simulants tested. The detection mechanism is here explained in terms of hydrogen bonding formation between the tested CWA simulants and GO. Copyright © 2015 Elsevier B.V. All rights reserved.

Process for biological material carbon-carbon bond formation

DOEpatents

Hollingsworth, R.I.; Jung, S.; Mindock, C.A.

1998-12-22

A process for providing vicinal dimethyl long chain between alkyl groups of organic compounds is described. The process uses intact or disrupted cells of various species of bacteria, particularly Thermoanaerobacter sp., Sarcina sp. and Butyrivibrio sp. The process can be conducted in an aqueous reaction mixture at room temperatures. 8 figs.

Process for biological material carbon-carbon bond formation

DOEpatents

Hollingsworth, Rawle I.; Jung, Seunho; Mindock, Carol A.

1998-01-01

A process for providing vicinal dimethyl long chain between alkyl groups of organic compounds is described. The process uses intact or disrupted cells of various species of bacteria, particularly Thermoanaerobacter sp., Sarcina sp. and Butyrivibrio sp. The process can be conducted in an aqueous reaction mixture at room temperatures.

Broadband Microwave Spectroscopy as a Tool to Study Intermolecular Interactions in the Diphenyl Ether - Water System

NASA Astrophysics Data System (ADS)

Fatima, Mariyam; Perez, Cristobal; Schnell, Melanie

2017-06-01

Many biological processes, such as chemical recognition and protein folding, are mainly controlled by the interplay of hydrogen bonds and dispersive forces. This interplay also occurs between organic molecules and solvent water molecules. Broadband rotational spectroscopy studies of weakly bound complexes are able to accurately reveal the structures and internal dynamics of molecular clusters isolated in the gas phase. Amongst them, water clusters with organic molecules are of particular interest. In this work, we investigate the interplay between different types of weak intermolecular interactions and how it controls the preferred interaction sites of aromatic ethers, where dispersive interactions may play a significant role. We present our results on diphenyl ether (C_{12}H_{10}O, 1,1'-Oxydibenzene) complexed with up to three molecules of water. Diphenyl ether is a flexible molecule, and it offers two competing binding sites for water: the ether oxygen and the aromatic π system. In order to determine the structure of the diphenyl ether-water complexes, we targeted transitions in the 2-8 GHz range using broadband rotational spectroscopy. We identify two isomers with one water, one with two water, and one with three water molecules. Further analysis from isotopic substitution measurements provided accurate structural information. The preferred interactions, as well as the observed structural changes induced upon complexation, will be presented and discussed.

Optimization of reactive simulated moving bed systems with modulation of feed concentration for production of glycol ether ester.

PubMed

Agrawal, Gaurav; Oh, Jungmin; Sreedhar, Balamurali; Tie, Shan; Donaldson, Megan E; Frank, Timothy C; Schultz, Alfred K; Bommarius, Andreas S; Kawajiri, Yoshiaki

2014-09-19

In this article, we extend the simulated moving bed reactor (SMBR) mode of operation to the production of propylene glycol methyl ether acetate (DOWANOL™ PMA glycol ether) through the esterification of 1-methoxy-2-propanol (DOWANOL™ PM glycol ether) and acetic acid using AMBERLYST™ 15 as a catalyst and adsorbent. In addition, for the first time, we integrate the concept of modulation of the feed concentration (ModiCon) to SMBR operation. The performance of the conventional (constant feed) and ModiCon operation modes of SMBR are analyzed and compared. The SMBR processes are designed using a model based on a multi-objective optimization approach, where a transport dispersive model with a linear driving force for the adsorption rate has been used for modeling the SMBR system. The adsorption equilibrium and kinetics parameters are estimated from the batch and single column injection experiments by the inverse method. The multiple objectives are to maximize the production rate of DOWANOL™ PMA glycol ether, maximize the conversion of the esterification reaction and minimize the consumption of DOWANOL™ PM glycol ether which also acts as the desorbent in the chromatographic separation. It is shown that ModiCon achieves a higher productivity by 12-36% over the conventional operation with higher product purity and recovery. Copyright © 2014 Elsevier B.V. All rights reserved.

40 CFR Table 6 to Subpart Jj of... - VHAP of Potential Concern

Code of Federal Regulations, 2011 CFR

2011-07-01

... glycol butyl ether, ethylene glycol ethyl ether (2-ethoxy ethanol), ethylene glycol hexyl ether, ethylene..., ethylene glycol mono-2-ethylhexyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether... glycol propyl ether, triethylene glycol butyl ether, triethylene glycol ethyl ether, triethylene glycol...

Purifying contaminated water. [DOE patent application

DOEpatents

Daughton, C.G.

1981-10-27

Process is presented for removing biorefactory compounds from contaminated water (e.g., oil shale retort waste-water) by contacting same with fragmented raw oil shale. Biorefractory removal is enhanced by preactivating the oil shale with at least one member of the group of carboxylic acids, alcohols, aldehydes, ketones, ethers, amines, amides, sulfoxides, mixed ether-esters and nitriles. Further purification is obtained by stripping, followed by biodegradation and removal of the cells.

2[prime] and 3[prime] Carboranyl uridines and their diethyl ether adducts

DOEpatents

Soloway, A.H.; Barth, R.F.; Anisuzzaman, A.K.; Alam, F.; Tjarks, W.

1992-12-15

A process is described for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. The carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of the compounds in methods for boron neutron capture therapy in mammalian tumor cells. No Drawings

2' and 3' Carboranyl uridines and their diethyl ether adducts

DOEpatents

Soloway, Albert H.; Barth, Rolf F.; Anisuzzaman, Abul K.; Alam, Fazlul; Tjarks, Werner

1992-01-01

There is disclosed a process for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. Said carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of said compounds in methods for boron neutron capture therapy in mammalian tumor cells.

IRIS Toxicological Review of Ethyl Tertiary Butyl Ether (Etbe) ...

EPA Pesticide Factsheets

In September 2016, EPA released the draft IRIS Toxicological Review of Ethyl Tertiary Butyl Ether (ETBE) for public comment and discussion. The draft assessment was reviewed internally by EPA and by other federal agencies and White House Offices before public release. Consistent with the May 2009 IRIS assessment development process, all written comments on IRIS assessments submitted by other federal agencies and White House Offices are made publicly available. Accordingly, interagency comments and the interagency science consultation materials provided to other agencies, including interagency review drafts of the IRIS Toxicological Review of Ethyl Tertiary Butyl Ether are posted on this site. EPA is undertaking an new health assessment for ethyl tertiary butyl ether (ETBE) for the Integrated Risk Information System (IRIS). The outcome of this project will be a Toxicological Review and IRIS Summary of ETBE that will be entered on the IRIS database. IRIS is an EPA database containing Agency scientific positions on potential adverse human health effects that may result from chronic (or lifetime) exposure to chemicals in the environment. IRIS contains chemical-specific summaries of qualitative and quantitative health information in support of two steps of the risk assessment process, i.e., hazard identification and dose-response evaluation. IRIS assessments are used nationally and internationally in combination with specific situational exposure assessment infor

Mass spectra of cyclic ethers formed in the low-temperature oxidation of a series of n-alkanes

PubMed Central

Herbinet, Olivier; Bax, Sarah; Glaude, Pierre-Alexandre; Carré, Vincent; Battin-Leclerc, Frédérique

2013-01-01

Cyclic ethers are important intermediate species formed during the low-temperature oxidation of hydrocarbons. Along with ketones and aldehydes, they could consequently represent a significant part of the heavy oxygenated pollutants observed in the exhaust gas of engines. Apart a few of them such as ethylene oxide and tetrahydrofuran, cyclic ethers have not been much studied and very few of them are available for calibration and identification. Electron impact mass spectra are available for very few of them, making their detection in the exhaust emissions of combustion processes very difficult. The main goal of this study was to complete the existing set of mass spectra for this class of molecules. Thus cyclic ethers have been analyzed in the exhaust gases of a jet-stirred reactor in which the low-temperature oxidation of a series of n-alkanes was taking place. Analyzes were performed by gas chromatography coupled to mass spectrometry and to MS/MS. The second goal of this study was to derive some rules for the fragmentation of cyclic ethers in electron impact mass spectrometry and allow the identification of these species when no mass spectrum is available. PMID:24092947

Removal of H{sub 2}S, methyl macapton dimethyl sulfide and dimethyl disulfide with biofiltration

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

Singleton, B.; Milligan, D.

1996-12-31

A pilot study describes the biofiltration process control that was necessary to remove H{sub 2}S, methyl mercaptan, dimethyl sulfide, and dimethyl disulfide, when mixed in an airstream. A pilot test at a waste water treatment facility was operated over a six month period. During that time H{sub 2}S was removed with very high efficiency at concentrations that reached to 400 ppm{sub v}; H{sub 2}S loading reached as high as 20 gms/m{sup 3}/hr. Methyl mercaptan and the organic sulfides were not removed sufficiently to deodorize the air-stream until a second stage biofilter was added. An odor analysis indicated that the odormore » detection level was approximately 250,000 odor units at the inlet and 1100 odor units at the outlet. The sulfur distribution in the media indicated that elemental sulfur and sulfate is deposited as a byproduct of the H{sub 2}S oxidation. Data from a fall scale biofilter treating H{sub 2}S from a pumping station is also presented. This data shows very efficient removal of H{sub 2}S, no organic reduced sulfur compounds were found in this air-stream.« less

Trans-ethyl methyl ether, the struggle for the detection of a complex molecule in hot cores

NASA Astrophysics Data System (ADS)

Fuchs, G. W.; Fuchs, U.; Giesen, T. F.; Wyrowski, F.

Many large and complex molecules of prebiotic importance have been found as constituents of interstellar clouds but their detection remains difficult and sometimes doubtful (Snyder et al. 2005). The complex spectrum of trans-ethyl methyl ether (EME) has been investigated in the laboratory (Fuchs et al. 2003) up to 350 GHz and is now known with high frequency precision, see Figure 1. In this work we present an extensive search for EME towards G34.26, NGC6334(I), Orion KL, SgrB2(N) and W51e2 in the 1 to 3 mm wavelength region. These sources have previously been shown to have a rich chemistry of complex molecules. The IRAM 30m telescope at Pico Veleta, Spain and the SEST 15m radio telescope in La Silla, Chile have been used for the observations. We looked at 5 - 11 frequency bands where EME has strong transitions. All sources were examined using long integration times up to 220 min (on+off), elevations greater 40◦ and under good weather conditions. For our analysis of the data we used the method of rotational-temperature-diagrams but also the myXCLASS (written by Peter Schilke) extension program to the GILDAS (Grenoble Image and Line Data Analysis Software) software which enabled us to simulate spectra of several molecules including their linewidth and intensities at the same time, see Figure 2. With this program a consistency check of molecular abundances and overall composition is possible even in dense spectra with many overlapping lines. The effect of the source size on the measured intensities has been considered and cross checks with other important molecules such as methanol, ethanol and di-methyl ether have been performed. Charnley et al. (2001) assigned one line in W51 e1/e2 and one line in Orion KL at 160.1 GHz, as well as a line in SgrB2(N) at 79.6 GHz to trans-ethyl methyl ether. From their isolated measurements, the column density of EME was estimated to be in the range 1014-1015 cm-2 in Sgr B2(N) corresponding to a fractional abundance of 10-10-10-9 and in the W51 region they estimate a fractional abundance of 10-10. However, our observations cannot confirm the tentative detection of EME in Orion KL within their given column density limits. There is evidence for the existence of the trans-ethyl methyl ether towards W51e2 with a column density of N=2×1014 cm-2 based on the detection of 14 lines which coincide with EME transition frequencies. We present new upper limits of 7-8×1013 cm-2 for the column densities of EME toward Orion KL, G34.26, NGC6334(I) and estimate the column density of SgrB2(N) to be of the same order. The W51e2 observations are discussed in more detail.

Synthesis of the water soluble ligands dmPTA and dmoPTA and the complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (dmPTA = N,N'-Dimethyl-1,3,5-triaza-7-phosphaadamantane, dmoPTA = 3,7-Dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, HdmoPTA = 3,7-H-3,7-Dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane).

PubMed

Mena-Cruz, Adrian; Lorenzo-Luis, Pablo; Romerosa, Antonio; Saoud, Mustapha; Serrano-Ruiz, Manuel

2007-07-23

The new water-soluble ligand dmPTA(OSO(2)CF(3))(2) (1) (dmPTA = N,N'-dimethyl-1,3,5-triaza-7-phosphaadamantane) has been synthesized by reaction of PTA with MeOSO(2)CF(3) in acetone (PTA = 1,3,5-triaza-7-phosphatricycle[3.3.1.1(3,7)]decane). The reaction of 1 with KOH gave rise to the new water-soluble ligand dmoPTA (3) (dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) by elimination of the -CH(2)- group located between both NCH(3) units. Compound dmPTA(BF(4))(2) (2) and complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (4) have also been synthesized, while compounds HdmoPTA(BF(4)) (3a) and [RuClCp(dmPTA)(PPh(3))](OSO(2)CF(3)) (5) were characterized but not isolated. The new ligands and the complex have been fully characterized by NMR, IR, elemental analysis, and X-ray crystal structure determination (ligand 1 and complex 4). The synthetic processes for 3 and 4 were studied.

Developing a novel catalytic approach for imine formation by using self-replicating catalyst

NASA Astrophysics Data System (ADS)

Nasir, Fatin Ilyani; Philp, Douglas; Hasbullah, Siti Aishah; Hassan, Nurul Izzaty

2015-09-01

Synthesis of imine compounds usually results in moderate yield due its reversibility characteristic and prone to hydrolysis. Hence, to increase the formation of imine compound, self-replicating catalyst was introduced. The self-replicating catalyst is the imine product itself. The first imine compound, 4-{[4-(3,5-Dimethyl-phenylcarbamoyl)-benzylidene]-amino}-phenyl)-acetic acid has been synthesized from 4-Amino-N-(3,5-dimethyl-phenyl)-benzamide and (4-formyl-phenyl)-acetic acid. Simultaneously, 4-formylbenzoic acid was reacted with thionyl chloride to produce 4-formylbenzoyl chloride, which was then reacted with 2-amino-4,6-dimethylpyridine in the presence of triethylamine to afford N-(4,6-dimethyl-pyridin-2-yl)-4-formyl-benzamide. N-(4,6-dimethyl-pyridin-2-yl)-4-formyl-benzamide formed then reacted with 4-amino-2-methylbenzoic acid to form the second imine derivative, 4-{[4-(4,6-dimethyl-pyridin-2-ylcarbamoyl)-benzylidene]-amino}-2-methyl-benzoic acid. The concentration time profile for the synthesis of self-replicating imine 1 reveals the classic sigmoidal shape characteristics of an autocatalytic process and the rate of the reaction are higher than that observed in the absence of recognition. In order to demonstrate the nature of self-replicating catalyst, a preformed imine 1 was doped into the reaction mixture of amine 1 and the corresponding aldehyde, 4-formylbenzoic acid. The insertion of substoichiometric amounts (15 mol%) of imine 1 at the start of the reaction has accelerated the rate formation of imine 1.

Molecular dynamics study of unfolding of lysozyme in water and its mixtures with dimethyl sulfoxide.

PubMed

Sedov, Igor A; Magsumov, Timur I

2017-09-01

All-atom explicit solvent molecular dynamics was used to study the process of unfolding of hen egg white lysozyme in water and mixtures of water with dimethyl sulfoxide at different compositions. We have determined the kinetic parameters of unfolding at a constant temperature 450K. For each run, the time of disruption of the tertiary structure of lysozyme t u was defined as the moment when a certain structural criterion computed from the trajectory reaches its critical value. A good agreement is observed between the results obtained using several different criteria. The secondary structure according to DSSP calculations is found to be partially unfolded to the moment of disruption of tertiary structure, but some of its elements keep for a long time after that. The values of t u averaged over ten 30ns-long trajectories for each solvent composition are shown to decrease very rapidly with addition of dimethyl sulfoxide, and rather small amounts of dimethyl sulfoxide are found to change the pathway of unfolding. In pure water, despite the loss of tertiary contacts and disruption of secondary structure elements, the protein preserves its compact globular state at least over 130ns of simulation, while even at 5mol percents of dimethyl sulfoxide it loses its compactness within 30ns. The proposed methodology is a generally applicable tool to quantify the rate of protein unfolding in simulation studies. Copyright © 2017 Elsevier Inc. All rights reserved.

Tandem intramolecular silylformylation and silicon-assisted cross-coupling reactions. synthesis of geometrically defined alpha,beta-unsaturated aldehydes.

PubMed

Denmark, Scott E; Kobayashi, Tetsuya

2003-06-27

The palladium- and copper-catalyzed cross-coupling reactions of cyclic silyl ethers with aryl iodides are reported. Silyl ethers 3 were readily prepared by intramolecular silylformylation of homopropargyl silyl ethers 2 under a carbon monoxide atmosphere. The reaction of cyclic silyl ethers 3with various aryl iodides 7 in the presence of [(allyl)PdCl](2), CuI, a hydrosilane, and KF.2H(2)O in DMF at room temperature provided the alpha,beta-unsaturated aldehyde coupling products 8 in high yields. The need for copper in this process suggested that transmetalation from silicon to copper is an important step in the mechanism. Although siloxane 3 and the product 8 are not stable under basic conditions, KF.2H(2)O provided the appropriate balance of reactivity toward silicon and reduced basicity. The addition of a hydrosilane to [(allyl)PdCl](2) was needed to reduce the palladium(II) to the active palladium(0) form.

Biomedical potentials of crown ethers: prospective antitumor agents.

PubMed

Kralj, Marijeta; Tusek-Bozić, Ljerka; Frkanec, Leo

2008-10-01

Crown ethers are of enormous interest and importance in chemistry, biochemistry, materials science, catalysis, separation, transport and encapsulated processes, as well as in the design and synthesis of various synthetic systems with specific properties, diverse capabilities, and programmable functions. Classical crown ethers are macrocyclic polyethers that contain 3-20 oxygen atoms separated from each other by two or more carbon atoms. They are exceptionally versatile in selectively binding a range of metal ions and a variety of organic neutral and ionic species. Crown ethers are currently being studied and used in a variety of applications beyond their traditional place in chemistry. This review presents additional applications and the ever-increasing biomedical potentials of these intriguing compounds, with particular emphasis on the prospects of their relevance as anticancer agents. We believe that further research in this direction should be encouraged, as crown compounds could either induce toxicities that are different from those of conventional antitumor drugs, or complement drugs in current use, thereby providing a valuable adjunct to therapy.

New water-soluble metal working fluids additives from phosphonic acid derivatives for aluminum alloy materials.

PubMed

Kohara, Ichitaro; Tomoda, Hideyuki; Watanabe, Shoji

2007-01-01

Water-soluble metal working fluids are used for processing of aluminum alloy materials. This short paper describes properties of new additives for water-soluble cutting fluids for aluminum alloy materials. Some alkyldiphosphonic acids were prepared with known method. Amine salts of these phosphonic acids showed anti-corrosion property for aluminum alloy materials. However, they have no hard water tolerance. Monoesters of octylphosphonic acid were prepared by the reaction of octylphosphonic acid dichloride with various alcohols in the presence of triethylamine. Amine salts of monoester of octylphosphonic acid with diethyleneglycol monomethyl ether, ethyleneglycol monomethyl ether and triethyleneglycol monomethyl ether showed both of a good anti-corrosion property for aluminum alloy materials and hard water tolerance.

Microbial Hydrocarbon Co-oxidation

PubMed Central

Raymond, R. L.; Jamison, V. W.; Hudson, J. O.

1967-01-01

Nocardia cultures, isolated from soil by use of n-paraffins as the sole carbon source, have been shown to bring about significant oxidation of several methyl-substituted mono- and dicyclic aromatic hydrocarbons. Oxygen uptake by washed cell suspensions was not a reliable indicator of oxidation. Under co-oxidation conditions in shaken flasks, o- and p-xylenes were oxidized to their respective mono-aromatic acids, o-toluic and p-toluic acids. In addition, a new fermentation product, 2, 3-dihydroxy-p-toluic acid, was found in the p-xylene oxidation system. Of 10 methyl-substituted naphthalenes tested (1-methyl, 2-methyl, 1, 3-dimethyl, 1, 4-dimethyl, 1, 5-dimethyl, 1, 8-dimethyl, 1, 6-dimethyl, 2, 3-dimethyl, 2, 6-dimethyl, 2, 7-dimethyl), only those containing a methyl group in the β position were oxidized at this position to the mono acid. PMID:6049305

Development of GREET Catalyst Module

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

Wang, Zhichao; Dunn, Jennifer B.; Cronauer, Donald C.

2014-09-01

Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™)more » catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.« less

Roles of molecular hydrogen and a hydrogen donor solvent in the cracking of moal model compounds with dispersed catalysts

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

Suzuki, Toshimitsu; Ikenaga, Na-oki; Sakota, Takahiro

1994-12-31

It is of great importance to evaluate quantitative hydrogen transfer process by using coal model compounds with a hydrogen-donor solvent. Cronauer el al. showed that in the cracking of benzyl phenyl ether the hydrogen required to stabilize free radicals comes from a donor solvent or intramolecular rearrangement and not from gaseous hydrogen in the absence of a catalyst. Korobkov et al. and Schlosberg et al. showed that the thermolysis of benzyl phenyl ether and dibenzyl ether were accomplished by intramolecular rearrangements. Yokokawa et al. reported that tetralin retarded the catalyzed hydrocracking of coal model compounds containing C-C and C-O bonds.more » However, few studies dealt with quantitative discussion in the hydrogen transfer process from a hydrogen-donor solvent or molecular hydrogen to free radicals derived from a model compound except a series of studies by Nicole and co-workers. On the other hand, it is well known that the amount of naphthalene produced from tetralin decreases after the liquefaction of coal in tetralin with catalyst as compared to the liquefaction in the absence of catalysts. To account for this, two mechanisms are proposed. One is that the catalyst hydrogenates naphthalene produced from tetralin, and the other is that the catalyst promotes the direct hydrogen transfer from molecular hydrogen to free radicals. The purpose of this work is to elucidate the role of catalyst and tetralin by means of the quantitative treatment of the hydrogen transfer reaction stabilizing thermally decomposed free radicals. Cracking of benzyl phenyl ether (BPE), dibenzyl ether (DBE), 1,2-diphenylethane, and 1,3-diphenylpropane was studied in tetralin in the presence of highly disposed catalyst.« less

IRIS Toxicological Review of Ethyl Tertiary Butyl Ether (Etbe) ...

EPA Pesticide Factsheets

In August 2013, EPA released the draft literature searches and associated search strategies, evidence tables, and exposure response arrays for ETBE to obtain input from stakeholders and the public prior to developing the draft IRIS assessment. Specifically, EPA was interested in comments on the following: Draft literature search strategies The approach for identifying studies The screening process for selecting pertinent studies The resulting list of pertinent studies Preliminary evidence tables The process for selecting studies to include in evidence tables The quality of the studies in the evidence tables The literature search strategy, which describes the processes for identifying scientific literature, contains the studies that EPA considered and selected to include in the evidence tables. The preliminary evidence tables and exposure-response arrays present the key study data in a standardized format. The evidence tables summarize the available critical scientific literature. The exposure-response figures provide a graphical representation of the responses at different levels of exposure for each study in the evidence table. The draft Toxicological Review of Ethyl Tertiary Butyl Ether provides scientific support and rationale for the hazard and dose-response assessment pertaining to chronic exposure to ethyl tertiary butyl ether.

Influenza Vaccine Manufacturing: Effect of Inactivation, Splitting and Site of Manufacturing. Comparison of Influenza Vaccine Production Processes

PubMed Central

Kon, Theone C.; Onu, Adrian; Berbecila, Laurentiu; Lupulescu, Emilia; Ghiorgisor, Alina; Kersten, Gideon F.; Cui, Yi-Qing; Amorij, Jean-Pierre; Van der Pol, Leo

2016-01-01

The aim of this study was to evaluate the impact of different inactivation and splitting procedures on influenza vaccine product composition, stability and recovery to support transfer of process technology. Four split and two whole inactivated virus (WIV) influenza vaccine bulks were produced and compared with respect to release criteria, stability of the bulk and haemagglutinin recovery. One clarified harvest of influenza H3N2 A/Uruguay virus prepared on 25.000 fertilized eggs was divided equally over six downstream processes. The main unit operation for purification was sucrose gradient zonal ultracentrifugation. The inactivation of the virus was performed with either formaldehyde in phosphate buffer or with beta-propiolactone in citrate buffer. For splitting of the viral products in presence of Tween®, either Triton™ X-100 or di-ethyl-ether was used. Removal of ether was established by centrifugation and evaporation, whereas removal of Triton-X100 was performed by hydrophobic interaction chromatography. All products were sterile filtered and subjected to a 5 months real time stability study. In all processes, major product losses were measured after sterile filtration; with larger losses for split virus than for WIV. The beta-propiolactone inactivation on average resulted in higher recoveries compared to processes using formaldehyde inactivation. Especially ether split formaldehyde product showed low recovery and least stability over a period of five months. PMID:26959983

Mode of Action Studies on Nitrodiphenyl Ether Herbicides

PubMed Central

Bowyer, John R.; Smith, Beverly J.; Camilleri, Patrick; Lee, Susan A.

1987-01-01

5-[2-Chloro-4-(trifluoromethyl)phenoxy]-2-nitroacetophenone oxime-o-(acetic acid, methyl ester) (DPEI), is a potent nitrodiphenyl ether herbicide which causes rapid leaf wilting, membrane lipid peroxidation, and chlorophyll destruction in a process which is both light- and O2-dependent. These effects resemble those of other nitrodiphenyl ether herbicides. Unlike paraquat, the herbicidal effects of DPEI are only slightly reduced by pretreatment with the photosynthetic electron transport inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea. DPEI is a weak inhibitor of photosynthetic electron transport (I50 15 micromolar for water to paraquat) in vitro, with at least one site of action at the cytochrome b6f complex. Ultrastructural studies and measurements of ethane formation resulting from lipid peroxidation indicate that mutants of barley lacking photosystem I (PSI) (viridis-zb63) or photosystem II (viridis-zd69) are resistant to paraquat but susceptible to DPEI. The results indicate that electron transfer through both photosystems is not essential for the toxic effects of nitrodiphenyl ether herbicides. Furthermore, the results show that neither cyclic electron transport around PSI, nor the diversion of electrons from PSI to O2 when NADPH consumption is blocked are essential for the phytotoxicity of nitrodiphenyl ether herbicides. Images Fig. 2 Fig. 3 Fig. 4 PMID:16665297

Leaching characteristics of polybrominated diphenyl ethers (PBDEs) from flame-retardant plastics.

PubMed

Kim, Yong-Jin; Osako, Masahiro; Sakai, Shin-ichi

2006-10-01

To investigate the effect of leachant on the leachability of polybrominated diphenyl ethers (PBDEs), we determined the leaching concentrations of PBDEs from flame-retardant plastic samples (TV housings and raw materials before molding processing) that are regarded as a source of PBDEs in landfill sites. The leachants used were distilled water, 20% methanol solution, and dissolved humic solution (DHS) of 1000 mg/l based on organic carbon. The leaching test conditions were a liquid-to-solid ratio of 100:1, and a contact period of five days, with twice-daily agitation in a temperature-controlled room of 30 degrees C without pH or ionic strength control. The leaching concentrations of PBDEs increased with increased content, and were found to be remarkably enhanced when methanol and DHS were used instead of distilled water. The enhancement of leachability in the presence of the latter was attributed to the cosolvency effect, and complex formations between the PBDEs and dissolved humic matter (DHM). PBDE concentrations in the leachate obtained from the leaching test and an actual landfill site revealed a significant presence of congeners below heptabromodiphenyl ethers (H7BDEs), detected in the leachate of the actual landfill, while significant amounts of nonabromodiphenyl ethers (N9BDEs) and decabromodiphenyl ether (D10BDE) were detected in the leachate of the leaching test.

Alkyl Azides, Diazides, Haloazides and Bridged Polycyclic Diazides

DTIC Science & Technology

1991-05-16

temperature. Most of the methyl ether was removed during this process. The ehtyl ether was distilled from the reaction mixture using a water aspirator into a...Street PROGRAM IPROJECT ITASK IWORK li1111? ArliiqIoh, VA 22217-5000 EILIMENT NO I NO. I oACCESSION P10) Alkyl Azides, Dlazides, laloazides and...REPRODUCE LEGIBLY. ALKYL AZIDES, DIAZIDES, HALOAZIDES AND BRIDGED POLYCYCLIC DIAZIDES Final REPORTe July 1, 1989-November 14, 1990 A6jd.%4gi0 F’or

Polyimides with carbonyl and ether connecting groups between the aromatic rings

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

Facile synthesis of highly substituted 3-aminofurans from thiazolium salts, aldehydes, and dimethyl acetylenedicarboxylate.

PubMed

Ma, Cheng; Ding, Hanfeng; Wu, Guangming; Yang, Yewei

2005-10-28

[reaction: see text] A facile preparation of 3-aminofuran derivatives via multicomponent reactions of thiazole carbenes, aldehydes, and dimethyl acetylenedicarboxylate (DMAD) is reported. In this process, the thiazole carbenes, generated in situ from thiazolium salts, reacted with aldehydes and DMAD at -78 to 0 degree C in CH(2)Cl(2) to afford the substituted furans in moderate to good yields. Eight substituted thiazolium salts were employed as carbene precursors in the reaction. Besides aryl aldehydes, alpha,beta-unsaturated aldehydes, aliphatic aldehydes, and arenedial were also investigated and found to be applicable to this reaction.

Detection of rare species of volatile organic selenium metabolites in male golden hamster urine.

PubMed

Kwak, Jae; Ohrnberger, Sarah A; Valencak, Teresa G

2016-07-01

Selenium has been considered as an essential trace element in mammals and its intake comes mainly from food. Mammals can metabolize both inorganic and organic species, and urinary excretion is the primary elimination route of selenium. Selenosugars and trimethylselenonium ion have been identified as major urinary metabolites. Other metabolites have been reported, but they were detected in some studies and not in others. Still, a large portion of the ingested selenium eliminated from the body is unknown. Volatile selenium species may account for a certain portion of the unknown species since they can easily be lost during sample analyses. While we analyzed male golden hamster urine in search of potential volatile pheromone(s), four volatile selenium compounds were detected. They were dimethyl selenenylsulfide, dimethyl diselenide, dimethyl bis(thio)selenide, and dimethyl selenodisulfide. When the urine samples were aged and dried for 48 h, dimethyl selenodisulfide tended to increase, while others decreased. The increase might be due to the formation of dimethyl selenodisulfide via reaction of dimethyl diselenide and dimethyl trisulfide whose concentration increased as urine aged. To our knowledge, dimethyl bis(thio)selenide and dimethyl selenodisulfide have never been demonstrated in urine. It remains to be determined whether these species are common metabolites in other animals or hamster-specific.

Application of the fiber-optic perfusion fluorometer to absorption and exsorption studies in hairless mouse skin.

PubMed

Shackleford, J M; Yielding, K L

1987-09-01

This study was undertaken to test the fiber-optic perfusion fluorometer as a direct means of evaluating skin absorption and exsorption in hairless mice. Skin-barrier compromise was accomplished in the absorption experiments by application of dimethyl sulfoxide to the skin surface or by partial removal of the stratum corneum with sticky tape. Absorbed fluorescein was measured easily in unanesthetized control (skin-barrier intact) and experimental mice. Unabsorbed chemical did not fluoresce 15 minutes after application, although it was present on the surface of the skin as a dry powder. The time course of fluorescein elimination from the skin was related to a rapid phase (vascular removal) and a slow phase (reservoir entrapment). In the exsorption experiments the fluorescein was injected intraperitoneally. Back skin on the right side was swabbed with either dimethyl sulfoxide or 1% capsaicin in alcohol prior to the injections, and differences in skin fluorescence on the left (control) and right sides were recorded. One application of dimethyl sulfoxide or capsaicin increased the level of skin exsorption. Three applications of dimethyl sulfoxide almost doubled the amount of exsorbed dye, whereas three applications of the capsaicin inhibited the exsorption process. It was concluded that the fiber-optic perfusion fluorometer provides an excellent technique in support of other methods of investigating the skin.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1996-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Poly(arylene ether)s containing pendent ethynyl groups

NASA Technical Reports Server (NTRS)

Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

1994-01-01

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350 C to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use.

PubMed

Manual Kollareth, Denny Joseph; Chang, Chuchun L; Hansen, Inge H; Deckelbaum, Richard J

2018-03-01

Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [ 3 H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [ 3 H]cholesteryl oleoyl ether and [ 3 H]cholesteryl hexadecyl ether from different suppliers, employing in vitro , in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro , in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.

Structural and Biochemical Characterization of the Early and Late Enzymes in the Lignin β-Aryl Ether Cleavage Pathway from Sphingobium sp. SYK-6.

PubMed

Pereira, Jose Henrique; Heins, Richard A; Gall, Daniel L; McAndrew, Ryan P; Deng, Kai; Holland, Keefe C; Donohue, Timothy J; Noguera, Daniel R; Simmons, Blake A; Sale, Kenneth L; Ralph, John; Adams, Paul D

2016-05-06

There has been great progress in the development of technology for the conversion of lignocellulosic biomass to sugars and subsequent fermentation to fuels. However, plant lignin remains an untapped source of materials for production of fuels or high value chemicals. Biological cleavage of lignin has been well characterized in fungi, in which enzymes that create free radical intermediates are used to degrade this material. In contrast, a catabolic pathway for the stereospecific cleavage of β-aryl ether units that are found in lignin has been identified in Sphingobium sp. SYK-6 bacteria. β-Aryl ether units are typically abundant in lignin, corresponding to 50-70% of all of the intermonomer linkages. Consequently, a comprehensive understanding of enzymatic β-aryl ether (β-ether) cleavage is important for future efforts to biologically process lignin and its breakdown products. The crystal structures and biochemical characterization of the NAD-dependent dehydrogenases (LigD, LigO, and LigL) and the glutathione-dependent lyase LigG provide new insights into the early and late enzymes in the β-ether degradation pathway. We present detailed information on the cofactor and substrate binding sites and on the catalytic mechanisms of these enzymes, comparing them with other known members of their respective families. Information on the Lig enzymes provides new insight into their catalysis mechanisms and can inform future strategies for using aromatic oligomers derived from plant lignin as a source of valuable aromatic compounds for biofuels and other bioproducts. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Structural and Biochemical Characterization of the Early and Late Enzymes in the Lignin β-Aryl Ether Cleavage Pathway from Sphingobium sp. SYK-6

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

Pereira, Jose Henrique; Heins, Richard A.; Gall, Daniel L.

There has been great progress in the development of technology for the conversion of lignocellulosic biomass to sugars and subsequent fermentation to fuels. However, plant lignin remains an untapped source of materials for production of fuels or high value chemicals. Biological cleavage of lignin has been well characterized in fungi, in which enzymes that create free radical intermediates are used to degrade this material. In contrast, a catabolic pathway for the stereospecific cleavage of β-aryl ether units that are found in lignin has been identified in Sphingobium sp. SYK-6 bacteria. β-Aryl ether units are typically abundant in lignin, corresponding tomore » 50–70% of all of the intermonomer linkages. Consequently, a comprehensive understanding of enzymatic β-aryl ether (β-ether) cleavage is important for future efforts to biologically process lignin and its breakdown products. The crystal structures and biochemical characterization of the NAD-dependent dehydrogenases (LigD, LigO, and LigL) and the glutathione-dependent lyase LigG provide new insights into the early and late enzymes in the β-ether degradation pathway. We present detailed information on the cofactor and substrate binding sites and on the catalytic mechanisms of these enzymes, comparing them with other known members of their respective families. Information on the Lig enzymes provides new insight into their catalysis mechanisms and can inform future strategies for using aromatic oligomers derived from plant lignin as a source of valuable aromatic compounds for biofuels and other bioproducts.« less

Structural and Biochemical Characterization of the Early and Late Enzymes in the Lignin β-Aryl Ether Cleavage Pathway from Sphingobium sp. SYK-6

DOE PAGES

Pereira, Jose Henrique; Heins, Richard A.; Gall, Daniel L.; ...

2016-03-03

There has been great progress in the development of technology for the conversion of lignocellulosic biomass to sugars and subsequent fermentation to fuels. However, plant lignin remains an untapped source of materials for production of fuels or high value chemicals. Biological cleavage of lignin has been well characterized in fungi, in which enzymes that create free radical intermediates are used to degrade this material. In contrast, a catabolic pathway for the stereospecific cleavage of β-aryl ether units that are found in lignin has been identified in Sphingobium sp. SYK-6 bacteria. β-Aryl ether units are typically abundant in lignin, corresponding tomore » 50–70% of all of the intermonomer linkages. Consequently, a comprehensive understanding of enzymatic β-aryl ether (β-ether) cleavage is important for future efforts to biologically process lignin and its breakdown products. The crystal structures and biochemical characterization of the NAD-dependent dehydrogenases (LigD, LigO, and LigL) and the glutathione-dependent lyase LigG provide new insights into the early and late enzymes in the β-ether degradation pathway. We present detailed information on the cofactor and substrate binding sites and on the catalytic mechanisms of these enzymes, comparing them with other known members of their respective families. Information on the Lig enzymes provides new insight into their catalysis mechanisms and can inform future strategies for using aromatic oligomers derived from plant lignin as a source of valuable aromatic compounds for biofuels and other bioproducts.« less

Structural and Biochemical Characterization of the Early and Late Enzymes in the Lignin β-Aryl Ether Cleavage Pathway from Sphingobium sp. SYK-6*

PubMed Central

Pereira, Jose Henrique; Heins, Richard A.; Gall, Daniel L.; McAndrew, Ryan P.; Deng, Kai; Holland, Keefe C.; Donohue, Timothy J.; Noguera, Daniel R.; Simmons, Blake A.; Sale, Kenneth L.; Ralph, John; Adams, Paul D.

2016-01-01

There has been great progress in the development of technology for the conversion of lignocellulosic biomass to sugars and subsequent fermentation to fuels. However, plant lignin remains an untapped source of materials for production of fuels or high value chemicals. Biological cleavage of lignin has been well characterized in fungi, in which enzymes that create free radical intermediates are used to degrade this material. In contrast, a catabolic pathway for the stereospecific cleavage of β-aryl ether units that are found in lignin has been identified in Sphingobium sp. SYK-6 bacteria. β-Aryl ether units are typically abundant in lignin, corresponding to 50–70% of all of the intermonomer linkages. Consequently, a comprehensive understanding of enzymatic β-aryl ether (β-ether) cleavage is important for future efforts to biologically process lignin and its breakdown products. The crystal structures and biochemical characterization of the NAD-dependent dehydrogenases (LigD, LigO, and LigL) and the glutathione-dependent lyase LigG provide new insights into the early and late enzymes in the β-ether degradation pathway. We present detailed information on the cofactor and substrate binding sites and on the catalytic mechanisms of these enzymes, comparing them with other known members of their respective families. Information on the Lig enzymes provides new insight into their catalysis mechanisms and can inform future strategies for using aromatic oligomers derived from plant lignin as a source of valuable aromatic compounds for biofuels and other bioproducts. PMID:26940872

FDEMS Sensing for Automated Intelligent Processing of PMR-15

NASA Technical Reports Server (NTRS)

Kranbuehl, David E.; Hood, D. K.; Rogozinski, J.; Barksdale, R.; Loos, Alfred C.; McRae, Doug

1993-01-01

The purpose of this grant was to develop frequency dependent dielectric measurements, often called FDEMS (frequency dependent electromagnetic sensing), to monitor and intelligently control the cure process in PMR-15, a stoichiometric mixture of a nadic ester, dimethyl ester, and methylendianiline in a monomor ratio.

PEEK (polyether-ether-ketone)-coated nitinol wire: Film stability for biocompatibility applications

NASA Astrophysics Data System (ADS)

Sheiko, Nataliia; Kékicheff, Patrick; Marie, Pascal; Schmutz, Marc; Jacomine, Leandro; Perrin-Schmitt, Fabienne

2016-12-01

High quality biocompatible poly-ether-ether-ketone (PEEK) coatings were produced on NiTi shape memory alloy wires using dipping deposition from colloidal aqueous PEEK dispersions after substrate surface treatment. The surface morphology and microstructure were investigated by Scanning Electron Microscopy at every step of the process from the as-received Nitinol substrate to the ultimate PEEK-coated NiTi wire. Nanoscratch tests were carried out to access the adhesive behavior of the polymer coated film to the NiTi. The results indicate that the optimum process conditions in cleaning, chemical etching, and electropolishing the NiTi, were the most important and determining parameters to be achieved. Thus, high quality PEEK coatings were obtained on NiTi wires, straight or curved (even with a U-shape) with a homogeneous microstructure along the wire length and a uniform thickness of 12 μm without any development of cracks or the presence of large voids. The biocompatibility of the PEEK coating film was checked in fibrobast cultured cells. The coating remains stable in biological environment with negligible Ni ion release, no cytotoxicity, and no delamination observed with time.

Curing kinetics and thermomechanical properties of latent epoxy/carbon fiber composites

NASA Astrophysics Data System (ADS)

Dalle Vacche, S.; Michaud, V.; Demierre, M.; Bourban, P.-E.; Månson, J.-A. E.

2016-07-01

In this work, resins based on diglycidyl ether of bisphenol A (DGEBA) epoxy and a latent hardener, dicyandiamide (DICY), as well as carbon fiber (CF) composites based on them, were prepared with three commercial accelerators: a methylene bis (phenyl dimethyl urea), a cycloaliphatic substituted urea, and a modified polyamine. The curing kinetics of the three DGEBA/DICY/accelerator systems were investigated by chemorheology and differential scanning calorimetry (DSC), in isothermal and over temperature change conditions. Differences in the reaction onset temperature, and in the glass transition temperature (Tg) were highlighted. For curing of thick resin samples, a slow curing cycle at the lowest possible temperature was used, followed by high temperature (160 - 180 °C) post-curing. Indeed, fast curing at higher temperatures caused the formation of hot spots and led to local burning of the samples. The obtained thermomechanical properties, assessed by ultimate tensile testing and dynamic mechanical analysis (DMA) in single cantilever configuration, were all in the expected range for epoxy resins, with tensile moduli close to 3 GPa and Tg > 140 °C. The longterm stability of these resins at room temperature was verified by DSC. Composite samples were prepared by hand lay-up by manually impregnating four layers of 5-harness satin CF textile, and curing in vacuum bag. Impregnation quality and void content were assessed by optical microscopy. The flexural properties of the post-cured composites were assessed by three-point bending test at room temperature and showed no relevant differences, all composites having bending moduli of 45 - 50 GPa. Finally, composites cured with a faster high temperature curing cycle (20 min at 140 °C) were prepared with the DGEBA/DICY/ methylene bis (phenyl dimethyl urea) system, obtaining similar properties as with the slower curing cycle, showing that the prepreg system allowed more flexibility in terms of curing cycle than the bulk resin samples.

Preparation of Sesquiterpenoids from Tussilago farfara L. by High-speed Counter-current Chromatography

PubMed Central

Cao, Kun; Xu, Yi; Zhao, Tian-Ming; Zhang, Qing

2016-01-01

Background: Sesquiterpenoids, such as tussilagone, has effects of raising blood pressure, antiplatelet aggregation, and anti-inflammation activities, which is regarded as index compound for quality control of Tussilago farfara L. Objective: This study was aimed to obtain an effective method for fast isolation of sesquiterpenoids from T. farfara L. by high-speed counter-current chromatography (HSCCC). Materials and Methods: A solvent optimization method for HSCCC was presented, i.e., the separation factors of compounds after the K values of solvent system should be investigated. Results: A ternary solvent system of n-hexane:methanol:water (5:8:2, v/v/v) was selected and applied for the HSCCC, and 56 mg of tussilagone (2) was isolated from T. farfara L., along with two other sesquiterpenoids 5.6 mg of 2,2-dimethyl-6-acetylchromanone (1) and 22 mg of 14-acetoxy-7 β-(3’-ethyl cis-crotonoyloxy)-lα-(2’-methylbutyryloxy)-notonipetranone (3) by HSCCC with high purities. Their chemical structures were elucidated by liquid chromatography-mass spectrometry and nuclear magnetic resonance experiments. Conclusion: These results offered an efficient strategy for preparation of potentially health-relevant phytochemicals from T. farfara L., which might be used for further chemical research and pharmacological studies by preparative HSCCC. SUMMARY The real separation efficiency has been verified by analytical HSCCC.A solvent optimization method for HSCCC was presented and applied to separate and prepare active compounds.A method for rapid and effective separation of target compound Tussilagone with high yield and purity from the flower buds of Tussilago farfara.Two other compounds 2,2-Dimethyl-6-acetylchromanone and 14-acetoxy-7β-(3’-ethyl cis-crotonoyloxy) -lα- (2’-methylbutyryloxy). notonipetranone hasbeen obtained with high purities from flower buds of Tussilago farfara. Abbreviations used: HSCCC: High-Speed Counter-Current Chromatography; LC-MS: Liquid Chromatograph-Mass Spectrometer; NMR: Nuclear Magnetic Resonance; TCM: Traditional Chinese Medicine; HPLC: High Performance Liquid Chromatography; ESI-MS: Electrospray Ionization Mass Spectrometry; PE: petroleum ether PMID:27867270

40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

40 CFR 721.10127 - Alkenyl dimethyl betaine (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkenyl dimethyl betaine (generic... Specific Chemical Substances § 721.10127 Alkenyl dimethyl betaine (generic). (a) Chemical substance and... dimethyl betaine (PMN P-06-693) is subject to reporting under this section for the significant new uses...

40 CFR 721.10666 - Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

...(fattyalkyl) dimethyl, salts with tannins (generic). 721.10666 Section 721.10666 Protection of Environment..., bis(fattyalkyl) dimethyl, salts with tannins (generic). (a) Chemical substance and significant new... compounds, bis(fattyalkyl) dimethyl, salts with tannins (PMN P-12-437) is subject to reporting under this...

40 CFR 721.10666 - Quaternary ammonium compounds, bis(fattyalkyl) dimethyl, salts with tannins (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

...(fattyalkyl) dimethyl, salts with tannins (generic). 721.10666 Section 721.10666 Protection of Environment..., bis(fattyalkyl) dimethyl, salts with tannins (generic). (a) Chemical substance and significant new... compounds, bis(fattyalkyl) dimethyl, salts with tannins (PMN P-12-437) is subject to reporting under this...

40 CFR 721.10352 - Dimethyl terephthalate, polymer with alkyl diol and substituted benzoates (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Dimethyl terephthalate, polymer with... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10352 Dimethyl terephthalate, polymer... subject to reporting. (1) The chemical substance identified generically as dimethyl terephthalate, polymer...

40 CFR 721.10352 - Dimethyl terephthalate, polymer with alkyl diol and substituted benzoates (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Dimethyl terephthalate, polymer with... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10352 Dimethyl terephthalate, polymer... subject to reporting. (1) The chemical substance identified generically as dimethyl terephthalate, polymer...

40 CFR 721.10352 - Dimethyl terephthalate, polymer with alkyl diol and substituted benzoates (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Dimethyl terephthalate, polymer with... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10352 Dimethyl terephthalate, polymer... subject to reporting. (1) The chemical substance identified generically as dimethyl terephthalate, polymer...

40 CFR 721.6167 - Piperdinium, 1,1-dimethyl-, chloride.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Piperdinium, 1,1-dimethyl-, chloride... Substances § 721.6167 Piperdinium, 1,1-dimethyl-, chloride. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as piperdinium, 1,1-dimethyl-, chloride. (PMN...

21 CFR 172.824 - Sodium mono- and dimethyl naphthalene sulfonates.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium mono- and dimethyl naphthalene sulfonates... sulfonates. The food additive sodium mono- and dimethyl naphthalene sulfonates may be safely used in... statement declaring the presence of sodium mono- and dimethyl naphthalene sulfonates. [42 FR 14491, Mar. 15...

40 CFR 63.5485 - Am I subject to this subpart?

Code of Federal Regulations, 2011 CFR

2011-07-01

... manufacturing includes both the Miscellaneous Viscose Processes source category and the Cellulose Ethers Production source category. The Miscellaneous Viscose Processes source category includes all of the operations that use the viscose process. These operations include the cellulose food casing, rayon...

Synthesis and evaluation of borates derived from boric acid and diols for the protection of wood against fungal decay and thermal degradation

Treesearch

George C. Chen

2004-01-01

N,N-dimethyl amino carbinol catechol borate(1). N,N-dimethyl amino carbinol-4-methyl catechol borate(2), N,N-dimethyl amino carbinol-4-t- butyl catechol borate(3). N,N-dimethyl amino carbinol-2,3-naphthyl borate 4) were synthesized by refluxing boric acid and diol in DMF(N,N-dimethyl formamide). The borates were characterized by NMR. Wood impregnated with borate 1,2 or...

The vibrational spectra and structures of dimethyl oxaloacetate and dimethyl oxaloacetate- d2

NASA Astrophysics Data System (ADS)

Schiering, David W.; Katon, J. E.

The complete vibrational spectra of dimethyl oxaloacetate and dimethyl oxaloacetate- d2 have been recorded and analyzed. The i.r. spectra were recorded at liquid N 2 as well as ambient temperature. Tentative vibrational assignments are proposed based on an enol structure in the crystalline phase. In solution, dimethyl oxaloacetate exists as a tautomeric mixture of keto and enol forms. Evidence for the existence of different enol conformers in CCl 4 and CS 2 solutions is also presented.

Enrichment of Desulfitobacterium spp. from forest and grassland soil using the O-demethylation of phenyl methyl ethers as a growth-selective process.

PubMed

Mingo, Felix Sebastian; Diekert, Gabriele; Studenik, Sandra

2016-02-01

The O-demethylation of phenyl methyl ethers under anaerobic conditions is a metabolic feature of acetogens and Desulfitobacterium spp. Desulfitobacteria as well as most acetogens are Gram-positive bacteria with a low GC content and belong to the phylum Firmicutes. The consumption of the phenyl methyl ether syringate was studied in enrichment cultures originating from five different topsoils. Desulfitobacterium spp. were detected in all topsoils via quantitative PCR. Desulfitobacteria could be enriched using the O-demethylation of syringate as a growth-selective process. The enrichment was significantly favoured by an external electron acceptor such as 3-chloro-4-hydroxyphenylacetate or thiosulfate. Upon cultivation in the presence of syringate and thiosulfate, which naturally occur in soil, a maximum number of 16S rRNA gene copies of Desulfitobacterium spp. was reached within the first three subcultivation steps and accounted for 3-10% of the total microbial community depending on the soil type. Afterwards, a loss of Desulfitobacterium gene copies was observed. Community analyses revealed that Proteobacteria, Acidobacteria, Actinobacteria and Bacteroidetes were the main phyla in the initial soil samples. Upon addition of syringate and thiosulfate as growth substrates, these phyla were rapidly outcompeted by Firmicutes, which were under-represented in soil. The main Firmicutes genera identified were Alkalibaculum, Clostridium, Sporobacterium, Sporomusa and Tissierella, which might be responsible for outcompeting the desulfitobacteria. Most of these organisms belong to the acetogens, which have previously been described to demethylate phenyl methyl ethers. The shift of the native community structure to almost exclusively Firmicutes supports the participation of members of this phylum in environmental demethylation processes.

EXPERIMENTAL AND MODELING STUDY OF PREMIXED LAMINAR FLAMES OF ETHANOL AND METHANE.

PubMed

Tran, Luc-Sy; Glaude, Pierre-Alexandre; Fournet, René; Battin-Leclerc, Frédérique

2013-04-18

To better understand the chemistry of the combustion of ethanol, the structure of five low pressure laminar premixed flames has been investigated: a pure methane flame (φ=1), three pure ethanol flames (φ=0.7, 1.0, and 1.3), and an ethanol/methane mixture flames (φ=1). The flames have been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 64.3 cm/s at 333 K. The results consist of mole fraction profiles of 20 species measured as a function of the height above the burner by probe sampling followed by online gas chromatography analyses. A mechanism for the oxidation of ethanol was proposed. The reactions of ethanol and acetaldehyde were updated and include recent theoretical calculations while that of ethenol, dimethyl ether, acetone, and propanal were added in the mechanism. This mechanism was also tested against experimental results available in the literature for laminar burning velocities and laminar premixed flame where ethenol was detected. The main reaction pathways of consumption of ethanol are analyzed. The effect of the branching ratios of reaction C 2 H 5 OH+OH→Products+H 2 O is also discussed.

Laminar Flame Velocity and Temperature Exponent of Diluted DME-Air Mixture

NASA Astrophysics Data System (ADS)

Naseer Mohammed, Abdul; Anwar, Muzammil; Juhany, Khalid A.; Mohammad, Akram

2017-03-01

In this paper, the laminar flame velocity and temperature exponent diluted dimethyl ether (DME) air mixtures are reported. Laminar premixed mixture of DME-air with volumetric dilutions of carbon dioxides (CO2) and nitrogen (N2) are considered. Experiments were conducted using a preheated mesoscale high aspect-ratio diverging channel with inlet dimensions of 25 mm × 2 mm. In this method, flame velocities are extracted from planar flames that were stabilized near adiabatic conditions inside the channel. The flame velocities are then plotted against the ratio of mixture temperature and the initial reference temperature. A non-linear power law regression is observed suitable. This regression analysis gives the laminar flame velocity at the initial reference temperature and temperature exponent. Decrease in the laminar flame velocity and increase in temperature exponent is observed for CO2 and N2 diluted mixtures. The addition of CO2 has profound influence when compared to N2 addition on both flame velocity and temperature exponent. Numerical prediction of the similar mixture using a detailed reaction mechanism is obtained. The computational mechanism predicts higher magnitudes for laminar flame velocity and smaller magnitudes of temperature exponent compared to experimental data.

A new bioactive monoterpene-flavonoid from Satureja khuzistanica.

PubMed

Malmir, Maryam; Gohari, Ahmad Reza; Saeidnia, Soodabeh; Silva, Olga

2015-09-01

A new monoterpene-flavonoid, saturejin (3'-(2,5-dihydroxy-p-cymene) 5,7,4'-trihydroxy flavone) (4), together with twelve known flavonoids consist of two flavanonols (aromadendrin (8) and taxifolin (12)), two flavanones (naringenin (3) and 5,7,3',5'-tetrahydroxy flavanone (9)) and eight flavones (xanthomicrol (1), acacetin (2), cirsimaritin (5), 7-methoxy luteolin (6), apigenin (7), cirsilineol (10), diosmetin (11) and 6-hydroxyluteolin 7,3'-dimethyl ether (13)), were isolated from an ethyl acetate extract and identified for the first time in the dried aerial parts of Satureja khuzistanica Jamzad, an endemic medicinal plant traditionally used as dental anesthetic, oral antiseptic and anti-inflammatory among the nomadic inhabitants of southwestern Iran. The structures of these compounds were determined using the usual spectroscopic methods including 2D-NMR and MS analyses. Saturejin showed a significant β-glucosidase inhibitory activity at concentration of 10 μg as well as positive antioxidant activity at the amount of 1 μg. These results could be correlated with the in vitro and in vivo anti-inflammatory, anti-oxidant and anti-diabetic properties reported from this medicinal plant. Similar activities were also described for some of the other isolated compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

PEO based polymer composite with added acetamide, NaI/I2 as gel polymer electrolyte for dye sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Narasimha Rao, B.; Padma suvarna, R.; Giribabu, L.; Raghavender, M.; kumar, V. Ramesh

2018-02-01

Poly (ethylene oxide) (PEO) based gel polymer electrolytes (GPEs) with added acetamide, NaI/I2 have been prepared for dye-sensitized solar cells application (DSSC). The Dye-sensitized solar cell investigated the performance of the optimized gel polymer electrolyte. GPEs synthesized by adding up of acetamide with different wt% in poly (ethylene oxide) (PEO) and poly (ethylene glycol) dimethyl ether (PEGDME) with NaI/I2. A maximum power conversion efficiency of 5.92% is achieved for PEO/PEGDME with 10 wt% acetamide in the photovoltaic performance under 100 mW/cm2 illumination and it exhibits maximum ionic conductivity (σ = 2.81×10-3 S/cm) among all electrolytes, compared to PEO without acetamide (η = 4.35%). The gain in open circuit voltage (Voc) was observed for GPEs due to the decrease in the recombination effect and electron lifetime increases by the addition of acetamide on the PEO. The fill factor (FF) is increased due to the growth in the ionic conductivity and amorphous nature of the GPE increases by the addition of acetamide on the PEO.

Electrolytes for Low-Temperature Operation of Li-CFx Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Whitacre, Jay F.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Bhalla, Pooja; Smith, Kiah

2009-01-01

A report describes a study of electrolyte compositions selected as candidates for improving the low-temperature performances of primary electrochemical cells that contain lithium anodes and fluorinated carbonaceous (CFx) cathodes. This study complements the developments reported in Additive for Low-Temperature Operation of Li-(CF)n Cells (NPO- 43579) and Li/CFx Cells Optimized for Low-Temperature Operation (NPO- 43585), which appear elsewhere in this issue of NASA Tech Briefs. Similar to lithium-based electrolytes described in several previous NASA Tech Briefs articles, each of these electrolytes consisted of a lithium salt dissolved in a nonaqueous solvent mixture. Each such mixture consisted of two or more of the following ingredients: propylene carbonate (PC); 1,2-dimethoxyethane (DME); trifluoropropylene carbonate; bis(2,2,2-trifluoroethyl) ether; diethyl carbonate; dimethyl carbonate; and ethyl methyl carbonate. The report describes the physical and chemical principles underlying the selection of the compositions (which were not optimized) and presents results of preliminary tests made to determine effects of the compositions upon the low-temperature capabilities of Li-CFx cells, relative to a baseline composition of LiBF4 at a concentration of 1.0 M in a solvent comprising equal volume parts of PC and DME.

Plasma-deposited tetraglyme surfaces greatly reduce total blood protein adsorption, contact activation, platelet adhesion, platelet procoagulant activity, and in vitro thrombus deposition.

PubMed

Cao, Lan; Chang, Mark; Lee, Chi-Ying; Castner, David G; Sukavaneshvar, Sivaprasad; Ratner, Buddy D; Horbett, Thomas A

2007-06-15

The ability of tetraethylene glycol dimethyl ether (tetraglyme) plasma deposited coatings exhibiting ultralow fibrinogen adsorption to reduce blood activation was studied with six in vitro methods, namely fibrinogen and von Willebrand's factor adsorption, total protein adsorption, clotting time in recalcified plasma, platelet adhesion and procoagulant activity, and whole blood thrombosis in a disturbed flow catheter model. Surface plasmon resonance results showed that tetraglyme surfaces strongly resisted the adsorption of all proteins from human plasma. The clotting time in the presence of tetraglyme surfaces was lengthened compared with controls, indicating a lower activation of the intrinsic coagulation cascade. Platelet adhesion and thrombin generation by adherent platelets were greatly reduced on tetraglyme-coated materials, compared with uncoated and Biospan-coated glass slides. In the in vitro disturbed blood flow model, tetraglyme plasma coated catheters had 50% less thrombus than did the uncoated catheters. Tetraglyme-coated materials thus had greatly reduced blood interactions as measured with all six methods. The improved blood compatibility of plasma-deposited tetraglyme is thus not only due to their reduced platelet adhesion and activation, but also to a generalized reduction in blood interactions. (c) 2007 Wiley Periodicals, Inc.

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

NASA Astrophysics Data System (ADS)

Sewilo, Marta; Indebetouw, Remy; Charnley, Steven; Zahorecz, Sarolta; Oliveira, Joana M.; van Loon, Jacco Th.; Ward, Jacob L.; Chen, C.-H. Rosie; Wiseman, Jennifer; Fukui, Yasuo; Kawamura, Akiko; Meixner, Margaret; Onishi, Toshikazu; Schilke, Peter

2018-01-01

We report the detection of the complex organic molecules (COMs) dimethyl ether (CH3OCH3) and methyl formate (CH3OCHO), and their parent species methanol (CH3OH), toward the N113 star-formation region in the Large Magellanic Cloud (LMC) with the Atacama Large Millimeter/submillimeter Array (ALMA). This constitutes the first detection of CH3OCH3 and CH3OCHO outside the Milky Way. We calculated the rotational temperatures (Trot ~ 130 K) and total column densities (Nrot ~ 1016 cm-2) for two sources in N113 with the COMs detection based on multiple transitions of CH3OH, and measured abundances for all detected species. The physical and chemical properties of these sources, and the association with H2O and OH maser emission indicate that they are hot molecular cores. The fractional abundances of COMs scaled by a factor of 2.5 to account for the lower metallicity in the LMC are comparable to those found at the lower end of the range in Galactic hot cores. Our results have important implications for studies of organic chemistry at higher redshift.

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

NASA Astrophysics Data System (ADS)

Sewiło, Marta; Indebetouw, Remy; Charnley, Steven B.; Zahorecz, Sarolta; Oliveira, Joana M.; van Loon, Jacco Th.; Ward, Jacob L.; Chen, C.-H. Rosie; Wiseman, Jennifer; Fukui, Yasuo; Kawamura, Akiko; Meixner, Margaret; Onishi, Toshikazu; Schilke, Peter

2018-02-01

We report the first extragalactic detection of the complex organic molecules (COMs) dimethyl ether (CH3OCH3) and methyl formate (CH3OCHO) with the Atacama Large Millimeter/submillimeter Array (ALMA). These COMs, together with their parent species methanol (CH3OH), were detected toward two 1.3 mm continuum sources in the N 113 star-forming region in the low-metallicity Large Magellanic Cloud (LMC). Rotational temperatures ({T}{rot}∼ 130 K) and total column densities ({N}{rot}∼ {10}16 cm‑2) have been calculated for each source based on multiple transitions of CH3OH. We present the ALMA molecular emission maps for COMs and measured abundances for all detected species. The physical and chemical properties of two sources with COMs detection, and the association with H2O and OH maser emission, indicate that they are hot cores. The fractional abundances of COMs scaled by a factor of 2.5 to account for the lower metallicity in the LMC are comparable to those found at the lower end of the range in Galactic hot cores. Our results have important implications for studies of organic chemistry at higher redshift.

[Medicinal chemistry and pharmacology focused on cannabidiol, a major component of the fiber-type cannabis].

PubMed

Takeda, Shuso

2013-01-01

Considerable attention has focused on cannabidiol (CBD), a major non-psychotropic constituent of fiber-type cannabis plant, and it has been reported to possess diverse biological activities. Although CBD is obtained from non-enzymatic decarboxylation of its parent molecule, cannabidiolic acid (CBDA), several studies have investigated whether CBDA itself is biologically active. In the present report, the author summarizes findings indicating that; 1) CBDA is a selective cyclooxygenase-2 (COX-2) inhibitor, and ii) CBDA possesses an anti-migrative potential for highly invasive cancer cells, apparently through a mechanism involving inhibition of cAMP-dependent protein kinase A, coupled with an activation of the small GTPase, RhoA. Further, the author introduces recent findings on the medicinal chemistry and pharmacology of the CBD derivative, CBD-2',6'-dimethyl ether (CBDD), that exhibits inhibitory activity toward 15-lipoxygenase (15-LOX), an enzyme responsible for the production of oxidized low-density lipoprotein (LDL). These studies establish CBD as both an important experimental tool and as a lead compound for pharmaceutical development. In this review, the author further discusses the potential uses of CBD and its derivatives in future medicines.

A novel lithium/sulfur battery based on sulfur/graphene nanosheet composite cathode and gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yongguang; Zhao, Yan; Bakenov, Zhumabay

2014-03-01

A novel sulfur/graphene nanosheet (S/GNS) composite was prepared via a simple ball milling of sulfur with commercial multi-layer graphene nanosheet, followed by a heat treatment. High-resolution transmission and scanning electronic microscopy observations showed the formation of irregularly interlaced nanosheet-like structure consisting of graphene with uniform sulfur coating on its surface. The electrochemical properties of the resulting composite cathode were investigated in a lithium cell with a gel polymer electrolyte (GPE) prepared by trapping 1 mol dm-3 solution of lithium bistrifluoromethanesulfonamide in tetraethylene glycol dimethyl ether in a polymer matrix composed of poly(vinylidene fluoride-co-hexafluoropropylene)/poly(methylmethacrylate)/silicon dioxide (PVDF-HFP/PMMA/SiO2). The GPE battery delivered reversible discharge capacities of 809 and 413 mAh g-1 at the 1st and 50th cycles at 0.2C, respectively, along with a high coulombic efficiency over 50 cycles. This performance enhancement of the cell was attributed to the suppression of the polysulfide shuttle effect by a collective effect of S/GNS composite cathode and GPE, providing a higher sulfur utilization. PACS: 82.47.Aa; 82.45.Gj; 62.23.Kn

Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

PubMed

Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

2016-02-01

The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-soluble resist for environmentally friendly lithography

NASA Astrophysics Data System (ADS)

Lin, Qinghuang; Simpson, Logan L.; Steinhaeusler, Thomas; Wilder, Michelle; Willson, C. Grant; Havard, Jennifer M.; Frechet, Jean M. J.

1996-05-01

This paper describes an 'environmentally friendly,' water castable, water developable photoresist system. The chemically amplified negative-tone resist system consists of three water-soluble components: a polymer, poly(methyl acrylamidoglycolate methyl ether), [poly(MAGME)]; a photoacid generator, dimethyl dihydroxyphenylsulfonium triflate and a crosslinker, butanediol. Poly(MAGME) was synthesized by solution free radical polymerization. In the three-component resist system, the acid generated by photolysis of the photoacid generator catalyzes the crosslinking of poly(MAGME) in the exposed regions during post-exposure baking, thus rendering the exposed regions insoluble in water. Negative tone relief images are obtained by developing with pure water. The resist is able to resolve 1 micrometer line/space features (1:1 aspect ratio) with an exposure dose of 100 mJ/cm2 at 248 nm. The resist can be used to generate etched copper relief images on printed circuit boards using aqueous sodium persulfate as the etchant. The crosslinking mechanism has been investigated by model compound studies using 13C NMR. These studies have revealed that the acid catalyzed reaction of the poly(MAGME) with butanediol proceeds via both transesterification and transacetalization (transaminalization) reactions at low temperatures, and also via transamidation at high temperatures.

Exploring the Effects of Different Types of Surfactants on Zebrafish Embryos and Larvae

PubMed Central

Wang, Yanan; Zhang, Yuan; Li, Xu; Sun, Mingzhu; Wei, Zhuo; Wang, Yu; Gao, Aiai; Chen, Dongyan; Zhao, Xin; Feng, Xizeng

2015-01-01

Currently, surfactants are widely distributed in the environment. As organic pollutants, their toxicities have drawn extensive attention. In this study, the effects of anionic [sodium dodecyl sulphate (SDS) ], cationic [dodecyl dimethyl benzyl ammonium chloride (1227)] and non-ionic [fatty alcohol polyoxyethylene ether (AEO) ] surfactants on zebrafish larval behaviour were evaluated. Five behavioural parameters were recorded using a larval rest/wake assay, including rest total, number of rest bouts, rest bouts length, total activity and waking activity. The results revealed that 1227 and AEO at 1 μg/mL were toxic to larval locomotor activity and that SDS had no significant effects. Moreover, we tested the toxicities of the three surfactants in developing zebrafish embryos. AEO exposure resulted in smaller head size, smaller eye size and shorter body length relative to SDS and 1227. All three surfactants incurred concentration-dependent responses. Furthermore, in situ hybridisation indicated that smaller head size may be associated with a decreased expression of krox20. The altered expression of ntl demonstrated that the developmental retardation stemmed from inhibited cell migration and growth. These findings provide references for ecotoxicological assessments of different types of surfactants, and play a warning role in the application of surfactants. PMID:26053337

40 CFR 721.10159 - 1-Docosanamine, N,N-dimethyl-.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 1-Docosanamine, N,N-dimethyl-. 721... Substances § 721.10159 1-Docosanamine, N,N-dimethyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-docosanamine, N,N-dimethyl- (PMN P-07-587...

40 CFR 180.261 - N-(Mercaptomethyl) phthali-mide S-(O,O-dimethyl phosphoro-dithioate) and its oxygen analog...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-dimethyl phosphoro-dithioate) and its oxygen analog; tolerances for residues. 180.261 Section 180.261...-mide S-(O,O-dimethyl phosphoro-dithioate) and its oxygen analog; tolerances for residues. (a) General...-(O,O-dimethyl phosphorodithioate) and its oxygen analog N-(mercaptomethyl) phthalimide S-(O,O...

40 CFR 721.1225 - Benzene, 1,2-dimethyl-, poly-propene derivatives, sulfonated, po-tas-sium salts.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 1,2-dimethyl-, poly-propene... Significant New Uses for Specific Chemical Substances § 721.1225 Benzene, 1,2-dimethyl-, poly-propene... reporting. (1) The chemical substance identified as benzene, 1,2-dimethyl-, polypropene derivatives...

40 CFR 721.1225 - Benzene, 1,2-dimethyl-, poly-propene derivatives, sulfonated, po-tas-sium salts.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 1,2-dimethyl-, poly-propene... Significant New Uses for Specific Chemical Substances § 721.1225 Benzene, 1,2-dimethyl-, poly-propene... reporting. (1) The chemical substance identified as benzene, 1,2-dimethyl-, polypropene derivatives...

40 CFR 721.1225 - Benzene, 1,2-dimethyl-, poly-propene derivatives, sulfonated, po-tas-sium salts.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 1,2-dimethyl-, poly-propene... Significant New Uses for Specific Chemical Substances § 721.1225 Benzene, 1,2-dimethyl-, poly-propene... reporting. (1) The chemical substance identified as benzene, 1,2-dimethyl-, polypropene derivatives...

40 CFR 721.10159 - 1-Docosanamine, N,N-dimethyl-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 1-Docosanamine, N,N-dimethyl-. 721... Substances § 721.10159 1-Docosanamine, N,N-dimethyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1-docosanamine, N,N-dimethyl- (PMN P-07-587...

Kinetics and thermodynamics of oxidation mediated reaction in L-cysteine and its methyl and ethyl esters in dimethyl sulfoxide-d6 by NMR spectroscopy

NASA Astrophysics Data System (ADS)

Dougherty, Ryan J.; Singh, Jaideep; Krishnan, V. V.

2017-03-01

L-Cysteine (L-Cys), L-Cysteine methyl ester (L-CysME) or L-Cysteine ethyl ester (L-CysEE), when dissolved in dimethyl sulfoxide, undergoes an oxidation process. This process is slow enough and leads to nuclear magnetic resonance (NMR) spectral changes that could be monitored in real time. The oxidation mediated transition is modeled as a pseudo-first order kinetics and the thermodynamic parameters are estimated using the Eyring's formulation. L-Cysteine and their esters are often used as biological models due to the remarkable thiol group that can be found in different oxidation states. This oxidation mediated transition is due to the combination of thiol oxidation to a disulfide followed by solvent-induced effects may be relevant in designing cysteine-based molecular models.

Process for conversion of lignin to reformulated, partially oxygenated gasoline

DOEpatents

Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

2001-01-09

A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

The biosorption capacity of biochar for 4-bromodiphengl ether: study of its kinetics, mechanism, and use as a carrier for immobilized bacteria.

PubMed

Du, Jingting; Sun, Pengfei; Feng, Zhuo; Zhang, Xin; Zhao, Yuhua

2016-02-01

Polybrominated diphenyl ethers (PBDEs) are known as ubiquitous pollutants in ecological systems and thus pose a great threat to the health of humans and other organisms due to their bioamplification and bioaccumulation along the food chain. The present study was designed to investigate the biosorption capacity of biochar for the removal of 4-monobromodiphengl ether and its synergistic effect when used as a carrier to immobilize the 4-monobromodiphengl ether-degrading strain Sphingomonas sp. DZ3. The raw biochar material was prepared by pyrolyzing maize straw at 350 °C under oxygen-limited conditions. The maximum biosorption capacity of biochar for 4-bromodiphengl ether was determined to be 50.23 mg/L under an initial concentration of 800 mg/L at pH 7.0 and 40 °C. The data obtained from the biosorption studies were fitted successfully with the pseudo-first-order kinetic and Freundlich isotherm models. The Weber-Morris model analysis indicated that intraparticle diffusion was the limiting step in the biosorption of 4-bromodiphengl ether onto the biosorbent. The values of thermodynamic parameters △G0 were calculated as -24.61 kJ/mol (20 °C), -24.35 kJ/mol (30 °C), and -23.98 kJ/mol (40 °C), △S(0) was -8.45 kJ/mol/K, and △H(0) was 21.36 kJ/mol. The artificial neural network analysis indicated that the initial concentration appeared to be the most influential parameter on the biosorption processes. The removal rate of 4-bromodiphengl ether achieved using the biochar-microorganism system was increased by 63 and 83% compared with the rates obtained with biochar and the strain individually, respectively. The morphology of the biochar and immobilized strain was determined using a scanning electron microscope, and information of the surface functional groups of biochar was obtained through an infrared spectra study.

DNA Replication Origin Function Is Promoted by H3K4 Di-methylation in Saccharomyces cerevisiae

PubMed Central

Rizzardi, Lindsay F.; Dorn, Elizabeth S.; Strahl, Brian D.; Cook, Jeanette Gowen

2012-01-01

DNA replication is a highly regulated process that is initiated from replication origins, but the elements of chromatin structure that contribute to origin activity have not been fully elucidated. To identify histone post-translational modifications important for DNA replication, we initiated a genetic screen to identify interactions between genes encoding chromatin-modifying enzymes and those encoding proteins required for origin function in the budding yeast Saccharomyces cerevisiae. We found that enzymes required for histone H3K4 methylation, both the histone methyltransferase Set1 and the E3 ubiquitin ligase Bre1, are required for robust growth of several hypomorphic replication mutants, including cdc6-1. Consistent with a role for these enzymes in DNA replication, we found that both Set1 and Bre1 are required for efficient minichromosome maintenance. These phenotypes are recapitulated in yeast strains bearing mutations in the histone substrates (H3K4 and H2BK123). Set1 functions as part of the COMPASS complex to mono-, di-, and tri-methylate H3K4. By analyzing strains lacking specific COMPASS complex members or containing H2B mutations that differentially affect H3K4 methylation states, we determined that these replication defects were due to loss of H3K4 di-methylation. Furthermore, histone H3K4 di-methylation is enriched at chromosomal origins. These data suggest that H3K4 di-methylation is necessary and sufficient for normal origin function. We propose that histone H3K4 di-methylation functions in concert with other histone post-translational modifications to support robust genome duplication. PMID:22851644

DNA replication origin function is promoted by H3K4 di-methylation in Saccharomyces cerevisiae.

PubMed

Rizzardi, Lindsay F; Dorn, Elizabeth S; Strahl, Brian D; Cook, Jeanette Gowen

2012-10-01

DNA replication is a highly regulated process that is initiated from replication origins, but the elements of chromatin structure that contribute to origin activity have not been fully elucidated. To identify histone post-translational modifications important for DNA replication, we initiated a genetic screen to identify interactions between genes encoding chromatin-modifying enzymes and those encoding proteins required for origin function in the budding yeast Saccharomyces cerevisiae. We found that enzymes required for histone H3K4 methylation, both the histone methyltransferase Set1 and the E3 ubiquitin ligase Bre1, are required for robust growth of several hypomorphic replication mutants, including cdc6-1. Consistent with a role for these enzymes in DNA replication, we found that both Set1 and Bre1 are required for efficient minichromosome maintenance. These phenotypes are recapitulated in yeast strains bearing mutations in the histone substrates (H3K4 and H2BK123). Set1 functions as part of the COMPASS complex to mono-, di-, and tri-methylate H3K4. By analyzing strains lacking specific COMPASS complex members or containing H2B mutations that differentially affect H3K4 methylation states, we determined that these replication defects were due to loss of H3K4 di-methylation. Furthermore, histone H3K4 di-methylation is enriched at chromosomal origins. These data suggest that H3K4 di-methylation is necessary and sufficient for normal origin function. We propose that histone H3K4 di-methylation functions in concert with other histone post-translational modifications to support robust genome duplication.

Odor composition analysis and odor indicator selection during sewage sludge composting

PubMed Central

Zhu, Yan-li; Zheng, Guo-di; Gao, Ding; Chen, Tong-bin; Wu, Fang-kun; Niu, Ming-jie; Zou, Ke-hua

2016-01-01

ABSTRACT On the basis of total temperature increase, normal dehydration, and maturity, the odor compositions of surface and internal piles in a well-run sewage sludge compost plant were analyzed using gas chromatography–mass spectrometry with a liquid nitrogen cooling system and a portable odor detector. Approximately 80 types of substances were detected, including 2 volatile inorganic compounds, 4 sulfur organic compounds, 16 benzenes, 27 alkanes, 15 alkenes, and 19 halogenated compounds. Most pollutants were mainly produced in the mesophilic and pre-thermophilic periods. The sulfur volatile organic compounds contributed significantly to odor and should be controlled primarily. Treatment strategies should be based on the properties of sulfur organic compounds. Hydrogen sulfide, methyl mercaptan, dimethyl disulfide, dimethyl sulfide, ammonia, and carbon disulfide were selected as core indicators. Ammonia, hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl mercaptan, dimethylbenzene, phenylpropane, and isopentane were designated as concentration indicators. Benzene, m-xylene, p-xylene, dimethylbenzene, dichloromethane, toluene, chlorobenzene, trichloromethane, carbon tetrachloride, and ethylbenzene were selected as health indicators. According to the principle of odor pollution indicator selection, dimethyl disulfide was selected as an odor pollution indicator of sewage sludge composting. Monitoring dimethyl disulfide provides a highly scientific method for modeling and evaluating odor pollution from sewage sludge composting facilities. Implications: Composting is one of the most important methods for sewage sludge treatment and improving the low organic matter content of many agricultural soils. However, odors are inevitably produced during the composting process. Understanding the production and emission patterns of odors is important for odor control and treatment. Core indicators, concentration indicators, and health indicators provide an index system to odor evaluation. An odor pollution indicator provides theoretical support for further modelling and evaluating odor pollution from sewage sludge composting facilities. PMID:27192607

Optimizing human hepatocyte models for metabolic phenotype and function: effects of treatment with dimethyl sulfoxide (DMSO).

PubMed

Nikolaou, Nikolaos; Green, Charlotte J; Gunn, Pippa J; Hodson, Leanne; Tomlinson, Jeremy W

2016-11-01

Primary human hepatocytes are considered to be the "gold standard" cellular model for studying hepatic fatty acid and glucose metabolism; however, they come with limitations. Although the HepG2 cell line retains many of the primary hepatocyte metabolic functions they have a malignant origin and low rates of triglyceride secretion. The aim of this study was to investigate whether dimethyl sulfoxide supplementation in the media of HepG2 cells would enhance metabolic functionality leading to the development of an improved in vitro cell model that closely recapitulates primary human hepatocyte metabolism. HepG2 cells were cultured in media containing 1% dimethyl sulfoxide for 2, 4, 7, 14, and 21 days. Gene expression, protein levels, intracellular triglyceride, and media concentrations of triglyceride, urea, and 3-hydroxybutyrate concentrations were measured. Dimethyl sulfoxide treatment altered the expression of genes involved in lipid (FAS, ACC1, ACC2, DGAT1, DGAT2, SCD) and glucose (PEPCK, G6Pase) metabolism as well as liver functionality (albumin, alpha-1-antitrypsin, AFP). mRNA changes were paralleled by alterations at the protein level. DMSO treatment decreased intracellular triglyceride content and lactate production and increased triglyceride and 3-hydroxybutyrate concentrations in the media in a time-dependent manner. We have demonstrated that the addition of 1% dimethyl sulfoxide to culture media changes the metabolic phenotype of HepG2 cells toward a more primary human hepatocyte phenotype. This will enhance the currently available in vitro model systems for the study of hepatocyte biology related to pathological processes that contribute to disease and their response to specific therapeutic interventions. © 2016 The Authors. Physiological Reports published by Wiley Periodicals, Inc. on behalf of the American Physiological Society and The Physiological Society.

Odor composition analysis and odor indicator selection during sewage sludge composting.

PubMed

Zhu, Yan-Li; Zheng, Guo-di; Gao, Ding; Chen, Tong-Bin; Wu, Fang-Kun; Niu, Ming-Jie; Zou, Ke-Hua

2016-09-01

On the basis of total temperature increase, normal dehydration, and maturity, the odor compositions of surface and internal piles in a well-run sewage sludge compost plant were analyzed using gas chromatography-mass spectrometry with a liquid nitrogen cooling system and a portable odor detector. Approximately 80 types of substances were detected, including 2 volatile inorganic compounds, 4 sulfur organic compounds, 16 benzenes, 27 alkanes, 15 alkenes, and 19 halogenated compounds. Most pollutants were mainly produced in the mesophilic and pre-thermophilic periods. The sulfur volatile organic compounds contributed significantly to odor and should be controlled primarily. Treatment strategies should be based on the properties of sulfur organic compounds. Hydrogen sulfide, methyl mercaptan, dimethyl disulfide, dimethyl sulfide, ammonia, and carbon disulfide were selected as core indicators. Ammonia, hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl mercaptan, dimethylbenzene, phenylpropane, and isopentane were designated as concentration indicators. Benzene, m-xylene, p-xylene, dimethylbenzene, dichloromethane, toluene, chlorobenzene, trichloromethane, carbon tetrachloride, and ethylbenzene were selected as health indicators. According to the principle of odor pollution indicator selection, dimethyl disulfide was selected as an odor pollution indicator of sewage sludge composting. Monitoring dimethyl disulfide provides a highly scientific method for modeling and evaluating odor pollution from sewage sludge composting facilities. Composting is one of the most important methods for sewage sludge treatment and improving the low organic matter content of many agricultural soils. However, odors are inevitably produced during the composting process. Understanding the production and emission patterns of odors is important for odor control and treatment. Core indicators, concentration indicators, and health indicators provide an index system to odor evaluation. An odor pollution indicator provides theoretical support for further modelling and evaluating odor pollution from sewage sludge composting facilities.

40 CFR 721.10366 - Benzene, 4-bromo-1,2-dimethyl-.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 4-bromo-1,2-dimethyl-. 721... Substances § 721.10366 Benzene, 4-bromo-1,2-dimethyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 4-bromo-1,2-dimethyl-(PMN P-10-76...

40 CFR 721.10366 - Benzene, 4-bromo-1,2-dimethyl-.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 4-bromo-1,2-dimethyl-. 721... Substances § 721.10366 Benzene, 4-bromo-1,2-dimethyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 4-bromo-1,2-dimethyl-(PMN P-10-76...

40 CFR 721.10366 - Benzene, 4-bromo-1,2-dimethyl-.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 4-bromo-1,2-dimethyl-. 721... Substances § 721.10366 Benzene, 4-bromo-1,2-dimethyl-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as benzene, 4-bromo-1,2-dimethyl-(PMN P-10-76...

Bis-Indolyl Benzenoids, Hydroxypyrrolidine Derivatives and Other Constituents from Cultures of the Marine Sponge-Associated Fungus Aspergillus candidus KUFA0062

PubMed Central

Ramos, Alice A.; Inácio, Ângela; Dethoup, Tida; Lee, Michael; Sekeroglu, Nazim; Rocha, Eduardo

2018-01-01

A previously unreported bis-indolyl benzenoid, candidusin D (2e) and a new hydroxypyrrolidine alkaloid, preussin C (5b) were isolated together with fourteen previously described compounds: palmitic acid, clionasterol, ergosterol 5,8-endoperoxides, chrysophanic acid (1a), emodin (1b), six bis-indolyl benzenoids including asterriquinol D dimethyl ether (2a), petromurin C (2b), kumbicin B (2c), kumbicin A (2d), 2″-oxoasterriquinol D methyl ether (3), kumbicin D (4), the hydroxypyrrolidine alkaloid preussin (5a), (3S, 6S)-3,6-dibenzylpiperazine-2,5-dione (6) and 4-(acetylamino) benzoic acid (7), from the cultures of the marine sponge-associated fungus Aspergillus candidus KUFA 0062. Compounds 1a, 2a–e, 3, 4, 5a–b, and 6 were tested for their antibacterial activity against Gram-positive and Gram-negative reference and multidrug-resistant strains isolated from the environment. Only 5a exhibited an inhibitory effect against S. aureus ATCC 29213 and E. faecalis ATCC29212 as well as both methicillin-resistant S. aureus (MRSA) and vancomycin-resistant enterococci (VRE) strains. Both 1a and 5a also reduced significant biofilm formation in E. coli ATCC 25922. Moreover, 2b and 5a revealed a synergistic effect with oxacillin against MRSA S. aureus 66/1 while 5a exhibited a strong synergistic effect with the antibiotic colistin against E. coli 1410/1. Compound 1a, 2a–e, 3, 4, 5a–b, and 6 were also tested, together with the crude extract, for cytotoxic effect against eight cancer cell lines: HepG2, HT29, HCT116, A549, A 375, MCF-7, U-251, and T98G. Except for 1a, 2a, 2d, 4, and 6, all the compounds showed cytotoxicity against all the cancer cell lines tested. PMID:29642369

Xanthine oxidase inhibitory activities of extracts and flavonoids of the leaves of Blumea balsamifera.

PubMed

Nessa, Fazilatun; Ismail, Zhari; Mohamed, Nornisah

2010-12-01

Blumea balsamifera DC (Compositae) leaves have been recommended for use as a folk medicine in the treatment of various diseases related to urolithiasis in southeast Asia. Phytochemical studies of this plant revealed it contains four classes of flavonoids (e.g., flavonols, flavones, flavanones, and dihydroflavonol derivatives). In view of the broad pharmacological activity of flavonoids, this study was carried out to determine the xanthine oxidase (XO) inhibitory and enzymatically produced superoxide radical scavenging activity of different organic extracts and that of the isolated flavonoids from B. balsamifera leaves. The inhibitory activity of XO was assayed spectrophotometrically at 295 nm. The superoxide radicals scavenging activity was assessed by NBT reduction method, spectrophotometrically at 560 nm. A dose response curve was plotted for determining IC₅₀ values. The methanol extract (IC₅₀ = 0.111 mg/mL) showed higher XO inhibitory activity than the chloroform (0.138 mg/mL) and pet-ether extracts (0.516 mg/mL). IC₅₀ values of scavenging of superoxide radicals for extracts decreased in the order of: methanol (0.063 mg/mL) > chloroform (0.092 mg/mL) > pet-ether (0.321 mg/mL). The XO inhibitory activity of the isolated flavonoids and reference compounds tested decreased in the order of: allopurinol > luteolin > quercetin > tamarixetin > 5,7,3',5'-tetrahydroxyflavanone > rhamnetin > luteolin-7-methyl ether > blumeatin > dihydroquercetin-4'-methyl ether > dihydroquercetin-7,4'-dimethyl ether > L-ascorbic acid. The results indicated that the flavone derivatives were more active than the flavonol derivatives. The flavanone derivatives were moderately active and the dihydroflavonol derivatives were the least. The higher flavonoid content of extracts contributed to their higher XO inhibitory activity.

Antinociceptive activity of extracts and secondary metabolites from wild growing and micropropagated plants of Renealmia alpinia

PubMed Central

Gómez-Betancur, Isabel; Cortés, Natalie; Benjumea, Dora; Osorio, Edison; León, Francisco; Cutler, Stephen J.

2015-01-01

Ethnopharmacological relevance Renealmia alpinia is native to the American continent and can be found from Mexico to Brazil, and in the Caribbean islands. It is known as “matandrea” in Colombia, and it has been commonly used in traditional medicine to treat painful diseases and ailments. Based on its traditional uses, it is of interest to evaluate the pharmacologic effects of this plant and its secondary metabolites. Materials and methods Methanol and aqueous extracts of wild and micropropagated R. alpinia (leaves) were obtained and chemically compared by High Performance Thin Layer Chromatography (HPTLC). The antinociceptive activity of these extracts was examined using an in vivo assay (Siegmund test). Additionally, the dichloromethane extract of R. alpinia was fractionated and pure compounds were isolated by chromatographic methods. The structure elucidation of isolated compounds was performed by NMR experiments and spectroscopic techniques and comparison with the literature data. Purified compounds were evaluated for their in vitro binding affinity for opioids and cannabinoids receptors. Results The dichloromethane extract of the plant’s aerial part afforded sinostrobin (1), naringenin 7,4′-dimethyl ether (2), 2′,6′-dihydroxy-4′-methoxychalcone (3), 4-methoxy-6-(2-phenylethenyl)-2H-pyran-2-one (4), naringenin 7-methyl ether (5) and 3,5-heptanediol, 1,7-diphenyl (6), which were isolated using chromatographic methods. Their chemical structures were established by physical and spectroscopic techniques. The antinociceptive effects observed in mice by extracts of wild and micropropagated plants were similar. The compounds isolated from R. alpinia do not show affinity to opioid or cannabinoid receptors. Conclusion Aqueous and methanol extracts of R. alpinia provide antinociceptive and analgesic effects in an in vivo model. These results contribute additional insight as to why this plant is traditionally used for pain management. Also, this is the first comprehensive report of a phytochemical study of R. alpinia. PMID:25686780

Challenges associated with the sampling and analysis of organosulfur compounds in air using real-time PTR-ToF-MS and off-line GC-FID

NASA Astrophysics Data System (ADS)

Perraud, V.; Meinardi, S.; Blake, D. R.; Finlayson-Pitts, B. J.

2015-12-01

Organosulfur compounds (OSC) are naturally emitted via various processes involving phytoplankton and algae in marine regions, from animal metabolism and from biomass decomposition inland. These compounds are malodorant and reactive. Their oxidation to methanesulfonic and sulfuric acids leads to the formation and growth of atmospheric particles, which are known to have negative effects on visibility, climate and human health. In order to predict particle formation events, accurate measurements of the OSC precursors are essential. Here, two different approaches, proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and canister sampling coupled with GC-FID are compared for both laboratory standards [dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and methanethiol (MTO)] and for a complex sample. Results show that both techniques produce accurate quantification of DMS. While PTR-ToF-MS provides real-time measurements of all four OSCs individually, significant fragmentation of DMDS and DMTS occurs, which can complicate their identification in complex mixtures. Canister sampling coupled with GC-FID provides excellent sensitivity for DMS, DMDS and DMTS. However, MTO was observed to react on metal surfaces to produce DMDS and, in the presence of hydrogen sulfide, even DMTS. Avoiding metal in sampling systems seems to be necessary for measuring all but dimethyl sulfide in air.

Ethers as Oxygen Donor and Carbon Source in Non-hydrolytic Sol-Gel: One-Pot, Atom-Economic Synthesis of Mesoporous TiO2 -Carbon Nanocomposites.

PubMed

Escamilla-Pérez, Angel Manuel; Louvain, Nicolas; Boury, Bruno; Brun, Nicolas; Mutin, P Hubert

2018-04-03

Mesoporous TiO 2 -carbon nanocomposites were synthesized using an original non-hydrolytic sol-gel (NHSG) route, based on the reaction of simple ethers (diisopropyl ether or tetrahydrofuran) with titanium tetrachloride. In this atom-economic, solvent-free process, the ether acts not only as an oxygen donor but also as the sole carbon source. Increasing the reaction temperature to 180 °C leads to the decomposition of the alkyl chloride by-product and to the formation of hydrocarbon polymers, which are converted to carbon by pyrolysis under argon. The carbon-TiO 2 nanocomposites and their TiO 2 counterparts (obtained by calcination) were characterized by nitrogen physisorption, XRD, solid state 13 C NMR and Raman spectroscopies, SEM, and TEM. The nanocomposites are mesoporous with surface areas of up to 75 m 2  g -1 and pore sizes around 10 nm. They are composed of aggregated anatase nanocrystals coated by an amorphous carbon film. Playing on the nature of the ether and on the reaction temperature allows control over the carbon content in the nanocomposites. The nature of the ether also influences the size of the TiO 2 crystallites and the morphology of the nanocomposite. To further characterize the carbon coating, the behavior of the carbon-TiO 2 nanocomposites and bare TiO 2 samples toward lithium insertion-deinsertion was investigated in half-cells. This simple NHSG approach should provide a general method for the synthesis of a wide range of carbon-metal oxide nanocomposites. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

H3 K79 dimethylation marks developmental activation of the beta-globin gene but is reduced upon LCR-mediated high-level transcription.

PubMed

Sawado, Tomoyuki; Halow, Jessica; Im, Hogune; Ragoczy, Tobias; Bresnick, Emery H; Bender, M A; Groudine, Mark

2008-07-15

Genome-wide analyses of the relationship between H3 K79 dimethylation and transcription have revealed contradictory results. To clarify this relationship at a single locus, we analyzed expression and H3 K79 modification levels of wild-type (WT) and transcriptionally impaired beta-globin mutant genes during erythroid differentiation. Analysis of fractionated erythroid cells derived from WT/Delta locus control region (LCR) heterozygous mice reveals no significant H3 K79 dimethylation of the beta-globin gene on either allele prior to activation of transcription. Upon transcriptional activation, H3 K79 di-methylation is observed along both WT and DeltaLCR alleles, and both alleles are located in proximity to H3 K79 dimethylation nuclear foci. However, H3 K79 di-methylation is significantly increased along the DeltaLCR allele compared with the WT allele. In addition, analysis of a partial LCR deletion mutant reveals that H3 K79 dimethylation is inversely correlated with beta-globin gene expression levels. Thus, while our results support a link between H3 K79 dimethylation and gene expression, high levels of this mark are not essential for high level beta-globin gene transcription. We propose that H3 K79 dimethylation is destabilized on a highly transcribed template.

40 CFR 721.10056 - Benzenemethanaminium, N-(3-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides.

Code of Federal Regulations, 2014 CFR

2014-07-01

...)-N,N-dimethyl-, N-soya acyl derivs., chlorides. 721.10056 Section 721.10056 Protection of Environment...-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides. (a) Chemical substance and significant new uses...-dimethyl-, N-soya acyl derivs., chlorides (PMN P-03-47; CAS No. 90194-13-1) is subject to reporting under...

40 CFR 721.10056 - Benzenemethanaminium, N-(3-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides.

Code of Federal Regulations, 2013 CFR

2013-07-01

...)-N,N-dimethyl-, N-soya acyl derivs., chlorides. 721.10056 Section 721.10056 Protection of Environment...-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides. (a) Chemical substance and significant new uses...-dimethyl-, N-soya acyl derivs., chlorides (PMN P-03-47; CAS No. 90194-13-1) is subject to reporting under...

40 CFR 721.10056 - Benzenemethanaminium, N-(3-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides.

Code of Federal Regulations, 2012 CFR

2012-07-01

...)-N,N-dimethyl-, N-soya acyl derivs., chlorides. 721.10056 Section 721.10056 Protection of Environment...-aminopropyl)-N,N-dimethyl-, N-soya acyl derivs., chlorides. (a) Chemical substance and significant new uses...-dimethyl-, N-soya acyl derivs., chlorides (PMN P-03-47; CAS No. 90194-13-1) is subject to reporting under...

40 CFR 721.10408 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene...

Code of Federal Regulations, 2013 CFR

2013-07-01

...)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2,2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl)oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...

40 CFR 721.10408 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene...

Code of Federal Regulations, 2014 CFR

2014-07-01

...)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2,2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl)oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...

40 CFR 721.10408 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene...

Code of Federal Regulations, 2012 CFR

2012-07-01

...)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2,2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl)oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...

Solvation and Acid Strength Effects on Catalysis by Faujasite Zeolites

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

Gounder, Rajamani P.; Jones, Andrew J.; Carr, Robert T.

2012-02-01

Kinetic, spectroscopic, and chemical titration data indicate that differences in monomolecular isobutane cracking and dehydrogenation and methanol dehydration turnover rates (per H+) among FAU zeolites treated thermally with steam (H-USY) and then chemically with ammonium hexafluorosilicate (CDHUSY) predominantly reflect differences in the size and solvating properties of their supercage voids rather than differences in acid strength. The number of protons on a given sample was measured consistently by titrations with Na+, with CH3 groups via reactions of dimethyl ether, and with 2,6-di-tert-butylpyridine during methanol dehydration catalysis; these titration values were also supported by commensurate changes in acidic OH infrared bandmore » areas upon exposure to titrant molecules. The number of protons, taken as the average of the three titration methods, was significantly smaller than the number of framework Al atoms (Alf) obtained from X-ray diffraction and 27Al magic angle spinning nuclear magnetic resonance spectroscopy on H-USY (0.35 H+/Alf) and CD-HUSY (0.69 H+/Alf). These data demonstrate that the ubiquitous use of Alf sites as structural proxies for active H+ sites in zeolites can be imprecise, apparently because distorted Al structures that are not associated with acidic protons are sometimes detected as Alf sites. Monomolecular isobutane cracking and dehydrogenation rate constants, normalized non-rigorously by the number of Alf species, decreased with increasing Na+ content on both H-USY and CD-HUSY samples and became undetectable at sub-stoichiometric exchange levels (0.32 and 0.72 Na+/Alf ratios, respectively), an unexpected finding attributed incorrectly in previous studies to the presence of minority ‘‘super-acidic’’ sites. These rate constants, when normalized rigorously by the number of residual H+ sites were independent of Na+ content on both H-USY and CD-HUSY samples, reflecting the stoichiometric replacement of protons that are uniform in reactivity by Na+ cations. Monomolecular isobutane cracking and dehydrogenation rate constants (per H+; 763 K), however, were higher on H-USY than CD-HUSY (by a factor of 1.4). Equilibrium constants for the formation of protonated methanol dimers via adsorption of gaseous methanol onto adsorbed methanol monomers, determined from kinetic studies of methanol dehydration to dimethyl ether (433 K), were also higher on H-USY than CD-HUSY (by a factor of 2.1). These larger constants predominantly reflect stronger dispersive interactions in H-USY, consistent with its smaller supercage voids that result from the occlusion of void space by extraframework Al (Alex) residues. These findings appear to clarify enduring controversies about the mechanistic interpretation of the effects of Na+ and Alex species on the catalytic reactivity of FAU zeolites. They also illustrate the need to normalize rates by the number of active sites instead of more convenient but less accurate structural proxies for such sites.« less

Oxidation of dimethyl-ether and ethylene in the atmosphere and combustion environment and thermodynamic studies on hydrofluorocarbons usingab initio calculation methods

NASA Astrophysics Data System (ADS)

Yamada, Takahiro

1999-08-01

Reaction pathways and kinetics are analyzed on CH3OC.H2 unimolecular decay and on the complete CH3OC.H2 + O2 reaction system using thermodynamic properties DHdegf 298,Sdeg 298, and Cp(T) 300 <= T/K <= 1500) derived by two ab initio calculation methods, CBS-q and G2. These are used to determine thermodynamic properties of reactants, intermediate radicals and transition state (TS) compounds. Quantum Rice-Ramsperger-Kassel (QRRK) analysis is used to calculate energy dependent rate constants, k(E), and master equation is used to account for collisional stabilization. Comparison of calculated fall-off with experiment indicates that the CBS-q and G2 calculated Ea,rxn for the rate controlling transition state (β-scission reaction to CH 2O + C.H2OOH) needs to be lowered by factor of 3.3 kcal/mol and 4.0 kcal/mol respectively in order to match the data of Sehested et al. Experimental results on dimethyl-ether pyrolysis and oxidation reaction systems are compared with a detailed reaction mechanism model. The computer code CHEMKIN II is used for numerical integration. Overall agreement of the model data with experimental data is very good. Reaction pathways are analyzed and kinetics are determined on formation and reactions of the adduct resulting from OH addition to ethylene using the above ab initio methods. Hydrogen atom tunneling is included by use of Eckart formalism. Rate constants are compared with experimentally determined product branching ratios (C.H2CH 2OH stabilization: CH2O + CH3: CH3CHO + H). ab initio calculations are performed to estimate thermodynamic properties of nine fluorinated ethane compounds (fluoroethane to hexafluoroethane), eight fluoropropane (1-fluoropropane, 1,1- and 1,2- difluoropropane, 1,1,1- and 1,1,2-trifluoropropane, 1,1,1,2- and 1,1,2,2-tetrafluoropropane and 1,1,1,2,2- pentafluoropropane), and 2-fluoro,2-methylpropane. Standard entropies and heat capacities are calculated using the rigid-rotor-harmonic-oscillator approximation with direct integration over energy levels of the intramolecular rotation potential energy curve. Enthalpies of formation are estimated using G2MP2 total energies and isodesmic reactions. Thermodynamic properties for fluorinated carbon groups C/C/F/H2, C/C/F2/H, C/C/F3, C/C2/F/H, C/C2/F2 and C/C3/F for fluorinated alkane compounds, CD/F/H and CD/F2 for fluorinated alkene compounds and CT/F for fluorinated alkyne compounds are estimated. Fluorine-fluorine interaction terms F/F, 2F/F, 3F/F, 2F/2F, 3F/2F and 3F/3F for alkane compounds, F//F, 2F//F and 2F/2F for alkene compounds, and F///F for alkyne compound are also estimated.

A four-component coupling reaction of carbon dioxide, amines, cyclic ethers and 3-triflyloxybenzynes for the synthesis of functionalized carbamates.

PubMed

Xiong, Wenfang; Qi, Chaorong; Cheng, Ruixiang; Zhang, Hao; Wang, Lu; Yan, Donghao; Jiang, Huanfeng

2018-04-27

A novel four-component coupling reaction of carbon dioxide, amines, cyclic ethers and 3-triflyloxybenzynes has been developed for the first time, providing an efficient method for the synthesis of a series of functionalized carbamate derivatives in moderate to high yields. The process proceeds under mild, transition metal-free and fluoride-free conditions, leading to the formation of two new C-O bonds, one new C-N bond and one C-H bond in a single step.

Asymmetric Synthesis of Rauhut-Currier type Products by a Regioselective Mukaiyama Reaction under Bifunctional Catalysis.

PubMed

Frias, María; Mas-Ballesté, Rubén; Arias, Saira; Alvarado, Cuauhtemoc; Alemán, José

2017-01-18

The reactivity and the regioselective functionalization of silyl-diene enol ethers under a bifunctional organocatalyst provokes a dramatic change in the regioselectivity, from the 1,5- to the 1,3-functionalization. This variation makes possible the 1,3-addition of silyl-dienol ethers to nitroalkenes, giving access to the synthesis of tri- and tetrasubstituted double bonds in Rauhut-Currier type products. The process takes place under smooth conditions, nonanionic conditions, and with a high enantiomeric excess. A rational mechanistic pathway is presented based on DFT and mechanistic experiments.

Microbial Transformations of Selenium

PubMed Central

Doran, J. W.; Alexander, M.

1977-01-01

Resting cell suspensions of a strain of Corynebacterium isolated from soil formed dimethyl selenide from selenate, selenite, elemental selenium, selenomethionine, selenocystine, and methaneseleninate. Extracts of the bacterium catalyzed the production of dimethyl selenide from selenite, elemental selenium, and methaneseleninate, and methylation of the inorganic Se compounds was enhanced by S-adenosylmethionine. Neither trimethylselenonium nor methaneselenonate was metabolized by the Corynebacterium. Resting cell suspensions of a methionine-utilizing pseudomonad converted selenomethionine to dimethyl diselenide. Six of 10 microorganisms able to grow on cystine used selenocystine as a sole source of carbon and formed elemental selenium, and one of the isolates, a pseudomonad, was found also to produce selenide. Soil enrichments converted trimethylselenonium to dimethyl selenide. Bacteria capable of utilizing trimethylselenonium, dimethyl selenide, and dimethyl diselenide as carbon sources were isolated from soil. PMID:16345188

Isolation and characterization of an ether-type polyurethane-degrading micro-organism and analysis of degradation mechanism by Alternaria sp.

PubMed

Matsumiya, Y; Murata, N; Tanabe, E; Kubota, K; Kubo, M

2010-06-01

To degrade ether-type polyurethane (ether-PUR), ether-PUR-degrading micro-organism was isolated. Moreover, ether-PUR-degrading mechanisms were analysed using model compounds of ether-PUR. A fungus designated as strain PURDK2, capable of changing the configuration of ether-PUR, has been isolated. This isolated fungus was identified as Alternaria sp. Using a scanning electron microscope, the grid structure of ether-PUR was shown to be melted and disrupted by the fungus. The degradation of ether-PUR by the fungus was analysed, and the ether-PUR was degraded by the fungus by about 27.5%. To analyse the urethane-bond degradation by the fungus, a degraded product of ethylphenylcarbamate was analysed using GC/MS. Aniline and ethanol were detected by degradation with the supernatant, indicating that the fungus secreted urethane-bond-degrading enzyme(s). PURDK2 also degraded urea bonds when diphenylmethane-4,4'-dibutylurea was used as a substrate. The enzyme(s) from PURDK2 degraded urethane and urea bonds to convert the high molecular weight structure of ether-PUR to small molecules; and then the fungus seems to use the small molecules as an energy source. Ether-PUR-degrading fungus, strain PURDK2, was isolated, and the urethane- and urea-bonds-degrading enzymes from strain PURDK2 could contribute to the material recycling of ether-PUR.

Kinetic evaluation and process performance of a fixed film bioreactor removing phthalic acid and dimethyl phthalate.

PubMed

Pirsaheb, Meghdad; Mesdaghinia, Ali-Reza; Shahtaheri, Seyed Jamaleddin; Zinatizadeh, Ali Akbar

2009-08-15

Phthalate esters are toxic organic contaminants which can enter into the environment through various industrial processes. In this study, a 6-liter fixed film bioreactor was used to examine biodegradation of phthalic acid (PA) and dimethyl phthalate (DMP) in synthetic wastewater. Effect on the process of two operating factors, namely hydraulic retention time (HRT) (at four levels ranging between 6 and 48 h) and initial phthalate concentrations (at six levels ranging from 10mg to 500 mg/l), was investigated. The process was stable at all operating conditions, except for the condition with influent PA and DMP of 500 mg/l and HRT of 6h. More than 95% removal efficiency was achieved for the conditions with HRT longer than 10h. Remarkable amount of DMP (398 mg/kg of sludge) was adsorbed on the biomass due to its higher hydrophobicity compared to PA (171 mg/kg). The kinetic parameters (mu(m,)K(s), Y and K(d)) were determined and compared for both substrates, PA and DMP.

40 CFR 721.2465 - Xanthylium, 9-(2-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate.

Code of Federal Regulations, 2013 CFR

2013-07-01

...)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. 721.2465 Section 721.2465 Protection of...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. (a) Chemical substance and significant...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate (PMN P-00-1195; CAS No. 26694-69-9) is...

40 CFR 721.2465 - Xanthylium, 9-(2-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate.

Code of Federal Regulations, 2012 CFR

2012-07-01

...)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. 721.2465 Section 721.2465 Protection of...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. (a) Chemical substance and significant...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate (PMN P-00-1195; CAS No. 26694-69-9) is...

40 CFR 721.2465 - Xanthylium, 9-(2-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate.

Code of Federal Regulations, 2011 CFR

2011-07-01

...)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. 721.2465 Section 721.2465 Protection of...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. (a) Chemical substance and significant...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate (PMN P-00-1195; CAS No. 26694-69-9) is...

40 CFR 721.2465 - Xanthylium, 9-(2-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate.

Code of Federal Regulations, 2014 CFR

2014-07-01

...)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. 721.2465 Section 721.2465 Protection of...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate. (a) Chemical substance and significant...-(ethoxycarbonyl)phenyl)-3,6-bis(ethylamino)-2,7-dimethyl-, ethyl sulfate (PMN P-00-1195; CAS No. 26694-69-9) is...

40 CFR 721.10055 - 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. 721.10055 Section 721.10055 Protection of...-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. (a) Chemical substance and...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts (PMN P-03-46; CAS No. 136504-87-5) is subject to...

40 CFR 721.10055 - 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. 721.10055 Section 721.10055 Protection of...-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. (a) Chemical substance and...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts (PMN P-03-46; CAS No. 136504-87-5) is subject to...

40 CFR 721.10055 - 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. 721.10055 Section 721.10055 Protection of...-amino-N-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts. (a) Chemical substance and...-(carboxymethyl)-N,N-dimethyl-, N-soya acyl derivs., inner salts (PMN P-03-46; CAS No. 136504-87-5) is subject to...

40 CFR 721.10174 - 1-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-peanut-oil acyl derivs., inner salts.

Code of Federal Regulations, 2011 CFR

2011-07-01

...-(carboxymethyl)-N,N-dimethyl-, N-peanut-oil acyl derivs., inner salts. 721.10174 Section 721.10174 Protection of...-amino-N-(carboxymethyl)-N,N-dimethyl-, N-peanut-oil acyl derivs., inner salts. (a) Chemical substance...-Propanaminium, 3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-peanut-oil acyl derivs., inner salts (PMN P-04-139...

Solid sorbents for removal of carbon dioxide from gas streams at low temperatures

DOEpatents

Sirwardane, Ranjani V.

2005-06-21

New low-cost CO.sub.2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO.sub.2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35.degree. C.

Synthesis of ketones from biomass-derived feedstock.

PubMed

Meng, Qinglei; Hou, Minqiang; Liu, Huizhen; Song, Jinliang; Han, Buxing

2017-01-31

Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H 2 O/CH 2 Cl 2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H 2 O/CH 2 Cl 2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass.

Chemical composition, antioxidant activity and larvicidal effects of essential oil from leaves of Apium graveolens.

PubMed

Nagella, Praveen; Ahmad, Ateeque; Kim, Sun-Jin; Chung, Ill-Min

2012-04-01

The leaves of Apium graveolens were extracted and the essential oil composition, immunotoxicity effects, and antioxidant activity were studied. The analyses were conducted by gas chromatography and mass spectroscopy (GC-MS), which revealed the essential oils of A. graveolens leaves. Twenty-eight components, representing 73.72% of the total oil were identified from the leaves. The major components are 4-chloro-4,4-dimethyl-3-(1-imidazolyl)-valerophenone (19.90%), 1-dodecanol (16.55%), 9-octadecen-12-ynoic acid, methyl ester (4.93%), ethyl 4,4-D2-N-hexyl ether (4.11%), 3-(hydroxymethyl)-1-phenyl-1-heptadecyn-3-ol (3.28%), 1,4-methano-1H-indene, octahydro-4-methyl-8-methylene-7-(1-methylethyl)-, [1S-(1α,3αα,4α,7α,7αα)]- (2.99%), 3,4-dihydro-2H-1,5-(3″-t-butyl)benzodioxepine (2.56%), Z-10-tetradecen-1-ol acetate (2.53%), 9H-pyrrolo[3',4':3,4]pyrrolo[2,1-α]phthalazine-9, 11(10H)-dione, 10-ethyl-8-phenyl (2.07%). The leaf oil had significant toxic effects against the larvae of A. aegypti with an LC(50) value of 59.32 ppm and an LC(90) value of 127.69 ppm. The essential oil from the A. graveolens leaves was investigated for scavenging of the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical activity and the results demonstrate that the essential oil from the A. graveolens has potential as a natural antioxidant and thus inhibit unwanted oxidation process. The above data indicate that the major compounds may play an important role in the toxicity of essential oils and also as natural antioxidant.

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

NASA Astrophysics Data System (ADS)

Bacmann, A.; Faure, A.

2015-05-01

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

Volatile organic compound emissions from green waste composting: Characterization and ozone formation

NASA Astrophysics Data System (ADS)

Kumar, Anuj; Alaimo, Christopher P.; Horowitz, Robert; Mitloehner, Frank M.; Kleeman, Michael J.; Green, Peter G.

2011-04-01

Composting of green waste separated from the disposed solid waste stream reduces biodegradable inputs into landfills, and contributes valuable soil amendments to agriculture. Agencies in regions with severe air quality challenges, such as California's San Joaquin Valley (SJV), have raised concerns about gases emitted during the composting process, which are suspected to contribute to persistent high levels of ground-level ozone formation. The goal of the current study is to thoroughly characterize volatile organic compound (VOC) emissions from green waste compost piles of different ages (fresh tipped piles, 3-6 day old windrows, and 2-3 week old windrows). Multiple sampling and analytical approaches were applied to ensure the detection of most gaseous organic components emitted. More than 100 VOCs were detected and quantified in this study, including aliphatic alkanes, alkenes, aromatic hydrocarbons, biogenic organics, aldehydes, ketones, alcohols, furans, acids, esters, ether, halogenated hydrocarbons and dimethyl disulfide (DMDS). Alcohols were found to be the dominating VOC in the emissions from a compost pile regardless of age, with fluxes ranging from 2.6 to 13.0 mg m -2 min -1 with the highest emissions coming from the younger composting windrows (3-6 days). Average VOC emissions other than alcohols were determined to be 2.3 mg m -2 min -1 from younger windows, which was roughly two times higher than either the fresh tipping pile (1.2 mg m -2 min -1) or the older windrows (1.4 mg m -2 min -1). It was also observed that the older windrows emit a slightly larger proportion of more reactive compounds. Approximately 90% of the total VOCs were found to have maximum incremental reactivity of less than 2. Net ozone formation potential of the emissions was also assessed.

Antioxidant properties of dimethyl sulfoxide and its viability as a solvent in the evaluation of neuroprotective antioxidants.

PubMed

Sanmartín-Suárez, Carolina; Soto-Otero, Ramón; Sánchez-Sellero, Inés; Méndez-Álvarez, Estefanía

2011-01-01

Dimethyl sulfoxide is an amphiphilic compound whose miscibility with water and its ability to dissolve lipophilic compounds make it an appreciated solvent in biomedical research. However, its reported antioxidant properties raise doubts about its use as a solvent in evaluating new antioxidants. The goal of this investigation was to evaluate its antioxidant properties and carry out a comparative study on the antioxidant properties of some known neuroprotective antioxidants in the presence and absence of dimethyl sulfoxide. The antioxidant properties of dimethyl sulfoxide were studied in rat brain homogenates by determining its ability to reduce both lipid peroxidation (TBARS formation) and protein oxidation (increase in protein carbonyl content and decrease in free thiol content) induced by ferrous chloride/hydrogen peroxide. Its ability to reduce the production of hydroxyl radicals by 6-hydroxydopamine autoxidation was also estimated. The same study was also performed with three known antioxidants (α-phenyl-N-tert-butylnitrone; 2-methyl-2-nitrosopropane; 5,5-dimethyl-1-pyrroline N-oxide) in the presence and absence of dimethyl sulfoxide. Our results showed that dimethyl sulfoxide is able to reduce both lipid peroxidation and protein carbonyl formation induced by ferrous chloride/hydrogen peroxide in rat brain homogenates. It can also reduce the production of hydroxyl radicals during 6-hydroxydopamine autoxidation. However, it increases the oxidation of protein thiol groups caused by ferrous chloride/hydrogen peroxide in rat brain homogenate. Despite the here reported antioxidant and pro-oxidant properties of dimethyl sulfoxide, the results obtained with α-phenyl-N-tert-butylnitrone, 2-methyl-2-nitrosopropane, and 5,5-dimethyl-1-pyrroline N-oxide corroborate the antioxidant properties attributed to these compounds and support the potential use of dimethyl sulfoxide as a solvent in the study of the antioxidant properties of lipophilic compounds. Dimethyl sulfoxide is a very useful solvent that may be used at relatively low concentrations in the development of new antioxidants with neuroprotective properties. Copyright © 2010 Elsevier Inc. All rights reserved.

A new route to synthesize aryl acetates from carbonylation of aryl methyl ethers

PubMed Central

Yang, Youdi; Li, Shaopeng; Han, Buxing

2018-01-01

Ether bond activation is very interesting because the synthesis of many valuable compounds involves conversion of ethers. Moreover, C–O bond cleavage is also very important for the transformation of biomass, especially lignin, which abundantly contains ether bonds. Developing efficient methods to activate aromatic ether bonds has attracted much attention. However, this is a challenge because of the inertness of aryl ether bonds. We proposed a new route to activate aryl methyl ether bonds and synthesize aryl acetates by carbonylation of aryl methyl ethers. The reaction could proceed over RhCl3 in the presence of LiI and LiBF4, and moderate to high yields of aryl acetates could be obtained from transformation of various aryl methyl ethers with different substituents. It was found that LiBF4 could assist LiI to cleave aryl methyl ether bonds effectively. The reaction mechanism was proposed by a combination of experimental and theoretical studies. PMID:29795781

Removal of dimethyl sulfide by the combination of non-thermal plasma and biological process.

PubMed

Wei, Z S; Li, H Q; He, J C; Ye, Q H; Huang, Q R; Luo, Y W

2013-10-01

A bench scale system integrated with a non-thermal plasma (NTP) and a biotricking filtration (BTF) unit for the treatment of gases containing dimethyl sulfide (DMS) was investigated. DMS removal efficiency in the integrated system was up to 96%. Bacterial communities in the BTF were assessed by PCR-DGGE, which play the dominant role in the biological processes of metabolism, sulfur oxidation, sulfate-reducing and carbon oxidation. The addition of ozone from NTP made microbial community in BTF more complicated and active for DMS removal. The NTP oxidize DMS to simple compounds such as methanol and carbonyl sulfide; the intermediate organic products and DMS are further oxidized to sulfate, carbon dioxide, water vapors by biological degradation. These results show that NTP-BTF is achievable and open new possibilities for applying the integrated with NTP and BTF to odour gas treatment. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.