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.

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.

Novel Small Molecules Disabling the IL-6/IL-6R/GP130 Heterohexamer Complex

DTIC Science & Technology

2013-10-01

formylated at the C4 position using Vilsmeier-Haack conditions. At this stage, Wittig olefination of the aldehyde and hydrogenation of the resulting olefin...butyllithium and acetaldehyde. The resulting alcohol was subsequently oxidized to the methyl ketone with PDC. Bromination of the ketone could then be...protection of 2,4-dihydroxybenzaldehyde as the methoxymethyl (MOM) ether derivative. Conversion of the aldehyde to the styrene derivative via Wittig

Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites.

PubMed

Korchev, A S; Shulyak, T S; Slaten, B L; Gale, W F; Mills, G

2005-04-28

Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.

VOLATILE ORGANIC CHEMICALS IN 10 PUBLIC-ACCESS BUILDINGS

EPA Science Inventory

The U.S. EPA carried out studies of indoor air quality in 10 buildings. Qualitative analysis identified over 200 aromatics, halogens, esters, alcohols, phenols, ethers, ketones, aldehydes, and epoxides, in addition to several hundred aliphatic hydrocarbons. The total organic load...

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.; Gillette, J. S.; Clemett, S. J.; Zare, R. N.

1999-01-01

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

QUANTITATIVE ANALYSIS OF 68 POLAR COMPOUNDS FROM TEN CHEMICAL CLASSES BY DIRECT AQUEOUS INJECTION GAS CHROMATOGRAPHY

EPA Science Inventory

Porous polymer packings have been used successfully in many applications of direct aqueous injection gas chromatography. The authors have expanded the use of aqueous injection to the quantitative analysis of 68 alcohols, acetates, ketones, ethers, sulfides, aldehydes, diols, dion...

Low dielectric fluorinated poly(phenylene ether ketone) film and coating

NASA Technical Reports Server (NTRS)

Cassidy, Patrick E. (Inventor); Tullos, Gordon L. (Inventor); St.clair, Anne K. (Inventor)

1990-01-01

The present invention relates to film and coating materials prepared from novel fluorinated poly(phenylene ether ketones). A fluorinated poly(phenylene ether ketone) is prepared by reacting a bisphenol with 1,1,1,3,3,3 hexafluoro-2,2-bis 4-(4-halobenzoyl) phenyl propane (wherein halo is fluoro or chloro), which is a novel monomer formed as the reaction product of halobenzene (wherein halo is fluoro or chloro) and 1,1,1,3,3,3 hexafluoro-2,2-bis (p-chloro formyl phenyl) propane. Especially beneficial results of this invention are that films and coating materials prepared from the novel fluorinated poly(phenylene ether ketone) are essentially optically transparent/colorless and have a lower dielectric constant than otherwise comparable, commercially available poly(phenylene ether ketones). Moreover, unlike the otherwise comparable commercially available materials, the novel fluorinated poly(phenylene ether ketones) of the present invention can be solution cast or sprayed to produce the films and coatings. Furthermore, the long term thermal stability of the polymers of the present invention is superior to that of the commercially available materials.

Preparation and Characterization of Various Poly(ether ether ketone) Containing Imidazolium Moiety for Anion Exchange Membrane Fuel Cell Application.

PubMed

Lee, Byeol-Nim; Son, Tae Yang; Park, Chi Hoon; Kim, Tae Hyun; Nam, Sang Yong

2018-09-01

In this study, various poly(ether ether ketone) were synthesized using three different monomers and the imidazolium group was introduced into synthesized poly(ether ether ketone)s by using substitution reaction. Synthesized polymers were used to prepare anion exchange membranes and to evaluate its properties. Thermal, chemical and structural properties were carried out using thermogravimetric analysis, nuclear magnetic resonance. The anion exchange membranes with different imidazolium moieties were characterized by several different analytical techniques such as water up take, ion exchange capacity, hydroxide conductivity for checking the possibility to apply the anion exchange membrane fuel cell. Consequently, results of characterization were studied to understand the correlation between stabilities of the membrane and functional group and polymer backbone structures. And we confirm membrane performance was improved by increasing imidazolium cation groups.

Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

PubMed

Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

2011-07-14

Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

Ultraviolet-induced surface grafting of octafluoropentyl methacrylate on polyether ether ketone for inducing antibiofilm properties.

PubMed

Amdjadi, Parisa; Nojehdehian, Hanieh; Najafi, Farhood; Ghasemi, Amir; Seifi, Massoud; Dashtimoghadam, Erfan; Fahimipour, Farahnaz; Tayebi, Lobat

2017-07-01

Since octafluoropentyl methacrylate is an antifouling polymer, surface modification of polyether ether ketone with octafluoropentyl methacrylate is a practical approach to obtaining anti-biofilm biocompatible devices. In the current study, the surface treatment of polyether ether ketone by the use of ultraviolet irradiation, so as to graft (octafluoropentyl methacrylate) polymer chains, was initially implemented and then investigated. The Fourier-transform infrared and nuclear magnetic resonance spectra corroborated the appearance of new signals associated with the fluoroacrylate group. Thermogravimetric curves indicated enhanced asymmetry in the polymer structure due to the introduction of the said new groups. Measuring the peak area in differential scanning calorimetry experiments also showed additional bond formation. Static water contact angle measurements indicated a change in wettability to the more hydrophobic surface. The polyether ether ketone-octafluoropentyl methacrylate surface greatly reduced the protein adsorption. This efficient method can modulate and tune the surface properties of polyether ether ketone according to specific applications.

Influence of Layer Thickness and Raster Angle on the Mechanical Properties of 3D-Printed PEEK and a Comparative Mechanical Study between PEEK and ABS.

PubMed

Wu, Wenzheng; Geng, Peng; Li, Guiwei; Zhao, Di; Zhang, Haibo; Zhao, Ji

2015-09-01

Fused deposition modeling (FDM) is a rapidly growing 3D printing technology. However, printing materials are restricted to acrylonitrile butadiene styrene (ABS) or poly (lactic acid) (PLA) in most Fused deposition modeling (FDM) equipment. Here, we report on a new high-performance printing material, polyether-ether-ketone (PEEK), which could surmount these shortcomings. This paper is devoted to studying the influence of layer thickness and raster angle on the mechanical properties of 3D-printed PEEK. Samples with three different layer thicknesses (200, 300 and 400 μm) and raster angles (0°, 30° and 45°) were built using a polyether-ether-ketone (PEEK) 3D printing system and their tensile, compressive and bending strengths were tested. The optimal mechanical properties of polyether-ether-ketone (PEEK) samples were found at a layer thickness of 300 μm and a raster angle of 0°. To evaluate the printing performance of polyether-ether-ketone (PEEK) samples, a comparison was made between the mechanical properties of 3D-printed polyether-ether-ketone (PEEK) and acrylonitrile butadiene styrene (ABS) parts. The results suggest that the average tensile strengths of polyether-ether-ketone (PEEK) parts were 108% higher than those for acrylonitrile butadiene styrene (ABS), and compressive strengths were 114% and bending strengths were 115%. However, the modulus of elasticity for both materials was similar. These results indicate that the mechanical properties of 3D-printed polyether-ether-ketone (PEEK) are superior to 3D-printed ABS.

Influence of Layer Thickness and Raster Angle on the Mechanical Properties of 3D-Printed PEEK and a Comparative Mechanical Study between PEEK and ABS

PubMed Central

Wu, Wenzheng; Geng, Peng; Li, Guiwei; Zhao, Di; Zhang, Haibo; Zhao, Ji

2015-01-01

Fused deposition modeling (FDM) is a rapidly growing 3D printing technology. However, printing materials are restricted to acrylonitrile butadiene styrene (ABS) or poly (lactic acid) (PLA) in most Fused deposition modeling (FDM) equipment. Here, we report on a new high-performance printing material, polyether-ether-ketone (PEEK), which could surmount these shortcomings. This paper is devoted to studying the influence of layer thickness and raster angle on the mechanical properties of 3D-printed PEEK. Samples with three different layer thicknesses (200, 300 and 400 μm) and raster angles (0°, 30° and 45°) were built using a polyether-ether-ketone (PEEK) 3D printing system and their tensile, compressive and bending strengths were tested. The optimal mechanical properties of polyether-ether-ketone (PEEK) samples were found at a layer thickness of 300 μm and a raster angle of 0°. To evaluate the printing performance of polyether-ether-ketone (PEEK) samples, a comparison was made between the mechanical properties of 3D-printed polyether-ether-ketone (PEEK) and acrylonitrile butadiene styrene (ABS) parts. The results suggest that the average tensile strengths of polyether-ether-ketone (PEEK) parts were 108% higher than those for acrylonitrile butadiene styrene (ABS), and compressive strengths were 114% and bending strengths were 115%. However, the modulus of elasticity for both materials was similar. These results indicate that the mechanical properties of 3D-printed polyether-ether-ketone (PEEK) are superior to 3D-printed ABS. PMID:28793537

N-Triflylthiophosphoramide Catalyzed Enantioselective Mukaiyama Aldol Reaction of Aldehydes with Silyl Enol Ethers of Ketones

PubMed Central

Cheon, Cheol Hong; Yamamoto, Hisashi

2010-01-01

The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to Brønsted acid itself depending on the reaction temperature. PMID:20465277

N-triflylthiophosphoramide catalyzed enantioselective Mukaiyama aldol reaction of aldehydes with silyl enol ethers of ketones.

PubMed

Cheon, Cheol Hong; Yamamoto, Hisashi

2010-06-04

The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to the Brønsted acid itself depending on the reaction temperature.

27 CFR 21.32 - Formula No. 1.

Code of Federal Regulations, 2012 CFR

2012-04-01

... methyl isobutyl ketone; 1 gallon of mixed isomers of nitropropane; or 1 gallon of methyl n- butyl ketone.... 551.Acetaldehyde. 552.Other aldehydes. 561.Ethyl ether. 562.Other ethers. 571.Ethylene dibromide. 572...

27 CFR 21.32 - Formula No. 1.

Code of Federal Regulations, 2010 CFR

2010-04-01

... methyl isobutyl ketone; 1 gallon of mixed isomers of nitropropane; or 1 gallon of methyl n- butyl ketone.... 551.Acetaldehyde. 552.Other aldehydes. 561.Ethyl ether. 562.Other ethers. 571.Ethylene dibromide. 572...

27 CFR 21.32 - Formula No. 1.

Code of Federal Regulations, 2011 CFR

2011-04-01

... methyl isobutyl ketone; 1 gallon of mixed isomers of nitropropane; or 1 gallon of methyl n- butyl ketone.... 551.Acetaldehyde. 552.Other aldehydes. 561.Ethyl ether. 562.Other ethers. 571.Ethylene dibromide. 572...

27 CFR 21.32 - Formula No. 1.

Code of Federal Regulations, 2013 CFR

2013-04-01

... methyl isobutyl ketone; 1 gallon of mixed isomers of nitropropane; or 1 gallon of methyl n- butyl ketone.... 551.Acetaldehyde. 552.Other aldehydes. 561.Ethyl ether. 562.Other ethers. 571.Ethylene dibromide. 572...

27 CFR 21.32 - Formula No. 1.

Code of Federal Regulations, 2014 CFR

2014-04-01

... methyl isobutyl ketone; 1 gallon of mixed isomers of nitropropane; or 1 gallon of methyl n- butyl ketone.... 551.Acetaldehyde. 552.Other aldehydes. 561.Ethyl ether. 562.Other ethers. 571.Ethylene dibromide. 572...

Inorganic Halogen Oxidizer Research

DTIC Science & Technology

1975-02-26

K. 0. Christe and C. J. Schack, Advances Inorg. Chem. Radiochem. 15. "The NF * Radical Cation. Esr Studies of Radiation Effects in NF„+ Salts...and 25°) in a wide variety of polar and nonpolar solvents, such as aqueous solutions, alcohols, ketones , esters, ethers , and aromatic and halogenated... Studies of Radiation Effects in NF, Salts = 4 S. P. Mishra, M. C R. Symons, K. 0. Christe, R. D. Wilson and R. I. Wagner Received. . . August .9

One-pot synthesis of 2,5-dihydropyrroles from terminal alkynes, azides, and propargylic alcohols by relay actions of copper, rhodium, and gold.

PubMed

Miura, Tomoya; Tanaka, Takamasa; Matsumoto, Kohei; Murakami, Masahiro

2014-12-01

Relay actions of copper, rhodium, and gold formulate a one-pot multistep pathway, which directly gives 2,5-dihydropyrroles starting from terminal alkynes, sulfonyl azides, and propargylic alcohols. Initially, copper-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with propargylic alcohols under the catalysis of rhodium. The resulting alkenyl propargyl ethers subsequently undergo the thermal Claisen rearrangement to give α-allenyl-α-amino ketones. Finally, a gold catalyst prompts 5-endo cyclization to produce 2,5-dihydropyrroles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ketimine modifications as a route to novel amorphous and derived semicrystalline poly(arylene ether ketone) homo- and copolymers

NASA Technical Reports Server (NTRS)

Mohanty, D. K.; Lowery, R. C.; Lyle, G. D.; Mcgrath, J. E.

1987-01-01

A series of amine terminal amorphous poly(arylene ether ketone) oligomers of controlled molecular weights (2-15 K) were synthesized. These oligomers have been found to undergo 'self-crosslinking' reactions upon heating above 220 C, via the reaction of the terminal amine groups with the in-chain keto carbonyl functionalities. The resulting networks are ductile, chemically resistant, and nonporous. The networks obtained via generated ketimine functionality were characterized by solid state NMR. They have also been found to be remarkably stable toward hydrolysis. Ketimine functional bishalide monomers have also been synthesized. Such monomers have been utilized to synthesize a wide variety of amorphous poly(arylene ether) ketimine polymers. A high molecular weight hydroquinone functional poly(arylene ether) ketimine has been acid treated to regenerate a poly(arylene ether ketone) backbone in solution. This novel procedure thus allows for the synthesis of important matrix resins under relatively mild conditions.

Compendium of Post-Failure Analysis Techniques for Composite Materials.

DTIC Science & Technology

1987-01-01

HHdrocarbon 285.0 Ether or alcohol 286.5 Ketone 288.0 Ester 288.8 (Ref. 5) Figure 3-37. Carbon Peak Shifts in XPS 5-B70227Rt -130 " Hydrocarbon...structure overlays composite material since neutrons are not as attenuated by metal as X-rays, and are relatively sensitive to poly - meric materials...Thermal Aging 3-18 Glass Transition Temperature Determination - 3-37 TMA Penetration Test Setup 3-19 Glass Transition Temperature Determination - 3-37 TMA

Radical-induced generation of small silver particles in SPEEK/PVA polymer films and solutions: UV-Vis, EPR, and FT-IR studies.

PubMed

Korchev, A S; Konovalova, T; Cammarata, V; Kispert, L; Slaten, L; Mills, G

2006-01-03

The present study is centered on the processes involved in the photochemical generation of nanometer-sized Ag particles via illumination at 350 nm of aqueous solutions and cross linked films containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol). Optical and electron paramagnetic resonance experiments, including electron nuclear double resonance data, proved conclusively that the photogenerated chromophore exhibiting a band with lambda(max) = 565 nm is an alpha-hydroxy aromatic (ketyl) radical of the polymeric ketone. This reducing species was produced by illumination of either solutions or films, but the radical lifetime extended from minutes in the fluid phase to hours in the solid. Direct evidence is presented that this long-lived chromophore reduces Ag(I), Cu(II), and Au(III) ions in solution. A rate constant of k = 1.4 x 10(3) M(-)(1) s(-)(1) was obtained for the reduction of Ag(+) by the ketyl radical from the post-irradiation formation of Ag crystallites. FTIR results confirmed that the photoprocess yielding polymeric ketyl radicals involves a reaction between the macromolecules. The photochemical oxidation of the polymeric alcohol, as well as the formation of light-absorbing macromolecular products and polyols, indicates that the sulfonated polyketone experienced transformations similar to those encountered during illumination of the benzophenone/2-propanol system.

Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction

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

Ren, Shoujie; Ye, Philip; Borole, Abhijeet P

Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less

Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction

DOE PAGES

Ren, Shoujie; Ye, Philip; Borole, Abhijeet P

2017-01-05

Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less

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.

The Determination of the Smoke Hazards Resulting from the Burning of Shipboard Materials Utilized by the US Navy.

DTIC Science & Technology

1981-08-31

Interior Paairt r’ts RorzotalSapleIeun Forle Tranduer Figure I. Combustion Products Test Chamber. .. 2. *Sold hda 0 Ol~n kb 3’. 8.iIdg IN= W I Vll ue2...hydrocarbons (alkanes, alkenes, and alkynes), alcohols, aldehydes, ketones, ethers, carboxylic acids , aromatic hydrocarbons, polycyclic aromatic hydrocarbons...carboxylic acids , a few nitriles, acetaldehyde, and acetone. A few exotic fluorine containing organic compounds have unusually low refractive indices for

Synthesis of hydrocarbons by CO2 fluid conversion with hydrogen: Experimental modeling at 7.8 GPa and 1350°C

NASA Astrophysics Data System (ADS)

Sokol, A. G.; Tomilenko, A. A.; Bul'bak, T. A.; Sobolev, N. V.

2017-12-01

Synthesis of hydrocarbons by the interaction of a CO2 fluid with hydrogen mantle domains has been simulated in an experiment at 7.8 GPa and 1350°C. The synthesized fluid contains mainly aldehydes; lower amounts of ketones, alcohols, esters, and ethers; as well as noticeable amounts of isobutane and butane, alkenes, arenes, and polycyclic aromatic and heterocyclic hydrocarbons. The fluid is compositionally close to volatiles found in inclusions from mantle olivines and picroilmenites.

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.

Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors

DOE PAGES

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.; ...

2017-06-21

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

Polyether ether ketone encased monolith frits made of polyether ether ketone tubing with a 0.25 mm opening resulting in an improved separation performance in liquid chromatography.

PubMed

Park, Sin Young; Cheong, Won Jo

2016-05-01

Tiny polyether ether ketone encased monolith frits have been prepared by modified catalytic sulfonation of the inner surface of polyether ether tubing (1.6 mm od, 0.25 mm id) followed by modified formation of organic monolith and cutting of the tubing into slices. The frit was placed below the central hole of the column outlet union and supported by a combination of a silica capillary (0.365 mm od, 0.05 mm id) and a polyether ether ketone sleeve (1.6 mm od, 0.38 mm id) tightened with a nut and a ferrule when the column was packed to prevent sinking of the frit element into the union hole (0.25 mm opening) otherwise. The column packed this way with the frits investigated in this study has shown better separation performance owing to the reduced frit volume in comparison to the column packed with a commercial stainless-steel screen frit. This study establishes the strategy of disposable microcolumns in which cheap disposable frits are used whenever the column is re-packed to yield columns of even better chromatographic performance than the columns with commercial frits. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel proton exchange membranes based on structure-optimized poly(ether ether ketone ketone)s and nanocrystalline cellulose

NASA Astrophysics Data System (ADS)

Ni, Chuangjiang; Wei, Yingcong; Zhao, Qi; Liu, Baijun; Sun, Zhaoyan; Gu, Yan; Zhang, Mingyao; Hu, Wei

2018-03-01

Two sulfonated fluorenyl-containing poly(ether ether ketone ketone)s (SFPEEKKs) were synthesized as the matrix of composite proton exchange membranes by directly sulfonating copolymer precursors comprising non-sulfonatable fluorinated segments and sulfonatable fluorenyl-containing segments. Surface-modified nanocrystalline cellulose (NCC) was produced as the "performance-enhancing" filler by treating the microcrystalline cellulose with acid. Two families of SFPEEKK/NCC nanocomposite membranes with various NCC contents were prepared via a solution-casting procedure. Results revealed that the insertion of NCC at a suitable ratio could greatly enhance the proton conductivity of the pristine membranes. For example, the proton conductivity of SFPEEKK-60/NCC-4 (SFPEEKK with 60% fluorenyl segments in the repeating unit, and inserted with 4% NCC) composite membrane was as high as 0.245 S cm-1 at 90 °C, which was 61.2% higher than that of the corresponding pure SFPEEKK-60 membrane. This effect could be attributed to the formation of hydrogen bond networks and proton conduction paths through the interaction between -SO3H/-OH groups on the surface of NCC particles and -SO3H groups on the SFPEEKK backbones. Furthermore, the chemically modified NCC filler and the optimized chemical structure of the SFPEEKK matrix also provided good dimensional stability and mechanical properties of the obtained nanocomposites. In conclusion, these novel nanocomposites can be promising proton exchange membranes for fuel cells at moderate temperatures.

Tandem cyclopropanation with dibromomethane under Grignard conditions.

PubMed

Brunner, Gerhard; Eberhard, Laura; Oetiker, Jürg; Schröder, Fridtjof

2008-10-03

Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from alpha-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.

Widely different luminescence lifetimes of the [Delta]RRR, [Lambda]SSS and the [Delta]RRS, [Lambda]SSR diastereomers of fac-tris[(8-quinolyl)phenylmethylsily] iridium(III): Exciplex formation with solvents by distinct [sigma]-donor and [pi]-acceptor binding mechanisms

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

Djurovich, P.I.; Cook, W.; Joshi, R.

1994-01-13

Luminescence lifetimes ([tau][sub m]) of the [sigma]-bond-to-ligand charge-transfer (SBLCT) excited states of two diastereomers of fac-tris[(8-quinolyl)phenylmethylsilyl]iridium(III) differ by about a factor of 2 and are strongly solvent dependent. The [tau][sub m] values of the more symmetric [Delta]RRR, [Lambda]SSS diastereomer (A) are generally longer than those of the less symmetric [Delta]RRS, [Lambda]SSR diastereomer (B); [tau][sub m]'s of both diastereomers are substantially shortened relative to their values in aliphatic hydrocarbons by exciplex formation with a variety of weakly coordinating solvents including aromatic hydrocarbons, olefins, ethers, ketones, alcohols, and nitriles. Quenching constants (k[sub q]) due to exciplex formation are found to be muchmore » larger for B than they are for A in the [sigma]-donor solvents (cyclic ethers, ketones, alcohols, and nitriles); however, k[sub q] values of B are slightly smaller than those of A in [pi]-acceptor solvents (aromatic hydrocarbons, olefins). The results suggest that [sigma]-donor solvents form exciplexes by binding at the metal center, whereas [pi]-acceptor solvents bind at a quinolyl radical anion ligand site. A and B may prove useful as luminescent environmental probes which can distinguish between [sigma]-donor and [pi]-acceptor binding sites. 19 refs., 1 fig., 1 tab.« less

High-Performance Synthetic Fibers for Composites

DTIC Science & Technology

1992-04-01

under evaluation today include polyether ether ketone , polyamide, 23 polyamideimide, polyimide, polysulfone, and polyphenylene sulfide. Epoxy resins...shrinkage under intense neutron radiation . This attribute, together with other properties of high-temperature strength, toughness, and low nuclear...and (2) liquid or solid resins cross-linked with other esters in chopped-fiber and mineral-filled molding compounds. Polyether ether ketone (PEEK) A

Lipase-catalyzed kinetic resolution of novel antitubercular benzoxazole derivatives.

PubMed

Łukowska-Chojnacka, Edyta; Kowalkowska, Anna; Napiórkowska, Agnieszka

2018-04-01

Novel benzoxazole derivatives were synthesized, and their antitubercular activity against sensitive and drug-resistant Mycobacterium tuberculosis strains (M. tuberculosis H 37 Rv, M. tuberculosis sp. 210, M. tuberculosis sp. 192, Mycobacterium scrofulaceum, Mycobacterium intracellulare, Mycobacterium fortuitum, Mycobacterium avium, and Mycobacterium kansasii) was evaluated. The chemical step included preparation of ketones, alcohols, and esters bearing benzoxazole moiety. All racemic mixtures of alcohols and esters were separated in Novozyme SP 435-catalyzed transesterification and hydrolysis, respectively. The transesterification reactions were carried out in various organic solvents (tert-butyl methyl ether, toluene, diethyl ether, and diisopropyl ether), and depending on the solvent, the enantioselectivity of the reactions ranged from 4 to >100. The enzymatic hydrolysis of esters was performed in 2 phase tert-butyl methyl ether/phosphate buffer (pH = 7.2) system and provided also enantiomerically enriched products (ee 88-99%). The antitubercular activity assay has shown that synthesized compounds exhibit an interesting antitubercular activity. Racemic mixtures of alcohols, (±)-4-(1,3-benzoxazol-2-ylsulfanyl)butan-2-ol ((±)-3a), (±)-4-[(5-bromo-1,3-benzoxazol-2-yl)sulfanyl]butan-2-ol ((±)-3b), and (±)-4-[(5,7-dibromo-1,3-benzoxazol-2-yl)sulfanyl]butan-2-ol ((±)-3c), displayed as high activity against M. scrofulaceum, M. intracellulare, M. fortuitum, and M. kansasii as commercially available antituberculosis drug-Isoniazid. Moreover, these compounds exhibited twice higher activity toward M. avium (MIC 12.5) compared with Isoniazid (MIC 50). © 2017 Wiley Periodicals, Inc.

Material with high dielectric constant, low dielectric loss, and good mechanical and thermal properties produced using multi-wall carbon nanotubes wrapped with poly(ether sulphone) in a poly(ether ether ketone) matrix

NASA Astrophysics Data System (ADS)

Zhang, Shuling; Wang, Hongsong; Wang, Guibin; Jiang, Zhenhua

2012-07-01

A material with high dielectric constant, low dielectric loss, and good mechanical and thermal properties was produced using multi-wall carbon nanotubes (MWCNTs) wrapped with poly(ether sulphone) (PES) dispersed in a poly(ether ether ketone) (PEEK) matrix. The material was fabricated using melt-blending, and MWCNT/PEEK composites show different degrees of improvement in the measured dielectric, mechanical, and thermal properties as compared to pure PEEK. This is attributed to the high conductivity of MWCNTs, the effect of wrapping MWCNTs with PES, the good dispersion of the wrapped MWCNTs in PEEK, and the strong interfacial adhesion between the wrapped MWCNTs and the PEEK.

Radiation polymerisable compositions containing 3-sorboyloxy-2-hydroxypropyl groups

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

Green, G.E.

1976-02-03

Compounds having at least three 3-sorboyloxy-2-hydroxypropyl groups directly attached to ether oxygen atoms are polymerised by exposure to actinic radiation, preferably in the presence of a sensitizer such as Michler's ketone or benzoin. The compounds may be obtained by the reaction either of sorbic acid with a substance having at least three glycidyl ether groups or of glycidyl sorbate with a substance having at least three phenolic or alcoholic hydroxyl groups: if desired, not all of the glycidyl groups may be consumed, so that, after actinically induced polymerisation, the epoxide-containing polymer may be cross-linked by reaction with a curing agentmore » for epoxide resins. The compounds are useful in making printed circuits or printing plates for offset printing.« less

Implant Failure After Motec Wrist Joint Prosthesis Due to Failure of Ball and Socket-Type Articulation-Two Patients With Adverse Reaction to Metal Debris and Polyether Ether Ketone.

PubMed

Karjalainen, Teemu; Pamilo, Konsta; Reito, Aleksi

2018-04-21

We describe 2 cases of articulation-related failures resulting in revision surgery after a Motec total wrist arthroplasty: one with an adverse reaction to metal debris and the other with an adverse reaction to polyether ether ketone. In the first patient, blood cobalt and chrome levels were elevated and magnetic resonance imaging showed clear signs of a pseudotumor. The other patient had an extensive release of polyether ether ketone particles into the surrounding synovia due to adverse wear conditions in the cup, leading to the formation of a fluid-filled cyst sac with a black lining and diffuse lymphocyte-dominated inflammation in the synovia. We recommend regular follow-up including x-rays, monitoring of cobalt and chrome ion levels, and a low threshold for cross-sectional imaging in patients who have undergone total wrist arthroplasty with a Motec joint prosthesis. Wear-related problems can also develop in implants in which polyether ether ketone is the bulk material. Copyright © 2018 American Society for Surgery of the Hand. Published by Elsevier Inc. All rights reserved.

Modeling Joint Effects of Mixtures of Chemicals on Microorganisms Using Quantitative Structure Activity Relationships

DTIC Science & Technology

1993-08-22

Cyclohexane Alk 74 133 26 Pentane Alk 70 150 27 Hexane Alk 38 47 28 Heptane Alk 18 58 29 Octane Alk 8 60 30 Bis (2-chloroethyl) ether Alc 1,600 3,025 31...Triethanolarnine Amni 900 741 SAro- aromatic; Hal- balogemmaed aliphatic; Alk - alkanes; Alc- alcohols, este’s, ketones and et Aji- amineL -5- Correlation...chemicals using laboratory grown activated sludge by synthetic feed. They adapted the OECD Method 209, using inhibition of oxygen uptake rate as the measure

Production of chemicals and fuels from biomass

DOEpatents

Qiao, Ming; Woods, Elizabeth; Myren, Paul; Cortright, Randy; Kania, John

2018-01-23

Methods, reactor systems, and catalysts are provided for converting in a continuous process biomass to fuels and chemicals, including methods of converting the water insoluble components of biomass, such as hemicellulose, cellulose and lignin, to volatile C.sub.2+O.sub.1-2 oxygenates, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, and mixtures thereof. In certain applications, the volatile C.sub.2+O.sub.1-2 oxygenates can be collected and used as a final chemical product, or used in downstream processes to produce liquid fuels, chemicals and other products.

Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

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

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH 3CN) 6 2+] andmore » [O 3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CH 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2015-02-11

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH 3CN) 6 2+] andmore » [O 3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CH 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

Evaluation of certain food additives.

PubMed

2009-01-01

This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, including flavouring agents, with a view to recommending acceptable daily intakes (ADIs) and to preparing specifications for identity and purity. The first part of the report contains a general discussion of the principles governing the toxicological evaluation and assessment of intake of food additives (in particular, flavouring agents). A summary follows of the Committee's evaluations of technical, toxicological and intake data for certain food additives (asparaginase from Aspergillus niger expressed in A. niger, calcium lignosulfonate (40-65), ethyl lauroyl arginate, paprika extract, phospholipase C expressed in Pichia pastoris, phytosterols, phytostanols and their esters, polydimethylsiloxane, steviol glycosides and sulfites [assessment of dietary exposure]) and 10 groups of related flavouring agents (aliphatic branched-chain saturated and unsaturated alcohols, aldehydes, acids and related esters; aliphatic linear alpha,beta-unsaturated aldehydes, acids and related alcohols, acetals and esters; aliphatic secondary alcohols, ketones and related esters; alkoxy-substituted allylbenzenes present in foods and essential oils and used as flavouring agents; esters of aliphatic acyclic primary alcohols with aliphatic linear saturated carboxylic acids; furan-substituted aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers; miscellaneous nitrogen-containing substances; monocyclic and bicyclic secondary alcohols, ketones and related esters; hydroxy- and alkoxy-substituted benzyl derivatives; and substances structurally related to menthol). Specifications for the following food additives were revised: canthaxanthin; carob bean gum and carob bean gum (clarified); chlorophyllin copper complexes, sodium and potassium salts; Fast Green FCF; guar gum and guar gum (clarified); iron oxides; isomalt; monomagnesium phosphate; Patent Blue V; Sunset Yellow FCF; and trisodium diphosphate. Re-evaluation of flavouring agents for which estimated intake was based on anticipated poundage data was carried out for 2-isopropyl- N,2,3-trimethylbutyramide (No. 1595) and L-monomenthyl glutarate (No. 1414). Annexed to the report are tables summarizing the Committee's recommendations for intakes and toxicological evaluations of the food additives considered.

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.

21 CFR 172.515 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2012 CFR

2012-04-01

...-hydroxyundecanoic acid γ-lactone; peach aldehyde; aldehyde C-14. Undecenal. 2-Undecanone; methyl nonyl ketone. 9.... Acetanisole; 4′-methoxyacetophenone. Acetophenone; methyl phenyl ketone. Allyl anthranilate. Allyl butyrate... ethyl ether. Benzyl formate. 3-Benzyl-4-heptanone; benzyl dipropyl ketone. Benzyl isobutyrate. Benzyl...

21 CFR 172.515 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2013 CFR

2013-04-01

...-hydroxyundecanoic acid γ-lactone; peach aldehyde; aldehyde C-14. Undecenal. 2-Undecanone; methyl nonyl ketone. 9.... Acetanisole; 4′-methoxyacetophenone. Acetophenone; methyl phenyl ketone. Allyl anthranilate. Allyl butyrate... ethyl ether. Benzyl formate. 3-Benzyl-4-heptanone; benzyl dipropyl ketone. Benzyl isobutyrate. Benzyl...

21 CFR 172.515 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2011 CFR

2011-04-01

...-hydroxyundecanoic acid γ-lactone; peach aldehyde; aldehyde C-14. Undecenal. 2-Undecanone; methyl nonyl ketone. 9.... Acetanisole; 4′-methoxyacetophenone. Acetophenone; methyl phenyl ketone. Allyl anthranilate. Allyl butyrate... ethyl ether. Benzyl formate. 3-Benzyl-4-heptanone; benzyl dipropyl ketone. Benzyl isobutyrate. Benzyl...

21 CFR 172.515 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2010 CFR

2010-04-01

...-hydroxyundecanoic acid γ-lactone; peach aldehyde; aldehyde C-14. Undecenal. 2-Undecanone; methyl nonyl ketone. 9.... Acetanisole; 4′-methoxyacetophenone. Acetophenone; methyl phenyl ketone. Allyl anthranilate. Allyl butyrate... ethyl ether. Benzyl formate. 3-Benzyl-4-heptanone; benzyl dipropyl ketone. Benzyl isobutyrate. Benzyl...

Fuel cell performance of pendent methylphenyl sulfonated poly(ether ether ketone ketone)s

NASA Astrophysics Data System (ADS)

Zhang, Hanyu; Stanis, Ronald J.; Song, Yang; Hu, Wei; Cornelius, Chris J.; Shi, Qiang; Liu, Baijun; Guiver, Michael D.

2017-11-01

Meta- and para-linked homopolymers bearing 3-methylphenyl (Me) pendent groups were postsulfonated to create sulfonated poly(ether ether ketone ketone) (SPEEKK) backbone isomers, which are referred to as Me-p-SPEEKK and Me-m-SPEEKK. Their thermal and oxidative stability, mechanical properties, dimensional stability, methanol permeability, and proton conductivity are characterized. Me-p-SPEEKK and Me-m-SPEEKK proton conductivities at 100 °C are 116 and 173 mS cm-1, respectively. Their methanol permeabilities are 3.3-3.9 × 10-7 cm2 s-1, and dimensional swelling at 100 °C is 16.4-17.5%. Me-p-SPEEKK and Me-m-SPEEKK were fabricated into membrane electrode assemblies (MEAs), and electrochemical properties were evaluated within a direct methanol fuel cell (DMFC) and proton-exchange membrane fuel cell (PEMFC). When O2 is used as the oxidant at 80 °C and 100% RH, the maximum power density of Me-m-SPEEKK reaches 657 mW cm-2, which is higher than those of Nafion 115 (552 mW cm-2). DMFC performance is 85 mW cm-2 at 80 °C with 2.0 M methanol using Me-p-SPEEKK due to its low MeOH crossover. In general, these electrochemical results are comparable to Nafion. These ionomer properties, combined with a potentially less expensive and scalable polymer manufacturing process, may broaden their potential for many practical applications.

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

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

Morphology and properties of amine terminated poly(arylene ether ketone) and poly(arylene ether sulfone) modified epoxy resin systems

NASA Technical Reports Server (NTRS)

Cecere, J. A.; Mcgrath, J. E.; Hedrick, J. L.

1986-01-01

Epoxy resin networks cured with DDS were modified by incorporating tough ductile thermoplastics such as the amine terminated polyether sulfones and amine terminated polyether ketones. Both linear copolymers were able to significantly improve the fracture toughness values at the 15 and 30 weight percent concentrations examined. These improvements in fracture toughness were achieved without any significant change in the flexural modulus.

Production of chemicals and fuels from biomass

DOEpatents

Woods, Elizabeth; Qiao, Ming; Myren, Paul; Cortright, Randy D.; Kania, John

2015-12-15

Described are methods, reactor systems, and catalysts for converting biomass to fuels and chemicals in a batch and/or continuous process. The process generally involves the conversion of water insoluble components of biomass, such as hemicellulose, cellulose and lignin, to volatile C.sub.2+O.sub.1-2 oxygenates, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, and mixtures thereof. In certain applications, the volatile C.sub.2+O.sub.1-2 oxygenates can be collected and used as a final chemical product, or used in downstream processes to produce liquid fuels, chemicals and other products.

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).

40 CFR Appendix A to Part 439 - Tables

Code of Federal Regulations, 2014 CFR

2014-07-01

... Isobutyraldehyde 1 Aldehydes. n-Heptane 1 Alkanes. n-Hexane 1 Diethylamine 1 Amines. Triethylamine Benzene... Methyl formate Tetrahydrofuran 1 Ethers. Isopropyl ether Acetone 1 Ketones. 4-Methyl-2-pentanone (MIBK...

40 CFR Appendix A to Part 439 - Tables

Code of Federal Regulations, 2012 CFR

2012-07-01

... Isobutyraldehyde 1 Aldehydes. n-Heptane 1 Alkanes. n-Hexane 1 Diethylamine 1 Amines. Triethylamine Benzene... Methyl formate Tetrahydrofuran 1 Ethers. Isopropyl ether Acetone 1 Ketones. 4-Methyl-2-pentanone (MIBK...

40 CFR Appendix A to Part 439 - Tables

Code of Federal Regulations, 2013 CFR

2013-07-01

... Isobutyraldehyde 1 Aldehydes. n-Heptane 1 Alkanes. n-Hexane 1 Diethylamine 1 Amines. Triethylamine Benzene... Methyl formate Tetrahydrofuran 1 Ethers. Isopropyl ether Acetone 1 Ketones. 4-Methyl-2-pentanone (MIBK...

40 CFR Appendix A to Part 439 - Tables

Code of Federal Regulations, 2010 CFR

2010-07-01

... Aldehydes. n-Heptane 1 Alkanes. n-Hexane 1 Diethylamine 1 Amines. Triethylamine Benzene Aromatics. Toluene 1... Tetrahydrofuran 1 Ethers. Isopropyl ether Acetone 1 Ketones. 4-Methyl-2-pentanone (MIBK) Ammonia (aqueous...

40 CFR Appendix A to Part 439 - Tables

Code of Federal Regulations, 2011 CFR

2011-07-01

... Aldehydes. n-Heptane 1 Alkanes. n-Hexane 1 Diethylamine 1 Amines. Triethylamine Benzene Aromatics. Toluene 1... Tetrahydrofuran 1 Ethers. Isopropyl ether Acetone 1 Ketones. 4-Methyl-2-pentanone (MIBK) Ammonia (aqueous...

Cs₂CO₃-Initiated Trifluoro-Methylation of Chalcones and Ketones for Practical Synthesis of Trifluoromethylated Tertiary Silyl Ethers.

PubMed

Dong, Cheng; Bai, Xing-Feng; Lv, Ji-Yuan; Cui, Yu-Ming; Cao, Jian; Zheng, Zhan-Jiang; Xu, Li-Wen

2017-05-18

It was found that 1,2-trifluoromethylation reactions of ketones, enones, and aldehydes were easily accomplished using the Prakash reagent in the presence of catalytic amounts of cesium carbonate, which represents an experimentally convenient, atom-economic process for this anionic trifluoromethylation of non-enolisable aldehydes and ketones.

Synthesis and characterization of sulfonated poly ether ether ketone (sPEEK) membranes for low temperature fuel cells

NASA Astrophysics Data System (ADS)

Ali, Mawlood Maajal; Rizvi, S. J. A.; Azam, Ameer

2018-05-01

Poly ether ether ketone (PEEK) was sulfonated with 1.0 M sulphuric acid for varying durations to have various degrees of sulfonation (DS) from 43 to 55%. The FT-IR spectra confirmed the successful sulfonation of PEEK. The sulfonated PEEK (sPEEK) membranes were prepared by a solvent casting method using dimethylacetamide (DMAc) as solvent and upon drying the membranes were characterized. The DS% and ion exchange capacity (IEC) were determined by a back titration method. The IEC and DS of sPEEK was found to increase with the increment of sulfonation reaction time. Water uptake also increased with increase in the DS. The Thermogravimetric (TGA) curves revealed poor thermal stability of sPEEK. The proton conductivity of sPEEK membrane was found to considerably better with degree of sulfonation for fuel cell application.

Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications

NASA Astrophysics Data System (ADS)

Liang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, Yanfeng

2015-06-01

A series of novel ionic cross-linking sulfonated poly(ether ether ketone) (SPEEK) membranes containing the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic cross-linking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepared membranes exhibit good mechanical properties, adequate thermal stability, good oxidative stability, appropriate water uptake and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30 °C on the basis of applicable proton conductivity.

Influence of north climatic conditions on the peat lipids composition

NASA Astrophysics Data System (ADS)

Serebrennikova, O. V.; Strelnikova, E. B.; Duchko, M. A.; Preis, Yu I.

2018-03-01

The paper studies the composition of lipid organic compounds of peat from the northern regions of the Russian Federation. Peat was sampled in the northern taiga, forest-tundra and tundra zones, characterized by various hydrothermal conditions and vegetation cover. n-Alkanes, fatty acids and their ethers, aldehydes, ketones, alcohols, tocopherols, squalene, bi-, tri- and pentacyclic terpenoids, as well as steroids were identified in peat lipids by gas chromatography-mass spectrometry. The dependences of the total content of lipids and the majority of the investigated compounds classes on the ambient temperature and vegetation, as well as the correlation between the composition of n-alkanes and humidity were revealed.

27 CFR 21.117 - Methyl isobutyl ketone.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Methyl isobutyl ketone. 21.117 Section 21.117 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....117 Methyl isobutyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

27 CFR 21.117 - Methyl isobutyl ketone.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Methyl isobutyl ketone. 21.117 Section 21.117 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....117 Methyl isobutyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

Catalyst-free dehydrative α-alkylation of ketones with alcohols: green and selective autocatalyzed synthesis of alcohols and ketones.

PubMed

Xu, Qing; Chen, Jianhui; Tian, Haiwen; Yuan, Xueqin; Li, Shuangyan; Zhou, Chongkuan; Liu, Jianping

2014-01-03

Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by CC bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups as ion conductive binder in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wei, Zengbin; Xue, Lixin; Nie, Feng; Sheng, Jianfang; Shi, Qianru; Zhao, Xiulan

2014-06-01

In an attempt to reduce the Li+ concentration polarization and electrolyte depletion from the electrode porous space, sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups (SPEEK-FSA-Li) is prepared and attempted as ionic conductivity binder. Sulfonated aromatic poly(ether ether ketone) exhibits strong adhesion and chemical stability, and lithiated fluorinated sulfonic side chains help to enhance the ionic conductivity and Li+ ion diffusion due to the charge delocalization over the sulfonic chain. The performances are evaluated by cyclic voltammetry, electrochemical impedance spectroscopy, charge-discharge cycle testing, 180° peel testing, and compared with the cathode prepared with polyvinylidene fluoride binder. The electrode prepared with SPEEK-FSA-Li binder forms the relatively smaller resistances of both the SEI and the charge transfer of lithium ion transport. This is beneficial to lithium ion intercalation and de-intercalation of the cathode during discharging-charging, therefore the cell prepared with SPEEK-FSA-Li shows lower charge plateau potential and higher discharge plateau potential. Compared with PVDF, the electrode with ionic binder shows smaller decrease in capacity with the increasing of cycle rate. Meanwhile, adhesion strength of electrode prepared with SPEEK-FSA-Li is more than five times greater than that with PVDF.

27 CFR 21.118 - Methyl n-butyl ketone.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Methyl n-butyl ketone. 21.118 Section 21.118 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....118 Methyl n-butyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

27 CFR 21.118 - Methyl n-butyl ketone.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Methyl n-butyl ketone. 21.118 Section 21.118 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....118 Methyl n-butyl ketone. (a) Acidity (as acetic acid). 0.02 percent by weight, maximum. (b) Color...

Direct conversion of alcohols to α-chloro aldehydes and α-chloro ketones.

PubMed

Jing, Yuanyuan; Daniliuc, Constantin G; Studer, Armido

2014-09-19

Direct conversion of primary and secondary alcohols into the corresponding α-chloro aldehydes and α-chloro ketones using trichloroisocyanuric acid, serving both as stoichiometric oxidant and α-halogenating reagent, is reported. For primary alcohols, TEMPO has to be added as an oxidation catalyst, and for the transformation of secondary alcohols (TEMPO-free protocol), MeOH as an additive is essential to promote chlorination of the intermediary ketones.

Iridium-catalyzed Arene ortho-Silylation by Formal Hydroxyl-directed C-H Activation

PubMed Central

Simmons, Eric M.; Hartwig, John F.

2010-01-01

A strategy for the ortho-silylation of aryl ketone, benzaldehyde and benzyl alcohol derivatives has been developed in which a hydroxyl group formally serves as the directing element for Ir-catalyzed arene C-H bond activation. One-pot generation of a (hydrido)silyl ether from the carbonyl compound or alcohol is followed by dehydrogenative cyclization at 80–100 °C in the presence of norbornene as hydrogen acceptor and the combination of 1 mol % [Ir(cod)OMe]2 and 1,10-phenanthroline as catalyst to form benzoxasiloles. The synthetic utility of the benzoxasilole products is demonstrated by conversion to phenol or biaryl derivatives by Tamao-Fleming oxidation or Hiyama cross-coupling. Both of these transformations of the C-H silylation products exploit the Si-O bond in the system and proceed by activation of the silyl moiety with hydroxide, rather than fluoride. PMID:21077625

Accelerated simulations of aromatic polymers: application to polyether ether ketone (PEEK)

NASA Astrophysics Data System (ADS)

Broadbent, Richard J.; Spencer, James S.; Mostofi, Arash A.; Sutton, Adrian P.

2014-10-01

For aromatic polymers, the out-of-plane oscillations of aromatic groups limit the maximum accessible time step in a molecular dynamics simulation. We present a systematic approach to removing such high-frequency oscillations from planar groups along aromatic polymer backbones, while preserving the dynamical properties of the system. We consider, as an example, the industrially important polymer, polyether ether ketone (PEEK), and show that this coarse graining technique maintains excellent agreement with the fully flexible all-atom and all-atom rigid bond models whilst allowing the time step to increase fivefold to 5 fs.

Interstellar molecules - Origin by catalytic reactions on grain surfaces. [compound distribution analysis

NASA Technical Reports Server (NTRS)

Anders, E.; Hayatsu, R.; Studier, M. H.

1974-01-01

To determine the compound distribution formed by surface catalysis, mixtures of CO, D2, and ND2 were heated with nickel-iron or montmorillonite clay catalysts for 49-214 hours at 250 to 300 C. Compounds identified include most of the known polyatomic interstellar molecules, as well as homologous series of acetylenes, dienes, alcohols, aldehydes, ketones, ethers, esters, nitriles, amines, etc., and cyclic compounds such as furans and pyrroles. These homologous series are uniquely characteristic of surface catalysis. A search for the heavier members of these series, predicted to occur at 1/10th to 1/1,000th the abundance of the lightest members, thus comprises a crucial test of this mechanism.

Evaluation of certain food additives.

PubMed

2012-01-01

This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, including flavouring agents, with a view to concluding as to safety concerns and to preparing specifications for identity and purity. The first part of the report contains a general discussion of the principles governing the toxicological evaluation of and assessment of dietary exposure to food additives, including flavouring agents. A summary follows of the Committee's evaluations of technical, toxicological and dietary exposure data for five food additives (magnesium dihydrogen diphosphate; mineral oil (medium and low viscosity) classes II and III; 3-phytase from Aspergillus niger expressed in Aspergillus niger; serine protease (chymotrypsin) from Nocardiopsis prasina expressed in Bacillus licheniformis; and serine protease (trypsin) from Fusarium oxysporum expressed in Fusarium venenatum) and 16 groups of flavouring agents (aliphatic and aromatic amines and amides; aliphatic and aromatic ethers; aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers containing furan substitution; aliphatic linear alpha,beta-unsaturated aldehydes, acids and related alcohols, acetals and esters; amino acids and related substances; epoxides; furfuryl alcohol and related substances; linear and branched-chain aliphatic, unsaturated, unconjugated alcohols, aldehydes, acids and related esters; miscellaneous nitrogen-containing substances; phenol and phenol derivatives; pyrazine derivatives; pyridine, pyrrole and quinoline derivatives; saturated aliphatic acyclic branched-chain primary alcohols, aldehydes and acids; simple aliphatic and aromatic sulfides and thiols; sulfur-containing heterocyclic compounds; and sulfur-substituted furan derivatives). Specifications for the following food additives were revised: ethyl cellulose, mineral oil (medium viscosity), modified starches and titanium dioxide. Annexed to the report are tables summarizing the Committee's recommendations for dietary exposures to and toxicological evaluations of the food additives and flavouring agents considered.

Direct α-alkylation of ketones with alcohols in water.

PubMed

Xu, Guoqiang; Li, Qiong; Feng, Jiange; Liu, Qiang; Zhang, Zuojun; Wang, Xicheng; Zhang, Xiaoyun; Mu, Xindong

2014-01-01

The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2 O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5 -C11 or longer-chain ketones and alcohols, which are precursors to fuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electricity generation and removal performance of a microbial fuel cell using sulfonated poly (ether ether ketone) as proton exchange membrane to treat phenol/acetone wastewater.

PubMed

Wu, Hao; Fu, Yu; Guo, Chunyu; Li, Yanbo; Jiang, Nanzhe; Yin, Chengri

2018-07-01

The microbial fuel cell (MFC) has emerged as a promising technology for wastewater treatment and energy recovery, but the expensive cost of proton exchange membranes (PEMs) is a problem that need to be solved. In this study, a two-chamber MFC based on our self-made PEM sulfonated poly (ether ether ketone) membrane was set up to treat phenol/acetone wastewater and synchronously generate power. The maximum output voltage was 240-250 mV. Using phenol and acetone as substrates, the power generation time in an operation cycle was 289 h. The MFC exhibited good removal performance, with no phenol or acetone detected, respectively, when the phenol concentration was lower than 50 mg/L and the acetone concentration was lower than 100 mg/L. This study provides a cheap and eco-friendly way to treat phenol/acetone wastewater and generate useful energy by MFC technology. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation and tribological behaviors of poly (ether ether ketone) nanocomposite films containing graphene oxide nanosheets

NASA Astrophysics Data System (ADS)

Song, Hao-Jie; Li, Na; Yang, Jin; Min, Chun-Ying; Zhang, Zhao-zhu

2013-02-01

The composite films of poly (ether ether ketone) (PEEK) filled with different proportions of graphene oxide (GO) nanosheets were prepared by the cast method. The tribological behaviors of the composite films under boundary lubrication (water and liquid paraffin oil lubrication) were investigated and compared with that under dry sliding on an UMT-2 friction and wear machine, by running a steel sphere against the composite films. The results were as follows: GO nanosheets as the filler greatly improve the wear resistance of PEEK under boundary lubrication, though the composites show a different dependence of wear resistance on the filler content. Scanning electron microscopy and optical microscopy performed to analyze the wear scar surfaces after friction confirmed that the outstanding lubrication performance of GO could be attributed to their small size and extremely thin laminated structure, which allow the GO to easily enter the contact area, thereby preventing the rough surfaces from coming into direct contact.

Cross-linked sulfonated poly(ether ether ketone) by using diamino-organosilicon for proton exchange fuel cells.

PubMed

Kayser, Marie J; Reinholdt, Marc X; Kaliaguine, Serge

2011-03-31

Fuel cells are at the battlefront to find alternate sources of energy to the highly polluting, economically and environmentally constraining fossil fuels. This work uses an organosilicon molecule presenting two amine functions, bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS) with the aim of preparing cross-linked sulfonated poly(ether ether ketone) (SPEEK) based membranes. The hybrid membranes obtained at varying APTMDS loadings are characterized for their acid, proton conductivity, water uptake, and swelling properties. APTMDS may be considered as an extreme case of silica nanoparticle and is therefore most advantageously distributed within the polymeric matrix. The two amine groups can interact, via electrostatic interactions, with the sulfonic acid groups of SPEEK, resulting in a double anchoring of the molecule. The addition of a small amount of APTMDS is enhancing the mechanical and hydrolytic properties of the membranes and allows some unfolding of the polymer chains, rendering some acid sites accessible to water molecules and thus available for proton transport.

Interface and properties of inorganic fullerene tungsten sulphide nanoparticle reinforced poly (ether ether ketone) nanocomposites

NASA Astrophysics Data System (ADS)

Wang, Nannan; Yang, Zhuxian; Wang, Yuan; Thummavichai, Kunyapat; Xia, Yongde; Ghita, Oana; Zhu, Yanqiu

We report a simple and effective method to fabricate PEEK (poly ether ether ketone)/IF-WS2 (Inorganic Fullerene Tungsten Sulphide) nanocomposites with IF-WS2 content up to 8 wt%. We have used electron microscopies to characterise the morphology and structural features of the nancomposites, and FTIR and XPS to show that some chemical interface bondings were formed between the PEEK and IF-WS2. We demonstrate that the resulting PEEK/IF-WS2 nanocomposites showed an extraordinary 190% increase in thermal conductivity, 50 °C higher in degradation temperature, and mild improvements in strength and hardness. The increased degradation activation energy from 64 to 76 kJ/mol for neat PEEK and PEEK/IF-WS2 nanocomposites, respectively, is attributed to the synergistic interface between the PEEK matrix and IF-WS2 nanoparticles. The enhancements in both the mechanical and thermal properties will significantly expand the capacities of PEEK-based nanocomposites towards applications where thermal conductivity and stability are important.

Mechanical Properties Optimization of Poly-Ether-Ether-Ketone via Fused Deposition Modeling.

PubMed

Deng, Xiaohu; Zeng, Zhi; Peng, Bei; Yan, Shuo; Ke, Wenchao

2018-01-30

Compared to the common selective laser sintering (SLS) manufacturing method, fused deposition modeling (FDM) seems to be an economical and efficient three-dimensional (3D) printing method for high temperature polymer materials in medical applications. In this work, a customized FDM system was developed for polyether-ether-ketone (PEEK) materials printing. The effects of printing speed, layer thickness, printing temperature and filling ratio on tensile properties were analyzed by the orthogonal test of four factors and three levels. Optimal tensile properties of the PEEK specimens were observed at a printing speed of 60 mm/s, layer thickness of 0.2 mm, temperature of 370 °C and filling ratio of 40%. Furthermore, the impact and bending tests were conducted under optimized conditions and the results demonstrated that the printed PEEK specimens have appropriate mechanical properties.

New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

NASA Technical Reports Server (NTRS)

Wolfe, James F.

1993-01-01

The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

Bioenvironmental Engineer’s Guide to TVA-1000B Toxic Vapor Analyzer

DTIC Science & Technology

2014-01-01

chemicals including aromatics, unsaturated chlorinated hydrocarbons, aldehydes , ketones , ethylene oxide, hydrogen sulfide, and glycol ether solvents. The...Dimethoxyethane 9.65 Diethyl ketone 9.32 Ethyl amine 8.86 1,1-Dimethylhydrazine 7.28 Diethyl sulfide 8.43 Ethyl benzene 8.76 1,2-Dibromoethene 9.45...Chemical IP (eV) Chemical IP (eV) Chemical IP (eV) Freon 13 (chlorotrifluoromethane) 12.91 Isobutyric acid 10.02 Methyl butyl ketone 9.34

Extreme halophilic alcohol dehydrogenase mediated highly efficient syntheses of enantiopure aromatic alcohols.

PubMed

Alsafadi, Diya; Alsalman, Safaa; Paradisi, Francesca

2017-11-07

Enzymatic synthesis of enantiopure aromatic secondary alcohols (including substituted, hetero-aromatic and bicyclic structures) was carried out using halophilic alcohol dehydrogenase ADH2 from Haloferax volcanii (HvADH2). This enzyme showed an unprecedented substrate scope and absolute enatioselectivity. The cofactor NADPH was used catalytically and regenerated in situ by the biocatalyst, in the presence of 5% ethanol. The efficiency of HvADH2 for the conversion of aromatic ketones was markedly influenced by the steric and electronic factors as well as the solubility of ketones in the reaction medium. Furthermore, carbonyl stretching band frequencies ν (C[double bond, length as m-dash]O) have been measured for different ketones to understand the effect of electron withdrawing or donating properties of the ketone substituents on the reaction rate catalyzed by HvADH2. Good correlation was observed between ν (C[double bond, length as m-dash]O) of methyl aryl-ketones and the reaction rate catalyzed by HvADH2. The enzyme catalyzed the reductions of ketone substrates on the preparative scale, demonstrating that HvADH2 would be a valuable biocatalyst for the preparation of chiral aromatic alcohols of pharmaceutical interest.

Diene Hydroacylation from the Alcohol or Aldehyde Oxidation Level via Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation: Synthesis of β,γ-Unsaturated Ketones

PubMed Central

Shibahara, Fumitoshi; Bower, John F.; Krische, Michael J.

2011-01-01

Under the conditions of ruthenium catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a–1g to deliver β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. Under identical conditions, aldehydes 2a–2g couple to isoprene to provide an identical set of β,γ-unsaturated ketones 3a–3g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene and 1,2-dimethylbutadiene to representative alcohols 1b, 1c and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form β,γ-unsaturated ketones. In all cases, complete branch-regioselectivity is observed and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidations levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or β,γ-unsaturated ketone) are accessible. PMID:18841895

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.

From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

PubMed

Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

2014-10-22

The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

Rhodium-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Ketones: A General Approach to Chiral α-amino Ketones.

PubMed

Gao, Wenchao; Wang, Qingli; Xie, Yun; Lv, Hui; Zhang, Xumu

2016-01-01

Rhodium/DuanPhos-catalyzed asymmetric hydrogenation of aliphatic α-dehydroamino ketones has been achieved and afforded chiral α-amino ketones in high yields and excellent enantioselectives (up to 99 % ee), which could be reduced further to chiral β-amino alcohols by LiAlH(tBuO)3 with good yields. This protocol provides a readily accessible route for the synthesis of chiral α-amino ketones and chiral β-amino alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of crystalline morphology in poly (ether ether ketone) using dielectric relaxation spectroscopy

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

Kalika, D.S.; Krishnaswamy, R.K.

1993-12-31

The relaxation behavior of poly (ether ether ketone) [PEEK] has been investigated using dielectric relaxation spectroscopy; the glass-rubber ({alpha}) relaxation and a sub-glass ({beta}) relaxation were examined for the amorphous material and both cold-crystallized and melt-crystallized specimens. Analysis of the data using the Cole-Cole modification of the Debye equation allowed determination of the dielectric relaxation strength and relaxation broadening parameter for both transitions as a function of material crystallization history. The crystallized specimens displayed a positive offset in isochronal loss temperature for both the {alpha} and {beta} relaxations, with the {alpha} relaxation broadened significantly. The measured dipolar response was interpretedmore » using a three-phase morphological model encompassing a crystalline phase, a mobile amorphous phase, and a rigid amorphous phase. Determination of phase fractions based on dipolar mobilization across the glass-rubber relaxation revealed a finite rigid amorphous phase fraction for both the cold-crystallized specimens which was relatively insensitive to thermal history and degree of crystallinity (W{sub RAP}40.20).« less

Toughening of BIS maleimide resins: Synthesis and characterization of maleimide terminated poly(arylene ether) oligomers and polymers

NASA Technical Reports Server (NTRS)

Mcgrath, J. E.; Lyle, G. D.; Jurek, M. J.; Mohanty, D.; Hedrick, J. C.

1986-01-01

Amine functional poly(arylene ether) sulfones were previously reported. Herein, the chemistry was extended to amorphous poly(arylene ether) ketones because of their higher fracture toughness values, relative to the polysulfones. It was demonstrated that the amino functional oligomers undergo a self-crosslinking reaction at temperatures above about 220 C. This produces an insoluble, but ductile network that has excellent resistance. A ketamine structure hypothesis was proposed and verified using solid state magic angle NMR. In most cases, the water generated upon ketamine formation is too low to produce porosity and solid networks are obtained. The stability of the ketamine networks towards hydrolysis is excellent. The chemistry was further demonstrated to be able to crosslink preformed nonfunctional poly(arylene ether) ketones if a difunctional amine was utilized. This concept has the possibility of greatly improving the creep resistance of thermoplastics. Also, a new technique was developed for converting the amine functional oligomers cleanly into maleimide structures. This method involves reacting maleic anhydride with monomeric aminophenols in the presence of solvent mixtures.

Effect of degree of sulfonation and casting solvent on sulfonated poly(ether ether ketone) membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Xi, Jingyu; Li, Zhaohua; Yu, Lihong; Yin, Bibo; Wang, Lei; Liu, Le; Qiu, Xinping; Chen, Liquan

2015-07-01

The properties of sulfonated poly(ether ether ketone) (SPEEK) membranes with various degree of sulfonation (DS) and casting solvent are investigated for vanadium redox flow battery (VRFB). The optimum DS of SPEEK membrane is firstly confirmed by various characterizations such as physicochemical properties, ion selectivity, and VRFB single-cell performance. Subsequently the optimum casting solvent is selected for the optimum DS SPEEK membrane within N,N‧-dimethylformamide (DMF), N,N‧-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The different performance of SPEEK membranes prepared with various casting solvents can be attributed to the different interaction between solvent and -SO3H group of SPEEK. In the VRFB single-cell test, the optimum SPEEK membrane with DS of 67% and casting solvent of DMF (S67-DMF membrane) exhibits higher VRFB efficiencies and better cycle-life performance at 80 mA cm-2. The investigation of various DS and casting solvent will be effective guidance on the selection and modification of SPEEK membrane towards VRFB application.

Ion-exchange composite membranes pore-filled with sulfonated poly(ether ether ketone) and Engelhard titanosilicate-10 for improved performance of vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Kim, Jihoon; Lee, Yongkyu; Jeon, Jae-Deok; Kwak, Seung-Yeop

2018-04-01

A series of ion-exchange membranes for vanadium redox flow batteries (VRBs) are prepared by filling the pores of a poly(tetrafluoroethylene) (PTFE) substrate with sulfonated poly(ether ether ketone) (SPEEK) and microporous Engelhard titanosilicate-10 (ETS-10). The effects of ETS-10 incorporation and PTFE reinforcement on membrane properties and VRB single-cell performance are investigated using various characterization tools. The results show that these composite membranes exhibit improved mechanical properties and reduced vanadium-ion permeabilities owing to the interactions between ETS-10 and SPEEK, the suppressed swelling of PTFE, and the unique ETS-10 framework. The composite membrane with 3 wt% ETS-10 (referred to as "SE3/P") exhibits the best membrane properties and highest ion selectivity. The VRB system with the SE3/P membrane exhibits higher cell capacity, higher cell efficiency, and lower capacity decay than that with a Nafion membrane. These results indicate that this composite membrane has potential as an alternative to Nafion in VRB systems.

Composite perfluorohydrocarbon membranes, their preparation and use

DOEpatents

Ding, Yong; Bikson, Benjamin

2017-04-04

Composite porous hydrophobic membranes are prepared by forming a perfluorohydrocarbon layer on the surface of a preformed porous polymeric substrate. The substrate can be formed from poly (aryl ether ketone) and a perfluorohydrocarbon layer can be chemically grafted to the surface of the substrate. The membranes can be utilized for a broad range of fluid separations, such as microfiltration, nanofiltration, ultrafiltration as membrane contactors for membrane distillation and for degassing and dewatering of fluids. The membranes can further contain a dense ultra-thin perfluorohydrocarbon layer superimposed on the porous poly (aryl ether ketone) substrate and can be utilized as membrane contactors or as gas separation. membranes for natural gas treatment and gas dehydration.

Advanced selective non-invasive ketone body detection sensors based on new ionophores

NASA Astrophysics Data System (ADS)

Sathyapalan, A.; Sarswat, P. K.; Zhu, Y.; Free, M. L.

2014-12-01

New molecules and methods were examined that can be used to detect trace level ketone bodies. Diseases such as type 1 diabetes, childhood hypo-glycaemia-growth hormone deficiency, toxic inhalation, and body metabolism changes are linked with ketone bodies concentration. Here we introduce, selective ketone body detection sensors based on small, environmentally friendly organic molecules with Lewis acid additives. Density functional theory (DFT) simulation of the sensor molecules (Bromo-acetonaphthone tungstate (BANT) and acetonaphthophenyl ether propiono hydroxyl tungstate (APPHT)), indicated a fully relaxed geometry without symmetry attributes and specific coordination which enhances ketone bodies sensitivity. A portable sensing unit was made in which detection media containing ketone bodies at low concentration and new molecules show color change in visible light as well as unique irradiance during UV illumination. RGB analysis, electrochemical tests, SEM characterization, FTIR, absorbance and emission spectroscopy were also performed in order to validate the ketone sensitivity of these new molecules.

Organic monolith frits encased in polyether ether ketone tubing with improved durability for liquid chromatography.

PubMed

Park, Sin Young; Cheong, Won Jo

2015-09-01

This study introduces a preparation method for polymer-encased monolith frits with improved durability for liquid chromatography columns. The inner surface of the polyether ether ketone tubing is pretreated with sulfuric acid in the presence of catalysts (vanadium oxide and sodium sulfate). The tubing was rinsed with water and acetone, flushed with nitrogen, and treated with glycidyl methacrylate. After washing, the monolith reaction mixture composed of lauryl methacrylate, ethylene glycol dimethacrylate, initiator, and porogenic solvent was filled in the tubing and subjected to in situ polymerization. The tubing was cut into thin slices and used as frits for microcolumns. To check their durability, the frit slices were placed in a vial and a heavy impact was applied on the vial by a vortex mixer for various periods. The frits made in the presence of catalysts were found to be more durable than those made without catalysts. Furthermore, when the monolith-incorporated tubing was used as a chromatography column, the column prepared in the presence of catalysts resulted in a better separation efficiency. The separation performance of the columns installed with the polyether ether ketone encased monolith frits was comparable to that of the columns installed with the commercial stainless-steel screen frits. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly stereoselective three-component reactions of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or alpha,beta-unsaturated enals or enones.

PubMed

Huang, Xian; Xie, Meihua

2002-12-13

beta-Phenylseleno-alpha-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or alpha,beta-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of alpha,beta-unsaturated enones, functionalized allylic alcohols or functionalized gamma,delta-unsaturated ketones were obtained, depending on the structures of the ketones.

Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Chen, Liyun; Zhang, Shouhai; Chen, Yuning; Jian, Xigao

2017-07-01

A series of novel sulfonated poly(phthalazinone ether ketone)s containing pendant phenyl moieties (SPPEK-Ps) are synthesized and thoroughly characterized. The chemical structures of the polymers are confirmed by 1H NMR and FTIR analysis. The physicochemical properties and single cell performance of SPPEK-P membranes are systematically evaluated, revealing that the membranes are thermally, chemically and mechanically stable. The area resistances of SPPEK-P-90 and SPPEK-P-100 are 0.75 Ω cm2 and 0.34 Ω cm2, respectively. SPPEK-P membranes are impermeable to the bulky hydrated VO2+ ion and exhibited low V3+ ion permeability (SPPEK-P-90, 2.53 × 10-5 cm min-1) (Nafion 115 membrane: 9.0 × 10-4 cm min-1). Tests of SPPEK-P-90 in vanadium redox flow batteries (VRFBs) demonstrate a comparable columbic efficiency (CE) and energy efficiency (EE) to that of Nafion 115, where the CE is 98% and the EE is 83% at 60 mA cm-2. Moreover, the SPPEK-P-90 membrane exhibits stable performance in cell over 100 charge-discharge cycles (∼450 h).

27 CFR 21.23 - Formula No. 19.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Formula No. 19. 21.23 Section 21.23 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT... gallons of either methyl isobutyl ketone, mixed isomers of nitropropane, or methyl n- butyl ketone; and 1...

A nickel catalyst for the addition of organoboronate esters to ketones and aldehydes.

PubMed

Bouffard, Jean; Itami, Kenichiro

2009-10-01

A Ni(cod)(2)/IPr catalyst promotes the intermolecular 1,2-addition of arylboronate esters to unactivated aldehydes and ketones. Diaryl, alkyl aryl, and dialkyl ketones show good reactivity under mild reaction conditions (< or = 80 degrees C, nonpolar solvents, no strong base or acid additives). A dramatic ligand effect favors either carbonyl addition (IPr) or C-OR cross-coupling (PCy(3)) with aryl ether substrates. A Ni(0)/Ni(II) catalytic cycle initiated by the oxidative cyclization of the carbonyl substrate is proposed.

Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

PubMed

Heshmat, Mojgan; Privalov, Timofei

2017-07-06

By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proton affinities of hydrated molecules

NASA Astrophysics Data System (ADS)

Valadbeigi, Younes

2016-09-01

Proton affinities (PA) of non-hydrated, M, and hydrated forms, M(H2O)1,2,3, of 20 organic molecules including alcohols, ethers, aldehydes, ketones and amines were calculated by the B3LYP/6-311++G(d,p) method. For homogeneous families, linear correlations were observed between PAs of the M(H2O)1,2,3 and the PAs of the non-hydrated molecules. Also, the absolute values of the hydration enthalpies of the protonated molecules decreased linearly with the PAs. The correlation functions predicted that for an amine with PA < 1100 kJ/mol the PA(M(H2O)) is larger than the corresponding PA, while for an amine with PA > 1100 kJ/mol the PA(M(H2O)) is smaller than the PA.

Volatile compounds of sulfur in the Fe-C-S system at 5.3 GPa and 1300°C

NASA Astrophysics Data System (ADS)

Zhimulev, E. I.; Sonin, V. M.; Bul'bak, T. A.; Chepurov, A. I.; Tomilenko, A. A.; Pokhilenko, N. P.

2015-05-01

This report presents the results of experimental studies of the fluid phase in the Fe-C-S system at high P and T values (5.3 GPa and 1300°C) conforming to diamond synthesis. The samples for experiments were mounted on air; therefore, the volatile compounds detected after the experiments are characterized by a wide variety and complicated composition involving both inorganic and organic components. Among the inorganic compounds, CO2, H2O, N2, SO2, CS2, and COS were detected. The GC/MS analysis revealed hydrocarbons (paraffins, olefins, and arenes), including high-molecular compounds. The formation of heavy hydrocarbons confirms their thermodynamic stability under high pressure. Oxygenated hydrocarbons (alcohols, aldehydes, ketones, carboxylic acids, and ethers) were also detected.

Advanced emissions-speciation methodologies for the auto/oil air-quality improvement research program. 2. Aldehydes, ketones, and alcohols. SAE technical paper series

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

Swarin, S.J.; Loo, J.F.; Chladek, E.

1992-01-01

Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air Quality Improvement Research Program to provide emission data for comparison of individual reformulated fuels, individual vehicles, and for air modeling studies. The emission samples are collected in impingers which contain either 2,4-dinitrophenylhydrazine solution for the aldehydes and ketones or deionized water for the alcohols. Subsequent analyses by liquid chromatography for the aldehydes and ketones and gas chromatography for the alcohols utilized auto injectors and computerized data systems which permit high sample throughput with minimalmore » operator intervention. The quality control procedures developed and interlaboratory comparisons conducted as part of the program are also described. (Copyright (c) 1992 Society of Automotive Engineers, Inc.)« less

46. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, ...

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

46. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, CONTROL PANEL LEVEL (2ND DECK) OF ETHER AND ALCOHOL STILL BUILDING, LOOKING NORTH, SHOWING TWO ALCOHOL DISTILLATION TOWERS BEHIND 'MIXED SOLVENT UNIT' CONTROL PANEL. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

Properties investigation of sulfonated poly(ether ether ketone)/polyacrylonitrile acid-base blend membrane for vanadium redox flow battery application.

PubMed

Li, Zhaohua; Dai, Wenjing; Yu, Lihong; Liu, Le; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2014-11-12

Acid-base blend membrane prepared from sulfonated poly(ether ether ketone) (SPEEK) and polyacrylonitrile (PAN) was detailedly evaluated for vanadium redox flow battery (VRFB) application. SPEEK/PAN blend membrane exhibited dense and homogeneous cross-section morphology as scanning electron microscopy and energy-dispersive X-ray spectroscopy images show. The acid-base interaction of ionic cross-linking and hydrogen bonding between SPEEK and PAN could effectively reduce water uptake, swelling ratio, and vanadium ion permeability, and improve the performance and stability of blend membrane. Because of the good balance of proton conductivity and vanadium ion permeability, blend membrane with 20 wt % PAN (S/PAN-20%) showed higher Coulombic efficiency (96.2% vs 91.1%) and energy efficiency (83.5% vs 78.4%) than Nafion 117 membrane at current density of 80 mA cm(-2) when they were used in VRFB single cell. Besides, S/PAN-20% membrane kept a stable performance during 150 cycles at current density of 80 mA cm(-2) in the cycle life test. Hence the SPEEK/PAN acid-base blend membrane could be used as promising candidate for VRFB application.

Graft-crosslinked copolymers based on poly(arylene ether ketone)-gc-sulfonated poly(arylene ether sulfone) for PEMFC applications.

PubMed

Zhang, Xuan; Hu, Zhaoxia; Luo, Linqiang; Chen, Shanshan; Liu, Jianmei; Chen, Shouwen; Wang, Lianjun

2011-07-15

Novel poly(arylene ether ketone) polymers with fluorophenyl pendants and phenoxide-terminated wholly sulfonated poly(arylene ether sulfone) oligomers are prepared via Ni(0)-catalyzed and nucleophilic polymerization, respectively, and subsequently used as starting materials to obtain graft-crosslinked membranes as polymer electrolyte membranes. The phenoxide-terminated sulfonated moieties are introduced as hydrophilic parts as well as crosslinking units. The chemical structure and morphology of the obtained membranes are confirmed by (1) H NMR and tapping-mode AFM. The properties required for fuel cell applications, including water uptake and dimensional change, as well as proton conductivity, are investigated. AFM results show a clear nanoscale phase-separation microstructure of the obtained membranes. The membranes show good dimensional stability and reasonably high proton conductivities under 30-90% relative humidity. The anisotropic proton conductivity ratios (σ(formula see text) ) of the membranes in water are in the range 0.65-0.92, and increase with an increase in hydrophilic block length. The results indicate that the graft-crosslinked membranes are promising candidates for applications as polymer electrolyte membranes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

47. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, ...

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

47. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, 4TH LEVEL, LOOKING NORTH AT TOPS OF ALCOHOL AND ETHER DISTILLATION TOWERS. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide.

PubMed

Dong, Jia Jia; Unjaroen, Duenpen; Mecozzi, Francesco; Harvey, Emma C; Saisaha, Pattama; Pijper, Dirk; de Boer, Johannes W; Alsters, Paul; Feringa, Ben L; Browne, Wesley R

2013-09-01

An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2 O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stability of proton-bound clusters of alkyl alcohols, aldehydes and ketones in Ion Mobility Spectrometry.

PubMed

Jurado-Campos, Natividad; Garrido-Delgado, Rocío; Martínez-Haya, Bruno; Eiceman, Gary A; Arce, Lourdes

2018-08-01

Significant substances in emerging applications of ion mobility spectrometry such as breath analysis for clinical diagnostics and headspace analysis for food purity include low molar mass alcohols, ketones, aldehydes and esters which produce mobility spectra containing protonated monomers and proton-bound dimers. Spectra for all n- alcohols, aldehydes and ketones from carbon number three to eight exhibited protonated monomers and proton-bound dimers with ion drift times of 6.5-13.3 ms at ambient pressure and from 35° to 80 °C in nitrogen. Only n-alcohols from 1-pentanol to 1-octanol produced proton-bound trimers which were sufficiently stable to be observed at these temperatures and drift times of 12.8-16.3 ms. Polar functional groups were protected in compact structures in ab initio models for proton-bound dimers of alcohols, ketones and aldehydes. Only alcohols formed a V-shaped arrangement for proton-bound trimers strengthening ion stability and lifetime. In contrast, models for proton-bound trimers of aldehydes and ketones showed association of the third neutral through weak, non-specific, long-range interactions consistent with ion dissociation in the ion mobility drift tube before arriving at the detector. Collision cross sections derived from reduced mobility coefficients in nitrogen gas atmosphere support the predicted ion structures and approximate degrees of hydration. Copyright © 2018 Elsevier B.V. All rights reserved.

Dehydration, Dehydrogenation, and Condensation of Alcohols on Supported Oxide Catalysts Based on Cyclic (WO3)3 and (MoO3)3 Clusters

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

Rousseau, Roger J.; Dixon, David A.; Kay, Bruce D.

2014-01-01

Supported early transition metal oxides have important applications in numerous catalytic reactions. In this article we review preparation and activity of well-defined model WO3 and MoO3 catalysts prepared via deposition of cyclic gas-phase (WO3)3 and (MoO3)3 clusters generated by sublimation of WO3 and MoO3 powders. Conversion of small aliphatic alcohols to alkenes, aldehydes/ketons, and ethers is employed to probe the structure-activity relationships on model WO3 and MoO3 catalysts ranging from unsupported (WO3)3 and (MoO3)3 clusters embedded in alcohol matrices, to (WO3)3 clusters supported on surfaces of other oxides, and epitaxial and nanoporous WO3 films. Detailed theoretical calculations reveal the underlyingmore » reaction mechanisms and provide insight into the origin of the differences in the WO3 and MoO3 reactivity. For the range of interrogated (WO3)3 they further shed light into the role structure and binding of (WO3)3 clusters with the support play in determining their catalytic activity.« less

Integration of active and passive microwave signatures for characterization of soil properties

NASA Astrophysics Data System (ADS)

Laulhe, Sebastien

The reaction between an aminooxy moiety (RONH2) and a carbonyl group of either an aldehyde or a ketone --- known as an oximation reaction --- is a versatile click chemistry coupling that generates a robust oxime ether linkage. The oximation reaction is chemoselective and can be performed under mild conditions in a large variety of solvents, including water. The attractive properties of the aminooxy group and derived oximation reactions, reviewed in Chapter 1, inspired us to use this chemistry as a key feature of our research. Specifically, we prepare functionalized aminooxy compounds so that the oximation chemistry can then serve as a prelude to new synthetic or analytical methods. For example, Chapter 2 presents an improved preparation of O-(diphenylphosphinyl)hydroxylamine (DPPH), an aminooxy-containing reagent, using the classic Schotten-Baumann conditions. We show how DPPH can then be used as a chemoselective nitrogen transfer reagent for a one-pot aldehyde-to-nitrile functional group transformation. Sixteen aldehydes were smoothly transformed to their corresponding nitriles by heating at 85 °C with DPPH in toluene. The reaction can be accomplished in the presence of alcohol, ketone, ester, or amine functionality. In another application, we use functionalized aminooxy reagents to achieve quantitative multiplexed gas chromatography-mass spectrometry (GC-MS) analysis. Specifically, we chemoselectively derivatize carbonyl (aldehyde and ketone) metabolites using the aminooxy-containing reagents. Chapter 3 presents a focused fundamental study of the propensity of oxime ethers to undergo MS-induced fragmentations, such as the McLafferty rearrangement. In particular, we studied structural factors that promoted alpha,beta-fragmentation in oximes of both ketones and aldehydes, as well as the derived silyl ethers of these adducts. We determined that 1) the propensity of the McLafferty rearrangement was greatly enhanced by oxygen at the b-position of silyl oxime ethers, 2) the McLafferty rearrangement is more prominent for E-isomers of oxime and silyl oxime ethers than for the corresponding Z-isomers, and 3) Z-isomers of silyl oxime ethers with CH2 at the b-position generate nitrilium ions to a greater extent than their corresponding E-isomers. Chapter 4 describes the 3-step synthesis of a new class of stable isotope-labeled derivatizing reagents ---- a&barbelow;minooxye&barbelow;thyl p&barbelow;ropionate reagents (AEP) ---- that enable multiplexed GC-MS analysis of small molecule carbonyl compounds. The AEP reagents contain 1) an aminooxy moiety, and 2) a propionate ester moiety that generates a reporter isotope-labeled mass spectral tag (MST) in the form of an ethyl carbenium ion via an ester a-cleavage. The AEP MSTs appear in an m/z zone of minimal interference (ZMI) in the range m/z 32-34. This is a key feature in that unobstructed observation of reporter MSTs in this zone significantly improves simultaneous quantitation of carbonyl analytes from multiple samples without recourse to MS peak deconvolution strategies. Also, and in contrast to known isotope coding reagents for GC-MS, AEP reagents are not affected by the chromatographic isotope effect. The versatility of the technology for carbonyl metabolite profiling and absolute quantification is demonstrated by an analysis of turmeric extract, serving as a representative complex biological sample. A series of analogous methyl ketones were profiled from characteristic MS fragmentations of the AEP-derived oxime ether adducts, and two members, 2-nonanone and 2-undecanone, were quantified using AEP-labeled external standards. Finally, Chapter 5 concludes with additional demonstrations of click chemistry. We used oximation to ligate linker molecules to fluorophores and gold nanoparticles (AuNPs) to generate a fluorescent nano-entity for breast cancer location and diagnosis. Five homologous linkers, each consisting of a thiol-terminated hydrophobic domain coupled to an aminooxy-terminated PEG-based domain, were prerared using a 6-step synthesis in 7-25% overall yield. The aminooxy end subsequently was reacted with an aldehyde-functionalized cypate fluorophore, and the thiol end was used for attachment to gold nanoparticles. Linker attachment to cypate in this manner was superior to previously investigated amide coupling involving linker amines and cypate carboxylic acid. Collectively, the results from these investigations demonstrates a novel strategy that employs functionalized aminooxy substrates and reagents to first exploit the high yielding and selective click coupling with carbonyl substrates to set the stage for secondary synthetic or analytical operations. Approaches developed in this multifaceted study appear to be applicable to a variety of synthetic problems ranging from those of a purely chemical nature to other impacting biological systems.

Spiroborate Ester-Mediated Asymmetric Synthesis of β-Hydroxy Ethers and its Conversion to Highly Enantiopure β-Amino Ethers

PubMed Central

Huang, Kun; Ortiz-Marciales, Margarita; Correa, Wildeliz; Pomales, Edgardo; López, Xaira Y.

2009-01-01

Borane-mediated reduction of aryl and alkyl ketones with α-aryl- and α-pyridyloxy groups affords β-hydroxy ethers in high enantiomeric purity (up to 99% ee) and in good yield, using as catalyst 10 mol % of spiroborate ester 1 derived from (S)-diphenylprolinol. Representative β-hydroxy ethers are successfully converted to β-amino ethers, with minor epimerization, by phthalimide substitution under Mitsunobu’s conditions followed by hydrazinolysis, to obtain primary amino ethers or by imide reduction with borane to afford β-2,3-dihydro-1H-isoindol ethers. Non-racemic Mexiletine and nAChR analogues with potential biological activity are also synthesized in excellent yield by mesylation of key β-hydroxy pyridylethers and substitution with 5, 6 and 7 member ring heterocyclic amines. PMID:19413288

Determination of low molecular weight alcohols including fusel oil in various samples by diethyl ether extraction and capillary gas chromatography.

PubMed

Woo, Kang-Lyung

2005-01-01

Low molecular weight alcohols including fusel oil were determined using diethyl ether extraction and capillary gas chromatography. Twelve kinds of alcohols were successfully resolved on the HP-FFAP (polyethylene glycol) capillary column. The diethyl ether extraction method was very useful for the analysis of alcohols in alcoholic beverages and biological samples with excellent cleanliness of the resulting chromatograms and high sensitivity compared to the direct injection method. Calibration graphs for all standard alcohols showed good linearity in the concentration range used, 0.001-2% (w/v) for all alcohols. Salting out effects were significant (p < 0.01) for the low molecular weight alcohols methanol, isopropanol, propanol, 2-butanol, n-butanol and ethanol, but not for the relatively high molecular weight alcohols amyl alcohol, isoamyl alcohol, and heptanol. The coefficients of variation of the relative molar responses were less than 5% for all of the alcohols. The limits of detection and quantitation were 1-5 and 10-60 microg/L for the diethyl ether extraction method, and 10-50 and 100-350 microg/L for the direct injection method, respectively. The retention times and relative retention times of standard alcohols were significantly shifted in the direct injection method when the injection volumes were changed, even with the same analysis conditions, but they were not influenced in the diethyl ether extraction method. The recoveries by the diethyl ether extraction method were greater than 95% for all samples and greater than 97% for biological samples.

Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

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

Ide, Matthew S.; Hao, Bing; Neurock, Matthew

The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Althoughmore » Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.« less

Hydrogenation of carbonyl compounds of relevance to hydrogen storage in alcohols

NASA Astrophysics Data System (ADS)

Suárez, Andrés

2018-02-01

Alcohols are a promising source for the sustainable production of hydrogen that may also serve as rechargeable liquid organic hydrogen carriers (LOHCs). Metal-catalyzed acceptorless dehydrogenation of alcohols produces carbonyl derivatives as H2-depleted by-products, which by means of a hydrogenation reaction can be reconverted to the initial alcohols. Hence, reversible H2-storage systems based on pairs of secondary alcohols/ketones and primary alcohols/carboxylic acid derivatives may be envisaged. In this contribution, the hydrogenation of carbonyl derivatives, including ketones, esters, amides and carboxylic acids, is reviewed from the perspective of the hydrogen storage in alcohols.

Analysis of fingerprints features of infrared spectra of various processed products of Radix Aconiti kusnezoffii

NASA Astrophysics Data System (ADS)

Tu-ya; Yang, Ping; Sun, Su-qin; Zhou, Qun; Bao, Xiao-hua; Noda, Isao

2010-06-01

Fourier-transform infrared spectroscopy (FTIR) and two-dimensional correlation infrared spectroscopy (2D-IR)) are employed to analyze various processed products and ether extracts of Radix Aconiti kusnezoffii. There is a resemblance among the spectra of different processed products. The major difference lies in the absorption peak at 1641 cm -1 in the IR spectra, which reflects the transformation of raw aconite to the processed products. There are distinctive differences in the absorption peaks in the range of 1800-1500 cm -1 in the second derivative spectra, which has better resolution, of different processed products. 2D-IR spectra, which elevate the resolution further, can present even more differences among the products in the range of 1800-800 cm -1. Analysis of ether extracts of various processed products proves that there are alcohols, esters, carboxylic acids or ketones in all of them. However, their contents in different samples have obvious differences. With the advantages of high resolution, high-speed and convenience, IR can quickly and precisely distinguish various processed products of Radix A. kusnezoffii, and can be applied to predict the tendency of transformation of the complicated chemical mixture systems under heat perturbation.

Thermodynamic properties of hyperbranched polymer, Boltorn U3000, using inverse gas chromatography.

PubMed

Domańska, Urszula; Zołek-Tryznowska, Zuzanna

2009-11-19

Mass-fraction activity coefficients at infinite dilution (Omega13(infinity)) of alkanes (C5-C10), cycloalkanes (C5-C8), alkenes (C5-C8), alkynes (C5-C8), aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylene, thiophene), alcohols (C1-C5), water, ethers (tetrahydrofuran (THF), methyl-tert-butylether (MTBE), diethyl-, di-n-propyl-, di-n-butyl ether), and ketones (propanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone) in the hyperbranched polymer, Boltorn U3000 (B-U3000), have been determined by inverse gas chromatography (IGC) using the polymer as the stationary phase. The measurements were carried out at different temperatures between 308.15 and 348.15 K. The density and thermophysical properties of polymer were described. The specific retention volume (V(g)), the Flory-Huggins interaction parameter (chi13(infinity)), the molar enthalpy of sorption (the partial molar enthalpies of solute dissolution) (Delta(s)H), the partial molar excess enthalpy at infinite dilution of the solute and polymer (DeltaH1(E,infinity)), the partial molar Gibbs excess energy at infinite dilution (DeltaG1(E,infinity)), and the solubility parameter (delta3) were calculated.

Method and composition for testing for the presence of an alkali metal

DOEpatents

Guon, Jerold

1981-01-01

A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

Synthesis of Benzannulated Medium-ring Lactams via a Tandem Oxidative Dearomatization-Ring Expansion Reaction.

PubMed

Guney, Tezcan; Wenderski, Todd A; Boudreau, Matthew W; Tan, Derek S

2018-06-23

Medium-ring natural products exhibit diverse biological activities but such scaffolds are underrepresented in probe and drug discovery efforts due to the limitations of classical macrocyclization reactions. We report herein a tandem oxidative dearomatization-ring-expanding rearoma¬tization (ODRE) reaction that generates benzannulated medium-ring lactams directly from simple bicyclic substrates. The reaction accommodates diverse aryl substrates (haloarenes, aryl ethers, aryl amides, heterocycles) and strategic incorporation of a bridgehead alcohol generates a versatile ketone moiety in the products amenable to downstream modifications. Cheminformatic analysis indicates that these medium rings access regions of chemical space that overlap with related natural products and are distinct from synthetic drugs, setting the stage for their use in discovery screening against novel biological targets. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

PubMed

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Development of many-body polarizable force fields for Li-battery components: 1. Ether, alkane, and carbonate-based solvents.

PubMed

Borodin, Oleg; Smith, Grant D

2006-03-30

Classical many-body polarizable force fields were developed for n-alkanes, perflouroalkanes, polyethers, ketones, and linear and cyclic carbonates on the basis of quantum chemistry dimer energies of model compounds and empirical thermodynamic liquid-state properties. The dependence of the electron correlation contribution to the dimer binding energy on basis-set size and level of theory was investigated as a function of molecular separation for a number of alkane, ether, and ketone dimers. Molecular dynamics (MD) simulations of the force fields accurately predicted structural, dynamic, and transport properties of liquids and unentangled polymer melts. On average, gas-phase dimer binding energies predicted with the force field were between those from MP2/aug-cc-pvDz and MP2/aug-cc-pvTz quantum chemistry calculations.

Lithium diffusion in polyether ether ketone and polyimide stimulated by in situ electron irradiation and studied by the neutron depth profiling method

NASA Astrophysics Data System (ADS)

Vacik, J.; Hnatowicz, V.; Attar, F. M. D.; Mathakari, N. L.; Dahiwale, S. S.; Dhole, S. D.; Bhoraskar, V. N.

2014-10-01

Diffusion of lithium from a LiCl aqueous solution into polyether ether ketone (PEEK) and polyimide (PI) assisted by in situ irradiation with 6.5 MeV electrons was studied by the neutron depth profiling method. The number of the Li atoms was found to be roughly proportional to the diffusion time. Regardless of the diffusion time, the measured depth profiles in PEEK exhibit a nearly exponential form, indicating achievement of a steady-state phase of a diffusion-reaction process specified in the text. The form of the profiles in PI is more complex and it depends strongly on the diffusion time. For the longer diffusion time, the profile consists of near-surface bell-shaped part due to Fickian-like diffusion and deeper exponential part.

Repairing a Facial Cleft by Polyether-Ether-Ketone Implant Combined With Titanium Mesh.

PubMed

Deng, Yuan; Tang, Weiwei; Li, Zhengkang

2018-05-15

The Tessier Number 4 cleft is one of the rarest, most complex craniofacial anomalies that presents difficulties in surgical treatment. In this article, we report a case of simultaneous facial depression, eye displacement, and medial canthus deformity. In this case, the maxillary bony defect was reconstructed using computer-assisted design computer-assisted manufacturing (CAD-CAM) polyether-ether-ketone (PEEK) material, and the orbital floor defect was repaired with AO prefabricated titanium mesh. Additionally, the medial canthus was modified with canthopexy and a single Z-plasty flap. Owing to its relative rarity and varied clinical presentations, no definitive operative methods have been accepted for Tessier No. 4 facial cleft. This study presents the combination of CAD-CAM manufactured PEEK material and titanium mesh as an alternative approach for reconstructing the bony defect of Tessier No. 4 facial clefts.

Considerations of the Effects of Naphthalene Moieties on the Design of Proton-Conductive Poly(arylene ether ketone) Membranes for Direct Methanol Fuel Cells.

PubMed

Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Wei, Yuxue; Zhao, Chengji; Na, Hui

2016-09-14

Novel sulfonated poly(arylene ether ketones) (SDN-PAEK-x), consisting of dual naphthalene and flexible sulfoalkyl groups, were prepared via polycondensation, demethylation, and sulfobutylation grafting reaction. Among them, SDN-PAEK-1.94 membrane with the highest ion exchange capacity (IEC = 2.46 mequiv·g(-1)) exhibited the highest proton conductivity, which was 0.147 S· cm(-1) at 25 °C and 0.271 S·cm(-1) at 80 °C, respectively. The introduction of dual naphthalene moieties is expected to achieve much enhanced properties compared to those of sulfonated poly(arylene ether ketones) (SNPAEK-x), consisting of single naphthalene and flexible sulfoalkyl groups. Compared with SNPAEK-1.60 with a similar IEC, SDN-PAEK-1.74 membrane showed higher proton conductivity, higher IEC normalized conductivity, and higher effective proton mobility, although it had lower analytical acid concentration. The SDN-PAEK-x membranes with IECs higher than 1.96 mequiv·g(-1) also exhibited higher proton conductivity than that of recast Nafion membrane. Furthermore, SDN-PAEK-1.94 displayed a better single cell performance with a maximum power density of 60 mW·cm(-2) at 80 °C. Considering its high proton conductivity, excellent single cell performance, good mechanical stabilities, low membrane swelling, and methanol permeability, SDN-PAEK-x membranes are promising candidates as alternative polymer electrolyte membranes to Nafion for direct methanol fuel cell applications.

ADVANCED EMISSIONS SPECIATION METHODOLOGIES FOR THE AUTO/OIL AIR QUALITY IMPROVEMENT RESEARCH PROGRAM - II. ALDEHYDES, KETONES, AND ALCOHOLS

EPA Science Inventory

Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air quality Improvement Research Program to provide emission data for comparison of...

Enantioselective Reduction of Ketones Catalyzed by Rare-Earth Metals Complexed with Phenoxy Modified Chiral Prolinols.

PubMed

Song, Peng; Lu, Chengrong; Fei, Zenghui; Zhao, Bei; Yao, Yingming

2018-06-01

Enantioselective reduction of ketones and α,β-unsaturated ketones by pinacolborane (HBpin) has been well-established by using chiral rare-earth metal catalysts with phenoxy modified prolinols. A number of highly optically active alcohols were obtained from reduction of simple ketones catalyzed by ytterbium complex 1 [L 4 Yb(L 4 H)] (H 2 L 4 = ( S)-2- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol). Moreover, α,β-unsaturated ketones were selectively reduced to a wide range of chiral allylic alcohols with excellent yields, high enantioselectivity, and complete chemoselectivity, catalyzed by a single component chiral ytterbium complex 2 [L 1 Yb(L 1 H)] (H 2 L 1 = ( S)-2,4-di- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol).

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.

Super Hydrides.

DTIC Science & Technology

1994-10-31

and alpha-hindered ketones. We have now shown that this reagent is extremely efficient for the reduction of aryl and alkyl perfluoroalkyl ketones...including alpha- perfluoroalkyl alpha-acetylenic ketones, generally providing (greater than or equal) 90% ee for the product alcohols. A systematic study

Transetherification method

DOEpatents

Hearn, D.

1985-04-09

Transetherification is carried out in a catalytic distillation reactor, wherein the catalytic structure also serves as a distillation structure, by feeding a first ether to the catalyst bed to at least partially dissociate it into a first olefin and a first alcohol while concurrently therewith feeding either a second olefin (preferably a tertiary olefin) having a higher boiling point than said first olefin or a second alcohol having a higher boiling point than said first alcohol to the catalyst whereby either the second olefin and the first alcohol or the first olefin and the second alcohol react to form a second ether which has a higher boiling point than the first ether, which second ether is concurrently removed as a bottoms in the concurrent reaction-distillation to force that reaction to completion, while the unreacted first olefin or first alcohol is removed in the overhead. 1 fig.

Transetherification method

DOEpatents

Hearn, Dennis

1985-01-01

Transetherification is carried out in a catalytic distillation reactor, wherein the catalytic structure also serves as a distillation structure, by feeding a first ether to the catalyst bed to at least partially dissociate it into a first olefin and a first alcohol while concurrently therewith feeding either a second olefin (preferably a tertiary olefin) having a higher boiling point than said first olefin or a second alcohol having a higher boiling point than said first alcohol to the catalyst whereby either the second olefin and the first alcohol or the first olefin and the second alcohol react to form a second ether which has a higher boiling point than the first ether, which second ether is concurrently removed as a bottoms in the concurrent reaction-distillation to force that reaction to completion, while the unreacted first olefin or first alcohol is removed in the overhead.

Highly efficient Cu(I)-catalyzed oxidation of alcohols to ketones and aldehydes with diaziridinone.

PubMed

Zhu, Yingguang; Zhao, Baoguo; Shi, Yian

2013-03-01

A novel and efficient Cu(I)-catalyzed oxidation of alcohols has been achieved with di-tert-butyldiaziridinone as the oxidant under mild conditions. A wide variety of primary and secondary alcohols with various functional groups can be oxidized to aldehydes and ketones in high yields. The reaction proceeds under neutral conditions making it compatible with acid- or base-sensitive substrates, and it is amenable to gram scale.

Highly Efficient Cu(I)-Catalyzed Oxidation of Alcohols to Ketones and Aldehydes with Diaziridinone

PubMed Central

Zhu, Yingguang; Zhao, Baoguo

2013-01-01

A novel and efficient Cu(I)-catalyzed oxidation of alcohols has been achieved with di-tert-butyldiaziridinone as oxidant under mild conditions. A wide variety of primary and secondary alcohols with various functional groups can be oxidized to aldehydes and ketones in high yields. The reaction proceeds under neutral conditions making it compatible with acid or base-sensitive substrates, and it is amenable to gram scale. PMID:23413952

Sulfoximine-mediated syntheses of optically active alcohols. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Stark, C. J., Jr.

1978-01-01

Several routes are described for the production of optically active secondary and tertiary alcohols. In all cases, the asymmetry emanates from the use of (+)-(S)-N,S-dimethyl-S-phenyl-sulfoximine (1) at some point in the variation of the diastereomers. One route relies upon the separation of the diastereomers produced from the condensation of (+)-(S)-(N-methylphenyl-sulfonimidoyl) methyllithium with prochiral aldehydes and ketones. Subsequent carbon-sulfur bond cleavage of the separated diastereomeric beta-hydroxysulfoximines yields optically active alcohols. Alternatively, beta-hydroxysulfoximines were produced from the reduction of chiral beta-ketosulfoximines. The reductions were most successfully achieved with diborane generated externally and bubbled into a toluene solution of the ketone at -78 C. Optically active alcohols were also produced from prochiral ketones by reduction with diborane or lithium aluminum hydride complexes of resolved diastereomers of beta-hydroxysulfoximines.

Durability and degradation analysis of hydrocarbon ionomer membranes in polymer electrolyte fuel cells accelerated stress evaluation

NASA Astrophysics Data System (ADS)

Shimizu, Ryo; Tsuji, Junichi; Sato, Nobuyuki; Takano, Jun; Itami, Shunsuke; Kusakabe, Masato; Miyatake, Kenji; Iiyama, Akihiro; Uchida, Makoto

2017-11-01

The chemical durabilities of two proton-conducting hydrocarbon polymer electrolyte membranes, sulfonated benzophenone poly(arylene ether ketone) (SPK) semiblock copolymer and sulfonated phenylene poly(arylene ether ketone) (SPP) semiblock copolymer are evaluated under accelerated open circuit voltage (OCV) conditions in a polymer electrolyte fuel cell (PEFC). Post-test characterization of the membrane electrodes assemblies (MEAs) is carried out via gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. These results are compared with those of the initial MEAs. The SPP cell shows the highest OCV at 1000 h, and, in the post-test analysis, the SPP membrane retains up to 80% of the original molecular weight, based on the GPC results, and 90% of the hydrophilic structure, based on the NMR results. The hydrophilic structure of the SPP membrane is more stable after the durability evaluation than that of the SPK. From these results, the SPP membrane, with its simple hydrophilic structure, which does not include ketone groups, is seen to be significantly more resistant to radical attack. This structure leads to high chemical durability and thus impedes the chemical decomposition of the membrane.

Fatigue data for polyether ether ketone (PEEK) under fully-reversed cyclic loading

PubMed Central

Shrestha, Rakish; Simsiriwong, Jutima; Shamsaei, Nima

2016-01-01

In this article, the data obtained from the uniaxial fully-reversed fatigue experiments conducted on polyether ether ketone (PEEK), a semi-crystalline thermoplastic, are presented. The tests were performed in either strain-controlled or load-controlled mode under various levels of loading. The data are categorized into four subsets according to the type of tests, including (1) strain-controlled fatigue tests with adjusted frequency to obtain the nominal temperature rise of the specimen surface, (2) strain-controlled fatigue tests with various frequencies, (3) load-controlled fatigue tests without step loadings, and (4) load-controlled fatigue tests with step loadings. Accompanied data for each test include the fatigue life, the maximum (peak) and minimum (valley) stress–strain responses for each cycle, and the hysteresis stress–strain responses for each collected cycle in a logarithmic increment. A brief description of the experimental method is also given. PMID:26937465

Fatigue data for polyether ether ketone (PEEK) under fully-reversed cyclic loading.

PubMed

Shrestha, Rakish; Simsiriwong, Jutima; Shamsaei, Nima

2016-03-01

In this article, the data obtained from the uniaxial fully-reversed fatigue experiments conducted on polyether ether ketone (PEEK), a semi-crystalline thermoplastic, are presented. The tests were performed in either strain-controlled or load-controlled mode under various levels of loading. The data are categorized into four subsets according to the type of tests, including (1) strain-controlled fatigue tests with adjusted frequency to obtain the nominal temperature rise of the specimen surface, (2) strain-controlled fatigue tests with various frequencies, (3) load-controlled fatigue tests without step loadings, and (4) load-controlled fatigue tests with step loadings. Accompanied data for each test include the fatigue life, the maximum (peak) and minimum (valley) stress-strain responses for each cycle, and the hysteresis stress-strain responses for each collected cycle in a logarithmic increment. A brief description of the experimental method is also given.

Two-carbon homologation of aldehydes and ketones to α,β-unsaturated aldehydes.

PubMed

Petroski, Richard J; Vermillion, Karl; Cossé, Allard A

2011-06-17

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps.

Compatibility Assessment of Fuel System Thermoplastics with Bio-Blendstock Fuel Candidates Using Hansen Solubility Analysis

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

Kass, Michael D.; West, Brian H.

The compatibility of key fuel system infrastructure plastics with 39 bio-blendstock fuel candidates was examined using Hansen solubility analysis. Fuel types included multiple alcohols, esters, ethers, ketones, alkenes and one alkane. These compounds were evaluated as neat molecules and as blends with the gasoline surrogate, dodecane, and a mix of dodecane and 10% ethanol (E10D). The plastics included polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyoxymethylene (POM), polybutylene terephthalate (PBT), polypropylene (PP), high density polyethylene (HDPE), along with several nylon grades. These materials have been rigorously studied with other fuel types, and their volume change resultsmore » were found to correspond well with their predicted solubility levels.The compatibility was assessed using Hansen solubility parameters and in many instances peak solubility occurred for blends rather than the neat fuel components. The results showed that good compatibilities can be expected for PPS, PVDF, PET, nylons, acetal, PEI, PVC, HDPE and PBT. PTFE showed potential incompatibilities at low blend concentrations, especially when E10D was used as the base fuel blend. Although, the nylons show good overall compatibility, the results do indicate that mid-range and high alcohol contents may not be suitable for Nylon 6 and Nylon 11 in applications requiring low volume swell. Poor potential compatibility was limited to two plastic types; PETG exposed to mid and high blend levels of the ethers and PP exposed to sabinene and the aromatics. In general, the data showed good compatibility for the majority of the candidate fuels and plastics.« less

Compatibility Assessment of Fuel System Thermoplastics with Bio-Blendstock Fuel Candidates Using Hansen Solubility Analysis

DOE PAGES

Kass, Michael D.; West, Brian H.

2018-01-03

The compatibility of key fuel system infrastructure plastics with 39 bio-blendstock fuel candidates was examined using Hansen solubility analysis. Fuel types included multiple alcohols, esters, ethers, ketones, alkenes and one alkane. These compounds were evaluated as neat molecules and as blends with the gasoline surrogate, dodecane, and a mix of dodecane and 10% ethanol (E10D). The plastics included polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyoxymethylene (POM), polybutylene terephthalate (PBT), polypropylene (PP), high density polyethylene (HDPE), along with several nylon grades. These materials have been rigorously studied with other fuel types, and their volume change resultsmore » were found to correspond well with their predicted solubility levels.The compatibility was assessed using Hansen solubility parameters and in many instances peak solubility occurred for blends rather than the neat fuel components. The results showed that good compatibilities can be expected for PPS, PVDF, PET, nylons, acetal, PEI, PVC, HDPE and PBT. PTFE showed potential incompatibilities at low blend concentrations, especially when E10D was used as the base fuel blend. Although, the nylons show good overall compatibility, the results do indicate that mid-range and high alcohol contents may not be suitable for Nylon 6 and Nylon 11 in applications requiring low volume swell. Poor potential compatibility was limited to two plastic types; PETG exposed to mid and high blend levels of the ethers and PP exposed to sabinene and the aromatics. In general, the data showed good compatibility for the majority of the candidate fuels and plastics.« less

Dual palladium- and proline-catalyzed allylic alkylation of enolizable ketones and aldehydes with allylic alcohols.

PubMed

Usui, Ippei; Schmidt, Stefan; Breit, Bernhard

2009-03-19

The dual Pd/proline-catalyzed alpha-allylation reaction of a variety of enolizable ketones and aldehydes with allylic alcohols is described. In this reaction, the choice of a large-bite angle ligand Xantphos and proline as the organocatalyst was essential for generation of the crucial pi-allyl Pd intermediate from allylic alcohol, followed by nucleophilic attack of the enamine formed in situ from the corresponding enolizable carbonyl substrate and proline.

Composition of secondary alcohols, ketones, alkanediols, and ketols in Arabidopsis thaliana cuticular waxes

PubMed Central

Wen, Miao; Jetter, Reinhard

2009-01-01

Arabidopsis wax components containing secondary functional groups were examined (i) to test the biosynthetic relationship between secondary alcohols and ketols and (ii) to determine the regiospecificity and substrate preference of the enzyme involved in ketol biosynthesis. The stem wax of Arabidopsis wild type contained homologous series of C27 to C31 secondary alcohols (2.4 μg cm−2) and C28 to C30 ketones (6.0 μg cm−2) dominated by C29 homologues. In addition, compound classes containing two secondary functional groups were identified as C29 diols (∼0.05 μg cm−2) and ketols (∼0.16 μg cm−2). All four compound classes showed characteristic isomer distributions, with functional groups located between C-14 and C-16. In the mah1 mutant stem wax, diols and ketols could not be detected, while the amounts of secondary alcohols and ketones were drastically reduced. In two MAH1-overexpressing lines, equal amounts of C29 and C31 secondary alcohols were detected. Based on the comparison of homologue and isomer compositions between the different genotypes, it can be concluded that biosynthetic pathways lead from alkanes to secondary alcohols, and via ketones or diols to ketols. It seems plausible that MAH1 is the hydroxylase enzyme involved in all these conversions in Arabidopsis thaliana. PMID:19346242

Quantitative prediction of solvation free energy in octanol of organic compounds.

PubMed

Delgado, Eduardo J; Jaña, Gonzalo A

2009-03-01

The free energy of solvation, DeltaGS0, in octanol of organic compounds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a DeltaGS0 range from about -50 to 0 kJ.mol(-1). The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ.mol(-1), just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set.

Quantitative Prediction of Solvation Free Energy in Octanol of Organic Compounds

PubMed Central

Delgado, Eduardo J.; Jaña, Gonzalo A.

2009-01-01

The free energy of solvation, ΔGS0, in octanol of organic compunds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a ΔGS0 range from about −50 to 0 kJ·mol−1. The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ·mol−1, just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set. PMID:19399236

L-Arginine modified multi-walled carbon nanotube/sulfonated poly(ether ether ketone) nanocomposite films for biomedical applications

NASA Astrophysics Data System (ADS)

Kaya, Hatice; Bulut, Osman; Kamali, Ali Reza; Ege, Duygu

2018-06-01

Favorable implant-tissue interactions are crucial to achieve successful osseointegration of the implants. Poly(ether ether ketone) (PEEK) is an interesting alternative to titanium in orthopedics because of its low cost, high biocompatibility and comparable mechanical properties with cancellous bone. Despite these advantages; however, the untreated surface of PEEK fails to osseointegrate due to its bioinert and hydrophobic behavior. This paper deals with the surface modification of PEEK with a novel method. For this, PEEK was first treated with concentrated sulfuric acid to prepare sulfonated PEEK (SPEEK) films using a solvent casting method. Then, 1 and 2 wt% multi-walled carbon nanotube was incorporated into SPEEK to form nanocomposite films. The samples were characterized with Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy. After successful preparation of the nanocomposite films, L-arginine was covalently conjugated on the nanocomposite films to further improve their surface properties. Subsequently, the samples were characterized using X-ray Photoemission Spectroscopy (XPS), water contact angle measurements and Atomic Force Microscopy (AFM) and Dynamic Mechanical Thermal Analysis (DMTA). Finally, cell culture studies were carried out by using Alamar Blue assay to evaluate the biocompatibility of the films. The results obtained indicate the successful preparation of L-arginine-conjugated MWCNT/SPEEK nanocomposite films. The modified surface shows potential to improve implants' mechanical and biological performances.

Tribological assessment of a flexible carbon-fibre-reinforced poly(ether-ether-ketone) acetabular cup articulating against an alumina femoral head.

PubMed

Scholes, S C; Inman, I A; Unsworth, A; Jones, E

2008-04-01

New material combinations have been introduced as the bearing surfaces of hip prostheses in an attempt to prolong their life by overcoming the problems of failure due to wear-particle-induced osteolysis. This will hopefully reduce the need for revision surgery. The study detailed here used a hip simulator to assess the volumetric wear rates of large-diameter carbon-fibre-reinforced pitch-based poly(ether-ether-ketone) (CFR-PEEK) acetabular cups articulating against alumina femoral heads. The joints were tested for 25 x 10(6) cycles. Friction tests were also performed on these joints to determine the lubrication regime under which they operate. The average volumetric wear rate of the CFR-PEEK acetabular component of 54 mm diameter was 1.16 mm(3)/10(6) cycles, compared with 38.6 mm(3)/10(6) cycles for an ultra-high-molecular-weight polyethylene acetabular component of 28 mm diameter worn against a ceramic head. This extremely low wear rate was sustained over 25 x 10(6) cycles (the equivalent of up to approximately 25 years in vivo). The frictional studies showed that the joints worked under the mixed-boundary lubrication regime. The low wear produced by these joints showed that this novel joint couple offers low wear rates and therefore may be an alternative material choice for the reduction of osteolysis.

Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

2017-05-01

A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

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.

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).

Highly Selective Upgrading of Biomass-Derived Alcohol Mixtures for Jet/Diesel-Fuel Components.

PubMed

Liu, Qiang; Xu, Guoqiang; Wang, Xicheng; Liu, Xiaoran; Mu, Xindong

2016-12-20

In light of the increasing concern about the energy and environmental problems caused by the combustion of petroleum-based fuels (e.g., jet and diesel fuels), the development of new procedures for their sustainable production from renewable biomass-derived platform compounds has attracted tremendous attention recently. Long-chain ketones/alcohols are promising fuel components owing to the fuel properties that closely resemble those of traditional fuels. The focus of this report is the production of long-chain ketones/alcohols by direct upgrading of biomass-derived short-chain alcohol mixtures (e.g., isopropanol-butanol-ethanol mixtures) in pure water. An efficient Pd catalyst system was developed for these highly selective transformations. Long-chain ketones/alcohols (C 8 -C 19 ), which can be used as precursors for renewable jet/diesel fuel, were obtained in good-to-high selectivity (>90 %) by using the developed Pd catalyst. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

PubMed Central

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2014-01-01

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

Formation and reactions of negative ions relevant to chemical ionization mass spectrometry. I. Cl mass spectra of organic compounds produced by F− reactions

PubMed Central

Tiernan, T. O.; Chang, C.; Cheng, C. C.

1980-01-01

A systematic study of the negative-ion chemical ionization mass spectra produced by the reaction of F− with a wide variety of organic compounds has been accomplished. A time-of-flight mass spectrometer fitted with a modified high pressure ion source was employed for these experiments. The F− reagent ion was generated from CF3H or NF3, typically at an ion source pressure of 100 μm. In pure NF3, F− is the major ion formed and constitutes more than 90% of the total ion intensity. While F− is also the major primary ion formed in pure CF3H, it undergoes rapid ion-molecule reactions at elevated source pressures, yielding (HF)nF− (n = 1−3) ions, which makes CF3H less suitable as a chemical ionization reagent gas. Among the organic compounds investigated were carboxylic acids, ketones, aldehydes, esters, alcohols, phenols, halides, nitriles, nitrobenzene, ethers, amines and hydrocarbons. An intense (M − 1)− ion was observed in the F− chemical ionization mass spectra of carboxylic acids, ketones, aldehydes and phenols. Alcohols yield only (M + F)− ions upon reaction with F−. A weaker (M + F)− ion was also detected in the F− chemical ionization spectra of carboxylic acids, aldehydes, ketones and nitriles. The F− chemical ionization mass spectra of esters, halides, nitriles, nitrobenzene and ethers are characterized primarily by the ions, RCOO−, X−, CN−, NO2−, and OR−, respectively. In addition, esters show a very weak (M − 1)− ion (except formates). In the F− chemical ionization spectra of some aliphatic alkanes and o-xylene, a very weak (M + F)− ion was observed. Amines and aliphatic alkenes exhibit only insignificant fragment ions under similar conditions, while aromatic hydrocarbons, such as benzene and toluene are not reactive at all with the F− ion. The mechanisms of the various reactions mentioned are discussed, and several experimental complications are noted. In still other studies, the effects of varying several experimental parameters, including source pressure, relative proportions of the reagent and analyte, and other ion source parameters, on the observed chemical ionization mass spectra were also investigated. In a mixture of NF3 and n-butanol, for example, the ratio of the intensities of the ions characteristic of the alcohol to that of the (HF)nF− ion was found to decrease with increasing sample pressure, with increasing NF3 pressure, and with increasing electron energy. No significant effects on the spectra were observed to result from variation of the source repeller field or the source temperature. The addition of argon to the source as a potential moderator did not alter the F− chemical ionization spectrum significantly, but the use of oxygen appears to inhibit formation of the (HF)nF− cluster ion. The advantages of using F− as a chemical ionization reagent are discussed, and comparisons are made with other reagent ions. PMID:7428746

Characterization of an allylic/benzyl alcohol dehydrogenase from Yokenella sp. strain WZY002, an organism potentially useful for the synthesis of α,β-unsaturated alcohols from allylic aldehydes and ketones.

PubMed

Ying, Xiangxian; Wang, Yifang; Xiong, Bin; Wu, Tingting; Xie, Liping; Yu, Meilan; Wang, Zhao

2014-04-01

A novel whole-cell biocatalyst with high allylic alcohol-oxidizing activities was screened and identified as Yokenella sp. WZY002, which chemoselectively reduced the C=O bond of allylic aldehydes/ketones to the corresponding α,β-unsaturated alcohols at 30°C and pH 8.0. The strain also had the capacity of stereoselectively reducing aromatic ketones to (S)-enantioselective alcohols. The enzyme responsible for the predominant allylic/benzyl alcohol dehydrogenase activity was purified to homogeneity and designated YsADH (alcohol dehydrogenase from Yokenella sp.), which had a calculated subunit molecular mass of 36,411 Da. The gene encoding YsADH was subsequently expressed in Escherichia coli, and the purified recombinant YsADH protein was characterized. The enzyme strictly required NADP(H) as a coenzyme and was putatively zinc dependent. The optimal pH and temperature for crotonaldehyde reduction were pH 6.5 and 65°C, whereas those for crotyl alcohol oxidation were pH 8.0 and 55°C. The enzyme showed moderate thermostability, with a half-life of 6.2 h at 55°C. It was robust in the presence of organic solvents and retained 87.5% of the initial activity after 24 h of incubation with 20% (vol/vol) dimethyl sulfoxide. The enzyme preferentially catalyzed allylic/benzyl aldehydes as the substrate in the reduction of aldehydes/ketones and yielded the highest activity of 427 U mg(-1) for benzaldehyde reduction, while the alcohol oxidation reaction demonstrated the maximum activity of 79.9 U mg(-1) using crotyl alcohol as the substrate. Moreover, kinetic parameters of the enzyme showed lower Km values and higher catalytic efficiency for crotonaldehyde/benzaldehyde and NADPH than for crotyl alcohol/benzyl alcohol and NADP(+), suggesting the nature of being an aldehyde reductase.

Characterization of an Allylic/Benzyl Alcohol Dehydrogenase from Yokenella sp. Strain WZY002, an Organism Potentially Useful for the Synthesis of α,β-Unsaturated Alcohols from Allylic Aldehydes and Ketones

PubMed Central

Ying, Xiangxian; Wang, Yifang; Xiong, Bin; Wu, Tingting; Xie, Liping; Yu, Meilan

2014-01-01

A novel whole-cell biocatalyst with high allylic alcohol-oxidizing activities was screened and identified as Yokenella sp. WZY002, which chemoselectively reduced the C=O bond of allylic aldehydes/ketones to the corresponding α,β-unsaturated alcohols at 30°C and pH 8.0. The strain also had the capacity of stereoselectively reducing aromatic ketones to (S)-enantioselective alcohols. The enzyme responsible for the predominant allylic/benzyl alcohol dehydrogenase activity was purified to homogeneity and designated YsADH (alcohol dehydrogenase from Yokenella sp.), which had a calculated subunit molecular mass of 36,411 Da. The gene encoding YsADH was subsequently expressed in Escherichia coli, and the purified recombinant YsADH protein was characterized. The enzyme strictly required NADP(H) as a coenzyme and was putatively zinc dependent. The optimal pH and temperature for crotonaldehyde reduction were pH 6.5 and 65°C, whereas those for crotyl alcohol oxidation were pH 8.0 and 55°C. The enzyme showed moderate thermostability, with a half-life of 6.2 h at 55°C. It was robust in the presence of organic solvents and retained 87.5% of the initial activity after 24 h of incubation with 20% (vol/vol) dimethyl sulfoxide. The enzyme preferentially catalyzed allylic/benzyl aldehydes as the substrate in the reduction of aldehydes/ketones and yielded the highest activity of 427 U mg−1 for benzaldehyde reduction, while the alcohol oxidation reaction demonstrated the maximum activity of 79.9 U mg−1 using crotyl alcohol as the substrate. Moreover, kinetic parameters of the enzyme showed lower Km values and higher catalytic efficiency for crotonaldehyde/benzaldehyde and NADPH than for crotyl alcohol/benzyl alcohol and NADP+, suggesting the nature of being an aldehyde reductase. PMID:24509923

Proceedings of the International Conference for the Promotion of Advanced Fire Resistant Aircraft Interior Materials, Held in Atlantic City, New Jersey on February 9 - 11, 1993

DTIC Science & Technology

1993-02-11

aged for 14 days at 120OF and 95% relative humidity (hot and humid ). After... aging tests indicate, Uralane 5774-A/B is not adversely affected by hot and humid environments . In fact, in many cases, mechanical strengths improved...Presently included in these industrially important thermoplastics are the poly (arylene ether ketone )s (PEKs) and poly (arylene ether sulfone)s (PESs). Poly

Special Issue on Powering the Future Force: New Power & Energy Technologies for the Warfighter (AMMTIAC Quarterly, Volume 4, Number 1 / WSTIAC Quarterly, Volume 9, Number 1)

DTIC Science & Technology

2009-04-27

an aromatic acidic polymer such as SPEEK or SPSf. Figure 5 shows four basic polymers in which benzimidazole (BIm), amino- benzimidazole (ABIm...Z., A. Manthiram, and M. D. Guiver, “Blend Membranes Based on Sulfonated Polyetheretherketone and Polysulfone Bearing Benzimidazole Side Groups for...Sulfonated Poly(ether ether ketone) and Polysulfone Bearing Benzimidazole Side Groups for Direct Methanol Fuel Cells,” Electrochemical and Solid State Letters

The crystallization of tough thermoplastic resins in the presence of carbon fibers

NASA Technical Reports Server (NTRS)

Theil, M. H.

1986-01-01

The crystallization kinetics of the thermoplastic resins poly(phenylene sulfide) (PPS) and poly(aryl-ether-ether-ketone) (PEEK) in the presence and in the abscence of carbon fibers was studied. How carbon fiber surfaces in composites affect the crystallization of tough thermoplastic polymers that may serve as matrix resins were determined. The crystallization kinetics of such substances can provide useful information about the crystallization mechanisms and, thus, indicate if the presence of carbon fibers cause any changes in such mechanisms.

Liquid-liquid extraction of ethanol from aqueous solutions with amyl acetate, benzyl alcohol, and methyl isobutyl ketone at 298. 15. Kappa

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

Solimo, H.N.; Martinez, H.E.; Riggio, R.

1989-04-01

Experimental mutual solubility and tie-line data were determined for three ternary liquid-liquid systems containing water, ethanol, and amyl acetate, benzyl alcohol, and methyl isobutyl ketone at 298.15{Kappa} in order to obtain their complete phase diagrams and to determine which is the most suitable solvent for extraction of ethanol from aqueous solutions. Tie lines were determined correlating the density of the binodal curve as a function of composition and the plait points using the Othmer and Tobias method. The experimental data were also correlated with the UNIFAC group contribution method. A qualitative agreement was obtained. Experimental results show that amyl acetatemore » is a better solvent than methyl isobutyl ketone and benzyl alcohol.« less

Development of General Antisera for Trichothecanes

DTIC Science & Technology

1986-07-01

by treatment with selenium dioxide. The alcohol was further oxidized with pyridinium chlorochromate to the unsatu- rated ketone A-3. The ketone was...A-10. Thus, A-7 was oxidized as described above with pyridinIum chlorochromate and sodium acetate In methylene chloride to give A-8 In 72% yield...analog by treatment with selenium dioxide. Further oxidation with pyri inium chlorochromate yielded the unsaturated 8- ketone. This ketone was readily

Infrared and reflectron time-of-flight mass spectroscopic analysis of methane (CH4)-carbon monoxide (CO) ices exposed to ionization radiation--toward the formation of carbonyl-bearing molecules in extraterrestrial ices.

PubMed

Kaiser, Ralf I; Maity, Surajit; Jones, Brant M

2014-02-28

Ice mixtures of methane and carbon monoxide were exposed to ionizing radiation in the form of energetic electrons at 5.5 K to investigate the formation of carbonyl bearing molecules in extraterrestrial ices. The radiation induced chemical processing of the mixed ices along with their isotopically labeled counterparts was probed online and in situ via infrared spectroscopy (solid state) aided with reflectron time-of-flight mass spectrometry (ReTOFMS) coupled to single photon photoionization (PI) at 10.49 eV (gas phase). Deconvolution of the carbonyl absorption feature centered at 1727 cm(-1) in the processed ices and subsequent kinetic fitting to the temporal growth of the newly formed species suggests the formation of acetaldehyde (CH3CHO) together with four key classes of carbonyl-bearing molecules: (i) alkyl aldehydes, (ii) alkyl ketones, (iii) α,β-unsaturated ketones/aldehydes and (iv) α,β,γ,δ-unsaturated ketones/α,β-dicarbonyl compounds in keto-enol form. The mechanistical studies indicate that acetaldehyde acts as the key building block of higher aldehydes (i) and ketones (ii) with unsaturated ketones/aldehydes (iii) and/or α,β-dicarbonyl compounds (iv) formed from the latter. Upon sublimation of the newly synthesized molecules, ReTOFMS together with isotopic shifts of the mass-to-charge ratios was exploited to identify eleven product classes containing molecules with up to six carbon atoms, which can be formally derived from C1-C5 hydrocarbons incorporating up to three carbon monoxide building blocks. The classes are (i) saturated aldehydes/ketones, (ii) unsaturated aldehydes/ketones, (iii) doubly unsaturated aldehydes/ketones, (iv) saturated dicarbonyls (aldehydes/ketones), (v) unsaturated dicarbonyls (aldehydes/ketones), (vi) saturated tricarbonyls (aldehydes/ketones), molecules containing (vii) one carbonyl - one alcohol (viii), two carbonyls - one alcohol, (ix) one carbonyl - two alcohol groups along with (x) alcohols and (xi) diols. Reaction pathways to synthesize these classes were derived as well. The present experiments provide clear evidence for the formation of key organic molecules--acetaldehyde, acetone, and potentially vinylalcohol--which are among the 15 carbonyl containing organic molecules detected in the interstellar medium. Despite numerous previous experimental investigations probing the effect of ionizing radiation on simple astrophysical ice representatives, our results suggest that more complex organic molecules can be formed in extraterrestrial ices than previously suggested. An outlook on further identification of individual isomers is also presented.

[1,5]-Anion relay via intramolecular proton transfer to generate 3,3-bis(silyl) allyloxy lithium: a useful scaffold for syn-addition to aldehydes and ketones.

PubMed

Lin, Xinglong; Ye, Xincui; Sun, Xianwei; Zhang, Yuebao; Gao, Lu; Song, Zhenlei

2014-02-21

A [1,5]-anion relay has been achieved in 3,3-bis(silyl) benzyl enol ether. Deprotonation at the sterically more accessible benzyl position triggers an intramolecular proton transfer to generate the thermodynamically more stable 3,3-bis(silyl) allyloxy lithium. This endo-oriented allyl anion is stable at -78 °C and undergoes diastereoselective syn-addition at the γ-position with aldehydes and ketones to give monobenzyl-substituted 1,2-diols.

Organic-Solvent-Free Phase-Transfer Oxidation of Alcohols Using Hydrogen Peroxide

NASA Astrophysics Data System (ADS)

Hulce, Martin; Marks, David W.

2001-01-01

Organic-solvent-free oxidations of alcohols using aqueous hydrogen peroxide in the presence of sodium tungstate and phase-transfer catalysts provide a general, safe, simple, and cost-effective means to prepare ketones. Six representative alcohols, 1-phenylethanol, 1-phenylpropanol, benzhydrol, 4-methylbenzhydrol, cis,trans-4-tert-butylcyclohexanol, and benzyl alcohol are oxidized to the corresponding aldehyde or ketone over 1-3 hours in 81-99% yields. Purities are very high, with only small to trace amounts of starting alcohol remaining. Experiments can be readily designed for one or two 3-hour laboratory periods, integrating the various techniques of extraction, drying, filtration, column chromatography, gas chromatography, NMR and IR spectroscopy, and reaction kinetics.

Comparison of clinical results for the use of ethyl acetate and diethyl ether in the formalin-ether sedimentation technique performed on polyvinyl alcohol-preserved specimens.

PubMed Central

Garcia, L S; Shimizu, R

1981-01-01

One hundred fecal specimens preserved in polyvinyl alcohol fixative were examined by the Formalin-ether sedimentation technique with ethyl acetate substituted for diethyl ether. Technical performance of the procedures, appearance and amount of sediment obtained, and organism morphology were comparable. Also, ethyl acetate is less flammable and, therefore, less dangerous to use than diethyl ether. Results of parasite recovery when diethyl ether or ethyl acetate was used revealed few clinical relevant differences, most of which could also have been attributed to other variables inherent in this type of diagnostic testing. PMID:7229014

Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.

1988-01-01

The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

DOEpatents

Crabtree, R.H.; Brown, S.H.

1988-02-16

The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

Wear resistance of poly(2-methacryloyloxyethyl phosphorylcholine)-grafted carbon fiber reinforced poly(ether ether ketone) liners against metal and ceramic femoral heads.

PubMed

Yamane, Shihori; Kyomoto, Masayuki; Moro, Toru; Hashimoto, Masami; Takatori, Yoshio; Tanaka, Sakae; Ishihara, Kazuhiko

2018-04-01

Younger, active patients who undergo total hip arthroplasty (THA) have increasing needs for wider range of motion and improved stability of the joint. Therefore, bearing materials having not only higher wear resistance but also mechanical strength are required. Carbon fiber-reinforced poly(ether ether ketone) (CFR-PEEK) is known as a super engineering plastic that has great mechanical strength. In this study, we focused on poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-grafted CFR-PEEK and investigated the effects of PMPC grafting and the femoral heads materials on the wear properties of CFR-PEEK liners. Compared with untreated CFR-PEEK, the PMPC-grafted CFR-PEEK surface revealed higher wettability and lower friction properties under aqueous circumstances. In the hip simulator wear test, wear particles generated from the PMPC-grafted CFR-PEEK liners were fewer than those of the untreated CFR-PEEK liners. There were no significant differences in the size and the morphology of the wear particles between the differences of PMPC-grafting and the counter femoral heads. Zirconia-toughened alumina (ZTA) femoral heads had significantly smoother surfaces compared to cobalt-chromium-molybdenum alloy femoral heads after the hip simulator test. Thus, we conclude that the bearing combination of the PMPC-grafted CFR-PEEK liner and ZTA head is expected to be a lifelong bearing interface in THA. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1028-1037, 2018. © 2017 Wiley Periodicals, Inc.

Reactions of NO 3 with the man-made emissions 2-methylpent-2-ene, ( Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone

NASA Astrophysics Data System (ADS)

Pfrang, Christian; Tooze, Christopher; Nalty, Andrew; Canosa-Mas, Carlos E.; Wayne, Richard P.

Rate coefficients for reactions of nitrate radicals (NO 3) with the anthropogenic emissions 2-methylpent-2-ene, ( Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3±1.1)×10 -12, (9.3±3.2)×10 -12, (1.7±1.3)×10 -12 and (9.4±2.7)×10 -17 cm 3 molecule -1 s -1. We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO 3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, ( Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.

Sulfonated Holey Graphene Oxide (SHGO) Filled Sulfonated Poly(ether ether ketone) Membrane: The Role of Holes in the SHGO in Improving Its Performance as Proton Exchange Membrane for Direct Methanol Fuel Cells.

PubMed

Jiang, Zhong-Jie; Jiang, Zhongqing; Tian, Xiaoning; Luo, Lijuan; Liu, Meilin

2017-06-14

Sulfonated holey graphene oxides (SHGOs) have been synthesized by the etching of sulfonated graphene oxides with concentrated HNO 3 under the assistance of ultrasonication. These SHGOs could be used as fillers for the sulfonated aromatic poly(ether ether ketone) (SPEEK) membrane. The obtained SHGO-incorporated SPEEK membrane has a uniform and dense structure, exhibiting higher performance as proton exchange membranes (PEMs), for instance, higher proton conductivity, lower activation energy for proton conduction, and comparable methanol permeability, as compared to Nafion 112. The sulfonated graphitic structure of the SHGOs is believed to be one of the crucial factors resulting in the higher performance of the SPEEK/SHGO membrane, since it could increase the local density of the -SO 3 H groups in the membrane and induce a strong interfacial interaction between SHGO and the SPEEK matrix, which improve the proton conductivity and lower the swelling ratio of the membrane, respectively. Additionally, the proton conductivity of the membrane could be further enhanced by the presence of the holes in the graphitic planes of the SHGOs, since it provides an additional channel for transport of the protons. When used, direct methanol fuel cell with the SPEEK/SHGO membrane is found to exhibit much higher performance than that with Nafion 112, suggesting potential use of the SPEEK/SHGO membrane as the PEMs.

Improved adaptability of polyaryl-ether-ether-ketone with texture pattern and graphite-like carbon film for bio-tribological applications

NASA Astrophysics Data System (ADS)

Ren, Siming; Huang, Jinxia; Cui, Mingjun; Pu, Jibin; Wang, Liping

2017-04-01

With the development of surface treatment technology, an increasing number of bearings, seals, dynamic friction drive or even biomedical devices involve a textured surface to improve lubrication and anti-wear. The present investigation has been conducted in order to evaluate the friction and wear behaviours of textured polyaryl-ether-ether-ketone (PEEK) coated with a graphite-like carbon (GLC) film sliding against stainless steel pin in biological medium. Compared with pure PEEK, the PEEK coated with GLC film shows excellent tribological performance with a low friction of 0.08 and long lifetime (wear volumes are about 3.78 × 10-4 mm3 for un-textured one and 2.60 × 10-4 mm3 for textured GLC film after 36,000 s of sliding) under physiological saline solution. In particular, the GLC film with appropriate dimple area density is effective to improve friction reduction and wear resistance properties of PEEK substrate under biological solution, which is attributed to the entrapment of wear debris in the dimples to inhibit the graphitization and the fluid dynamic pressure effect derived from the texture surface to increase the thickness in elastohydrodynamic lubrication (EHL) film during sliding motions. Moreover, the friction coefficient of GLC film under physiological saline solution decreases with the increase in the applied load. With the increasing applied load, the texture surface is responsible for accounting the improved wear resistance and a much lower graphitization of the GLC film during whole test.

Craniofacial reconstruction using patient-specific implants polyether ether ketone with computer-assisted planning.

PubMed

Manrique, Oscar J; Lalezarzadeh, Frank; Dayan, Erez; Shin, Joseph; Buchbinder, Daniel; Smith, Mark

2015-05-01

Reconstruction of bony craniofacial defects requires precise understanding of the anatomic relationships. The ideal reconstructive technique should be fast as well as economical, with minimal donor-site morbidity, and provide a lasting and aesthetically pleasing result. There are some circumstances in which a patient's own tissue is not sufficient to reconstruct defects. The development of sophisticated software has facilitated the manufacturing of patient-specific implants (PSIs). The aim of this study was to analyze the utility of polyether ether ketone (PEEK) PSIs for craniofacial reconstruction. We performed a retrospective chart review from July 2009 to July 2013 in patients who underwent craniofacial reconstruction using PEEK-PSIs using a virtual process based on computer-aided design and computer-aided manufacturing. A total of 6 patients were identified. The mean age was 46 years (16-68 y). Operative indications included cancer (n = 4), congenital deformities (n = 1), and infection (n = 1). The mean surgical time was 3.7 hours and the mean hospital stay was 1.5 days. The mean surface area of the defect was 93.4 ± 43.26 cm(2), the mean implant cost was $8493 ± $837.95, and the mean time required to manufacture the implants was 2 weeks. No major or minor complications were seen during the 4-year follow-up. We found PEEK implants to be useful in the reconstruction of complex calvarial defects, demonstrating a low complication rate, good outcomes, and high patient satisfaction in this small series of patients. Polyether ether ketone implants show promising potential and warrant further study to better establish the role of this technology in cranial reconstruction.

Indium-mediated asymmetric Barbier-type propargylations: additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents.

PubMed

Haddad, Terra D; Hirayama, Lacie C; Buckley, Jannise J; Singaram, Bakthan

2012-01-20

We report a simple, efficient, and general method for the indium-mediated enantioselective propargylation of aromatic and aliphatic aldehydes under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 90%) and enantiomeric excess (up to 95%). The extension of this methodology to ketones demonstrated the need for electrophilic ketones more reactive than acetophenone as the reaction would not proceed with just acetophenone. Using the Lewis acid indium triflate [In(OTf)(3)] induced regioselective formation of the corresponding homoallenic alcohol product from acetophenone. However, this methodology demonstrated excellent chemoselectivity in formation of only the corresponding secondary homopropargylic alcohol product in the presence of a ketone functionality. Investigation of the organoindium intermediates under our reaction conditions shows the formation of allenylindium species, and we suggest that these species contain an indium(III) center. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.

Gas-chromatographic resolution of enantiomeric secondary alcohols. Stereoselective reductive metabolism of ketones in rabbit-liver cytosol.

PubMed

Gal, J; DeVito, D; Harper, T W

1981-01-01

Chiral secondary alcohols were treated with (S)-(-)-1-phenylethyl isocyanate. For each racemic alcohol, the resulting diastereomeric urethane derivatives were resolved on flexible fused-silica capillary GLC columns with retention times of 15 min or less. Derivatization of individual enantiomers showed that the urethane derivatives of (R)-(-)-2-octanol, (R)-(+)-1-phenylethyl alcohol, and (S)-(+)-2,2,2-trifluoro-1-phenylethanol are eluted before the corresponding diastereomers. The procedure is simple and rapid, and is suitable for the determination of the enantiomeric composition of chiral alcohols extracted from biological media. A series of aliphatic alcohols, aryl alkyl carbinols, and arylalkyl alkyl carbinols were resolved with the procedure, and the degree of resolution varied from good to excellent. Eight achiral ketones were incubated, individually, with rabbit-liver 90,000 g supernatant fractions, and the enantiomeric composition of the alcohol metabolites was determined with the GLC procedure. The reductions proceeded with high stereoselectivity to give alcohol products of 90% or greater enantiomeric purity. The reduction of 2-octanone and acetophenone gave predominant alcohols of (S)-configuration, in agreement with the Baumann-Prelog rule. The configuration of the predominant alcohols arising in the reduction of the remainder of the ketones could not be firmly established, but the evidence suggests that they are also of the (S)-configuration. Fluorine or methyl substitution in the ortho position of acetophenone produced an increase in the stereoselectivity, and the alcohol produced from ortho-methylacetophenone was enantiomerically greater than 99% pure.

Recent Developments in the Use of Organoboranes in Organic Synthesis

ERIC Educational Resources Information Center

Cragg, G. M. L.

1969-01-01

Describes how the carbonylation of organoboranes in a suitable solvent can produce various alcohols, ketones, aldehydes and oxymethylation derivatives. The synthesis of alpha-alkylated ketone using alkylboranes is discussed. (RR)

Heterogeneous Heterobimetallic Catalysis Enabling Expeditious Access to CF3-Containing vic-Amino Alcohols.

PubMed

Karasawa, Tomoya; Kumagai, Naoya; Shibasaki, Masakatsu

2018-01-05

A highly anti-selective catalytic asymmetric nitroaldol reaction of trifluoromethyl ketones based on Nd/Na and Pr/Na heterobimetallic catalysts was developed. These catalysts function as heterogeneous catalysts to engage nitroethane and a range of trifluoromethyl ketones in a stereoselective assembly to afford CF 3 -appended vic-nitroalkanols that could be readily converted to enantioenriched vic-amino alcohols, which are privileged structural motifs in medicinal chemistry.

Bilateral Malar Reconstruction Using Patient-Specific Polyether Ether Ketone Implants in Treacher-Collins Syndrome Patients With Absent Zygomas.

PubMed

Sainsbury, David C G; George, Alan; Forrest, Christopher R; Phillips, John H

2017-03-01

The authors performed bilateral malar reconstruction using polyether ether ketone implants in 3 patients with Treacher-Collins syndrome with absent, as opposed to hypoplastic, zygomata. These patient-specific implants were fabricated using computed-aided design software reformatted from three-dimensional bony preoperative computed tomography images. The first time the authors performed this procedure the implant compressed the globe resulting in temporary anisocoria that was quickly recognized intraoperatively. The implant was immediately removed and the patient made a full-recovery with no ocular disturbance. The computer-aided design and manufacturing process was adjusted to include periorbital soft-tissue boundaries to aid in contouring the new implants. The same patient, and 2 further patients, subsequently underwent malar reconstruction using this soft tissue periorbital boundary fabrication process with an additional 2 mm relief removed from the implant's orbital surface. These subsequent procedures were performed without complication and with pleasing aesthetic results. The authors describe their experience and the salutary lessons learnt.

Mechanical properties of orthodontic wires covered with a polyether ether ketone tube.

PubMed

Shirakawa, Nobukazu; Iwata, Toshio; Miyake, Shinjiro; Otuka, Takero; Koizumi, So; Kawata, Toshitugu

2018-03-21

To evaluate the esthetics and frictional force of an orthodontic wire passed through a newly designed tube made of a polyether ether ketone (PEEK) resin. Two types of standard PEEK tubes were prepared at 0.5 × 0.6ф and 0.8 × 0.9ф, and different archwires were passed through the tubes. Color values were determined according to brightness and hues. Friction was assessed with different bracket-wire combinations, and surface roughness was determined by stereomicroscopy before and after the application of friction. The PEEK tube showed a color difference that was almost identical to that of coated wires conventionally used in clinical practice, indicating a sufficient esthetic property. The result of the friction test showed that the frictional force was greatly reduced by passing the archwire through the PEEK tube in almost all of the archwires tested. Use of the new PEEK tube demonstrated a good combination of esthetic and functional properties for use in orthodontic appliances.

Low-temperature direct heterogeneous bonding of polyether ether ketone and platinum.

PubMed

Fu, Weixin; Shigetou, Akitsu; Shoji, Shuichi; Mizuno, Jun

2017-10-01

Direct heterogeneous bonding between polyether ether ketone (PEEK) and Pt was realized at the temperatures lower than 150°C. In order to create sufficient bondability to diverse materials, the surface was modified by vacuum ultraviolet (VUV) irradiation, which formed hydrate bridges. For comparison, direct bonding between surfaces atomically cleaned via Ar fast atom bombardment (FAB) was conducted in a vacuum. The VUV irradiation was found to be effective for creating an ultrathin hydrate bridge layer from the residual water molecules in the chamber. Tight bonds were formed through dehydration of the hydrate bridges by heating at 150°C, which also contributed to enhancing interdiffusion across the interface. The VUV-modified surfaces showed bondability as good as that of the FAB-treated surfaces, and the VUV-modified samples had shear strengths at the same level as those of FAB-treated surfaces. This technology will be of practical use in the packaging of lightweight, flexible biomedical devices. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of two and antibacterial activity of one novel oxime ether derivatives of erythromycin A.

PubMed

Dondas, H A; Yaktubay, N

2003-10-01

The synthesis of novel erythromycin A 9-O-(2-ethenesulfony-ethyl)-oxime and erythromycin A 9-O-(3-oxo-butyl)-oxime from erythromycin A (EA) by the Michael reaction is described and to describe the effects of transformation of ketone in position 9 of EA to an oxime ether. This transformation occurred in a single step without protecting of any functional moiety of erythromycin oxime and zero waste manner in good yield. The antibacterial screen of EA 9-O-(2-ethenesulfony-ethyl)-oxime is also reported.

Poly(aryl-ether-ether-ketone) as a Possible Metalized Film Capacitor Dielectric: Accurate Description of the Band Gap Through Ab Initio Calculation

DTIC Science & Technology

2014-12-01

from standard HSE06 hybrid functional with α = 0.25 and ω = 0.11 bohr–1 and b) from HSE with α = 0.093 and ω of 0.11 bohr–1...better agreement for the band gap value for future calculations, a systemic study was conducted for the (α, ω) parameter space of the HSE ...orthogonal). Future HSE calculations will be performed with the updated parameters. Fig. 7 Density of States of PEEK based on the optimized

Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.

1989-01-01

The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

DOEpatents

Crabtree, R.H.; Brown, S.H.

1989-10-17

The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

Iridium Catalysts with f-Amphox Ligands: Asymmetric Hydrogenation of Simple Ketones.

PubMed

Wu, Weilong; Liu, Shaodong; Duan, Meng; Tan, Xuefeng; Chen, Caiyou; Xie, Yun; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu

2016-06-17

A series of modular and rich electronic tridentate ferrocene aminophosphoxazoline ligands (f-amphox) have been successfully developed and used in iridium-catalytic asymmetric hydrogenation of simple ketones to afford corresponding enantiomerically enriched alcohols under mild conditions with superb activities and excellent enantioselectivities (up to 1 000 000 TON, almost all products up to >99% ee, full conversion). The resulting chiral alcohols and their derivatives are important intermediates in pharmaceuticals.

Development of Asymmetric Deacylative Allylation

PubMed Central

Grenning, Alexander J.; Van Allen, Christie K.; Maji, Tapan; Lang, Simon B.

2013-01-01

Herein we present the development of asymmetric deacylative allylation of ketone enolates. The reaction directly couples readily available ketone pronucleophiles with allylic alcohols using facile retro-Claisen cleavage to form reactive intermediates in situ. The simplicity and robustness of the reaction conditions is demonstrated by the preparation of > 6 grams of an allylated tetralone from commercially available materials. Furthermore, use of non-racemic PHOX ligands allows intermolecular formation of quaternary stereocenters directly from allylic alcohols. PMID:23734611

Asymmetric Direct 1,2-Addition of Aryl Grignard Reagents to Aryl Alkyl Ketones.

PubMed

Osakama, Kazuki; Nakajima, Makoto

2016-01-15

The enantioselective addition of Grignard reagents to ketones was promoted by a BINOL derivative bearing alkyl chains at the 3,3'-positions. This is the first asymmetric direct aryl Grignard addition to ketones reported to date. A variety of tertiary diaryl alcohols could be obtained in high yields and enantioselectivities without using any other metal source.

36. BUILDINGS NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, AND ...

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

36. BUILDINGS NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, AND NO. 523, REFRIGERATION PLANT BUILDING, LOOKING EAST. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

Lewis base activation of Lewis acids: catalytic, enantioselective vinylogous aldol addition reactions.

PubMed

Denmark, Scott E; Heemstra, John R

2007-07-20

The generality of Lewis base catalyzed, Lewis acid mediated, enantioselective vinylogous aldol addition reactions has been investigated. The combination of silicon tetrachloride and chiral phosphoramides is a competent catalyst for highly selective additions of a variety of alpha,beta-unsaturated ketone-, 1,3-diketone-, and alpha,beta-unsaturated amide-derived dienolates to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded high enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although alpha,beta-unsaturated ketone-derived dienolate did not react with aliphatic aldehydes, alpha,beta-unsaturated amide-derived dienolates underwent addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivities achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride-chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.

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.

44. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, ...

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

44. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, LOOKING UP DISTILLATION TOWER FROM 2ND LEVEL. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

Iridium-Catalyzed Hydrogen Transfer Reactions

NASA Astrophysics Data System (ADS)

Saidi, Ourida; Williams, Jonathan M. J.

This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

CONVERSION OF DIMETHYL ETHER-BORON TRIFLUORIDE COMPLEX TO POTASSIUM FLUOBORATE

DOEpatents

Eberle, A.R.

1957-06-18

A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

Conversion of dimethyl ether--boron trifluoride complex to potassium fluoborate

DOEpatents

Eberle, A.R.

1957-06-18

A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

Porous titanium-6 aluminum-4 vanadium cage has better osseointegration and less micromotion than a poly-ether-ether-ketone cage in sheep vertebral fusion.

PubMed

Wu, Su-Hua; Li, Yi; Zhang, Yong-Quan; Li, Xiao-Kang; Yuan, Chao-Fan; Hao, Yu-Lin; Zhang, Zhi-Yong; Guo, Zheng

2013-12-01

Interbody fusion cages made of poly-ether-ether-ketone (PEEK) have been widely used in clinics for spinal disorders treatment; however, they do not integrate well with surrounding bone tissue. Ti-6Al-4V (Ti) has demonstrated greater osteoconductivity than PEEK, but the traditional Ti cage is generally limited by its much greater elastic modulus (110 GPa) than natural bone (0.05-30 GPa). In this study, we developed a porous Ti cage using electron beam melting (EBM) technique to reduce its elastic modulus and compared its spinal fusion efficacy with a PEEK cage in a preclinical sheep anterior cervical fusion model. A porous Ti cage possesses a fully interconnected porous structure (porosity: 68 ± 5.3%; pore size: 710 ± 42 μm) and a similar Young's modulus as natural bone (2.5 ± 0.2 GPa). When implanted in vivo, the porous Ti cage promoted fast bone ingrowth, achieving similar bone volume fraction at 6 months as the PEEK cage without autograft transplantation. Moreover, it promoted better osteointegration with higher degree (2-10x) of bone-material binding, demonstrated by histomorphometrical analysis, and significantly higher mechanical stability (P < 0.01), shown by biomechanical testing. The porous Ti cage fabricated by EBM could achieve fast bone ingrowth. In addition, it had better osseointegration and superior mechanical stability than the conventional PEEK cage, demonstrating great potential for clinical application. © 2013 Wiley Periodicals, Inc. and International Center for Artificial Organs and Transplantation.

Stress shielding and fatigue limits of poly-ether-ether-ketone dental implants.

PubMed

Lee, Woo-Taek; Koak, Jai-Young; Lim, Young-Jun; Kim, Seong-Kyun; Kwon, Ho-Beom; Kim, Myung-Joo

2012-05-01

The poly-ether-ether-ketone (PEEK) polymer is of great interest as an alternative to titanium in orthopedics because of its biocompatibility and low elastic modulus. This study evaluated the fatigue limits of PEEK and the effects of the low elastic modulus PEEK in relation to existing dental implants. Compressive loading tests were performed with glass fiber-reinforced PEEK (GFR-PEEK), carbon fiber-reinforced PEEK (CFR-PEEK), and titanium rods. Among these tests, GFR-PEEK fatigue tests were performed according to ISO 14801. For the finite element analysis, three-dimensional models of dental implants and bone were constructed. The implants in the test groups were coated with a 0.5-mm thick and 5-mm long PEEK layer on the upper intrabony area. The strain energy densities (SED) were calculated, and the bone resorption was predicted. The fatigue limits of GFR-PEEK were 310 N and were higher than the static compressive strength of GFR-PEEK. The bone around PEEK-coated implants showed higher levels of SED than the bone in direct contact with the implants, and the wider diameter and stiffer implants showed lower levels of SED. The compressive strength of the GFR-PEEK and CFR-PEEK implants ranged within the bite force of the anterior and posterior dentitions, respectively, and the PEEK implants showed adequate fatigue limits for replacing the anterior teeth. Dental implants with PEEK coatings and PEEK implants may reduce stress shielding effects. Dental implant application of PEEK polymer-fatigue limit and stress shielding. Copyright © 2012 Wiley Periodicals, Inc.

Covalent immobilization of metal organic frameworks onto chemical resistant poly(ether ether ketone) jacket for stir bar extraction.

PubMed

Wang, Chenlu; Zhou, Wei; Liao, Xiaoyan; Wang, Xuemei; Chen, Zilin

2018-09-26

Preparation of stir bar extraction (SBSE) device with high physical and chemical stability is important and challenging by date. A novel poly (ether ether ketone) (PEEK) tube with excellent mechanical property and chemical stability was firstly used as jacket of metal bar for preparation of stir bar. By employing covalent modification method, the inherent chemical resistant problem of PEEK which restricts the modification of sorbents was well solved. After functionalization, plenty of benzoic acid groups were formed onto the PEEK jacket. Metal organic frameworks of aluminium-based Materials of Institute Lavoisier-68 (MIL-68) was in situ immobilized onto the PEEK surface (MIL-68@PEEK) by the bonding with benzoic acid groups. Afterwards, a facile dumbbell-shaped structure was designed for reducing the friction between sorbents and bottom of container. Due to superior property of the PEEK jacket and the covalent modification method, the MIL-68 modified PEEK jacket SBSE device showed good robustness. After coupling with HPLC-MS/MS, the MIL-68@PEEK-based SBSE device was used to analyse of three parabens including methyl paraben, ethyl paraben and propyl paraben. The method had low limit detection up to 1 pg mL -1 with good linearity (R 2  ≥ 0.9978) and good reproducibility (relative standard deviation ≤ 9.74%). The method has been applied to the detection of parabens in cosmetics and rabbit plasma after painted with cosmetics with recoveries between 73.25% and 104.23%. Copyright © 2018 Elsevier B.V. All rights reserved.

Dielectric characterization of high-performance spaceflight materials

NASA Astrophysics Data System (ADS)

Kleppe, Nathan; Nurge, Mark A.; Bowler, Nicola

2015-03-01

As commercial space travel increases, the need for reliable structural health monitoring to predict possible weaknesses or failures of structural materials also increases. Monitoring of these materials can be done through the use of dielectric spectroscopy by comparing permittivity or conductivity measurements performed on a sample in use to that of a pristine sample from 100 μHz to 3 GHz. Fluctuations in these measured values or of the relaxation frequencies, if present, can indicate chemical or physical changes occurring within the material and the possible need for maintenance/replacement. In this work, we establish indicative trends that occur due to changes in dielectric spectra during accelerated aging of various high-performance polymeric materials: ethylene vinyl alcohol (EVOH), Poly (ether ether ketone) (PEEK), polyphenylene sulfide (PPS), and ultra-high molecular weight polyethylene (UHMWPE). Uses for these materials range from electrical insulation and protective coatings to windows and air- or space-craft parts that may be subject to environmental damage over long-term operation. Samples were prepared by thermal exposure and, separately, by ultraviolet/water-spray cyclic aging. The aged samples showed statistically-significant trends of either increasing or decreasing real or imaginary permittivity values, relaxation frequencies, conduction or the appearance of new relaxation modes. These results suggest that dielectric testing offers the possibility of nondestructive evaluation of the extent of age-related degradation in these materials.

Enantioselective Reduction of Ketones and Imines Catalyzed by (CN-Box)Re(V)-Oxo Complexes

PubMed Central

Nolin, Kristine A.; Ahn, Richard W.; Kobayashi, Yusuke; Kennedy-Smith, Joshua J.

2012-01-01

The development and application of chiral, non-racemic Re(V)-oxo complexes to the enantioselective reduction of prochiral ketones is described. In addition to the enantioselective reduction of prochiral ketones, we report the application of these complexes to (1) a tandem Meyer-Schuster rearrangement/reduction to access enantioenriched allylic alcohols and (2) the enantioselective reduction of imines. PMID:20623567

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

PubMed Central

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

1949-01-01

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

Sensor arrays for detecting analytes in fluids

NASA Technical Reports Server (NTRS)

Freund, Michael S. (Inventor); Lewis, Nathan S. (Inventor)

2000-01-01

A sensor array for detecting an analyte in a fluid, comprising at least first and second chemically sensitive resistors electrically connected to an electrical measuring apparatus, wherein each of the chemically sensitive resistors comprises a mixture of nonconductive material and a conductive material. Each resistor provides an electrical path through the mixture of nonconductive material and the conductive material. The resistors also provide a difference in resistance between the conductive elements when contacted with a fluid comprising an analyte at a first concentration, than when contacted with an analyte at a second different concentration. A broad range of analytes can be detected using the sensors of the present invention. Examples of such analytes include, but are not limited to, alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics, organic derivatives, biomolecules, sugars, isoprenes, isoprenoids and fatty acids. Moreover, applications for the sensors of the present invention include, but are not limited to, environmental toxicology, remediation, biomedicine, material quality control, food monitoring and agricultural monitoring.

Emission rates of organics from vegetation in California's Central Valley

NASA Astrophysics Data System (ADS)

Winer, Arthur M.; Arey, Janet; Atkinson, Roger; Aschmann, Sara M.; Long, William D.; Morrison, C. Lynn; Olszyk, David M.

Rates of emission of speciated hydrocarbons have been determined for more than 30 of the most dominant (based on acreage) agricultural and natural plant types found in California's Central Valley. These measurements employed flow-through Teflon chambers, sample collection on solid adsorbent and thermal desorption gas chromatography (GC) and GC-mass spectrometry analysis to identify more than 40 individual organic compounds. In addition to isoprene and the monoterpenes, we observed sesquiterpenes, alcohols, acetates, aldehydes, ketones, ethers, esters, alkanes, alkenes and aromatics as emissions from these plant species. Mean emission rates for total monoterpenes ranged from none detected in the case of beans, grapes, rice and wheat, to as high as 12-30 μg h -1 g -1 for pistachio and tomato (normalized to dry leaf and total biomass, respectively). Other agricultural species exhibiting substantial rates of emission of monoterpenes included carrot, cotton, lemon, orange and walnut. All of the plant species studied showed total assigned compound emission rates in the range between 0.1 and 36 νg h -1 g -1.

Methanol ice VUV photoprocessing: GC-MS analysis of volatile organic compounds

NASA Astrophysics Data System (ADS)

Abou Mrad, Ninette; Duvernay, Fabrice; Chiavassa, Thierry; Danger, Grégoire

2016-05-01

Next to water, methanol is one of the most abundant molecules in astrophysical ices. A new experimental approach is presented here for the direct monitoring via gas chromatography coupled to mass spectrometry (GC-MS) of a sublimating photoprocessed pure methanol ice. Unprecedentedly, in a same analysis, compelling evidences for the formation of 33 volatile organic compounds are provided. The latter are C1-C6 products including alcohols, aldehydes, ketones, esters, ethers and carboxylic acids. Few C3 and all C4 detected compounds have been identified for the first time. Tentative detections of few C5 and C6 compounds are also presented. GC-MS allows for the first time the direct quantification of C2-C4 photoproducts and shows that their abundances decrease with the increase of their carbon chain length. These qualitative and quantitative measurements provide important complementary results to previous experiments, and present interesting similarities with observations of sources rich in methanol.

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.

Readily Accessible and Highly Efficient Ferrocene-Based Amino-Phosphine-Alcohol (f-Amphol) Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of Simple Ketones.

PubMed

Yu, Jianfei; Duan, Meng; Wu, Weilong; Qi, Xiaotian; Xue, Peng; Lan, Yu; Dong, Xiu-Qin; Zhang, Xumu

2017-01-18

We have successfully developed a series of novel and modular ferrorence-based amino-phosphine-alcohol (f-Amphol) ligands, and applied them to iridium-catalyzed asymmetric hydrogenation of various simple ketones to afford the corresponding chiral alcohols with excellent enantioselectivities and conversions (98-99.9 % ee, >99 % conversion, turnover number up to 200 000). Control experiments and density functional theory (DFT) calculations have shown that the hydroxyl group of our f-Amphol ligands played a key role in this asymmetric hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

DOE PAGES

Jiang, Xingyu; Chen, Wenyong; Hartwig, John F.

2016-04-01

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.

Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones

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

Jiang, Xingyu; Chen, Wenyong; Hartwig, John F.

The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Here, are the diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.

A One-Pot Tandem Strategy in Catalytic Asymmetric Vinylogous Aldol Reaction of Homoallylic Alcohols.

PubMed

Hou, Xufeng; Jing, Zhenzhong; Bai, Xiangbin; Jiang, Zhiyong

2016-06-27

Reported is a rationally-designed one-pot sequential strategy that allows homoallylic alcohols to be employed in a catalytic, asymmetric, direct vinylogous aldol reaction with a series of activated acyclic ketones, including trifluoromethyl ketones, γ-ketoesters, and α-keto phosphonates, in high yields (up to 95%) with excellent regio- and enantio-selectivity (up to 99% ee). This modular combination, including Jones oxidation and asymmetric organocatalysis, has satisfactory compatibility and reliability even at a 20 mmol scale, albeit without intermediary purification.

Raspberry Ketone Analogs: Vapour Pressure Measurements and Attractiveness to Queensland Fruit Fly, Bactrocera tryoni (Froggatt) (Diptera: Tephritidae)

PubMed Central

Hanssen, Benjamin L.; Jamie, Joanne F.; Jamie, Ian M.; Siderhurst, Matthew S.; Taylor, Phillip W.

2016-01-01

The Queensland fruit fly, Bactrocera tryoni (Froggatt) (Q-fly), is a major horticultural pest in Eastern Australia. Effective monitoring, male annihilation technique (MAT) and mass trapping (MT) are all important for control and require strong lures to attract flies to traps or toxicants. Lure strength is thought to be related in part to volatility, but little vapour pressure data are available for most Q-fly lures. Raspberry ketone (4-(4-hydroxyphenyl)-2-butanone) and analogs that had esters (acetyl, difluoroacetyl, trifluoroacetyl, formyl, propionyl) and ethers (methyl ether, trimethylsilyl ether) in replacement of the phenolic group, and in one case also had modification of the 2-butanone side chain, were measured for their vapour pressures by differential scanning calorimetry (DSC), and their attractiveness to Q-fly was assessed in small cage environmentally controlled laboratory bioassays. Maximum response of one category of compounds, containing both 2-butanone side chain and ester group was found to be higher than that of the other group of compounds, of which either of 2-butanone or ester functionality was modified. However, linear relationship between vapour pressure and maximum response was not significant. The results of this study indicate that, while volatility may be a factor in lure effectiveness, molecular structure is the dominating factor for the series of molecules investigated. PMID:27196605

Evaluation of certain food additives.

PubMed

2015-01-01

This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, including flavouring agents, and to prepare specifications for identity and purity. The first part of the report contains a general discussion of the principles governing the toxicological evaluation of and assessment of dietary exposure to food additives, including flavouring agents. A summary follows of the Committee's evaluations of technical, toxicological and dietary exposure data for eight food additives (Benzoe tonkinensis; carrageenan; citric and fatty acid esters of glycerol; gardenia yellow; lutein esters from Tagetes erecta; octenyl succinic acid-modified gum arabic; octenyl succinic acid-modified starch; paprika extract; and pectin) and eight groups of flavouring agents (aliphatic and alicyclic hydrocarbons; aliphatic and aromatic ethers; ionones and structurally related substances; miscellaneous nitrogen-containing substances; monocyclic and bicyclic secondary alcohols, ketones and related esters; phenol and phenol derivatives; phenyl-substituted aliphatic alcohols and related aldehydes and esters; and sulfur-containing heterocyclic compounds). Specifications for the following food additives were revised: citric acid; gellan gum; polyoxyethylene (20) sorbitan monostearate; potassium aluminium silicate; and Quillaia extract (Type 2). Annexed to the report are tables summarizing the Committee's recommendations for dietary exposures to and toxicological evaluations of all of the food additives and flavouring agents considered at this meeting.

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

2016-09-01

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

Allergic Reaction to Polyether Ether Ketone Following Cross-Reactivity to Epoxy Resin.

PubMed

Kofler, Lukas; Wambacher, Markus; Schweinzer, Katrin; Scherl, Maritta; Kofler, Heinz

Polyether ether ketone (PEEK) is a thermoplastic polymer frequently used in engineering but also in medical devices. Only 1 case of allergic reaction to PEEK used as an implanted medical device has been reported so far; however, the route of sensitization remained unclear. Here we report on a 62-year-old male patient with a preknown, severe type IV allergy to epoxy resin. He reported strong pain in his shoulder after implantation of a PEEK-containing device after a rotator cuff injury. For testing, the device was implanted in a small pouch subcutaneously on the abdomen. The patient reported massive pain starting 8 hours after the implantation, strictly limited to the procedural area and showing perifocal erythema. A possible explanation of the sensitization mode is the source material for PEEK and epoxy resin, as both are mainly based on bisphenols. An allergic reaction to PEEK with preknown epoxy resin sensitization has not been reported so far. As epoxy resins are a frequent cause of occupational contact dermatitis and PEEK is widely used for medical and nonmedical devices, we believe that this is of great clinical relevance.

Morphology Effect on Proton Dynamics in Nafion® 117 and Sulfonated Polyether Ether Ketone

NASA Astrophysics Data System (ADS)

Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

2016-09-01

We report results of our experimental and theoretical studies on the dynamics of proton conductivity in Nafion® 117 and self-fabricated sulfonated polyether ether ketone (SPEEK) membranes. Knowing that the presence of water molecules in the diffusion process results in a lower energy barrier, we determined the diffusion barriers and corresponding tunneling probabilities of Nafion® 117 and SPEEK system using a simple theoretical model that excludes the medium (water molecules) in the initial calculations. We then propose an equation that relates the membrane conductivity to the tunneling probability. We recover the effect of the medium by introducing a correction term into the proposed equation, which takes into account the effect of the proton diffusion distance and the hydration level. We have also experimentally verified that the proposed equation correctly explain the difference in conductivity between Nafion® 117 and SPEEK. We found that membranes that are to be operated in low hydration environments (high temperatures) need to be designed with short diffusion distances to enhance and maintain high conductivity.

Characterization of oxidized coal surfaces: Quarterly report, May 1987-July 1987

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

Hercules, D.M.

1987-01-01

Work has progressed in the areas of (1) exploration or derivatization reactions for ambient temperature in-situ derivatization of aldehydes, ketones, and phenols on carbon surfaces; (2) analysis of these derivatives by secondary ion mass spectrometry (SIMS) and laser mass spectrometry (LMS); (3) derivatization and analysis of a naturally weathered coal; (4) construction of a reactor for controlled low temperature oxidation of coal; and (5) design of a protocol for handling coal samples. Specific derivatization reactions studied in this period included reactions of Girard's reagent, 2,4-dinitrophenylhydrazine and bisulfite with aldehydes and ketones and 4-triethylammonium-2-butene (TAB), trimethylsilyl ethers (TMS) and dimethylsilyl ethersmore » (DMS) with phenols and alcohols. Positive ion SIMS analysis of Girard's reagent derivatives and TAB derivatives on a silver support yielded molecular ion species (e.g., cations from the salts) for a wide range of carbonyl and phenolic compounds, respectively. Comparison of negative ion LMS spectra of naturally weathered Illinois No. 6 coal before and after treatment with 2,4-dinitrophenylhydrazine reveals the presence of two high mass ions in the spectrum of treated coal that are not present in the spectra of either the untreated coal or the derivatizing reagent. This provides both evidence for carbonyl functionality on the surface of naturally weathered Illinois No. 6 coal and support for the feasibility of in-situ derivatization and analysis of organic components in the coal matrix. 5 refs.« less

EVALUATION OF METHYL TERT-BUTYL ETHER (MTBE) AS AN INTERFERENCE ON COMMERCIAL BREATH-ALCOHOL ANALYZERS

EPA Science Inventory

Anecdotal reports suggest that high environmental or occupational exposures to the fuel oxygenate methyl tert-butyl ether (MTBE) may result in breath concentrations that are sufficiently elevated to cause a false positive on commercial breath-alcohol analyzers. We evaluated th...

40 CFR 79.52 - Tier 1.

Code of Federal Regulations, 2012 CFR

2012-07-01

... identity and concentration of individual species of aldehyde and ketone compounds containing eight or fewer...) “Advanced Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program—II. Aldehydes, Ketones, and Alcohols,” Auto Oil Air Quality Improvement Research Program, SP-920, 920321, SAE, February...

40 CFR 79.52 - Tier 1.

Code of Federal Regulations, 2011 CFR

2011-07-01

... identity and concentration of individual species of aldehyde and ketone compounds containing eight or fewer...) “Advanced Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program—II. Aldehydes, Ketones, and Alcohols,” Auto Oil Air Quality Improvement Research Program, SP-920, 920321, SAE, February...

40 CFR 79.52 - Tier 1.

Code of Federal Regulations, 2014 CFR

2014-07-01

... identity and concentration of individual species of aldehyde and ketone compounds containing eight or fewer...) “Advanced Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program—II. Aldehydes, Ketones, and Alcohols,” Auto Oil Air Quality Improvement Research Program, SP-920, 920321, SAE, February...

40 CFR 79.52 - Tier 1.

Code of Federal Regulations, 2013 CFR

2013-07-01

... identity and concentration of individual species of aldehyde and ketone compounds containing eight or fewer...) “Advanced Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program—II. Aldehydes, Ketones, and Alcohols,” Auto Oil Air Quality Improvement Research Program, SP-920, 920321, SAE, February...

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.

Occupational exposure to petroleum-based and oxygenated solvents and hypopharyngeal and laryngeal cancer in France: the ICARE study.

PubMed

Barul, Christine; Carton, Matthieu; Radoï, Loredana; Menvielle, Gwenn; Pilorget, Corinne; Bara, Simona; Stücker, Isabelle; Luce, Danièle

2018-04-05

To examine associations between occupational exposure to petroleum-based and oxygenated solvents and the risk of hypopharyngeal and laryngeal cancer. ICARE is a large, frequency-matched population-based case-control study conducted in France. Lifetime occupational history, tobacco smoking and alcohol consumption were collected. Analyses were restricted to men and included 383 cases of hypopharyngeal cancer, 454 cases of laryngeal cancer, and 2780 controls. Job-exposure matrices were used to assess exposure to five petroleum-based solvents (benzene; gasoline; white spirits; diesel, fuels and kerosene; special petroleum products) and to five oxygenated solvents (alcohols; ketones and esters; ethylene glycol; diethyl ether; tetrahydrofuran). Odds ratios (ORs) adjusted for smoking, alcohol drinking and other potential confounders and 95% confidence intervals (CI) were estimated with unconditional logistic models. No significant association was found between hypopharyngeal or laryngeal cancer risk and exposure to the solvents under study. Non-significantly elevated risks of hypopharyngeal cancer were found in men exposed to high cumulative levels of white spirits (OR = 1.46; 95% CI: 0.88-2.43) and tetrahydrofuran (OR = 2.63; 95CI%: 0.55-12.65), with some indication of a dose-response relationship (p for trend: 0.09 and 0.07 respectively). This study provides weak evidence for an association between hypopharyngeal cancer and exposure to white spirits and tetrahydrofuran, and overall does not suggest a substantial role of exposure to petroleum-based or oxygenated solvents in hypopharyngeal or laryngeal cancer risk.

STRUCTURE TOXICITY IN RELATIONSHIPS FOR A,B-UNSATURATED ALCOHOLS IN FISH

EPA Science Inventory

Previous toxicity testing with fathead minnows (Pimephales promelas) indicated that some unsaturated acetylenic and allylic alcohols can be metabolically activated, via alcohol dehydrogenase, to highly toxic a,B-unsaturated aldehydes and ketones or allene derivatives. lthough sev...

Improved synthesis of chiral alcohols with Escherichia coli cells co-expressing pyridine nucleotide transhydrogenase, NADP+-dependent alcohol dehydrogenase and NAD+-dependent formate dehydrogenase.

PubMed

Weckbecker, Andrea; Hummel, Werner

2004-11-01

Recombinant pyridine nucleotide transhydrogenase (PNT) from Escherichia coli has been used to regenerate NAD+ and NADPH. The pnta and pntb genes encoding for the alpha- and beta-subunits were cloned and co-expressed with NADP+-dependent alcohol dehydrogenase (ADH) from Lactobacillus kefir and NAD+-dependent formate dehydrogenase (FDH) from Candida boidinii. Using this whole-cell biocatalyst, efficient conversion of prochiral ketones to chiral alcohols was achieved: 66% acetophenone was reduced to (R)-phenylethanol over 12 h, whereas only 19% (R)-phenylethanol was formed under the same conditions with cells containing ADH and FDH genes but without PNT genes. Cells that were permeabilized with toluene showed ketone reduction only if both cofactors were present.

Etched poly(ether ether ketone) jacket stir bar with detachable dumbbell-shaped structure for stir bar sorptive extraction.

PubMed

Zhou, Wei; Wang, Chenlu; Wang, Xuemei; Chen, Zilin

2018-06-08

Development of stir bar sorptive extraction (SBSE) device with high stability and extraction efficiency is critical and challenging by date. In this work, etched poly(ether ether ketone) (PEEK) tube with high mechanical strength and large specific surface area was used as jacket for SBSE device. By etching with concentrated sulfuric acid, the smooth outer surface of PEEK become porous with plenty of micro holes, which was beneficial for coating of sorbents and significantly improved the extraction performance. After functionalized by bio-polydopamine method, strong hydrophobic p-naphtholbenzein molecular was immobilized onto the chemical resistant PEEK surface (PNB@E-PEEK) as stationary phase. We also firstly developed a simple detachable dumbbell-shaped structure for improving the workability of PEEK jacket stir bar. The dumbbell-shaped construction can eliminate the friction between stir bar and container, and the design of detachable structure make elution can be accomplished easier with small amount of organic solvent. It was interesting that the developed detachable dumbbell-shaped PNB@E-PEEK stir bar showed exceptional stability and extraction efficiency for SBSE enrichment of multiple analytes including several Sudan dyes, triazines, polycyclic aromatic hydrocarbons (PAHs), alkaloids and flavonoid. By coupling with high performance liquid chromatography-ultraviolet detection (HPLC-UV), PNB@E-PEEK stir bar based SBSE-HPLC-UV method was applied for the analysis of common Sudan dye pollutants. The method showed low limits of detection (0.02-0.03 ng/mL), good linearity (R 2  ≥ 0.9979) and good reproducibility (relative standard deviation ≤ 7.96%). It has been successfully applied to determine three dye pollutants in tap and lake water. Copyright © 2018 Elsevier B.V. All rights reserved.

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

Friction and wear performance of some thermoplastic polymers and polymer composites against unsaturated polyester

NASA Astrophysics Data System (ADS)

Unal, H.; Mimaroglu, A.; Arda, T.

2006-09-01

Wear experiments have been carried out with a range of unfilled and filled engineering thermoplastic polymers sliding against a 15% glass fibre reinforced unsaturated polyester polymer under 20, 40 and 60 N loads and 0.5 m/s sliding speed. Pin materials used in this experimental investigation are polyamide 66 (PA 66), poly-ether-ether-ketone (PEEK) and aliphatic polyketone (APK), glass fibre reinforced polyamide 46 (PA 46 + 30% GFR), glass fibre reinforced polytetrafluoroethylene (PTFE + 17% GFR), glass fibre reinforced poly-ether-ether-ketone (PEEK + 20% GFR), glass fibre reinforced poly-phylene-sulfide (PPS + 30% GFR), polytetrafluoroethylene filled polyamide 66 (PA 66 + 10% PTFE) and bronze filled pofytetrafluoroethylene (PTFE + 25% bronze) engineering polymers. The disc material is a 15% glass fibre reinforced unsaturated polyester thermoset polymer produced by Bulk Moulding Compound (BMC). Sliding wear tests were carried out on a pin-on-disc apparatus under 0.5 m/s sliding speed and load values of 20, 40 and 60 N. The results showed that the highest specific wear rate is for PPS + 30% GFR with a value of 1 × 10 -11 m 2/N and the lowest wear rate is for PTFE + 17% GFR with a value of 9.41 × 10 -15 m 2/N. For the materials and test conditions of this investigation, apart from polyamide 66 and PA 46 + 30% GFR polymers, the coefficient of friction and specific wear rates are not significantly affected by the change in load value. For polyamide 66 and PA 46 + 30% GFR polymers the coefficient of friction and specific wear rates vary linearly with the variation in load values.

Resonance stabilization effects on ketone autoxidation: Isomer-specific cyclic ether and ketohydroperoxide formation in the low-temperature (400–625 K) oxidation of diethyl ketone

DOE PAGES

Scheer, Adam M.; Eskola, Arkke J.; Osborn, David L.; ...

2016-10-11

Here, the pulsed photolytic chlorine-initiated oxidation of diethyl ketone [DEK; (CH 3CH 2) 2C=O], 2,2,4,4- d 4-DEK [ d 4-DEK; (CH 3CD 2) 2C=O], and 1,1,1,5,5,5-d 6-DEK [ d 6-DEK; (CD 3CH 2) 2C=O] is studied at 8 torr and 1–2 atm and from 400–625 K. Cl atoms produced by laser photolysis react with diethyl ketone to form either primary (3-pentan-on-1-yl, R P) or secondary (3-pentan-on-2-yl, R S) radicals, which in turn react with O 2. Multiplexed time-of-flight mass spectrometry, coupled to either a hydrogen discharge lamp or tunable synchrotron photoionizing radiation, is used to detect products as a functionmore » of mass, time, and photon energy. At 8 torr, the nature of the chain propagating cyclic ether + OH channel changes as a function of temperature. At 450 K, the production of OH is mainly in conjunction with formation of 2,4-dimethyloxetan-3-one, resulting from reaction of the resonance-stabilized secondary R S with O 2. In contrast, at 550 K and 8 torr, 2-methyl-tetrahydrofuran-3-one, originating from oxidation of the primary radical (RP), is observed as the dominant cyclic ether product. Formation of both of these cyclic ether production channels proceeds via a resonance-stabilized hydroperoxy alkyl (QOOH) intermediate. Little or no ketohydroperoxide (KHP) is observed under the low-pressure conditions. At higher O 2 concentrations and higher pressures (1–2 atm), a strong KHP signal appears as the temperature is increased above 450 K. Definitive isomeric identification from measurements on the deuterated DEK isotopologues indicates the favored pathway produces a γ-KHP via resonance-stabilized alkyl, QOOH, and HOOPOOH radicals. Time-resolved measurements reveal the KHP formation becomes faster and signal more intense upon increasing temperature from 450 to 575 K before intensity drops significantly at 625 K. The KHP time profile also shows a peak followed by a gradual depletion for the extent of experiment. Several tertiary products exhibit a slow accumulation in coincidence with the observed KHP decay. These products can be associated with decomposition of KHP by β-scission pathways or via isomerization of a γ-KHP into a cyclic peroxide intermediate (Korcek mechanism). The oxidation of d 4-DEK, where kinetic isotope effects disfavor γ-KHP formation, shows greatly reduced KHP formation and associated signatures from KHP decomposition products.« less

Method for producing hydrocarbon and alcohol mixtures. [Patent application

DOEpatents

Compere, A.L.; Googin, J.M.; Griffith, W.L.

1980-12-01

It is an object of this invention to provide an efficient process for extracting alcohols and ketones from an aqueous solution containing the same into hydrocarbon fuel mixtures, such as gasoline, diesel fuel and fuel oil. Another object of the invention is to provide a mixture consisting of hydrocarbon, alcohols or ketones, polyoxyalkylene polymer and water which can be directly added to fuels or further purified. The above stated objects are achieved in accordance with a preferred embodiment of the invention by contacting an aqueous fermentation liquor with a hydrocarbon or hydrocarbon mixture containing carbon compounds having 5 to 18 carbon atoms, which may include gasoline, diesel fuel or fuel oil. The hydrocarbon-aqueous alcohol solution is mixed in the presence or one or more of a group of polyoxyalkylene polymers described in detail hereinafter; the fermentation alcohol being extracted into the hydrocarbon fuel-polyoxyalkylene polymer mixture.

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.

Enzymatic network for production of ether amines from alcohols.

PubMed

Palacio, Cyntia M; Crismaru, Ciprian G; Bartsch, Sebastian; Navickas, Vaidotas; Ditrich, Klaus; Breuer, Michael; Abu, Rohana; Woodley, John M; Baldenius, Kai; Wu, Bian; Janssen, Dick B

2016-09-01

We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed for reactions containing 10 mM alcohol and up to 280 mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up. Biotechnol. Bioeng. 2016;113: 1853-1861. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Acidolysis small molecular phenolic ether used as accelerator in photosensitive diazonaphthaquinone systems

NASA Astrophysics Data System (ADS)

Zhou, Haihua; Zou, Yingquan

2006-03-01

The photosensitive compounds in the photosensitive coatings of positive PS plates are the diazonaphthaquinone derivatives. Some acidolysis small molecular phenolic ethers, which were synthesized by some special polyhydroxyl phenols with vinyl ethyl ether, are added in the positive diazonaphthaquinone photosensitive composition to improve its sensitivity, composed with photo-acid-generators. The effects to the photosensitivity, anti-alkali property, anti-isopropyl alcohol property, dot resolution and line resolution of the coatings are studied with different additive percent of the special phenolic ethers. In the conventional photosensitive diazonaphthaquinone systems for positive PS plates, the photosensitivity is improved without negative effects to resolution, anti-alkali and anti-isopropyl alcohol properties when added about 5% of the special acidolysis phenolic ethers, EAAE or DPHE, composed with photo-acid-generators.

Highly Enantioselective Production of Chiral Secondary Alcohols Using Lactobacillus paracasei BD101 as a New Whole Cell Biocatalyst and Evaluation of Their Antimicrobial Effects.

PubMed

Yılmaz, Durmuşhan; Şahin, Engin; Dertli, Enes

2017-11-01

Chiral secondary alcohols are valuable intermediates for many important enantiopure pharmaceuticals and biologically active molecules. In this work, we studied asymmetric reduction of aromatic ketones to produce the corresponding chiral secondary alcohols using lactic acid bacteria (LAB) as new biocatalysts. Seven LAB strains were screened for their ability to reduce acetophenones to their corresponding alcohols. Among these strains, Lactobacillus paracasei BD101 was found to be the most successful at reducing the ketones to the corresponding alcohols. The reaction conditions were further systematically optimized for this strain and high enantioselectivity (99%) and very good yields were obtained. These secondary alcohols were further tested for their antimicrobial activities against important pathogens and significant levels of antimicrobial activities were observed although these activities were altered depending on the secondary alcohols as well as their enantiomeric properties. The current methodology demonstrates a promising and alternative green approach for the synthesis of chiral secondary alcohols of biological importance in a cheap, mild, and environmentally useful process. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

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

Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

USGS Publications Warehouse

Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

1995-01-01

Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the ??-ether or ??-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic ??-ether and ??-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

Furfuryl ethyl ether: important aging flavor and a new marker for the storage conditions of beer.

PubMed

Vanderhaegen, Bart; Neven, Hedwig; Daenen, Luk; Verstrepen, Kevin J; Verachtert, Hubert; Derdelinckx, Guy

2004-03-24

Recently, it was reported that furfuryl ethyl ether is an important flavor compound indicative of beer storage and aging conditions. A study of the reaction mechanism indicates that furfuryl ethyl ether is most likely formed by protonation of furfuryl alcohol or furfuryl acetate followed by S(N)2-substitution of the leaving group by the nucleophilic ethanol. For the reaction in beer, a pseudo-first-order reaction kinetics was derived. A close correlation was found between the values predicted by the kinetic model and the actual furfuryl ethyl ether concentration evolution during storage of beer. Furthermore, 10 commercial beers of different types, aged during 4 years in natural conditions, were analyzed, and it was found that the furfuryl ethyl ether flavor threshold was largely exceeded in each type of beer. In these natural aging conditions, lower pH, darker color, and higher alcohol content were factors that enhanced furfuryl ethyl ether formation. On the other hand, sulfite clearly reduced furfuryl ethyl ether formation. All results show that the furfuryl ethyl ether concentration is an excellent time-temperature integrator for beer storage.

Allyl transfer to aldehydes and ketones by Brønsted acid activation of allyl and crotyl 1,3,2-dioxazaborolidines.

PubMed

Reilly, Maureen K; Rychnovsky, Scott D

2010-11-05

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism).

Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex.

PubMed

Brown, Elizabeth S; Robinson, Jerome R; McCoy, Aaron M; McGaff, Robert W

2011-06-14

We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.

HIGH LEVELS OF MONOAROMATIC COMPOUNDS LIMIT THE USE OF SOLID-PHASE MICROEXTRACTION OF METHYL TERTIARY BUTYL ETHER AND TERTIARY BUTYL ALCOHOL

EPA Science Inventory

Recently, two papers reported the use of solid-phase microextraction (SPME) with polydimethylsiloxane(PDMS)/Carboxen fibers to determine trace levels of methyl tertiary butyl ether (MTBE) and tertiary butyl alcohol (tBA) in water. Attempts were made to apply this technique to th...

Influence of the brewing process on furfuryl ethyl ether formation during beer aging.

PubMed

Vanderhaegen, Bart; Neven, Hedwig; Verstrepen, Kevin J; Delvaux, Freddy R; Verachtert, Hubert; Derdelinckx, Guy

2004-11-03

In beer, the development of a solvent-like stale flavor is associated with the formation of furfuryl ethyl ether. The synthesis rate of this important flavor compound is proportional to the concentration of furfuryl alcohol in beer. This study shows that furfuryl alcohol in beer is mainly formed by Maillard reactions initiated during wort boiling and malt production. A mechanism for its formation from alpha-(1,4)-oligoglucans and amino acids in wort and beer is proposed. During wort boiling, a quadratic relationship was found between the wort extract concentration, on the one hand, and the increase of furfuryl alcohol and furfural, on the other. The reduction of furfural by yeast during fermentation further increases the furfuryl alcohol content. In pale beers, the furfuryl alcohol concentration is essentially determined by the thermal load on wort during brewing operations. In dark beers, a considerable fraction of furfuryl alcohol may, however, come from the dark malts used. These results lead to important practical conclusions concerning the control over furfuryl ethyl ether in beer.

SOLVENT EXTRACTION PROCESS FOR PROTACTINIUM

DOEpatents

Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

1961-04-01

A process is described for separating protactinium from thorium present together as the nitrates in a 0.1 to 10 N nitric acid solution. The separation is carried out by extraction with an aliphatic alcohol, ketone, and/or ester having at least six carbon atoms, such as n-amyl acetate, 2-ethyl hexanol, and diisopropyl ketone.

The Oxidation of Secondary Alcohols with Cr (VI).

ERIC Educational Resources Information Center

Mason, Timothy J.

1982-01-01

Describes experiments in which acid chromate oxidation rates of four secondary alcohols are determined and related to the differences in strain relief involved in the conversion of the alcohols to their respective ketone products. All four oxidations can be completed in a 4-hour laboratory period. (Author/JN)

Local deformation behavior of surface porous polyether-ether-ketone.

PubMed

Evans, Nathan T; Torstrick, F Brennan; Safranski, David L; Guldberg, Robert E; Gall, Ken

2017-01-01

Surface porous polyether-ether-ketone has the ability to maintain the tensile monotonic and cyclic strength necessary for many load bearing orthopedic applications while providing a surface that facilitates bone ingrowth; however, the relevant deformation behavior of the pore architecture in response to various loading conditions is not yet fully characterized or understood. The focus of this study was to examine the compressive and wear behavior of the surface porous architecture using micro Computed Tomography (micro CT). Pore architectures of various depths (~0.5-2.5mm) and pore sizes (212-508µm) were manufactured using a melt extrusion and porogen leaching process. Compression testing revealed that the pore architecture deforms in the typical three staged linear elastic, plastic, and densification stages characteristic of porous materials. The experimental moduli and yield strengths decreased as the porosity increased but there was no difference in properties between pore sizes. The porous architecture maintained a high degree of porosity available for bone-ingrowth at all strains. Surface porous samples showed no increase in wear rate compared to injection molded samples, with slight pore densification accompanying wear. Copyright © 2016 Elsevier Ltd. All rights reserved.

Poly(ionic liquids)-coated stainless-steel wires packed into a polyether ether ketone tube for in-tube solid-phase microextraction.

PubMed

Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Luo, Chuannan; Sun, Min

2017-12-01

An in-tube solid-phase microextraction device was developed by packing poly(ionic liquids)-coated stainless-steel wires into a polyether ether ketone tube. An anion-exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)-coated stainless-steel wires were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. The extraction device was connected to high-performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03-20 μg/L, detection limits of 0.010-0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1-118.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of microstructural inclusions on fatigue life of polyether ether ketone (PEEK).

PubMed

Simsiriwong, Jutima; Shrestha, Rakish; Shamsaei, Nima; Lugo, Marcos; Moser, Robert D

2015-11-01

In this study, the effects of microstructural inclusions on fatigue life of polyether ether ketone (PEEK) was investigated. Due to the versatility of its material properties, the semi-crystralline PEEK polymer has been increasingly adopted in a wide range of applications particularly as a biomaterial for orthopedic, trauma, and spinal implants. To obtain the cyclic behavior of PEEK, uniaxial fully-reversed strain-controlled fatigue tests were conducted at ambient temperature and at 0.02 mm/mm to 0.04 mm/mm strain amplitudes. The microstructure of PEEK was obtained using the optical and the scanning electron microscope (SEM) to determine the microstructural inclusion properties in PEEK specimen such as inclusion size, type, and nearest neighbor distance. SEM analysis was also conducted on the fracture surface of fatigue specimens to observe microstructural inclusions that served as the crack incubation sites. Based on the experimental strain-life results and the observed microstructure of fatigue specimens, a microstructure-sensitive fatigue model was used to predict the fatigue life of PEEK that includes both crack incubation and small crack growth regimes. Results show that the employed model is applicable to capture microstructural effects on fatigue behavior of PEEK. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Thermodynamic properties (enthalpy, bond energy, entropy, and heat capacity) and internal rotor potentials of vinyl alcohol, methyl vinyl ether, and their corresponding radicals.

PubMed

da Silva, Gabriel; Kim, Chol-Han; Bozzelli, Joseph W

2006-06-29

Vinyl alcohols (enols) have been discovered as important intermediates and products in the oxidation and combustion of hydrocarbons, while methyl vinyl ethers are also thought to occur as important combustion intermediates. Vinyl alcohol has been detected in interstellar media, while poly(vinyl alcohol) and poly(methyl vinyl ether) are common polymers. The thermochemical property data on these vinyl alcohols and methyl vinyl ethers is important for understanding their stability, reaction paths, and kinetics in atmospheric and thermal hydrocarbon-oxygen systems. Enthalpies , entropies , and heat capacities (C(p)()(T)) are determined for CH(2)=CHOH, C(*)H=CHOH, CH(2)=C(*)OH, CH(2)=CHOCH(3), C(*)H=CHOCH(3), CH(2)=C(*)OCH(3), and CH(2)=CHOC(*)H(2). Molecular structures, vibrational frequencies, , and C(p)(T) are calculated at the B3LYP/6-31G(d,p) density functional calculation level. Enthalpies are also determined using the composite CBS-Q, CBS-APNO, and G3 methods using isodesmic work reactions to minimize calculation errors. Potential barriers for internal rotors are calculated at the B3LYP/6-31G(d,p) level and used to determine the hindered internal rotational contributions to entropy and heat capacity. The recommended ideal gas phase values calculated in this study are the following (in kcal mol(-1)): -30.0, -28.9 (syn, anti) for CH(2)=CHOH; -25.6, -23.9 for CH(2)=CHOCH(3); 31.3, 33.5 for C(*)H=CHOH; 27.1 for anti-CH(2)=C(*)OH; 35.6, 39.3 for C(*)H=CHOCH(3); 33.5, 32.2 for CH(2)=C(*)OCH(3); 21.3, 22.0 for CH(2)=CHOC(*)H(2). Bond dissociation energies (BDEs) and group additivity contributions are also determined. The BDEs reveal that the O-H, O-CH(3), C-OH, and C-OCH(3) bonds in vinyl alcohol and methyl vinyl ether are similar in energy to those in the aromatic molecules phenol and methyl phenyl ether, being on average around 3 kcal mol(-1) weaker in the vinyl systems. The keto-enol tautomerization enthalpy for the interconversion of vinyl alcohol to acetaldehyde is determined to be -9.7 kcal mol(-1), while the activation energy for this reaction is calculated as 55.9 kcal mol(-1); this is the simplest keto-enol tautomerization and is thought to be important in the reactions of vinyl alcohol. Formation of the formyl methyl radical (vinoxy radical/vinyloxy radical) from both vinyl alcohol and methyl vinyl ether is also shown to be important, and its reactions are discussed briefly.

Study of the Low Temperature Oxidation of Propane

PubMed Central

Cord, Maximilien; Husson, Benoit; Huerta, Juan Carlos Lizardo; Herbinet, Olivier; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Ruiz-Lopez, Manuel; Wang, Zhandong; Xie, Mingfeng; Cheng, Zhanjun; Qi, Fei

2013-01-01

The low-temperature oxidation of propane was investigated using a jet-stirred reactor at atmospheric pressure and two methods of analysis: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, which are not stable enough to be detected by gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of the temperature (530-730 K), with a particular attention to reaction products involved in the low temperature oxidation, such as cyclic ethers, aldehydes, alcohols, ketones, and hydroperoxides. A new model has been obtained from an automatically generated one, which was used as a starting point, with a large number of re-estimated thermochemical and kinetic data. The kinetic data of the most sensitive reactions, i.e., isomerizations of alkylperoxy radicals and the subsequent decompositions, have been calculated at the CBS-QB3 level of theory. The model allows a satisfactory prediction of the experimental data. A flow rate analysis has allowed highlighting the important reaction channels. PMID:23181456

Catalytic oxidation of volatile organic compounds (VOCs) - A review

NASA Astrophysics Data System (ADS)

Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.

2016-09-01

Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

IRON(III) NITRATE-CATALYZED FACILE SYNTHESIS OF DIPHENYLMETHYL (DPM) ETHERS FROM ALCOHOLS

EPA Science Inventory

Diphenyl methyl (DPM) ethers constitute important structural portion of some pharmaceutical entities and also as protective group for hydroxyl groups in synthetic chemistry. DPM ethers are normally prepared using concentrated acids or base as catalysts, which may result in the fo...

Evolution of Interstellar Ices

NASA Astrophysics Data System (ADS)

Allamandola, Louis J.; Bernstein, Max P.; Sandford, Scott A.; Walker, Robert L.

1999-10-01

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H2O, CH3OH, NH3, CO, CO2, and probably H2CO and H2. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents.

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

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

The in vivo response to a novel Ti coating compared with polyether ether ketone: evaluation of the periphery and inner surfaces of an implant.

PubMed

Walsh, William Robert; Pelletier, Matthew H; Christou, Chris; He, Jiawei; Vizesi, Frank; Boden, Scott D

2018-02-26

Increasing bone ongrowth and ingrowth of polyether ether ketone (PEEK) interbody fusion devices has the potential to improve clinical outcomes. This study evaluated the in vivo response of promoting new bone growth and bone apposition with NanoMetalene (NM) compared with PEEK alone in a cancellous implantation site with an empty aperture. This is a randomized control animal study. Implants and funding for this study were provided by SeaSpine (60,000 USD). Cylindrical dowels with two apertures were prepared as PEEK with a sub-micron layer of the titanium (NM). The titanium coating was applied over the entire implant (Group 1) or just the apertures (Group 2). Polyether ether ketone implants with no coating served as controls (Group 3). Implants were placed in the cancellous bone of the distal femur or proximal tibia with no graft material placed in the apertures in eight adult sheep. Bone ongrowth to the surface of the implant and ingrowth into the apertures was assessed at 4 and 8 weeks after surgery with micro-computed tomography (CT) and undecalcified histology. The apertures in the implants were notably empty in the PEEK group at 4 and 8 weeks. In contrast, new bone formation into the apertures was found in samples coated with NM even though no graft material was placed into the defect. The bone growing into the aperture tracked along the titanium layer. Apertures with the titanium coating demonstrated significantly more bone by micro-CT qualitative grading compared with PEEK with average bone coverage scores of Group 1 (NM) 1.62±0.89, Group 2 (NM apertures only) 1.62±0.77, and Group 3 (PEEK) 0.43±0.51, respectively, at 4 weeks (p<.01) and Group 1 (NM) 1.79±1.19, Group 2 (NM apertures only) 1.98±1.18, and Group 3 (PEEK) 0.69±0.87, respectively, at 8 weeks (p<.05). The amount of bone in the apertures (ingrowth) quantified using the volumetric data from the micro-CT supported an overall increase in bone volume inside the apertures with the titanium coating compared with PEEK. Histology showed newly formed woven bone tracked along the surface of the titanium in the apertures. The PEEK interface presented the typical nonreactive fibrous tissue inside the apertures at 4 weeks and some focal contact with bone on the outside at 4 weeks and 8 weeks. Micro-CT and histology demonstrated bone ongrowth to the surfaces coated with NM where the newly formed bone tracked along the thin titanium-coated surfaces. Polyether ether ketone surfaces presented the nonreactive fibrous tissue at the interface as previously reported in preclinical scenarios. Copyright © 2018. Published by Elsevier Inc.

Interstellar Alcohols

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Kress, M. E.; Tielens, A. G. G. M.; Millar, T. J.

1995-01-01

We have investigated the gas-phase chemistry in dense cores where ice mantles containing ethanol and other alcohols have been evaporated. Model calculations show that methanol, ethanol, propanol, and butanol drive a chemistry leading to the formation of several large ethers and esters. Of these molecules, methyl ethyl ether (CH3OC2H5) and diethyl ether (C2H5)2O attain the highest abundances and should be present in detectable quantities within cores rich in ethanol and methanol. Gas-phase reactions act to destroy evaporated ethanol and a low observed abundance of gas-phase C,H,OH does not rule out a high solid-phase abundance. Grain surface formation mechanisms and other possible gas-phase reactions driven by alcohols are discussed, as are observing strategies for the detection of these large interstellar molecules.

Allyl Transfer to Aldehydes and Ketones by Brønsted Acid Activation of Allyl and Crotyl 1,3,2-Dioxazaborolidines

PubMed Central

Reilly, Maureen K.; Rychnovsky, Scott D.

2010-01-01

Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (Type I mechanism). PMID:20942379

Synthesis of carboxylic acids, esters, alcohols and ethers containing a tetrahydropyran ring derived from 6-methyl-5-hepten-2-one.

PubMed

Hanzawa, Yohko; Hashimoto, Kahoko; Kasashima, Yoshio; Takahashi, Yoshiko; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu

2012-01-01

3-hydroxy acids, 3-hydroxy-3,7-dimethyloct-6-enoic acid (1) and 3-hydroxy-2,2,3,7-tetramethyloct-6-enoic acid (2), were prepared from 6-methyl-5-hepten-2-one, and they were subsequently used to prepare (2,6,6-trimethyltetrahydropyran-2-yl)acetic acid (3) and 2-methyl-2-(2,6,6-trimethyltetrahydropyran-2-yl)propanoic acid (4), respectively, via cyclization with an acidic catalyst such as boron trifluoride diethyl etherate or iodine. The reaction of carboxylic acids 3 and 4 with alcohols, including methanol, ethanol, and 1-propanol, produced the corresponding methyl, ethyl, and propyl esters, which all contained a tetrahydropyran ring. Reduction of carboxylic acids 3 and 4 afforded the corresponding alcohols. Subsequent reactions of these alcohols with several acyl chlorides produced novel esters. The alcohols also reacted with methyl iodide and sodium hydride to provide novel ethers. A one-pot cyclization-esterification of 1 to produce esters containing a tetrahydropyran ring, using iodine as a catalyst, was also investigated.

Abstracts of AF Materials Laboratory Reports. January 1973 - December 1973

DTIC Science & Technology

1974-07-01

substituted polymers with aryl ether , ketone and sulfone units in the backbone has been studied. The best resins seem to have come from simple...exposed to hostile environments such as heat aging plus salt spray, humid aging , humid aging and elevated temperature cycling, and fatigue...unclassified results of materials and process and radome characterization effort. Environmental exposure including thermal aging resulted in significant

SELECTIVE OXIDATION OF ALCOHOLS - COMPARING DIFFERENT CATALYTIC PROCESSES

EPA Science Inventory

Oxidation of alcohols to aldehydes, ketones or carboxylic acids is one of the most desirable chemical transformations in organic synthesis as these products are important precursors and intermediates for many drugs, vitamins and fragrances. Numerous methods are available for alc...

ALCOHOL OXIDATION - A COMPARATIVE STUDY OF DIFFERENT CATALYTIC PROCESSES

EPA Science Inventory

Oxidation of alcohols to aldehydes, ketones or carboxylic acids is one of the most desirable chemical transformations in organic synthesis as these products are important precursors and intermediates for many drugs, vitamins and fragrances. Numerous methods are available for alco...

Metabolism of Some Anionic Tallow-based Detergents by Sewage Microorganisms1

PubMed Central

Cordon, Theone C.; Maurer, Elmer W.; Nuñez-Ponzoa, M. V.; Stirton, A. J.

1968-01-01

A method in which the test detergent was the sole source of carbon was used to study the metabolism of several tallow-based detergents. These were tallow alcohol sulfates, long-chain ether alcohol sulfates, and esters of α-sulfo fatty acids. Sodium p-(1-methylundecyl)benzenesulfonate (LAS) was used as a reference material. The alcohol sulfates were the most rapidly and completely metabolized (96 to 99%), and one ether alcohol sulfate was 94% degraded. The other compounds were metabolized to the extent of 61 to 87%; LAS was 80% degraded. Except for the alcohol sulfates, loss of methylene blue activity (MBAS) occurred long before the chemical oxygen demand (COD) values had reached a minimum; with the alcohol sulfates, MBAS and COD decreased simultaneously. PMID:5636472

Purification and characterization of an anti-Prelog alcohol dehydrogenase from Oenococcus oeni that reduces 2-octanone to (R)-2-octanol.

PubMed

Meng, Fantao; Xu, Yan

2010-04-01

An anti-Prelog alcohol dehydrogenase from Oenococcus oeni that reduces 2-octanone to (R)-2-octanol was purified by 26-fold to homogeneity. The enzyme had a homodimeric structure consisting of 49 kDa subunits, required NADPH, but not NADH, as a cofactor and was a Zn-independent short-chain dehydrogenase. Aliphatic methyl ketones (chain length > or =6 carbon atoms) and aromatic methyl ketones were the preferred substrates for the enzyme, the best being 2-octanone. Maximum enzyme activity with 2-octanone was at 45 degrees C and at pH 8.0.

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

Flore, J.A.; Bukovac, M.J.

S-Ethyl dipropylthiocarbamate (EPTC, 2.24 kg/ha) altered wax composition on developing leaves of cabbage (Brassica oleracea L. (Capitata group) cv. Market Prize), but did not affect cutin composition. The alkane, ketone and secondary alcohol content of the epicuticular wax was reduced and ester content increased. C/sub 29/ constituents (alkane, ketone, aldehyde and sec-alcohol) accounted for 72.5% (34.1 ..mu..g/cm/sup 2/) and 40.2% (7.2 ..mu..g/cm/sup 2/) of the epicuticular wax on control and EPTC-treated leaves respectively. Homlog composition within a chemical group was not changed. Chemical composition was similar for abaxial and adaxial leaf surfaces, and the EPTC-induced change in chemical composition wasmore » similar for both surfaces. In contrast with epicuticular wax, cuticular wax contained higher percentages of fatty acids and primary alcohols, and lower percentages of alkanes, and ketones. All constituents except the unidentified polar materials and fatty acids were lower in cuticular wax extracted from EPTC-treated than non-treated plants. The main component of the cutin fraction from both control and EPTC-treated plants was identified as dihydroxyhexadecanoic acid. Cutin acids were not quantitatively changed by the EPTC treatment. 27 references, 3 figures, 5 tables.« less

Highly selective anti-Prelog synthesis of optically active aryl alcohols by recombinant Escherichia coli expressing stereospecific alcohol dehydrogenase.

PubMed

Li, Ming; Nie, Yao; Mu, Xiao Qing; Zhang, Rongzhen; Xu, Yan

2016-07-03

Biocatalytic asymmetric synthesis has been widely used for preparation of optically active chiral alcohols as the important intermediates and precursors of active pharmaceutical ingredients. However, the available whole-cell system involving anti-Prelog specific alcohol dehydrogenase is yet limited. A recombinant Escherichia coli system expressing anti-Prelog stereospecific alcohol dehydrogenase from Candida parapsilosis was established as a whole-cell system for catalyzing asymmetric reduction of aryl ketones to anti-Prelog configured alcohols. Using 2-hydroxyacetophenone as the substrate, reaction factors including pH, cell status, and substrate concentration had obvious impacts on the outcome of whole-cell biocatalysis, and xylose was found to be an available auxiliary substrate for intracellular cofactor regeneration, by which (S)-1-phenyl-1,2-ethanediol was achieved with an optical purity of 97%e.e. and yield of 89% under the substrate concentration of 5 g/L. Additionally, the feasibility of the recombinant cells toward different aryl ketones was investigated, and most of the corresponding chiral alcohol products were obtained with an optical purity over 95%e.e. Therefore, the whole-cell system involving recombinant stereospecific alcohol dehydrogenase was constructed as an efficient biocatalyst for highly enantioselective anti-Prelog synthesis of optically active aryl alcohols and would be promising in the pharmaceutical industry.

Posterior lumbar interbody fusion using non resorbable poly-ether-ether-ketone versus resorbable poly-L-lactide-co-D,L-lactide fusion devices. Clinical outcome at a minimum of 2-year follow-up.

PubMed

Jiya, Timothy U; Smit, T; van Royen, B J; Mullender, M

2011-04-01

Previous papers on resorbable poly-L-lactide-co-D,L-lactide (PLDLLA) cages in spinal fusion have failed to report adequately on patient-centred clinical outcome measures. Also comparison of PLDLLA cage with a traditionally applicable counterpart has not been previously reported. This is the first randomized prospective study that assesses clinical outcome of PLDLLA cage compared with a poly-ether-ether-ketone (PEEK) implant. Twenty-six patients were randomly assigned to undergo instrumented posterior lumbar interbody fusion (PLIF) whereby either a PEEK cage or a PLDLLA cage was implanted. Clinical outcome based on visual analogue scale scores for leg pain and back pain, as well as Oswestry Disability Index (ODI) and SF-36 questionnaires were documented and analysed. When compared with preoperative values, all clinical parameters have significantly improved in the PEEK group at 2 years after surgery with the exception of SF-36 general health, SF-36 mental health and SF-36 role emotional scores. No clinical parameter showed significant improvement at 2 years after surgery compared with preoperative values in the PLDLLA patient group. Only six patients (50%) in the PLDLLA group showed improvement in the VAS scores for leg and back pain as well as the ODI, as opposed to 10 patients (71%) in the PEEK group. One-third of the patients in the PLDLLA group actually reported worsening of their pain scores and ODI. Three cases of mild to moderate osteolysis were seen in the PLDLLA group. Following up on our preliminary report, these 2-year results confirm the superiority of the PEEK implant to the resorbable PLDLLA implant in aiding spinal fusion and alleviating symptoms following PLIF in patients with degenerative spondylolisthesis associated with either canal stenosis or foramen stenosis or both and emanating from a single lumbar segment.

21 CFR 176.210 - Defoaming agents used in the manufacture of paper and paperboard.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Defoaming agents used in the manufacture of paper...). (3) Miscellaneous: Alcohols and ketone alcohols mixture (still-bottom product from C12-C18 alcohol...-hydroxystearate. Methyl taurine-oleic acid condensate, molecular weight 486. a,a′-[Methylenebis[4-(1,1,3,3...

21 CFR 176.210 - Defoaming agents used in the manufacture of paper and paperboard.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Defoaming agents used in the manufacture of paper...). (3) Miscellaneous: Alcohols and ketone alcohols mixture (still-bottom product from C12-C18 alcohol...-hydroxystearate. Methyl taurine-oleic acid condensate, molecular weight 486. a,a′-[Methylenebis[4-(1,1,3,3...

21 CFR 176.210 - Defoaming agents used in the manufacture of paper and paperboard.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Defoaming agents used in the manufacture of paper...). (3) Miscellaneous: Alcohols and ketone alcohols mixture (still-bottom product from C12-C18 alcohol...-hydroxystearate. Methyl taurine-oleic acid condensate, molecular weight 486. a,a′-[Methylenebis[4-(1,1,3,3...

Flammability, Odor, and Offgassing Requirements and Test Procedures for Materials in Environments That Support Combustion

DTIC Science & Technology

1988-05-01

alcohol (1- octanol ) phenol n-propyl alcohol (1-propanol) isopropy1 alcohol (2-propanol) **2. Aldehydes acetaldehyde (ethanal) acrolein (propenal...59.0) D-7 MACs 7-Day ppm fmq/M^) 20 (105) 20 (82.0) 20 (70.4) 20 (70.4) Mol. Wt. methyl hexyl ketone (2- octanone ) 128.2 methyl

Catalytic Amination of Alcohols, Aldehydes, and Ketones

NASA Astrophysics Data System (ADS)

Klyuev, M. V.; Khidekel', M. L.

1980-01-01

Data on the catalytic amination of alcohols and carbonyl compounds are examined, the catalysts for these processes are described, and the problems of their effectiveness, selectivity, and stability are discussed. The possible mechanisms of the reactions indicated are presented. The bibliography includes 266 references.

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).

Lipase-Catalyzed Kinetic Resolution of Novel Antifungal N-Substituted Benzimidazole Derivatives.

PubMed

Łukowska-Chojnacka, Edyta; Staniszewska, Monika; Bondaryk, Małgorzata; Maurin, Jan K; Bretner, Maria

2016-04-01

A series of new N-substituted benzimidazole derivatives was synthesized and their antifungal activity against Candida albicans was evaluated. The chemical step included synthesis of appropriate ketones containing benzimidazole ring, reduction of ketones to the racemic alcohols, and acetylation of alcohols to the esters. All benzimidazole derivatives were obtained with satisfactory yields and in relatively short times. All synthesized compounds exhibit significant antifungal activity against Candida albicans 900028 ATCC (% cell inhibition at 0.25 μg concentration > 98%). Additionally, racemic mixtures of alcohols were separated by lipase-catalyzed kinetic resolution. In the enzymatic step a transesterification reaction was applied and the influence of a lipase type and solvent on the enantioselectivity of the reaction was studied. The most selective enzymes were Novozyme SP 435 and lipase Amano AK from Pseudomonas fluorescens (E > 100). © 2016 Wiley Periodicals, Inc.

Facile Rearrangement of 3-Oxoalkyl Radicals is Evident in Low-Temperature Gas-Phase Oxidation of Ketones

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

Scheer, Adam M.; Welz, Oliver; Sasaki, Darryl Y.

The pulsed photolytic chlorine-initiated oxidation of methyl-tert-butyl ketone (MTbuK), di-tert-butyl ketone (DTbuK), and a series of partially deuterated diethyl ketones (DEK) is studied in the gas phase at 8 Torr and 550–650 K. Products are monitored as a function of reaction time, mass, and photoionization energy using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. The results establish that the primary 3-oxoalkyl radicals of those ketones, formed by abstraction of a hydrogen atom from the carbon atom in γ-position relative to the carbonyl oxygen, undergo a rapid rearrangement resulting in an effective 1,2-acyl group migration, similar to that inmore » a Dowd–Beckwith ring expansion. Without this rearrangement, peroxy radicals derived from MTbuK and DTbuK cannot undergo HO2 elimination to yield a closed-shell unsaturated hydrocarbon coproduct. However, not only are these coproducts observed, but they represent the dominant oxidation channels of these ketones under the conditions of this study. For MTbuK and DTbuK, the rearrangement yields a more stable tertiary radical, which provides the thermodynamic driving force for this reaction. Even in the absence of such a driving force in the oxidation of partially deuterated DEK, the 1,2-acyl group migration is observed. Quantum chemical (CBS-QB3) calculations show the barrier for gas-phase rearrangement to be on the order of 10 kcal mol–1. The MTbuK oxidation experiments also show several minor channels, including β-scission of the initial radicals and cyclic ether formation.« less

Concentrations and co-occurrence correlations of 88 volatile organic compounds (VOCs) in the ambient air of 13 semi-rural to urban locations in the United States

USGS Publications Warehouse

Pankow, J.F.; Luo, W.; Bender, D.A.; Isabelle, L.M.; Hollingsworth, J.S.; Chen, C.; Asher, W.E.; Zogorski, J.S.

2003-01-01

The ambient air concentrations of 88 volatile organic compounds were determined in samples taken at 13 semi-rural to urban locations in Maine, Massachusetts, New Jersey, Pennsylvania, Ohio, Illinois, Louisiana, and California. The sampling periods ranged from 7 to 29 months, yielding a large data set with a total of 23,191 individual air concentration values, some of which were designated "ND" (not detected). For each compound at each sampling site, the air concentrations (ca, ppbV) are reported in terms of means, medians, and means of the detected values. The analytical method utilized adsorption/thermal desorption with air-sampling cartridges. The analytes included numerous halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. At some sites, the air concentrations of the gasoline-related aromatic compounds and the gasoline additive methyl tert-butyl ether were seasonally dependent, with concentrations that maximized in the winter. For each site studied here, the concentrations of some compounds were highly correlated one with another (e.g., the BTEX group (benzene, toluene, ethylbenzene, and the xylenes). Other aromatic compounds were also all generally correlated with one another, while the concentrations of other compound pairs were not correlated (e.g., benzene was not correlated with CFC-12). The concentrations found for the BTEX group were generally lower than the values that have been previously reported for urbanized and industrialized areas of other nations. ?? 2003 Elsevier Ltd. All rights reserved.

A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst.

PubMed

de Souza, Viviane P; Oliveira, Cristiane K; de Souza, Thiago M; Menezes, Paulo H; Alves, Severino; Longo, Ricardo L; Malvestiti, Ivani

2016-11-16

Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

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

Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine.

PubMed

Zhou, Ji-Ning; Fang, Qiang; Hu, Yi-Hu; Yang, Li-Yao; Wu, Fei-Fei; Xie, Lin-Jie; Wu, Jing; Li, Shijun

2014-02-14

A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.

Silica gel promotes reductions of aldehydes and ketones by N-heterocyclic carbene boranes.

PubMed

Taniguchi, Tsuyoshi; Curran, Dennis P

2012-09-07

N-Heterocyclic carbene boranes (NHC-boranes) such as 1,3-dimethylimidazol-2-ylidine trihydridoborane (diMe-Imd-BH(3)) serve as practical hydride donors for the reduction of aldehydes and ketones in the presence of silica gel. Primary and secondary alcohols are formed in good yields under ambient conditions. Aldehydes are selectively reduced in the presence of ketones. One, two, or even all three of the boron hydrides can be transferred. The process is attractive because all the components are stable and easy to handle and because both the reaction and isolation procedures are convenient.

Selective oxidation of alcohols using photoactive VO@g-C3N4.

EPA Science Inventory

A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.

Pendant dual sulfonated poly(arylene ether ketone) proton exchange membranes for fuel cell application

NASA Astrophysics Data System (ADS)

Nguyen, Minh Dat Thinh; Yang, Sungwoo; Kim, Dukjoon

2016-10-01

Poly(arylene ether ketone) (PAEK) possessing carboxylic groups at the pendant position is synthesized, and the substitution degree of pendant carboxylic groups is controlled by adjusting the ratio of 4,4-bis(4-hydroxyphenyl)valeric acid and 2,2-bis(4-hydroxyphenyl)propane. Dual sulfonated 3,3-diphenylpropylamine (SDPA) is grafted onto PAEK as a proton-conducting moiety via the amidation reaction with carboxylic groups. The transparent and flexible membranes with different degrees of sulfonation are fabricated so that we can test and compare their structure and properties with a commercial Nafion® 115 membrane for PEMFC applications. All prepared PAEK-SDPA membranes exhibit good oxidative and hydrolytic stability from Fenton's and high temperature water immersion test. SAXS analysis illustrates an excellent phase separation between the hydrophobic backbone and hydrophilic pendant groups, resulting in big ionic clusters. The proton conductivity was measured at different relative humidity, and its behavior was analyzed by hydration number of the membrane. Among a series of membranes, some samples (including B20V80-SDPA) show not only higher proton conductivity, but also higher integrated cell performance than those of Nafion® 115 at 100% relative humidity, and thus we expect these to be good candidate membranes for proton exchange membrane fuel cells (PEMFCs).

Electrospun sulfonated poly(ether ketone) nanofibers as proton conductive reinforcement for durable Nafion composite membranes

NASA Astrophysics Data System (ADS)

Klose, Carolin; Breitwieser, Matthias; Vierrath, Severin; Klingele, Matthias; Cho, Hyeongrae; Büchler, Andreas; Kerres, Jochen; Thiele, Simon

2017-09-01

We show that the combination of direct membrane deposition with proton conductive nanofiber reinforcement yields highly durable and high power density fuel cells. Sulfonated poly(ether ketone) (SPEK) was directly electrospun onto gas diffusion electrodes and then filled with Nafion by inkjet-printing resulting in a 12 μm thin membrane. The ionic membrane resistance (30 mΩ*cm2) was well below that of a directly deposited membrane reinforced with chemically inert (PVDF-HFP) nanofibers (47 mΩ*cm2) of comparable thickness. The power density of the fuel cell with SPEK reinforced membrane (2.04 W/cm2) is 30% higher than that of the PVDF-HFP reinforced reference sample (1.57 W/cm2). During humidity cycling and open circuit voltage (OCV) hold, the SPEK reinforced Nafion membrane showed no measurable degradation in terms of H2 crossover current density, thus fulfilling the target of 2 mA/cm2 of the DOE after degradation. The chemical accelerated stress test (100 h OCV hold at 90 °C, 30% RH, H2/air, 50/50 kPa) revealed a degradation rate of about 0.8 mV/h for the fuel cell with SPEK reinforced membrane, compared to 1.0 mV/h for the PVDF-HFP reinforced membrane.

Asymmetric hydrogenation of aromatic ketones by new recyclable ionic tagged ferrocene-ruthenium catalyst system.

PubMed

Xu, Di; Zhou, Zhi-Ming; Dai, Li; Tang, Li-Wei; Zhang, Jun

2015-05-01

Newly developed ferrocene-oxazoline-phosphine ligands containing quaternary ammonium ionic groups exhibited excellent catalytic performance for the ruthenium-catalyzed hydrogenation of aromatic ketonic substrates to give chiral secondary alcohols with high levels of conversions and enantioselectivities. Simple manipulation process, water tolerance, high activity and good recyclable property make this catalysis practical and appealing. Copyright © 2015 Elsevier Ltd. All rights reserved.

Laboratory Sampling Guide

DTIC Science & Technology

2012-05-11

their uses: Table 10. Types of Solid Sorbent Tubes Tube Type Typical Uses Anasorb® 747 Methyl Ethyl Ketone , Ethylene Oxide Charcoal Tube...Silica Gel Aliphatic Amines, Methanol, Aldehydes , Acid Mist 2.5.3 Passive Samplers. Passive samplers do not require a sampling pump (Figure 9). They...often encountered within the first 6 inches of soil. Water-soluble contaminants such as metals, acids, ketones , and alcohols will be encountered at

Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review

PubMed Central

Quartarone, Eliana; Angioni, Simone; Mustarelli, Piercarlo

2017-01-01

Polymer fuel cells operating above 100 °C (High Temperature Polymer Electrolyte Membrane Fuel Cells, HT-PEMFCs) have gained large interest for their application to automobiles. The HT-PEMFC devices are typically made of membranes with poly(benzimidazoles), although other polymers, such as sulphonated poly(ether ether ketones) and pyridine-based materials have been reported. In this critical review, we address the state-of-the-art of membrane fabrication and their properties. A large number of papers of uneven quality has appeared in the literature during the last few years, so this review is limited to works that are judged as significant. Emphasis is put on proton transport and the physico-chemical mechanisms of proton conductivity. PMID:28773045

Polymer and Composite Membranes for Proton-Conducting, High-Temperature Fuel Cells: A Critical Review.

PubMed

Quartarone, Eliana; Angioni, Simone; Mustarelli, Piercarlo

2017-06-22

Polymer fuel cells operating above 100 °C (High Temperature Polymer Electrolyte Membrane Fuel Cells, HT-PEMFCs) have gained large interest for their application to automobiles. The HT-PEMFC devices are typically made of membranes with poly(benzimidazoles), although other polymers, such as sulphonated poly(ether ether ketones) and pyridine-based materials have been reported. In this critical review, we address the state-of-the-art of membrane fabrication and their properties. A large number of papers of uneven quality has appeared in the literature during the last few years, so this review is limited to works that are judged as significant. Emphasis is put on proton transport and the physico-chemical mechanisms of proton conductivity.

Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

NASA Technical Reports Server (NTRS)

Siochi, Emilie

1995-01-01

Gel Permeation Chromatography (GPC) was used to analyze poly(arylene ether phosphine oxide)s whose backbones were identical except for the ketone content and placement. These samples were exposed to low Earth orbit environment (predominantly atomic oxygen) on space shuttle flights. The materials and their unexposed controls were then characterized by GPC to investigate the effect of atomic oxygen on the molecular weight distributions. Analysis of the soluble portion of the samples revealed that there was significant loss of high molecular weight species. The presence of insoluble material also suggested that crosslinking was induced by the atomic oxygen exposure and that this very likely occurred at the high molecular weight portion of the molecular weight distribution.

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.

A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

PubMed Central

Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

2016-01-01

Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at −1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier. PMID:27687772

Effect of eight solvents on ethanol analysis by Dräger 7110 Evidential breath analyzer.

PubMed

Laakso, Olli; Pennanen, Teemu; Himberg, Kimmo; Kuitunen, Tapio; Himberg, Jaakko-Juhani

2004-09-01

The Dräger 7110 MK III FIN Evidential breath analyzer is classified as a quantitative analyzer capable to provide sufficient evidence for establishing legal intoxication. The purpose of this study was to evaluate ethanol specificity of this instrument in the presence of other solvents. Effects of eight possible interfering compounds on ethanol analysis were determined in a procedure simulating a human breathing. Most of the compounds studied had either a negligible effect on ethanol analysis (acetone, methyl ethyl ketone, and methyl isobutyl ketone) or were detected in very low concentrations before influencing ethanol readings (methanol, ethyl acetate, and diethyl ether). However, 1-propanol and 2-propanol increased the ethanol readings significantly. Thus, Dräger ethanol readings should be interpreted carefully in the presence of propanol.

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... pesticides, hazardous waste, organic chemicals including: alcohols, aldehydes, formaldehydes, phenols...: ketones, nitriles, organo-metallic compounds containing chromium, cadmium, mercury, copper, zinc; and...

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... pesticides, hazardous waste, organic chemicals including: alcohols, aldehydes, formaldehydes, phenols...: ketones, nitriles, organo-metallic compounds containing chromium, cadmium, mercury, copper, zinc; and...

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... pesticides, hazardous waste, organic chemicals including: alcohols, aldehydes, formaldehydes, phenols...: ketones, nitriles, organo-metallic compounds containing chromium, cadmium, mercury, copper, zinc; and...

TiO2 supported gold nanoparticles: An efficient photocatalyst for oxidation of alcohol to aldehyde and ketone in presence of visible light irradiation

NASA Astrophysics Data System (ADS)

Gogoi, Nibedita; Borah, Geetika; Gogoi, Pradip K.; Chetia, Tridip Ranjan

2018-01-01

An efficient heterogeneous photocatalyst composed of Au nanoparticle supported on TiO2 (anatase) is prepared by sol-gel method. This prepared nanocomposite showed good catalytic activity in the oxidation of various alcohols to aldehyde and ketone under irradiation of visible light. Various spectroscopic techniques including UV-Visible absorption spectral studies and photoluminescence study are employed to characterize the catalyst. It was also characterized by XRD, TEM, BET, XPS and ICP-AES analysis. In contrast to air and H2O2, use of TBHP as oxidant gave good yield. The reaction conditions with respect to solvent and amount of catalyst are optimized.

Identification of dissolved organic matter in raw water supply from reservoirs and canals as precursors to trihalomethanes formation.

PubMed

Musikavong, Charongpun; Wattanachira, Suraphong

2013-01-01

The characteristic and quantity of dissolved organic matter (DOM) as trihalomethanes precursors in water from the U-Tapao Basin, Songkhla, Thailand was investigated. The sources of water in the basin consisted of two reservoirs and the U-Tapao canal. The canal receives water discharge from reservoirs, treated and untreated wastewater from agricultural processes, communities and industries. Water downstream of the canal is utilized as a raw water supply. Water samples were collected from two reservoirs, upstream and midstream of the canal, and the raw water supply in the rainy season and summer. The DOM level in the canal water was higher than that of the reservoir water. The highest trihalomethane formation potential (THMFP) was formed in the raw water supply. Fourier-transform infrared peaks of the humic acid were detected in the reservoir and canal waters. Aliphatic hydrocarbon and organic nitrogen were the major chemical classes in the reservoir and canal water characterized by a pyrolysis gas chromatography mass spectrometer. The optimal condition of the poly aluminum chloride (PACl) coagulation was obtained at a dosage of 40 mg/L at pH 7. This condition could reduce the average UV-254 to 57%, DOC to 64%, and THMFP to 42%. In the coagulated water, peaks of O-H groups or H-bonded NH, C˭O of cyclic and acyclic compounds, ketones and quinines, aromatic C˭C, C-O of alcohols, ethers, and carbohydrates, deformation of COOH, and carboxylic acid salts were detected. The aliphatic hydrocarbon, organic nitrogen and aldehydes and ketones were the major chemical classes. These DOM could be considered as the prominent DOM for the water supply plant that utilized PACl as a coagulant.

C-C cross-coupling of primary and secondary benzylic alcohols using supported gold-based bimetallic catalysts.

PubMed

Liu, Xiang; Ding, Ran-Sheng; He, Lin; Liu, Yong-Mei; Cao, Yong; He, He-Yong; Fan, Kang-Nian

2013-04-01

Clean alcohol-alcohol cross-coupling: A clean and efficient one-pot direct C-C cross-coupling of equimolar amounts of primary and secondary alcohols by a facile hydrogen autotransfer pathway is achieved over a robust and easily recovered hydrotalcite-supported Au-Pd bimetallic catalyst system. A variety of primary and secondary alcohols have been selectively converted into the corresponding β-alkylated ketones in good yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., organic chemicals including: alcohols, aldehydes, formaldehydes, phenols, peroxides, organic salts, amines..., glycerines, and organic polymers; refractory organic compounds including: ketones, nitriles, organo-metallic...

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery.

PubMed

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-02-06

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

PubMed Central

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-01-01

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on. PMID:24500376

SPEEK/PVDF/PES Composite as Alternative Proton Exchange Membrane for Vanadium Redox Flow Batteries

NASA Astrophysics Data System (ADS)

Fu, Zhimin; Liu, Jinying; Liu, Qifeng

2016-01-01

A membrane consisting of a blend of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and poly(ether sulfone) (PES) has been fabricated and used as an ion exchange membrane for application in vanadium redox flow batteries (VRBs). The vanadium ion permeability of the SPEEK/PVDF/PES membrane was one order of magnitude lower than that of Nafion 117 membrane. The low-cost composite membrane exhibited better performance than Nafion 117 membrane at the same operating condition. A VRB single cell with SPEEK/PVDF/PES membrane showed significantly lower capacity loss, higher coulombic efficiency (>95%), and higher energy efficiency (>82%) compared with Nafion 117 membrane. In the self-discharge test, the duration of the cell with the SPEEK/PVDF/PES membrane was nearly two times longer than that with Nafion 117 membrane. Considering these good properties and its low cost, SPEEK/PVDF/PES membrane is expected to have excellent commercial prospects as an ion exchange membrane for VRB systems.

Free volume study on the miscibility of PEEK/PEI blend using positron annihilation and dynamic mechanical thermal analysis

NASA Astrophysics Data System (ADS)

Ramani, R.; Alam, S.

2015-06-01

High performance polymer blend of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) was examined for their free volume behaviour using positron annihilation lifetime spectroscopy and dynamic mechanical thermal analysis methods. The fractional free volume obtained from PALS shows a negative deviation from linear additivity rule implying good miscibility between PEEK and PEI. The dynamic modulus and loss tangent were obtained for the blends at three different frequencies 1, 10 and 100 Hz at temperatures close to and above their glass transition temperature. Applying Time-Temperature-Superposition (TTS) principle to the DMTA results, master curves were obtained at a reference temperature To and the WLF coefficients c01 and c02 were evaluated. Both the methods give similar results for the dependence of fractional free volume on PEI content in this blend. The results reveal that free volume plays an important role in determining the visco-elastic properties in miscible polymer blends.

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.

Enantioselective, Organocatalytic Reduction of Ketones using Bifunctional Thiourea-Amine Catalysts

PubMed Central

Li, De Run; He, Anyu; Falck, J. R.

2010-01-01

Prochiral ketones are reduced to enantioenriched, secondary alcohols using catecholborane and a family of air-stable, bifunctional thiourea-amine organocatalysts. Asymmetric induction is proposed to arise from the in situ complexation between the borane and chiral thiourea-amine organocatalyst resulting in a stereochemically biased boronate-amine complex. The hydride in the complex is endowed with enhanced nucleophilicity while the thiourea concomitantly embraces and activates the carbonyl. PMID:20334398

The allylation reactions of aromatic aldehydes and ketones with tin dichloride in water.

PubMed

Bian, Yan-Jiang; Xue, Wei-Li; Yu, Xu-Guang

2010-01-01

The allylation reactions of aromatic aldehydes and ketones were carried out in 31-86% yield using SnCl(2)-H(2)O system under ultrasound irradiation at r.t. for 5h. The reactions in the same system gave homoallyl alcohols in 21-84% yield with stirring at r.t. for 24h. Compared with traditional stirring methods, ultrasonic irradiation is more convenient and efficient.

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

PubMed Central

Krylov, Igor B; Vil’, Vera A

2015-01-01

Summary The present review summarizes primary publications on the cross-dehydrogenative C–O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C–O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C–O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C–H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C–O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C–H activation processes involving intermolecular C–O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

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 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.

Chemoselective Deprotection of Triethylsilyl Ethers

PubMed Central

Chandra, Tilak; Broderick, William E.; Broderick, Joan B.

2009-01-01

An efficient and selective method was developed for the deprotection of triethylsilyl (TES) ethers using formic acid in methanol (5–10%) or in methylene chloride 2–5%) with excellent yields. TES ethers are selectively deprotected to the corresponding alcohols in high yields using formic acid in methanol under mild reaction conditions. Other hydroxyl protecting groups like t-butyldimethylsilyl (TBDMS) remain unaffected. PMID:20183570

Recent advances in biotechnological applications of alcohol dehydrogenases.

PubMed

Zheng, Yu-Guo; Yin, Huan-Huan; Yu, Dao-Fu; Chen, Xiang; Tang, Xiao-Ling; Zhang, Xiao-Jian; Xue, Ya-Ping; Wang, Ya-Jun; Liu, Zhi-Qiang

2017-02-01

Alcohol dehydrogenases (ADHs), which belong to the oxidoreductase superfamily, catalyze the interconversion between alcohols and aldehydes or ketones with high stereoselectivity under mild conditions. ADHs are widely employed as biocatalysts for the dynamic kinetic resolution of racemic substrates and for the preparation of enantiomerically pure chemicals. This review provides an overview of biotechnological applications for ADHs in the production of chiral pharmaceuticals and fine chemicals.

Copper-Catalyzed Coupling of 2-Siloxy-1-alkenes and Diazocarbonyl Compounds: Approach to Multisubstituted Furans, Pyrroles, and Thiophenes.

PubMed

Tan, Wei Wen; Yoshikai, Naohiko

2016-07-01

We report herein copper(II)-catalyzed cyclization reactions of silyl enol ethers derived from methyl ketones with α-diazo-β-ketoesters or α-diazoketones to afford 2-siloxy-2,3-dihydrofuran derivatives or 2,3,5-trisubstituted furans, respectively, under mild conditions. The former cyclization products serve as versatile 1,4-diketone surrogates, allowing facile preparation of 2,3,5-trisubstituted furans, pyrroles, and thiophenes.

Analytical Strategies Involved in the Detailed Componential Characterization of Biooil Produced from Lignocellulosic Biomass

PubMed Central

Li, Guo-Sheng; Wei, Xian-Yong

2017-01-01

Elucidation of chemical composition of biooil is essentially important to evaluate the process of lignocellulosic biomass (LCBM) conversion and its upgrading and suggest proper value-added utilization like producing fuel and feedstock for fine chemicals. Although the main components of LCBM are cellulose, hemicelluloses, and lignin, the chemicals derived from LCBM differ significantly due to the various feedstock and methods used for the decomposition. Biooil, produced from pyrolysis of LCBM, contains hundreds of organic chemicals with various classes. This review covers the methodologies used for the componential analysis of biooil, including pretreatments and instrumental analysis techniques. The use of chromatographic and spectrometric methods was highlighted, covering the conventional techniques such as gas chromatography, high performance liquid chromatography, Fourier transform infrared spectroscopy, nuclear magnetic resonance, and mass spectrometry. The combination of preseparation methods and instrumental technologies is a robust pathway for the detailed componential characterization of biooil. The organic species in biooils can be classified into alkanes, alkenes, alkynes, benzene-ring containing hydrocarbons, ethers, alcohols, phenols, aldehydes, ketones, esters, carboxylic acids, and other heteroatomic organic compounds. The recent development of high resolution mass spectrometry and multidimensional hyphenated chromatographic and spectrometric techniques has considerably elucidated the composition of biooils. PMID:29387086

A comparison of flame ionization and ozone chemiluminescence for the determination of atmospheric hydrocarbons.

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

Marley, N. A.; Gaffney, J. S.; Environmental Research

A reactive hydrocarbon analyzer has been constructed on the basis of chemiluminescence reaction with ozone. This detector is designed to operate at varying temperatures which take advantage of the different rates of reaction of the hydrocarbon classes with ozone to yield a measure of their atmospheric reactivity. When operated at high temperatures (170 C), all hydrocarbons will give a chemiluminescence signal. Reported here is a direct comparison of the ozone chemiluminescent detector (operated at a temperature of 170 C) with a flame ionization detector. This comparison was accomplished by connecting a capillary gas chromatograph to each of the two detectorsmore » by means of a switching valve. Twenty-seven compounds representing alkanes, alkenes, aromatics, and oxygenated hydrocarbons (aldehydes, ketones, alcohols, and ethers) were studied. For the compounds studied, analytical sensitivities were 10-1000 times better for the chemiluminescence detector. The results of this comparison indicate that the response of the chemiluminescent detector at 170 C correlates with a total carbon detector (flame ionization detection) and that total response is a measure of total carbon in the sample. The chemiluminescent system will be very useful for gas chromatographic detection of atmospheric hydrocarbons, particularly of oxygenates in complex mixtures.« less

Antibacterial activity of essential oil components and their potential use in seed disinfection.

PubMed

Lo Cantore, Pietro; Shanmugaiah, Vellasamy; Iacobellis, Nicola Sante

2009-10-28

Among the main (> or = 0.7%) components of some essential oils, considerable antibacterial activity was shown by terpenoid and phenylpropanoid derivatives containing phenol and alcohol functionalities. A reduced or no activity was shown by those derivatives containing ketones, aldehydes, ethers, and ester functionalities as well as the remaining terpenoids. Eugenol emulsion treatments (1-8 mg/mL) of bean seeds bearing about 2.6 x 10(6) cfu/seed of strain ICMP239 of Xanthomonas campestris pv. phaseoli var. fuscans determined a highly significant reduction of the bacteria on seeds. In particular, eugenol at 4 mg/mL disinfect seeds bearing about 7.0 x 10(2) cfu/seed and lower densities. However, after 72 h, incubation treatments with 2, 4, and 8 mg/mL of eugenol caused germination reduction of 3%, 7%, and 16%, respectively, which was significantly different from the controls. No effect on germination was observed with 1 mg/mL eugenol emulsion treatment. These data indicate eugenol as potentially useful for bean seed disinfection from X. campestris pv. phaseoli var. fuscans. Further studies on the effects on seed vitality and on formulation of essential oils are needed.

Are Some Fungal Volatile Organic Compounds (VOCs) Mycotoxins?

PubMed Central

Bennett, Joan W.; Inamdar, Arati A.

2015-01-01

Volatile organic compounds (VOCs) are carbon-compounds that easily evaporate at room temperature. Toxins are biologically produced poisons; mycotoxins are those toxins produced by microscopic fungi. All fungi emit blends of VOCs; the qualitative and quantitative composition of these volatile blends varies with the species of fungus and the environmental situation in which the fungus is grown. These fungal VOCs, produced as mixtures of alcohols, aldehydes, acids, ethers, esters, ketones, terpenes, thiols and their derivatives, are responsible for the characteristic moldy odors associated with damp indoor spaces. There is increasing experimental evidence that some of these VOCs have toxic properties. Laboratory tests in mammalian tissue culture and Drosophila melanogaster have shown that many single VOCs, as well as mixtures of VOCs emitted by growing fungi, have toxic effects. This paper describes the pros and cons of categorizing toxigenic fungal VOCs as mycotoxins, uses genomic data to expand on the definition of mycotoxin, and summarizes some of the linguistic and other conventions that can create barriers to communication between the scientists who study VOCs and those who study toxins. We propose that “volatoxin” might be a useful term to describe biogenic volatile compounds with toxigenic properties. PMID:26402705

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.

Characterization of a bio-oil from pyrolysis of rice husk by detailed compositional analysis and structural investigation of lignin.

PubMed

Lu, Yao; Wei, Xian-Yong; Cao, Jing-Pei; Li, Peng; Liu, Fang-Jing; Zhao, Yun-Peng; Fan, Xing; Zhao, Wei; Rong, Liang-Ce; Wei, Yan-Bin; Wang, Shou-Ze; Zhou, Jun; Zong, Zhi-Min

2012-07-01

Detailed compositional analysis of a bio-oil (BO) from pyrolysis of rice husk was carried out. The BO was extracted sequentially with n-hexane, CCl(4), CS(2), benzene and CH(2)Cl(2). In total, 167 organic species were identified with GC/MS in the extracts and classified into alkanes, alcohols, hydroxybenzenes, alkoxybenzenes, dioxolanes, aldehydes, ketones, carboxylic acids, esters, nitrogen-containing organic compounds and other species. The benzene ring-containing species (BRCCs) were attributed to the degradation of lignin while most of the rests were derived from the degradation of cellulose and hemicellulose. Along with guaiacyl and p-hydroxyphenyl units as the main components, a new type of linkage was suggested, i.e., C(ar)-CH(2)-C(ar) in 4,4'-methylenebis(2,6-dimethoxyphenol). Based on the species identified, a possible macromolecular structure of the lignin and the mechanism for its pyrolysis are proposed. The BO was also extracted with petroleum ether in ca. 17.8% of the extract yield and about 82.1% of the extracted components are BRCCs. Copyright © 2012 Elsevier Ltd. All rights reserved.

New Fluorinated Polymers

NASA Technical Reports Server (NTRS)

Fitch, John W., III

1997-01-01

This report summarizes progress during 1996 in our research effort along with a description of additional results associated with a TAG supplement to this grant (items 2 and 5 below). Progress is reported in five areas: 1) Polyamides Derived from [(p-HOOCC6H4)](sub 2)C(CF3)X (X= -CF3, OCH3, Cl); 2) Phosphorus-containing '12F-PEK' - Effect of Systematic Replacement of [(p-FC6H4COC6H4)](sub 2)C[(CF3)](sub 2) Monomer by [(p-FC6H4)](sub 2)(C6H5)PO; 3) Poly(ether ketone)s Derived from [(p-FC6H4COC6H4)](sub 2)(C6H5)PO; 4) New CF3-containing Organosilane Monomers and; 5) New Monomers for 12F-PEK Analogues with Improved Processability and Solubility.

Method for determination of methyl tert-butyl ether and its degradation products in water

USGS Publications Warehouse

Church, C.D.; Isabelle, L.M.; Pankow, J.F.; Rose, D.L.; Tratnyek, P.G.

1997-01-01

An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.

One-Pot Catalytic Enantio- and Diastereoselective Syntheses of anti-, syn-cis-Disubstituted, and syn-Vinyl Cyclopropyl Alcohols

PubMed Central

Kim, Hun Young; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

2009-01-01

Highly enantio- and diastereoselective methods for the synthesis of a variety of cyclopropyl alcohols are reported. These methods represent the first one-pot approaches to syn-vinyl cyclopropyl alcohols, syn-cis-disubstituted cyclopropyl alcohols, and anti-cyclopropyl alcohols from achiral precursors. The methods begin with enantioselective C–C bond formations promoted by a MIB-based zinc catalyst to generate allylic alkoxide intermediates. The intermediates are then subjected to in situ alkoxide-directed cyclopropanation to provide cyclopropyl alcohols. In the synthesis of vinyl cyclopropyl alcohols, hydroboration of enynes is followed by transmetalation of the resulting dienylborane to zinc to provide dienylzinc reagents. Enantioselective addition to aldehydes generates the requisite dienyl zinc alkoxides, which are then subjected to in situ cyclopropanation to furnish vinyl cyclopropyl alcohols. Cyclopropanation occurs at the double bond allylic to the alkoxide. Using this method, syn-vinylcyclopropyl alcohols are obtained in 65–85% yield, 76–93% ee, and >19:1 dr. To prepare anti-cyclopropanols, enantioselective addition of alkylzinc reagents to conjugated enals provides allylic zinc alkoxides. Because direct cyclopropanation provides syn-cyclopropyl alcohols, the intermediate allylic alkoxides were treated with TMSCl/Et3N to generate intermediate silyl ethers. In situ cyclopropanation of the allylic silyl ether resulted in cyclopropanation to form the anti-cyclopropyl silyl ether. Workup with TBAF affords the anti-cyclopropyl alcohols in one-pot in 60–82% yield, 89–99% ee, and ≥10:1 dr. For the synthesis of cis-disubstituted cyclopropyl alcohols, in situ generated (Z)-vinyl zinc reagents were employed in asymmetric addition to aldehydes to generate (Z)-allylic zinc alkoxides. In situ cyclopropanation provides syn-cis-disubstituted cyclopropyl alcohols in 42–70% yield, 88–97% ee, and >19:1 dr. These one-pot procedures enable the synthesis of a diverse array of cyclopropyl alcohol building blocks with high enantio- and diastereoselectivities. PMID:19954146

Asymmetric reduction of ketones and β-keto esters by (S)-1-phenylethanol dehydrogenase from denitrifying bacterium Aromatoleum aromaticum.

PubMed

Dudzik, A; Snoch, W; Borowiecki, P; Opalinska-Piskorz, J; Witko, M; Heider, J; Szaleniec, M

2015-06-01

Enzyme-catalyzed enantioselective reductions of ketones and keto esters have become popular for the production of homochiral building blocks which are valuable synthons for the preparation of biologically active compounds at industrial scale. Among many kinds of biocatalysts, dehydrogenases/reductases from various microorganisms have been used to prepare optically pure enantiomers from carbonyl compounds. (S)-1-phenylethanol dehydrogenase (PEDH) was found in the denitrifying bacterium Aromatoleum aromaticum (strain EbN1) and belongs to the short-chain dehydrogenase/reductase family. It catalyzes the stereospecific oxidation of (S)-1-phenylethanol to acetophenone during anaerobic ethylbenzene mineralization, but also the reverse reaction, i.e., NADH-dependent enantioselective reduction of acetophenone to (S)-1-phenylethanol. In this work, we present the application of PEDH for asymmetric reduction of 42 prochiral ketones and 11 β-keto esters to enantiopure secondary alcohols. The high enantioselectivity of the reaction is explained by docking experiments and analysis of the interaction and binding energies of the theoretical enzyme-substrate complexes leading to the respective (S)- or (R)-alcohols. The conversions were carried out in a batch reactor using Escherichia coli cells with heterologously produced PEDH as whole-cell catalysts and isopropanol as reaction solvent and cosubstrate for NADH recovery. Ketones were converted to the respective secondary alcohols with excellent enantiomeric excesses and high productivities. Moreover, the progress of product formation was studied for nine para-substituted acetophenone derivatives and described by neural network models, which allow to predict reactor behavior and provides insight on enzyme reactivity. Finally, equilibrium constants for conversion of these substrates were derived from the progress curves of the reactions. The obtained values matched very well with theoretical predictions.

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.

Chemoenzymatic one-pot synthesis in an aqueous medium: combination of metal-catalysed allylic alcohol isomerisation-asymmetric bioamination.

PubMed

Ríos-Lombardía, Nicolás; Vidal, Cristian; Cocina, María; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

2015-07-11

The ruthenium-catalysed isomerisation of allylic alcohols was coupled, for the first time, with asymmetric bioamination in a one-pot process in an aqueous medium. In the cases involving prochiral ketones, the ω-TA exhibited excellent enantioselectivity, identical to that observed in the single step. As a result, amines were obtained from allylic alcohols with high overall yields and excellent enantiomeric excesses.

Preparation and characterization of poly (arylene ether isoxazole)s by fluoride ion-mediated aromatic nucleophilic displacement reactions

NASA Technical Reports Server (NTRS)

Herbert, C. G.; Bass, R. G.

1994-01-01

As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether isoxazole)s have been prepared by fluoride ion-catalyzed aromatic nucleophilic substitution reactions with bis(trimethylsiloxyphenyl) isoxazoles and activated bisarylhalides in diphenyl sulfone. Initial investigation involving the preparation of these materials with isoxazole bisphenols and activated bisarylhalides in the presence of potassium carbonate indicated that, under reaction conditions necessary to prepare high-molecular-weight materials, the isoxazole monomer was converted to an enamino ketone. This side reaction was avoided by using fluoride as a base. However, trimethylsilyl ether derivatives of the isoxazole bisphenols were required in these polymerizations for the preparation of high-molecular-weight materials. Moderate to high inherent viscosity eta(sub inh): 0.43-0.87 dl/g) materials with good thermal stability (air: 409-477 C, helium: 435-512 C) can be prepared by the silyl ether method. Glass transition temperatures ranged from 182 to 225 C for polymers with phenyl pendants and from 170 to 214 C for those without. Molecular weight control by 2% endcapping and the incorporation of a phenyl pendant at the 4 position of the isoxazole is necessary to yield polymers soluble in polar aprotic solvents at room temperature. There is evidence, however, indicating the existence of crosslinks between the polymer chains when the silyl ether approach is utilized.

Defense Small Business Innovation Research Program (SBIR). Volume 3. Air Force Projects, Abstracts of Phase 1 Awards from FY 1989 SBIR Solicitation

DTIC Science & Technology

1990-04-01

MISSION REQUIREMENTS. THE MATRIX MATERIALS PROPOSED FOR THIS PHASE I INVESTIGATION ARE POLYETHER ETHER KETON (PEEK) AND POLYBUTELENE TERAPHTHALATE (PBT...NOISE AND RADIATION HARD, PARTICULARLY RADIATION HARD AGAINST NEUTRON IRRADIATION. A PROPOSAL IS MADE FOR THE DEVELOPMENT OF AN INNOVATIVE TECHNOLOGY...AND RADIATION -HARD APPLICATIONS. THE SOI WAFER WILL ELIMINATE LATCH-UP EFFECTS, REDUCE NEUTRON -CAPTURE VOLUME AND PROVIDE ELECTRICAL ISOLATION FOR

The Effect of Core and Veneering Design on the Optical Properties of Polyether Ether Ketone.

PubMed

Zeighami, S; Mirmohammadrezaei, S; Safi, M; Falahchai, S M

2017-12-01

This study aimed to evaluate the effect of core shade and core and veneering thickness on color parameters and translucency of polyether ether ketone (PEEK). Sixty PEEK discs (0.5 and 1 mm in thickness) with white and dentine shades were veneered with A2 shade indirect composite resin with 0.5, 1 and 1.5 mm thickness (n=5). Cores without the veneering material served as controls for translucency evaluation. Color parameters were measured by a spectroradiometer. Color difference (ΔE₀₀) and translucency parameters (TP) were computed. Data were analyzed using one-way ANOVA and Tukey's test (for veneering thickness) and independent t-test (for core shade and thickness) via SPSS 20.0 (p⟨0.05). Regarding the veneering thickness, white cores of 0.5 mm thickness showed significant differences in all color parameters. In white cores of 1 mm thickness and dentine cores of 0.5 and 1 mm thickness, there were statistically significant differences only in L∗, a∗ and h∗. The mean TP was significantly higher in all white cores of 1 mm thickness than dentine cores of 1 mm. Considering ΔE₀₀=3.7 as clinically unacceptable, only three groups had higher mean ΔE₀₀ values. Core shade, core thickness, and the veneering thickness affected the color and translucency of PEEK restorations. Copyright© 2017 Dennis Barber Ltd.

Carbon felt interlayer derived from rice paper and its synergistic encapsulation of polysulfides for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Yang, Kai; Zhong, Lei; Guan, Ruiteng; Xiao, Min; Han, Dongmei; Wang, Shuanjin; Meng, Yuezhong

2018-05-01

Lithium-sulfur (Li-S) batteries have remarkably high theoretical specific capacity as promising candidates for next-generation energy storage. However, the "polysulfides shuttle" effect hampers its commercial application. Here, we use a kind of rice paper as a raw material to get inorganic oxides doping carbon felt by the facile carbonization method, and then modified by a simple coating process using poly (fluorenyl ether ketone) and Super P slurry. The special structure of the carbon felt derived from rice paper and its modified layer endow the final electronic conductive interlayer with inherent polysulfides absorbents and ion Coulombic repulsion functions, respectively, which show synergistic effect for trapping polysulfides. As an interlayer of Li-S batteries, the obtained carbon felt/poly (fluorenyl ether ketone)& Super P (CFSS) interlayer shows excellent electrochemical performance in improving specific capacity and decreasing polarization. The batteries with CFSS interlayer exhibit a high capacity of 837 mA h g-1 at 2.0 C and a high initial capacity of 1073.4 mA h g-1 and good capacity retention of 824.5 mA h g-1 after 500 cycles at 0.5 C. CFSS interlayer also shows excellent anti-self-discharge performance. Therefore, the simple and economical CFSS interlayer can be considered as a promising component for high performance Li-S batteries.

Polyether ether ketone implants achieve increased bone fusion when coated with nano-sized hydroxyapatite: a histomorphometric study in rabbit bone

PubMed Central

Johansson, Pär; Jimbo, Ryo; Naito, Yoshihito; Kjellin, Per; Currie, Fredrik; Wennerberg, Ann

2016-01-01

Polyether ether ketone (PEEK) possesses excellent mechanical properties similar to those of human bone and is considered the best alternative material other than titanium for orthopedic spine and trauma implants. However, the deficient osteogenic properties and the bioinertness of PEEK limit its fields of application. The aim of this study was to limit these drawbacks by coating the surface of PEEK with nano-scaled hydroxyapatite (HA) minerals. In the study, the biological response to PEEK, with and without HA coating, was investigated. Twenty-four screw-like and apically perforated implants in the rabbit femur were histologically evaluated at 3 weeks and 12 weeks after surgery. Twelve of the 24 implants were HA coated (test), and the remaining 12 served as uncoated PEEK controls. At 3 weeks and 12 weeks, the mean bone–implant contact was higher for test compared to control (P<0.05). The bone area inside the threads was comparable in the two groups, but the perforating hole showed more bone area for the HA-coated implants at both healing points (P<0.01). With these results, we conclude that nano-sized HA coating on PEEK implants significantly improved the osteogenic properties, and in a clinical situation this material composition may serve as an implant where a rapid bone fusion is essential. PMID:27103801

Polyether ether ketone implants achieve increased bone fusion when coated with nano-sized hydroxyapatite: a histomorphometric study in rabbit bone.

PubMed

Johansson, Pär; Jimbo, Ryo; Naito, Yoshihito; Kjellin, Per; Currie, Fredrik; Wennerberg, Ann

2016-01-01

Polyether ether ketone (PEEK) possesses excellent mechanical properties similar to those of human bone and is considered the best alternative material other than titanium for orthopedic spine and trauma implants. However, the deficient osteogenic properties and the bioinertness of PEEK limit its fields of application. The aim of this study was to limit these drawbacks by coating the surface of PEEK with nano-scaled hydroxyapatite (HA) minerals. In the study, the biological response to PEEK, with and without HA coating, was investigated. Twenty-four screw-like and apically perforated implants in the rabbit femur were histologically evaluated at 3 weeks and 12 weeks after surgery. Twelve of the 24 implants were HA coated (test), and the remaining 12 served as uncoated PEEK controls. At 3 weeks and 12 weeks, the mean bone-implant contact was higher for test compared to control (P<0.05). The bone area inside the threads was comparable in the two groups, but the perforating hole showed more bone area for the HA-coated implants at both healing points (P<0.01). With these results, we conclude that nano-sized HA coating on PEEK implants significantly improved the osteogenic properties, and in a clinical situation this material composition may serve as an implant where a rapid bone fusion is essential.

Implant materials generate different peri-implant inflammatory factors: poly-ether-ether-ketone promotes fibrosis and microtextured titanium promotes osteogenic factors.

PubMed

Olivares-Navarrete, Rene; Hyzy, Sharon L; Slosar, Paul J; Schneider, Jennifer M; Schwartz, Zvi; Boyan, Barbara D

2015-03-15

An in vitro study examining factors produced by human mesenchymal stem cells on spine implant materials. The aim of this study was to examine whether the inflammatory microenvironment generated by cells on titanium-aluminum-vanadium (Ti-alloy, TiAlV) surfaces is affected by surface microtexture and whether it differs from that generated on poly-ether-ether-ketone (PEEK). Histologically, implants fabricated from PEEK have a fibrous connective tissue surface interface whereas Ti-alloy implants demonstrate close approximation with surrounding bone. Ti-alloy surfaces with complex micron/submicron scale roughness promote osteoblastic differentiation and foster a specific cellular environment that favors bone formation whereas PEEK favors fibrous tissue formation. Human mesenchymal stem cells were cultured on tissue culture polystyrene, PEEK, smooth TiAlV, or macro-/micro-/nano-textured rough TiAlV (mmnTiAlV) disks. Osteoblastic differentiation and secreted inflammatory interleukins were assessed after 7 days. Fold changes in mRNAs for inflammation, necrosis, DNA damage, or apoptosis with respect to tissue culture polystyrene were measured by low-density polymerase chain reaction array. Data were analyzed by analysis of variance, followed by Bonferroni's correction of Student's t-test. Cells on PEEK upregulated mRNAs for chemokine ligand-2, interleukin (IL) 1β, IL6, IL8, and tumor necrosis factor. Cells grown on the mmnTiAlV had an 8-fold reduction in mRNAs for toll-like receptor-4. Cells grown on mmnTiAlV had reduced levels of proinflammatory interleukins. Cells on PEEK had higher mRNAs for factors strongly associated with cell death/apoptosis, whereas cells on mmnTiAlV exhibited reduced cytokine factor levels. All results were significant (P < 0.05). These results suggest that fibrous tissue around PEEK implants may be due to several factors: reduced osteoblastic differentiation of progenitor cells and production of an inflammatory environment that favors cell death via apoptosis and necrosis. Ti alloy surfaces with complex macro/micro/nanoscale roughness promote osteoblastic differentiation and foster a specific cellular environment that favors bone formation. N/A.

Expandable Polyaryl-Ether-Ether-Ketone Spacers for Interbody Distraction in the Lumbar Spine

PubMed Central

Alimi, Marjan; Shin, Benjamin; Macielak, Michael; Hofstetter, Christoph P.; Njoku, Innocent; Tsiouris, Apostolos J.; Elowitz, Eric; Härtl, Roger

2015-01-01

Study Design Retrospective case series. Objective StaXx XD (Spine Wave, Inc., Shelton, CT, United States) is an expandable polyaryl-ether-ether-ketone (PEEK) wafer implant utilized in the treatment of lumbar degenerative disease. PEEK implants have been successfully used as interbody devices. Few studies have focused on expandable PEEK devices. The aim of the current study is to determine the radiographic and clinical outcome of expandable PEEK cages utilized for transforaminal lumbar interbody fusion in patients with lumbar degenerative diseases. Methods Forty-nine patients who underwent lumbar interbody fusion with implantation of expandable PEEK cages and posterior instrumentation were included. The clinical outcome was evaluated using the visual analog scale (VAS) and the Oswestry Disability Index (ODI). Radiographic parameters including disk height, foraminal height, listhesis, local disk angle of the index level/levels, regional lumbar lordosis, and graft subsidence were measured preoperatively, postoperatively, and at latest follow-up. Results At an average follow-up of 19.3 months, the minimum clinically important difference for the ODI and VAS back, buttock, and leg were achieved in 64, 52, 58, and 52% of the patients, respectively. There was statistically significant improvement in VAS back (6.42 versus 3.11, p < 0.001), VAS buttock (4.66 versus 1.97, p = 0.002), VAS leg (4.55 versus 1.96, p < 0.001), and ODI (21.7 versus 12.1, p < 0.001) scores. There was a significant increase in the average disk height (6.49 versus 8.18 mm, p = 0.037) and foraminal height (15.6 versus 18.53 mm, p = 0.0001), and a significant reduction in the listhesis (5.13 versus 3.15 mm, p = 0.005). The subsidence of 0.66 mm (7.4%) observed at the latest follow-up was not significant (p = 0.35). Conclusions Midterm results indicate that expandable PEEK spacers can effectively and durably restore disk and foraminal height and improve the outcome without significant subsidence. PMID:26131383

Volatile Compounds Produced by Lactobacillus paracasei During Oat Fermentation.

PubMed

Lee, Sang Mi; Oh, Jieun; Hurh, Byung-Serk; Jeong, Gwi-Hwa; Shin, Young-Keum; Kim, Young-Suk

2016-12-01

This study investigated the profiles of volatile compounds produced by Lactobacillus paracasei during oat fermentation using gas chromatography-mass spectrometry coupled with headspace solid-phase microextraction method. A total of 60 compounds, including acids, alcohols, aldehydes, esters, furan derivatives, hydrocarbons, ketones, sulfur-containing compounds, terpenes, and other compounds, were identified in fermented oat. Lipid oxidation products such as 2-pentylfuran, 1-octen-3-ol, hexanal, and nonanal were found to be the main contributors to oat samples fermented by L. paracasei with the level of 2-pentylfuran being the highest. In addition, the contents of ketones, alcohols, acids, and furan derivatives in the oat samples consistently increased with the fermentation time. On the other hand, the contents of degradation products of amino acids, such as 3-methylbutanal, benzaldehyde, acetophenone, dimethyl sulfide, and dimethyl disulfide, decreased in oat samples during fermentation. Principal component analysis (PCA) was applied to discriminate the fermented oat samples according to different fermentation times. The fermented oats were clearly differentiated on PCA plots. The initial fermentation stage was mainly affected by aldehydes, whereas the later samples of fermented oats were strongly associated with acids, alcohols, furan derivatives, and ketones. The application of PCA to data of the volatile profiles revealed that the oat samples fermented by L. paracasei could be distinguished according to fermentation time. © 2016 Institute of Food Technologists®.

Analysis of Fluorotelomer Alcohols in Soils: Optimization of Extraction and Chromatography

EPA Science Inventory

This article describes the development of an analytical method for the determination of fluorotelomer alcohols (FTOHs) in soil. The sensitive and selective determination of the telomer alcohols was performed by extraction with mthyl tert-butyl ether (MTBE) and analysis of the ext...

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Mosquito larvicidal activity of Rauvolfia serpentina L. seeds against Culex quinquefasciatus Say.

PubMed

Das, Dipanwita; Chandra, Goutam

2012-01-01

To establish the larvicidal activities, if any of solvent extracts of Rauvolfia serpentina (R. serpentina) L. seeds against Culex quinquefasciatus (Cx. quinquefasciatus) Say, 1823 as target species. Seeds of R. serpentina were extracted with five solvents graded according to the polarity [viz. petroleum ether, benzene, ethyl acetate, acetone and absolute alcohol] continuing one after another with the same seeds. Mortality rate with petroleum ether extract was significantly higher than other extracts. The mortality rates of late 3rd instar larvae were 50.33±5.51, 10.00±1.00, 0.00±0.00, 21.33±1.53 and 0.00±0.00 in 100 ppm concentration of petroleum ether, benzene, ethyl acetate, acetone and absolute alcohol respectively, after 24 h of exposure period. Results of this study show that petroleum ether extract of R. serpentina seed may be considered as a potent source of mosquito larvicidal agent. Copyright © 2012 Hainan Medical College. Published by Elsevier B.V. All rights reserved.

Influences of the chemical structure of entrainers on the activity coefficients in presence of biodiesel

NASA Astrophysics Data System (ADS)

Mäder, A.; Fleischmann, A.; Fang, Ye; Ruck, W.; Krahl, J.

2012-05-01

In this work we analyzed the strength of the intermolecular forces between biodiesel and the entrainer and their influence on the entrainer's ability to interact with biodiesel. Furthermore we investigated the influence of the chemical structure of an entrainer to the interaction with biodiesel. For this purpose the activity coefficients γ∞ at infinite dilution of acids, aldehydes, ketones and alcohols in biodiesel were measured with the method of headspace gas chromatography (HSGC). Short-chained acids showed the highest interaction of the analyzed entrainers caused by their ability to build hydrogen bonds with biodiesel. Increased chain length of the acids cause reduced interaction with biodiesel, which is mainly due to the higher obstruction of the acid molecule and therefore the reduced ability to build hydrogen bonds with biodiesel. Aldehydes, ketones and alcohols showed lower interaction with biodiesel compared to the acids. Longer-chained alcohols showed increased interaction with biodiesel due to the raised London Forces and an inductive +I effect of the molecule chain.

Determination of hydride transfer stereospecificity of NADH-dependent alcohol-aldehyde/ketone oxidoreductase from Sulfolobus solfataricus.

PubMed

Trincone, A; Lama, L; Rella, R; D'Auria, S; Raia, C A; Nicolaus, B

1990-10-18

This paper describes the determination of stereospecificity of hydride transfer reaction of an alcohol dehydrogenase isolated from the archaebacterium Sulfolobus solfataricus. The 1H-NMR and EI-MS data indicate that the enzyme transfers the pro-R hydrogen from coenzyme to substrate and is therefore an A-specific dehydrogenase.

Methods of making organic compounds by metathesis

DOEpatents

Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

2015-09-01

Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

[The composition of volatile components of cepe (Boletus edulis) and oyster mushrooms (Pleurotus ostreatus)].

PubMed

Misharina, T A; Mukhutdinova, S M; Zharikova, G G; Terenina, M B; Krikunova, N I

2009-01-01

The composition of aroma compounds in cooked and canned cepe (Boletus edulis) and in cooked oyster mushrooms (Pleurotus ostreatus) is studied using capillary gas chromatography and chromatography-mass spectrometry. It is found that unsaturated alcohols and ketones containing eight atoms of carbon determine the aroma of raw mushrooms and take part in the formation of the aroma of cooked mushrooms as well. The content of these compounds was the highest in canned cepes. In oyster mushrooms, the concentration of these alcohols and ketones was lower in comparison with cepes. The content of aliphatic and aromatic aldehydes was much higher in oyster mushrooms. Volatile aliphatic and heterocyclic Maillard reaction products and isomeric octenols and octenones formed the aroma of cooked and canned mushrooms.

General and highly α-regioselective zinc-mediated prenylation of aldehydes and ketones.

PubMed

Zhao, Li-Ming; Jin, Hai-Shan; Wan, Li-Jing; Zhang, Li-Ming

2011-03-18

A simple, efficient, and general α-prenylation approach for the synthesis of a variety of α-prenylated alcohols has been successfully developed. A wide range of α-prenylated alcohol derivatives could be obtained in good yields by highly α-regioselective zinc-mediated prenylation of various aldehydes and ketones with prenyl bromide at 120 °C in HMPA. By simply altering the reaciton solvent and temperature, the method allows the achievement of a highly notable opposite regiocontrol, providing the expected regiochemical product. The method provides a convenient route for the direct α-prenylation of carbonyl compounds in a highly α-regioselective manner using a cheap and convenient mediator. Two possible pathways are proposed to account for the formation of these synthetically difficult-to-obtain molecules.

Structure elucidation and chemical synthesis of stigmolone, a novel type of prokaryotic pheromone.

PubMed

Hull, W E; Berkessel, A; Plaga, W

1998-09-15

Approximately 2 micromol of a novel prokaryotic pheromone, involved in starvation-induced aggregation and formation of fruiting bodies by the myxobacterium Stigmatella aurantiaca, were isolated by a large-scale elution procedure. The pheromone was purified by HPLC, and high-resolution MS, IR, 1H-NMR, and 13C-NMR were used to identify the active substance as the hydroxy ketone 2,5, 8-trimethyl-8-hydroxy-nonan-4-one, which has been named stigmolone. The analysis was complicated by a solvent-dependent equilibrium between stigmolone and the cyclic enol-ether 3,4-dihydro-2,2, 5-trimethyl-6-(2-methylpropyl)-2H-pyran formed by intramolecular nucleophilic attack of the 8-OH group at the ketone C4 followed by loss of H2O. Both compounds were synthesized chemically, and their structures were confirmed by NMR analysis. Natural and synthetic stigmolone have the same biological activity at ca. 1 nM concentration.

REDUCTIVE ACTIVATION OF DIOXYGEN FOR DEGRADATION OF METHYL TERT-BUTYL ETHER BY BIFUNCTION

EPA Science Inventory

Bifunctional aluminum is prepared by sulfating aluminum metal with sulfuric acid. The use of bifunctional aluminum to degrade methyl tert-butyl ether (MTBE) in the presence of dioxygen has been examined using batch systems. Primary degradation products were tert-butyl alcohol, ...

Diastereoselective Additions of Allylmetal Reagents to Free and Protected syn-α,β-Dihydroxyketones Enable Efficient Synthetic Routes to Methyl Trioxacarcinoside A

PubMed Central

Smaltz, Daniel J.; Švenda, Jakub

2012-01-01

Two routes to the 2,6-dideoxysugar methyl trioxacarcinoside A are described. Each was enabled by an apparent α-chelation-controlled addition of an allylmetal reagent to a ketone substrate containing a free α-hydroxyl group and a β-hydroxyl substituent, either free or protected as the corresponding di-tert-butylmethyl silyl ether. Both routes provide practical access to gram-quantities of trioxacarcinose A in a form suitable for glycosidic coupling reactions. PMID:22404560

The Preparation and Physical Properties of Several Aliphatic Hydrocarbons and Intermediates

DTIC Science & Technology

1947-05-01

34. •: • : - •’•«-" In’ order to-determine the optimum conditions for conversion of the glycol to 2,3-&imethyl-i,3~’butadiene, a series of- test runs were made...pentene to ^,lt--dimethyl-2-pentanone (methyl neopentyl ketone), (b) oxida- tion of this ketone to t-butylacetic acid, (c) conversion, of the acid to...Kenneth C: The Dehydration of Tertiary Alcohols Containing a Neopentyl System. H - Methyliso- propyl-tert-butylcarbinol, Methyldl-tert-butylcarbinol

Risk of liver cancer and exposure to organic solvents and gasoline vapors among Finnish workers.

PubMed

Lindbohm, Marja-Liisa; Sallmén, Markku; Kyyrönen, Pentti; Kauppinen, Timo; Pukkala, Eero

2009-06-15

We investigated the association between exposure to various groups of solvents and gasoline vapors and liver cancer. A cohort of economically active Finns born between 1906 and 1945 was followed up during the period 1971-1995. The incident cases of primary liver cancer (n = 2474) were identified in a record linkage with the Finnish Cancer Registry. Occupations from the 1970 census were converted to exposures using a job-exposure matrix. Cumulative exposure was calculated as the product of estimated prevalence, level and duration of exposure, and we used Poisson regression to calculate the relative risks (RR). Among the occupations entailing exposure to organic solvents, an elevated liver cancer incidence was observed in male printers, and varnishers and lacquerers. Among men, the risk was increased in the highest exposure category of aromatic hydrocarbons [RR 1.77, 95% confidence interval (CI) 1.30-2.40], aliphatic/alicyclic hydrocarbons (RR 1.47, 95% CI 0.99-2.18), chlorinated hydrocarbons (RR 2.65, 95% CI 1.38-5.11) and "other solvents" (RR 2.14, 95% CI 1.23-3.71). Among women, the risk was increased for the group "other solvents" that includes mainly alcohols, ketones, esters and glycol ethers (RR 2.73, 95% CI 1.21-6.16). Our finding of an increased risk among workers exposed to chlorinated hydrocarbons is in line with several earlier studies on trichloroethylene. The results also suggest a link between exposure to other types of solvents and the risk of liver cancer. The possibility that alcohol consumption contributes to the observed risks cannot be totally excluded. Copyright 2008 UICC.

40 CFR Table 2a to Subpart E of... - Reactivity Factors

Code of Federal Regulations, 2011 CFR

2011-07-01

... 2.10 Isobutyl Acetate 110-19-0 0.67 Methyl Amyl Ketone 110-43-0 2.80 Hexane 110-54-3 1.45 n-Propyl...-63-0 0.71 Acetone (Propanone) 67-64-1 0.43 n-Propanol (n-Propyl Alcohol) 71-23-8 2.74 n-Butyl Alcohol (Butanol) 71-36-3 3.34 n-Pentanol (Amyl Alcohol) 71-41-0 3.35 Benzene 71-43-2 0.81 1,1,1-Trichloroethane 71...

40 CFR Table 2a to Subpart E of... - Reactivity Factors

Code of Federal Regulations, 2014 CFR

2014-07-01

... 0.67 Methyl Amyl Ketone 110-43-0 2.80 Hexane 110-54-3 1.45 n-Propyl Formate 110-74-7 0.93 2... (2-Propanol) 67-63-0 0.71 Acetone (Propanone) 67-64-1 0.43 n-Propanol (n-Propyl Alcohol) 71-23-8 2.74 n-Butyl Alcohol (Butanol) 71-36-3 3.34 n-Pentanol (Amyl Alcohol) 71-41-0 3.35 Benzene 71-43-2 0.81 1...

40 CFR Table 2a to Subpart E of... - Reactivity Factors

Code of Federal Regulations, 2013 CFR

2013-07-01

... 0.67 Methyl Amyl Ketone 110-43-0 2.80 Hexane 110-54-3 1.45 n-Propyl Formate 110-74-7 0.93 2... (2-Propanol) 67-63-0 0.71 Acetone (Propanone) 67-64-1 0.43 n-Propanol (n-Propyl Alcohol) 71-23-8 2.74 n-Butyl Alcohol (Butanol) 71-36-3 3.34 n-Pentanol (Amyl Alcohol) 71-41-0 3.35 Benzene 71-43-2 0.81 1...

40 CFR Table 2a to Subpart E of... - Reactivity Factors

Code of Federal Regulations, 2010 CFR

2010-07-01

... 2.10 Isobutyl Acetate 110-19-0 0.67 Methyl Amyl Ketone 110-43-0 2.80 Hexane 110-54-3 1.45 n-Propyl...-63-0 0.71 Acetone (Propanone) 67-64-1 0.43 n-Propanol (n-Propyl Alcohol) 71-23-8 2.74 n-Butyl Alcohol (Butanol) 71-36-3 3.34 n-Pentanol (Amyl Alcohol) 71-41-0 3.35 Benzene 71-43-2 0.81 1,1,1-Trichloroethane 71...

40 CFR Table 2a to Subpart E of... - Reactivity Factors

Code of Federal Regulations, 2012 CFR

2012-07-01

... 0.67 Methyl Amyl Ketone 110-43-0 2.80 Hexane 110-54-3 1.45 n-Propyl Formate 110-74-7 0.93 2... (2-Propanol) 67-63-0 0.71 Acetone (Propanone) 67-64-1 0.43 n-Propanol (n-Propyl Alcohol) 71-23-8 2.74 n-Butyl Alcohol (Butanol) 71-36-3 3.34 n-Pentanol (Amyl Alcohol) 71-41-0 3.35 Benzene 71-43-2 0.81 1...

Solvent free oxidation of primary alcohols and diols using thymine iron(III) catalyst.

PubMed

Al-Hunaiti, Afnan; Niemi, Teemu; Sibaouih, Ahlam; Pihko, Petri; Leskelä, Markku; Repo, Timo

2010-12-28

In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl(3) under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.

Selective Ether/Ester C–O Cleavage of an Acetylated Lignin Model via Tandem Catalysis

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

Lohr, Tracy L.; Li, Zhi; Marks, Tobin J.

2015-11-06

Lignin, a heterogeneous phenolic polymer which constitutes roughly 15 to 20 wt % of lignocellulosic biomass (cellulose, hemicellose, and lignin), represents one of the few renewable sources of aromatic monomers.(1) Current lignin depolymerization methodologies, including base-catalyzed,(2) acid-catalyzed,(3) metal-catalyzed,(4) ionic liquid (IL)-assisted,(5) and supercritical-fluid-assisted(2b, 6) approaches, typically afford low yields (~10–20% or less) of low molecular weight aromatics under relatively harsh reaction conditions (>300 °C).(7) Recent advances include using oxidized lignin and lignin models,(8) where oxidation of the Cα alcohol facilitates depolymerizaton, with aromatic monomer yields reaching up to 52% for aspen “hardwood” lignin.(9) The most common structural lignin motifs containmore » a β-O-4 aryl-ether linkage,(10) a primary alcohol in the γ skeletal position, and a secondary alcohol in the α position (Scheme 1). Our laboratory has previously demonstrated an effective strategy for thermodynamically leveraged etheric and esteric C–O bond hydrogenolysis using a tandem metal triflate + supported palladium catalytic system.(11) A homogeneous M(OTf)n catalyst mediates endothermic ether or near thermoneutral ester C–O bond scission (the reverse of hydroelementation), which is coupled to exothermic Pd-catalyzed hydrogenation of the resulting C=C unsaturation, driving the overall process downhill. We next asked whether this tandem system might be applicable to cleaving the β-O-4 aryl-ether bond in lignin and lignin models. The promising results of that investigation are communicated here.« less

CNN pincer ruthenium catalysts for hydrogenation and transfer hydrogenation of ketones: experimental and computational studies.

PubMed

Baratta, Walter; Baldino, Salvatore; Calhorda, Maria José; Costa, Paulo J; Esposito, Gennaro; Herdtweck, Eberhardt; Magnolia, Santo; Mealli, Carlo; Messaoudi, Abdelatif; Mason, Sax A; Veiros, Luis F

2014-10-13

Reaction of [RuCl(CNN)(dppb)] (1-Cl) (HCNN=2-aminomethyl-6-(4-methylphenyl)pyridine; dppb=Ph2 P(CH2 )4 PPh2 ) with NaOCH2 CF3 leads to the amine-alkoxide [Ru(CNN)(OCH2 CF3 )(dppb)] (1-OCH2 CF3 ), whose neutron diffraction study reveals a short RuO⋅⋅⋅HN bond length. Treatment of 1-Cl with NaOEt and EtOH affords the alkoxide [Ru(CNN)(OEt)(dppb)]⋅(EtOH)n (1-OEt⋅n EtOH), which equilibrates with the hydride [RuH(CNN)(dppb)] (1-H) and acetaldehyde. Compound 1-OEt⋅n EtOH reacts reversibly with H2 leading to 1-H and EtOH through dihydrogen splitting. NMR spectroscopic studies on 1-OEt⋅n EtOH and 1-H reveal hydrogen bond interactions and exchange processes. The chloride 1-Cl catalyzes the hydrogenation (5 atm of H2 ) of ketones to alcohols (turnover frequency (TOF) up to 6.5×10(4) h(-1) , 40 °C). DFT calculations were performed on the reaction of [RuH(CNN')(dmpb)] (2-H) (HCNN'=2-aminomethyl-6-(phenyl)pyridine; dmpb=Me2 P(CH2 )4 PMe2 ) with acetone and with one molecule of 2-propanol, in alcohol, with the alkoxide complex being the most stable species. In the first step, the Ru-hydride transfers one hydrogen atom to the carbon of the ketone, whereas the second hydrogen transfer from NH2 is mediated by the alcohol and leads to the key "amide" intermediate. Regeneration of the hydride complex may occur by reaction with 2-propanol or with H2 ; both pathways have low barriers and are alcohol assisted. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

PubMed Central

Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2015-01-01

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au–allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. PMID:26248980

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., organic chemicals including: alcohols, aldehydes, formaldehydes, phenols, peroxides, organic salts, amines, amides, other nitrogen compounds, other aromatic compounds, aliphatic organic chemicals, glycols, glycerines, and organic polymers; refractory organic compounds including: ketones, nitriles, organo-metallic...

A New Synthesis of Tertiary Alkyl N-Arylcarbamates from Isocyanates.

ERIC Educational Resources Information Center

Bailey, William J.; Griffith, James R.

1978-01-01

The method involves the dissolution of a small piece of metallic lithium in a small quantity of tertiary alcohol followed by addition to a mixture of the isocyanate and the tertiary alcohol in ether. This should be useful in organic chemistry laboratory courses for the identification of tertiary alcohols. (Author/BB)

Flexural fatigue of short glass fiber reinforced a blend of polyphenylene ether ketone and polyphenylene sulfide

NASA Astrophysics Data System (ADS)

Zhou, Jiang; D'Amore, Alberto; Yang, Yuming; He, Tianbai; Li, Binyao; Nicolais, Luigi

1994-05-01

Flexural fatigue tests were conducted on injection molded glass fiber reinforced a blend of polyphenylene ether ketone and polyphenylene sulfide composite using four-point bending with different stress ratios and different frequencies. The fatigue behavior of this material was described. The constructed S-N curves shift their trends obviously at the maximum cyclic stress being about 80% of the ultimate flexural strength. Examinations of failure surfaces for various loading conditions show that the fatigue failure mechanisms appear to be matrix yielding at high stresses and crack growth at low stresses. Analyses of the fatigue data at various stress ratios reveal that the data at low stress superimpose to form a single curve which is nearly linear when they are plotted as stress range versus number of cycles to failure in bilogarithmic axes, while the data at high stresses also converge to yield a single curve when they are plotted as ( S max S range)1/2 against specimen lifetimes ( S max is the maximum stress and S range is the stress range). These results show that for the studied material the main factor influencing the lifetime is the stress range at low stresses and the parameter ( S max S range)1/2 at high stresses. Comparison of fatigue data in the frequency range of 0.89 7.0 Hz was made, no significant effect of frequency on the fatigue behavior is found.

Preparation, characterization and in vitro response of bioactive coatings on polyether ether ketone.

PubMed

Durham, John W; Allen, Matthew J; Rabiei, Afsaneh

2017-04-01

Polyether ether ketone (PEEK) is a highly heat-resistant thermoplastic with excellent strength and elastic modulus similar to human bone, making it an attractive material for orthopedic implants. However, the hydrophobic surface of PEEK implants induces fibrous encapsulation which is unfavorable for stable implant anchorage. In this study, PEEK was coated via ion-beam-assisted deposition (IBAD) using a two-layer design of yttria-stabilized zirconia (YSZ) as a heat-protection layer, and hydroxyapatite (HA) as a top layer to improve osseointegration. Microstructural analysis of the coatings showed a dense, uniform columnar grain structure in the YSZ layer and no delamination from the substrate. The HA layer was found to be amorphous and free of porosities in its as-deposited state. Subsequent heat treatment via microwave energy followed by autoclaving crystallized the HA layer, confirmed by SEM and XRD analysis. An in vitro study using MC3T3 preosteoblast cells showed improved bioactivity in heat-treated sample groups. Cell proliferation, differentiation, and mineralization were analyzed by MTT assay and DNA content, osteocalcin expression, and Alizarin Red S (AR-S) content, respectively. Initial cell growth was increased, and osteogenic maturation and mineralization were accelerated most on coatings that underwent a combined microwave and autoclave heat treatment process as compared to uncoated PEEK and amorphous HA surfaces. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 560-567, 2017. © 2015 Wiley Periodicals, Inc.

Titanium and polyether ether ketone (PEEK) patient-specific sub-periosteal implants: two novel approaches for rehabilitation of the severely atrophic anterior maxillary ridge.

PubMed

Mounir, M; Atef, M; Abou-Elfetouh, A; Hakam, M M

2018-05-01

The aim of this study was to assess two new protocols for single-stage rehabilitation of the severely atrophic maxillary ridge using customized porous titanium or polyether ether ketone (PEEK) sub-periosteal implants. Ten patients with a severely atrophic anterior maxillary alveolar ridge were divided randomly into two groups (five patients in each) to receive customized sub-periosteal implants fabricated via CAD/CAM technology: group 1, porous titanium implants; group 2, PEEK implants. Prosthetic loading with fixed acrylic bridges was performed 1 month postoperative. The implants were followed-up for 12 months and evaluated for the presence of any sign of radiographic bone resorption, mobility, infection, prosthetic fracture, or implant exposure. The immediate postoperative period was uneventful except for one case complicated by wound dehiscence in group 1. At 12 months, all implants were functionally stable and the patients were comfortable with the prostheses. No signs of radiographic bone resorption, mobility, infection, or prosthetic fracture were observed. Within the limitations of this study, the application of customized porous titanium and PEEK sub-periosteal implants produced through CAD/CAM technology appears to be an acceptable method for single-stage prosthetic rehabilitation of the severely atrophic edentulous anterior maxilla. This study was awarded the best case study at the academy of osseintegration annual meeting 2017, Orlando, Florida. Copyright © 2017 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

High strength, surface porous polyether-ether-ketone for load-bearing orthopaedic implants

PubMed Central

Evans, Nathan T.; Torstrick, F. Brennan; Lee, Christopher S.D.; Dupont, Kenneth M.; Safranski, David L.; Chang, W. Allen; Macedo, Annie E.; Lin, Angela; Boothby, Jennifer M.; Whittingslow, Daniel C.; Carson, Robert A.; Guldberg, Robert E.; Gall, Ken

2015-01-01

Despite its widespread clinical use in load-bearing orthopaedic implants, polyether-ether-ketone (PEEK) is often associated with poor osseointegration. In this study, a surface porous PEEK material (PEEK-SP) was created using a melt extrusion technique. The porous layer thickness was 399.6±63.3 µm and possessed a mean pore size of 279.9±31.6 µm, strut spacing of 186.8±55.5 µm, porosity of 67.3±3.1%, and interconnectivity of 99.9±0.1%. Monotonic tensile tests showed that PEEK-SP preserved 73.9% of the strength (71.06±2.17 MPa) and 73.4% of the elastic modulus (2.45±0.31 GPa) of as-received, injection molded PEEK. PEEK-SP further demonstrated a fatigue strength of 60.0 MPa at one million cycles, preserving 73.4% of the fatigue resistance of injection molded PEEK. Interfacial shear testing showed the pore layer shear strength to be 23.96±2.26 MPa. An osseointegration model in the rat revealed substantial bone formation within the pore layer at 6 and 12 weeks via µCT and histological evaluation. Ingrown bone was more closely apposed to the pore wall and fibrous tissue growth was reduced in PEEK-SP when compared to non-porous PEEK controls. These results indicate that PEEK-SP could provide improved osseointegration while maintaining the structural integrity necessary for load-bearing orthopaedic applications. PMID:25463499

Investigation of phonon transport and thermal boundary conductance at the interface of functionalized SWCNT and poly (ether-ketone)

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

Huang, Haoxiang; Kumar, Satish, E-mail: satish.kumar@me.gatech.edu; Chen, Liang

2016-09-07

Carbon nanostructures such as carbon nanotube (CNT), graphene, and carbon fibers can be used as fillers in amorphous polymers to improve their thermal properties. In this study, the effect of covalent bonding of CNT with poly(ether ketone) (PEK) on interfacial thermal interactions is investigated using non-equilibrium molecular dynamics simulations. The number of covalent bonds between (20, 20) CNT and PEK is varied in the range of 0–80 (0%–6.25%), and the thermal boundary conductance is computed. The analysis reveals that covalent functionalization of CNT atoms can enhance the thermal boundary conductance by an order of magnitude compared to the non-functionalized CNT-PEKmore » interface at a high degree of CNT functionalization. Besides strengthening the thermal coupling, covalent functionalization is also shown to modify the phonon spectra of CNT. The transient spectral energy analysis shows that the crosslinks cause faster energy exchange from CNT to PEK in different frequency bands. The oxygen atom of hydroxyl group of PEK contributes energy transfer in the low frequency band, while aromatic and carbonyl carbon atoms play a more significant role in high frequency bands. In addition, by analyzing the relaxation time of the spectral temperature of different frequency bands of CNT, it is revealed that with increasing number of bonds, both lower frequency vibrational modes and higher frequency modes efficiently couple across the CNT-PEK interface and contribute in thermal energy transfer from CNT to the matrix.« less

27 CFR 21.127 - Shellac (refined).

Code of Federal Regulations, 2010 CFR

2010-04-01

... Gutzeit Method (AOAC method 25.020; for incorporation by reference, see § 21.6(c)). (b) Color. White or orange. (c) Rosin content. None when tested by the following method: Add 20 ml of absolute alcohol or... petroleum ether and mix thoroughly. Add approximately 2 liters of water and separate a portion of the ether...

KINETICS OF THE GAS-PHASE REACTIONS OF NO3 RADICALS WITH A SERIES OF ALCOHOLS, GLYCOL ETHERS, ETHERS, AND CHLOROALKENES. (R825252)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

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

Kinetic Resolution of α-Hydroxy-Substituted Oxime Ethers by Enantioselective Cu-H-Catalyzed Si-O Coupling.

PubMed

Dong, Xichang; Kita, Yuji; Oestreich, Martin

2018-04-12

A catalyst-controlled enantioselective alcohol silylation by Cu-H-catalyzed dehydrogenative Si-O coupling of hydroxy groups α to an oxime ether and simple hydrosilanes is reported. The selectivity factors reached in this kinetic resolution are generally high (s≈50), and these reactions thereby provide reliable access to highly enantioenriched α-hydroxy-substituted oxime ethers. The synthetic usefulness of these compounds is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Imidazopyridines via Copper-Catalyzed, Formal Aza-[3 + 2] Cycloaddition Reaction of Pyridine Derivatives with α-Diazo Oxime Ethers.

PubMed

Park, Sangjune; Kim, Hyunseok; Son, Jeong-Yu; Um, Kyusik; Lee, Sooho; Baek, Yonghyeon; Seo, Boram; Lee, Phil Ho

2017-10-06

The Cu-catalyzed, formal aza-[3 + 2] cycloaddition reaction of pyridine derivatives with α-diazo oxime ethers in trifluoroethanol was used to synthesize imidazopyridines via the release of molecular nitrogen and elimination of alcohol. These methods enabled modular synthesis of a wide range of N-heterobicyclic compounds such as imidazopyridazines, imidazopyrimidines, and imidazopyrazines with an α-imino Cu-carbenoid generated from the α-diazo oxime ethers and copper.

Kinetic modeling of α-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms.

PubMed

Paraskevas, Paschalis D; Sabbe, Maarten K; Reyniers, Marie-Françoise; Papayannakos, Nikos G; Marin, Guy B

2014-10-09

Hydrogen-abstraction reactions play a significant role in thermal biomass conversion processes, as well as regular gasification, pyrolysis, or combustion. In this work, a group additivity model is constructed that allows prediction of reaction rates and Arrhenius parameters of hydrogen abstractions by hydrogen atoms from alcohols, ethers, esters, peroxides, ketones, aldehydes, acids, and diketones in a broad temperature range (300-2000 K). A training set of 60 reactions was developed with rate coefficients and Arrhenius parameters calculated by the CBS-QB3 method in the high-pressure limit with tunneling corrections using Eckart tunneling coefficients. From this set of reactions, 15 group additive values were derived for the forward and the reverse reaction, 4 referring to primary and 11 to secondary contributions. The accuracy of the model is validated upon an ab initio and an experimental validation set of 19 and 21 reaction rates, respectively, showing that reaction rates can be predicted with a mean factor of deviation of 2 for the ab initio and 3 for the experimental values. Hence, this work illustrates that the developed group additive model can be reliably applied for the accurate prediction of kinetics of α-hydrogen abstractions by hydrogen atoms from a broad range of oxygenates.

Occupational risk assessment of paint industry workers

PubMed Central

de Oliveira, Hugo M.; Dagostim, Gracilene P.; da Silva, Arielle Mota; Tavares, Priscila; da Rosa, Luiz A. Z. C.; de Andrade, Vanessa M.

2011-01-01

Background: Thousands of chemical compounds are used in paint products, like pigments, extenders, binders, additives, and solvents (toluene, xylene, ketones, alcohols, esters, and glycol ethers). Paint manufacture workers are potentially exposed to the chemicals present in paint products although the patterns and levels of exposure to individual agents may differ from those of painters. The aim of the present study was to evaluate genome damage induced in peripheral blood lymphocytes and oral mucosa cells of paint industry workers. Materials and Methods: Genotoxicity was evaluated using the alkaline Comet assay in blood lymphocytes and oral mucosa cells, and the Micronucleus test in oral mucosa cells. For the micronucleus test in exfoliated buccal cells, no significant difference was detected between the control and paint industry workers. Results: The Comet assay in epithelia buccal cells showed that the damage index (DI) and damage frequency (DF) observed in the exposed group were significantly higher relative to the control group (P≤0.05). In the same way, the Comet assay data in peripheral blood leukocytes showed that both analysis parameters (DI and DF) were significantly greater than that for the control group (P≤0.05). Conclusions: Chronic occupational exposure to paints may lead to a slightly increased risk of genetic damage among paint industry workers. PMID:22223950

Fatty Aldehyde and Fatty Alcohol Metabolism: Review and Importance for Epidermal Structure and Function

PubMed Central

Rizzo, William B.

2014-01-01

Normal fatty aldehyde and alcohol metabolism is essential for epidermal differentiation and function. Long-chain aldehydes are produced by catabolism of several lipids including fatty alcohols, sphingolipids, ether glycerolipids, isoprenoid alcohols and certain aliphatic lipids that undergo α- or ω-oxidation. The fatty aldehyde generated by these pathways is chiefly metabolized to fatty acid by fatty aldehyde dehydrogenase (FALDH, alternately known as ALDH3A2), which also functions to oxidize fatty alcohols as a component of the fatty alcohol:NAD oxidoreductase (FAO) enzyme complex. Genetic deficiency of FALDH/FAO in patients with Sjögren-Larsson syndrome (SLS) results in accumulation of fatty aldehydes, fatty alcohols and related lipids (ether glycerolipids, wax esters) in cultured keratinocytes. These biochemical changes are associated with abnormalities in formation of lamellar bodies in the stratum granulosum and impaired delivery of their precursor membranes to the stratum corneum (SC). The defective extracellular SC membranes are responsible for a leaky epidermal water barrier and ichthyosis. Although lamellar bodies appear to be the pathogenic target for abnormal fatty aldehyde/alcohol metabolism in SLS, the precise biochemical mechanisms are yet to be elucidated. Nevertheless, studies in SLS highlight the critical importance of FALDH and normal fatty aldehyde/alcohol metabolism for epidermal function. PMID:24036493

Lewis base catalyzed aldol additions of chiral trichlorosilyl enolates and silyl enol ethers.

PubMed

Denmark, Scott E; Fujimori, Shinji; Pham, Son M

2005-12-23

[structures: see text] The consequences of double diastereodifferentiation in chiral Lewis base catalyzed aldol additions using chiral enoxysilanes derived from lactate, 3-hydroxyisobutyrate, and 3-hydroxybutyrate have been investigated. Trichlorosilyl enolates derived from the chiral methyl and ethyl ketones were subjected to aldolization in the presence of phosphoramides, and the intrinsic selectivity of these enolates and the external stereoinduction from chiral catalyst were studied. In the reactions with the lactate derived enolate, the strong internal stereoinduction dominated the stereochemical outcome of the aldol addition. For the 3-hydroxyisobutyrate- and 3-hydroxybutyrate derived enolates, the catalyst-controlled diastereoselectivities were observed, and the resident stereogenic centers exerted marginal influence. The corresponding trimethylsilyl enol ethers were employed in SiCl4/bisphosphoramide catalyzed aldol additions, and the effect of double diastereodifferentiation was also investigated. The overall diastereoselection of the process was again controlled by the strong external influence of the catalyst.

Effects of LEO Environment on Tensile Properties of PEEK Films

NASA Astrophysics Data System (ADS)

Nakamura, Takashi; Nakamura, Hiroshi; Shimamura, Hiroyuki

2009-01-01

To clarify the effects of space environment on mechanical properties of polymer, exposure experiments were conducted utilizing the International Space Station Russian Service Module. Poly-ether-ether-ketone (PEEK) films under tensile stress were exposed to low Earth orbit (LEO) environment, and reference samples were irradiated with atomic oxygen (AO), electron beam (EB), and ultraviolet light (UV) in ground facilities. By comparing the results of flight and ground tests, the degradation behavior and the influential factors in LEO were investigated. The following results were obtained. (1) UV was found to be the harshest factor in LEO on tensile properties, since it decreased elongation to 15% of pristine sample after 46-months exposure. (2) AO in LEO eroded the specimen surface with a cone-like morphology and reduced the thickness; however, it had no significant effect on tensile properties. (3) EB irradiation in LEO had no measurable effects on the material properties.

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

Electrophilic fluorinating reagent mediated synthesis of fluorinated alpha-keto Ethers, benzil, and 6,6'-dialkoxy-2,2'-bipyridines.

PubMed

Manandhar, Sudha; Singh, Rajendra P; Eggers, Gary V; Shreeve, Jean'ne M

2002-09-06

Interactions of various fluorinated and nonfluorinated alcohols with trans-stilbene in the presence of electrophilic reagents were studied. Under neat conditions, reactions of trans-stilbene (1) with fluorinated alcohols, R(f)OH (R(f) = CF3CH2-, CFH2CH2-, CF3CF2CH2-, CF2H(CF2)3CH2-, (CF3)2CH-, (CF3)3C- (2a-f) in the presence of an electrophilic reagent, 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) or N,N-difluoro-2,2'-bipyridinium bis(tetrafluoroborate) (MEC-31), gave alpha-keto ethers (3a-f) and benzil (4) in good to moderate yields. alpha-Keto ether and benzil formation was very much dependent on the reaction time, the degree of fluorination of the alcohols, and whether a solvent such as CH3CN, DMF or DMA was utilized. In solution, alpha-keto ethers and benzil did not form. Interestingly, under neat conditions, nonfluorinated alcohols, ROH (R = CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH3CH2CH2CH2CH2CH2-) (5g-k) did not react with trans-stilbene in the presence of MEC-31 but gave 6,6'-dialkoxy-2,2'-bipyridines (6g-k), regioselectively, in excellent isolated yields. On the other hand, fluorinated alcohols did not react with MEC-31. Reaction of MEC-31 with an excess of diethylene glycol (7) gave the bipyridine derivative (8) in 88% isolated yield. Reaction of 8 either with diethylaminosulfur trifluoride (DAST) or bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor) readily produced the corresponding difluoro derivative (9) in 85% isolated yield. All new compounds have been characterized by spectroscopic and elemental analysis.

Highly efficient and generalized asymmetric synthesis of quaternary stereogenic carbon-containing β-amino indanones/indanoles via Mannich-type additions between 1-indanones and N-tert-butanesulfinylketimines.

PubMed

Wu, Lingmin; Xie, Chen; Mei, Haibo; Soloshonok, Vadim A; Han, Jianlin; Pan, Yi

2014-07-14

Here we report that, unlike other ketones, 1-indanone and acetophenone derived enolates undergo Mannich-type addition reactions with N-tert-butanesulfinyl ketimines with excellent yields (up to 98%) and diastereoselectivity (>99/1). The resulting compounds represent a new type of biologically relevant β-aminoketone derivative bearing quaternary stereogenic carbon, which could be further converted into the corresponding β-amino ketones and β-amino alcohols, possessing three consecutive stereogenic centres.

Synthesis of enantiomerically enriched drug precursors and an insect pheromone via reduction of ketones using commercially available carbonyl reductase screening kit "Chiralscreen® OH".

PubMed

Nagai, Toshiya; Sakurai, Saki; Natori, Naoki; Hataoka, Manaka; Kinoshita, Takako; Inoue, Hiroyoshi; Hanaya, Kengo; Shoji, Mitsuru; Sugai, Takeshi

2018-04-01

Commercially available "Chiralscreen® OH" starter kit containing five types of carbonyl reductases (E001, E007, E031, E039, and E078) was used for the reduction of several aromatic and aliphatic ketones to obtain enantiomerically enriched drug precursors and an insect pheromone. Almost stereochemically pure secondary alcohols, used in the synthesis of drugs such as (R)-rasagiline mesylate, (S)-rivastigmine, (R)-chlorphenesin carbamate, and (R)-mexiletine, and the insect pheromone (4S,5R)-sitophilure, were conveniently obtained. The enzymes worked well with ketones containing at least one non-bulky substituent at the carbonyl group. The diverse stereochemical preference of the above five carbonyl reductases was clarified. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2015-06-05

The kinetics of oxidation of various alcohols by purified rat liver alcohol dehydrogenase (ADH) were compared with the kinetics of elimination of the alcohols in rats in order to investigate the roles of ADH and other factors that contribute to the rates of metabolism of alcohols. Primary alcohols (ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol) and diols (1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol) were eliminated in rats with zero-order kinetics at doses of 5-20 mmol/kg. Ethanol was eliminated most rapidly, at 7.9 mmol/kgh. Secondary alcohols (2-propanol-d7, 2-propanol, 2-butanol, 3-pentanol, cyclopentanol, cyclohexanol) were eliminated with first order kinetics at doses of 5-10 mmol/kg, and the corresponding ketones were formed and slowly eliminated with zero or first order kinetics. The rates of elimination of various alcohols were inhibited on average 73% (55% for 2-propanol to 90% for ethanol) by 1 mmol/kg of 4-methylpyrazole, a good inhibitor of ADH, indicating a major role for ADH in the metabolism of the alcohols. The Michaelis kinetic constants from in vitro studies (pH 7.3, 37 °C) with isolated rat liver enzyme were used to calculate the expected relative rates of metabolism in rats. The rates of elimination generally increased with increased activity of ADH, but a maximum rate of 6±1 mmol/kg h was observed for the best substrates, suggesting that ADH activity is not solely rate-limiting. Because secondary alcohols only require one NAD(+) for the conversion to ketones whereas primary alcohols require two equivalents of NAD(+) for oxidation to the carboxylic acids, it appears that the rate of oxidation of NADH to NAD(+) is not a major limiting factor for metabolism of these alcohols, but the rate-limiting factors are yet to be identified. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Contribution of Liver Alcohol Dehydrogenase to Metabolism of Alcohols in Rats

PubMed Central

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

2015-01-01

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

Microbial formation of esters.

PubMed

Park, Yong Cheol; Shaffer, Catherine Emily Horton; Bennett, George N

2009-11-01

Small aliphatic esters are important natural flavor and fragrance compounds and have numerous uses as solvents and as chemical intermediates. Besides the chemical or lipase-catalyzed formation of esters from alcohols and organic acids, small volatile esters are made by several biochemical routes in microbes. This short review will cover the biosynthesis of esters from acyl-CoA and alcohol condensation, from oxidation of hemiacetals formed from aldehydes and alcohols, and from the insertion of oxygen adjacent to the carbonyl group in a straight chain or cyclic ketone by Baeyer-Villiger monooxygenases. The physiological role of the ester-forming reactions can allow degradation of ketones for use as a carbon source and may play a role in detoxification of aldehydes or recycling cofactors. The enzymes catalyzing each of these processes have been isolated and characterized, and a number of genes encoding the proteins from various microbes have been cloned and functionally expressed. The use of these ester-forming organisms or recombinant organisms expressing the appropriate genes as biocatalysts in biotechnology to make specific esters and chiral lactones has been studied in recent years.

Laboratory Studies of Aedes aegypti Attraction to Ketones, Sulfides, and Primary Chloroalkanes Tested Alone and in Combination with L-Lactic Acid.

PubMed

Bernier, Ulrich R; Kline, Daniel L; Allan, Sandra A; Barnard, Donald R

2015-03-01

The attraction of female Aedes aegypti to single compounds and binary compositions containing L-lactic acid and an additional saturated compound from a set of ketones, sulfides, and chloroalkanes was studied using a triple-cage dual-port olfactometer. These chemical classes were studied because of their structural relation to acetone, dimethyl disulfide, and dichloromethane, which have all been reported to synergize attraction to L-lactic acid. Human odors, carbon dioxide, and the binary mixture of L-lactic acid and CO₂served as controls for comparison of attraction responses produced by the binary mixtures. All tested mixtures that contained chloroalkanes attracted mosquitoes at synergistic levels, as did L-lactic acid and CO₂. Synergism was less frequent in mixtures of L-lactic acid with sulfides and ketones; in the case of ketones, synergistic attraction was observed only for L-lactic acid combined with acetone or butanone. Suppression or inhibition of attraction response was observed for combinations that contained ketones of C7-C12 molecular chain length (optimum in the C8-C10 range). This inhibition effect is similar to that observed previously for specific ranges of carboxylic acids, aldehydes, and alcohols.

DETERMINATION OF SURFACTANT SODIUM LAURYL ETHER SULFATE BY ION PAIRING CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY DETECTION

EPA Science Inventory

A method for the determination of the anionic Steol CS-330 surfactant is described. CS-330 is a complex mixture of oligomers due to the various sizes of fatty alcohols and the number of moles of the ethoxylation. The main component of CS-330 is sodium lauryl ether sulfate (SLES)....

Essential Oils in Foods: From Ancient Times to the 21st Century.

PubMed

Sendra, Esther

2016-06-14

Medicinal plants and culinary herbs have been used since ancient times. Essential oils (EO) are a mixture of numerous compounds, mainly terpenes, alcohols, acids, esters, epoxides, aldehydes, ketones,aminesandsulfides,thatareprobablyproducedbyplantsasaresponsetostress[1].[...].

40 CFR 419.31 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... STANDARDS PETROLEUM REFINING POINT SOURCE CATEGORY Petrochemical Subcategory § 419.31 Specialized... apply. (b) The term petrochemical operations shall mean the production of second-generation petrochemicals (i.e., alcohols, ketones, cumene, styrene, etc.) or first generation petrochemicals and...

40 CFR 419.31 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... STANDARDS PETROLEUM REFINING POINT SOURCE CATEGORY Petrochemical Subcategory § 419.31 Specialized... apply. (b) The term petrochemical operations shall mean the production of second-generation petrochemicals (i.e., alcohols, ketones, cumene, styrene, etc.) or first generation petrochemicals and...

ACUTE TOXICITY OF SELECTED ORGANIC COMPOUNDS TO FATHEAD MINNOWS

EPA Science Inventory

Static nonrenewal laboratory bioassays were conducted with 26 organic compounds commonly used by industry. The selected compounds represented the five following chemical classes: acids, alcohols, hydrocarbons, ketones and aldehydes, and phenols. Juvenile fathead minnows (Pimephal...

New insights into the formation mechanism of Ag, Au and AgAu nanoparticles in aqueous alkaline media: alkoxides from alcohols, aldehydes and ketones as universal reducing agents.

PubMed

Gomes, Janaina F; Garcia, Amanda C; Ferreira, Eduardo B; Pires, Cleiton; Oliveira, Vanessa L; Tremiliosi-Filho, Germano; Gasparotto, Luiz H S

2015-09-07

In this report we present new insights into the formation mechanism of Ag, Au and AgAu nanoparticles with alcohols, aldehydes and ketones in alkaline medium at room temperature. We selected methanol, ethanol, glycerol, formaldehyde, acetaldehyde and acetone to demonstrate their capability of reducing gold and silver ions under the above-mentioned conditions. We showed that the particles are also formed with potassium tert-butoxide in the absence of hydroxides. Our results strongly suggest that alkoxides, formed from any molecule containing a hydroxyl or a functional group capable of generating them in alkaline medium, are the actual and universal reducing agent of silver and gold ions, in opposition to the currently accepted mechanisms. The universality of the reaction mechanism proposed in this work may impact on the production of noble nanoparticles with simple chemicals normally found in standard laboratories.

Electrical resistance of CNT-PEEK composites under compression at different temperatures

PubMed Central

2011-01-01

Electrically conductive polymers reinforced with carbon nanotubes (CNTs) have generated a great deal of scientific and industrial interest in the last few years. Advanced thermoplastic composites made of three different weight percentages (8%, 9%, and 10%) of multiwalled CNTs and polyether ether ketone (PEEK) were prepared by shear mixing process. The temperature- and pressure-dependent electrical resistance of these CNT-PEEK composites have been studied and presented in this paper. It has been found that electrical resistance decreases significantly with the application of heat and pressure. PMID:21711952

Chemical conversion of corticosteroids to 3 alpha,5 alpha-tetrahydro derivatives. Synthesis of 5 alpha-cortol 3-glucuronides and 5 alpha-cortolone 3-glucuronides.

PubMed

Hosoda, H; Osanai, K; Nambara, T

1991-12-01

The synthesis of the 3-glucuronides of 5 alpha-cortol-20 alpha, 5 alpha-cortolone-20 alpha and their 20 beta-epimers is described. The 5 alpha-cortol 20,21-diacetates (12, 17) and 5 alpha-cortolone 20,21-diacetates (14, 19) were the key intermediates. Sodium borohydride reduction of the carbonyl group at C-20 in 5 alpha-tetrahydrocortisol 3-tert-butyldimethylsilyl ether 17,21-acetonide (8) gave the 20 alpha-hydroxy-acetonide (9). Selective removal of the acetonide ring was successful when the 20 alpha-acetoxy-17 alpha,21-acetonide (10) was treated with 50% acetic acid. Subsequent acetylation with acetic anhydride in pyridine, followed by removal of the protecting group at C-3 in the silyl ether-acetate (11) gave the desired 20 alpha-intermediate (12). The 11-ketone (14) was prepared from 11 by oxidation with pyridinium chlorochromate, followed by desilylation. The 20 beta-acetates (17, 19) were synthesized from 21-acetoxy-3 alpha,11 beta,17 alpha-trihydroxy-5 alpha-pregnan-20-one 3-tert-butyldimethylsilyl ether (15). Introduction of the glucuronyl residue at C-3 was carried out by means of the Koenigs-Knorr reaction.

Formation of Alkenes via Degradation of tert-Alkyl Ethers and Alcohols by Aquincola tertiaricarbonis L108 and Methylibium spp. ▿†

PubMed Central

Schäfer, Franziska; Muzica, Liudmila; Schuster, Judith; Treuter, Naemi; Rosell, Mònica; Harms, Hauke; Müller, Roland H.; Rohwerder, Thore

2011-01-01

Bacterial degradation pathways of fuel oxygenates such as methyl tert-butyl and tert-amyl methyl ether (MTBE and TAME, respectively) have already been studied in some detail. However, many of the involved enzymes are still unknown, and possible side reactions have not yet been considered. In Aquincola tertiaricarbonis L108, Methylibium petroleiphilum PM1, and Methylibium sp. strain R8, we have now detected volatile hydrocarbons as by-products of the degradation of the tert-alkyl ether metabolites tert-butyl and tert-amyl alcohol (TBA and TAA, respectively). The alkene isobutene was formed only during TBA catabolism, while the beta and gamma isomers of isoamylene were produced only during TAA conversion. Both tert-alkyl alcohol degradation and alkene production were strictly oxygen dependent. However, the relative contribution of the dehydration reaction to total alcohol conversion increased with decreasing oxygen concentrations. In resting-cell experiments where the headspace oxygen content was adjusted to less than 2%, more than 50% of the TAA was converted to isoamylene. Isobutene formation from TBA was about 20-fold lower, reaching up to 4% alcohol turnover at low oxygen concentrations. It is likely that the putative tert-alkyl alcohol monooxygenase MdpJ, belonging to the Rieske nonheme mononuclear iron enzymes and found in all three strains tested, or an associated enzymatic step catalyzed the unusual elimination reaction. This was also supported by the detection of mdpJK genes in MTBE-degrading and isobutene-emitting enrichment cultures obtained from two treatment ponds operating at Leuna, Germany. The possible use of alkene formation as an easy-to-measure indicator of aerobic fuel oxygenate biodegradation in contaminated aquifers is discussed. PMID:21742915

Sample Preservation - The Key to a Successful Failure Analysis

DTIC Science & Technology

2008-09-01

Acidic Lemon Juice 3 Acidic Vinegar 4 Acidic Tomatoes 5 Acidic Human Skin 6 Acidic Milk 7 Neutral 8 Alkaline Sea Water 9 Alkaline Baking Soda...subsequently removed with alcohol when fractography is performed, although problems may exist with rough fracture surfaces. For these surfaces, a...cleaning Loosely adhering debris and dust Least Organic-solvent cleaning in ultrasonic bath  Toluene or xylene  Ketones  Alcohol  Oil and

A Novel Carbonyl Reductase with Anti-Prelog Stereospecificity from Acetobacter sp. CCTCC M209061: Purification and Characterization

PubMed Central

Wang, Xiao-Ting; Zong, Min-Hua; Lou, Wen-Yong

2014-01-01

A novel carbonyl reductase (AcCR) catalyzing the asymmetric reduction of ketones to enantiopure alcohols with anti-Prelog stereoselectivity was found in Acetobacter sp. CCTCC M209061 and enriched 27.5-fold with an overall yield of 0.4% by purification. The enzyme showed a homotetrameric structure with an apparent molecular mass of 104 kDa and each subunit of 27 kDa. The gene sequence of AcCR was cloned and sequenced, and a 762 bp gene fragment was obtained. Either NAD(H) or NADP(H) can be used as coenzyme. For the reduction of 4′-chloroacetophenone, the Km value for NADH was around 25-fold greater than that for NADPH (0.66 mM vs 0.026 mM), showing that AcCR preferred NADPH over NADH. However, when NADH was used as cofactor, the response of AcCR activity to increasing concentration of 4′-chloroacetophenone was clearly sigmoidal with a Hill coefficient of 3.1, suggesting that the enzyme might possess four substrate-binding sites cooperating with each other The Vmax value for NADH-linked reduction was higher than that for NADPH-linked reduction (0.21 mM/min vs 0.17 mM/min). For the oxidation of isopropanol, the similar enzymological properties of AcCR were found using NAD+ or NADP+ as cofactor. Furthermore, a broad range of ketones such as aryl ketones, α-ketoesters and aliphatic ketones could be enantioselectively reduced into the corresponding chiral alcohols by this enzyme with high activity. PMID:24740089

Coupled reactions on bioparticles: Stereoselective reduction with cofactor regeneration on PhaC inclusion bodies.

PubMed

Spieler, Valerie; Valldorf, Bernhard; Maaß, Franziska; Kleinschek, Alexander; Hüttenhain, Stefan H; Kolmar, Harald

2016-07-01

Chiral alcohols are important building blocks for specialty chemicals and pharmaceuticals. The production of chiral alcohols from ketones can be carried out stereo selectively with alcohol dehydrogenases (ADHs). To establish a process for cost-effective enzyme immobilization on solid phase for application in ketone reduction, we used an established enzyme pair consisting of ADH from Rhodococcus erythropolis and formate dehydrogenase (FDH) from Candida boidinii for NADH cofactor regeneration and co-immobilized them on modified poly-p-hydroxybutyrate synthase (PhaC)-inclusion bodies that were recombinantly produced in Escherichia coli cells. After separate production of genetically engineered and recombinantly produced enzymes and particles, cell lysates were combined and enzymes endowed with a Kcoil were captured on the surface of the Ecoil presenting particles due to coiled-coil interaction. Enzyme-loaded particles could be easily purified by centrifugation. Total conversion of 4'-chloroacetophenone to (S)-4-chloro-α-methylbenzyl alcohol could be accomplished using enzyme-loaded particles, catalytic amounts of NAD(+) and formate as substrates for FDH. Chiral GC-MS analysis revealed that immobilized ADH retained enantioselectivity with 99 % enantiomeric excess. In conclusion, this strategy may become a cost-effective alternative to coupled reactions using purified enzymes. Copyright © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A colorimetric chiral sensor based on chiral crown ether for the recognition of the two enantiomers of primary amino alcohols and amines.

PubMed

Cho, Eun Na Rae; Li, Yinan; Kim, Hee Jin; Hyun, Myung Ho

2011-04-01

A new colorimetric chiral sensor material consisting of three different functional sites such as chromophore (2,4-dinitrophenylazophenol dye), binding site (crown ether), and chiral barrier (3,3'-diphenyl-1,1'-binaphthyl group) was prepared and applied to the recognition of the two enantiomers of primary amino alcohols and amines. Among five primary amino alcohols and two primary amines tested, the two enantiomers of phenylalaninol show the highest difference in the absorption maximum wavelength (Δλ(max)=43.5 nm) and in the association constants (K(S)/K(R)=2.51) upon complexation with the colorimetric chiral sensor material and, consequently, the two enantiomers of phenylalaninol were clearly distinguished from each other by the color difference. Copyright © 2010 Wiley-Liss, Inc.

Organic functional group transformations in water at elevated temperature and pressure: Reversibility, reactivity, and mechanisms

NASA Astrophysics Data System (ADS)

Shipp, Jessie; Gould, Ian R.; Herckes, Pierre; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

2013-03-01

Many transformation reactions involving hydrocarbons occur in the presence of H2O in hydrothermal systems and deep sedimentary systems. We investigate these reactions using laboratory-based organic chemistry experiments at high temperature and pressure (300 °C and 100 MPa). Organic functional group transformation reactions using model organic compounds based on cyclohexane with one or two methyl groups provided regio- and stereochemical markers that yield information about reversibility and reaction mechanisms. We found rapidly reversible interconversion between alkanes, alkenes, dienes, alcohols, ketones, and enones. The alkane-to-ketone reactions were not only completely reversible, but also exhibited such extensive reversibility that any of the functional groups along the reaction path (alcohol, ketone, and even the diene) could be used as the reactant and form all the other groups as products. There was also a propensity for these ring-based structures to dehydrogenate; presumably from the alkene, through a diene, to an aromatic ring. The product suites provide strong evidence that water behaved as a reactant and the various functional groups showed differing degrees of reactivity. Mechanistically-revealing products indicated reaction mechanisms that involve carbon-centered cation intermediates. This work therefore demonstrates that a wide range of organic compound types can be generated by abiotic reactions at hydrothermal conditions.

Selective Oxidation of Alcohols Using Photoactive VO@g??C3N4

EPA Pesticide Factsheets

A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.This dataset is associated with the following publication:Verma, S., R.B. Nasir Baig, M. Nadagouda , and R. Varma. Selective oxidation of alcohols using photoactive VO@g-C3N4.. ACS Sustainable Chemistry & Engineering. American Chemical Society, Washington, DC, USA, 4(3): 1094-1098, (2015).

Methods for degrading lignocellulosic materials

DOEpatents

Vlasenko, Elena [Davis, CA; Cherry, Joel [Davis, CA; Xu, Feng [Davis, CA

2008-04-08

The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermentating microoganisms; and (c) recovering the organic substance from the fermentation.

Methods for degrading lignocellulosic materials

DOEpatents

Vlasenko, Elena [Davis, CA; Cherry, Joel [Davis, CA; Xu, Feng [Davis, CA

2011-05-17

The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermenting microorganisms; and (c) recovering the organic substance from the fermentation.

Methods for degrading lignocellulosic materials

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

Vlasenko, Elena; Cherry, Joel; Xu, Feng

2008-04-08

The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolyticmore » enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermentating microoganisms; and (c) recovering the organic substance from the fermentation.« less

PHOTOCATALYTIC REACTORS AND KINETICS FOR CLEAN CHEMICAL SYNTHESIS [POSTER PRESENTATION

EPA Science Inventory

Semiconductor photocatalysis has been tested at a potential technology for synthesizing alcohols, ketones and aldehydes from linear and cyclic hydrocarbons. The technology couples UV light with photocatalyst overcoming many of the drawbacks of conventional reacors. Various hydr...

Organic Lecture Demonstrations.

ERIC Educational Resources Information Center

Silversmith, Ernest F.

1988-01-01

Provides a listing of 35 demonstrations designed to generate interest in organic chemistry and help put points across. Topics include opening lecture; molecular structure and properties; halogenation; nucleophilic substitution, alkenes and dienes, stereochemistry, spectroscopy, alcohols and phenols, aldehydes and ketones; carboxylic acids, amines,…

Electrochemical and photoelectrochemical reduction of furfurals

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

Choi, Kyoung-Shin; Roylance, John James; Kubota, Stephen R.

Electrochemical cells and photoelectrochemical cells for the reduction of furfurals are provided. Also provided are methods of using the cells to carry out the reduction reactions. Using the cells and methods, furfurals can be converted into furan alcohols or linear ketones.

C-nor-9,11-secoestranes as modified estrogens and fertility regulation.

PubMed

Lal, K; Sharma, I; Agarwal, A K; Agnihotri, A; Ray, S

1988-06-01

The synthesis of C-nor-9,11-secoestradiol (4) has been achieved from 17 beta-acetoxy-11-chloro-3-methoxy-C-nor-9,11-secoestra-1,3,5(10)-tr ien-9-one (1) through a sequence of reactions without affecting the stereochemistry of estradiol-17 beta. Removal of the 9-keto function of 1 by hydrogenolysis and its subsequent treatment with Na/NH3 gives C-nor-9,11-secoestradiol 3-(methyl ether) (3), which has been demethylated under alkaline conditions to furnish C-nor-9,11-secoestradiol (4). Pyridinium chlorochromate oxidation of 3 gives the corresponding 17-ketone 6. Jones' oxidation of 4 to the ketone 5 and reaction of 5 and 6 with lithium acetylide gives corresponding 17 alpha-ethynyl derivatives 7 and 8. Relative binding affinity to estradiol-17 beta receptors and uterotropic, antiuterotrophic, and antiimplantation activities of compounds 3-8 have been studied. The effect of conformational flexibility on ligand-receptor interaction of these compounds is discussed.

Structure elucidation and chemical synthesis of stigmolone, a novel type of prokaryotic pheromone

PubMed Central

Hull, William E.; Berkessel, Albrecht; Plaga, Wulf

1998-01-01

Approximately 2 μmol of a novel prokaryotic pheromone, involved in starvation-induced aggregation and formation of fruiting bodies by the myxobacterium Stigmatella aurantiaca, were isolated by a large-scale elution procedure. The pheromone was purified by HPLC, and high-resolution MS, IR, 1H-NMR, and 13C-NMR were used to identify the active substance as the hydroxy ketone 2,5,8-trimethyl-8-hydroxy-nonan-4-one, which has been named stigmolone. The analysis was complicated by a solvent-dependent equilibrium between stigmolone and the cyclic enol-ether 3,4-dihydro-2,2,5-trimethyl-6-(2-methylpropyl)-2H-pyran formed by intramolecular nucleophilic attack of the 8-OH group at the ketone C4 followed by loss of H2O. Both compounds were synthesized chemically, and their structures were confirmed by NMR analysis. Natural and synthetic stigmolone have the same biological activity at ca. 1 nM concentration. PMID:9736725

The toxicity of selected gasoline components to glucose methanogenesis by aquifer microorganisms

USGS Publications Warehouse

Mormile, Melanie R.; Suflita, Joseph M.

1996-01-01

Six model hydrocarbons, representing various classes of chemicals found in gasoline, and methyl ethyl ketone, were assayed for their inhibitory effect on glucose methanogenesis in slurries prepared from aquifer sediments and ground water. Biogas (CH4and CO2) production was monitored with an automated pressure transducer system. Benzene, 1-methyl naphthalene, and methyltert-butyl ether (MTBE) were found to have no inhibitory influence on biogas production rates at concentrations up to 71·7 mg/L. Similarly, octane, cyclohexane, indan, and methyl ethyl ketone (MEK) were found to have only marginal negative effects on the rate of biogas production in aquifer slurries, at concentrations ranging from 51·7 to 72·1 mg/L. Thus, gasoline components had low apparent toxicities to microorganisms responsible for glucose methanogenesis in aquifier slurries. As the concentrations of the assayed hydrocarbons are about 100 times those typically reported after an aquifer has been contaminated with gasoline, it is unlikely that individual hydrocarbons will substantially impact anaerobic metabolic processes.

Dual Bioactivities of Essential Oil Extracted from the Leaves of Artemisia argyi as an Antimelanogenic versus Antioxidant Agent and Chemical Composition Analysis by GC/MS

PubMed Central

Huang, Huey-Chun; Wang, Hsiao-Fen; Yih, Kuang-Hway; Chang, Long-Zen; Chang, Tsong-Min

2012-01-01

The study was aimed at investigating the antimelanogenic and antioxidant properties of essential oil when extracted from the leaves of Artemisia argyi, then analyzing the chemical composition of the essential oil. The inhibitory effect of the essential oil on melanogenesis was evaluated by a mushroom tyrosinase activity assay and B16F10 melanoma cell model. The antioxidant capacity of the essential oil was assayed by spectrophotometric analysis, and the volatile chemical composition of the essential oil was analyzed with gas chromatography-mass spectrometry (GC/MS). The results revealed that the essential oil significantly inhibits mushroom tyrosinase activity (IC50 = 19.16 mg/mL), down-regulates B16F10 intracellular tyrosinase activity and decreases the amount of melanin content in a dose-dependent pattern. Furthermore, the essential oil significantly scavenged 2,2-diphenyl-1-picryl-hydrazyl (DPPH) and 2,2′-azino-bis (3-ethylbenzthiazoline- 6-sulphonic acid) ABTS radicals, showed an apparent reduction power as compared with metal-ion chelating activities. The chemicals constituents in the essential oil are ether (23.66%), alcohols (16.72%), sesquiterpenes (15.21%), esters (11.78%), monoterpenes (11.63%), ketones (6.09%), aromatic compounds (5.01%), and account for a 90.10% analysis of its chemical composition. It is predicted that eucalyptol and the other constituents, except for alcohols, in the essential oil may contribute to its antioxidant activities. The results indicated that essential oil extracted from A. argyi leaves decreased melanin production in B16F10 cells and showed potent antioxidant activity. The essential oil can thereby be applied as an inhibitor of melanogenesis and could also act as a natural antioxidant in skin care products. PMID:23203088

Dual bioactivities of essential oil extracted from the leaves of Artemisia argyi as an antimelanogenic versus antioxidant agent and chemical composition analysis by GC/MS.

PubMed

Huang, Huey-Chun; Wang, Hsiao-Fen; Yih, Kuang-Hway; Chang, Long-Zen; Chang, Tsong-Min

2012-11-12

The study was aimed at investigating the antimelanogenic and antioxidant properties of essential oil when extracted from the leaves of Artemisia argyi, then analyzing the chemical composition of the essential oil. The inhibitory effect of the essential oil on melanogenesis was evaluated by a mushroom tyrosinase activity assay and B16F10 melanoma cell model. The antioxidant capacity of the essential oil was assayed by spectrophotometric analysis, and the volatile chemical composition of the essential oil was analyzed with gas chromatography-mass spectrometry (GC/MS). The results revealed that the essential oil significantly inhibits mushroom tyrosinase activity (IC(50) = 19.16 mg/mL), down-regulates B16F10 intracellular tyrosinase activity and decreases the amount of melanin content in a dose-dependent pattern. Furthermore, the essential oil significantly scavenged 2,2-diphenyl-1-picryl-hydrazyl (DPPH) and 2,2'-azino-bis (3-ethylbenzthiazoline-6-sulphonic acid) ABTS radicals, showed an apparent reduction power as compared with metal-ion chelating activities. The chemicals constituents in the essential oil are ether (23.66%), alcohols (16.72%), sesquiterpenes (15.21%), esters (11.78%), monoterpenes (11.63%), ketones (6.09%), aromatic compounds (5.01%), and account for a 90.10% analysis of its chemical composition. It is predicted that eucalyptol and the other constituents, except for alcohols, in the essential oil may contribute to its antioxidant activities. The results indicated that essential oil extracted from A. argyi leaves decreased melanin production in B16F10 cells and showed potent antioxidant activity. The essential oil can thereby be applied as an inhibitor of melanogenesis and could also act as a natural antioxidant in skin care products.

Occupational exposure to solvents and risk of head and neck cancer in women: a population-based case-control study in France.

PubMed

Carton, Matthieu; Barul, Christine; Menvielle, Gwenn; Cyr, Diane; Sanchez, Marie; Pilorget, Corinne; Trétarre, Brigitte; Stücker, Isabelle; Luce, Danièle

2017-01-09

Our objective was to investigate the association between head and neck cancer and occupational exposure to chlorinated, oxygenated and petroleum solvents in women. Investigation of occupational and environmental CAuses of REspiratory cancers (ICARE), a French population-based case-control study, included 296 squamous cell carcinomas of the head and neck (HNSCC) in women and 775 female controls. Lifelong occupational history was collected. Job-exposure matrices allowed to assess exposure to 5 chlorinated solvents (carbon tetrachloride; chloroform; methylene chloride; perchloroethylene; trichloroethylene), 5 petroleum solvents (benzene; special petroleum product; gasoline; white spirits and other light aromatic mixtures; diesel, fuels and kerosene) and 5 oxygenated solvents (alcohols; ketones and esters; ethylene glycol; diethyl ether; tetrahydrofuran). OR and 95% CIs, adjusted for smoking, alcohol drinking, age and geographical area, were estimated with logistic models. Elevated ORs were observed among women ever exposed to perchloroethylene (OR=2.97, 95% CI 1.05 to 8.45) and trichloroethylene (OR=2.15, 95% CI 1.21 to 3.81). These ORs increased with exposure duration (OR=3.75, 95% CI 0.64 to 21.9 and OR=4.44, 95% CI 1.56 to 12.6 for 10 years or more, respectively). No significantly increased risk of HNSCC was found for occupational exposure to the other chlorinated, petroleum or oxygenated solvents. These findings suggest that exposure to perchloroethylene or trichloroethylene may increase the risk of HNSCC in women. In our study, there is no clear evidence that the other studied solvents are risk factors for HNSCC. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Asymmetric reduction of ketones with catecholborane using 2,6-BODOL complexes of titanium(IV) as catalysts.

PubMed

Sarvary, I; Almqvist, F; Frejd, T

2001-05-18

Reductions performed with Ti(IV) complexes of ligands based on bicyclo[2.2.2]octane diols 5 and 6 are effective catalysts in the reduction of prochiral ketones to optically active alcohols, with catecholborane as the reducing agent. Methyl ketones are favored and enantiomeric excesses (ee) of < or =98% have been achieved with acetophenone as the substrate. Several other substrates were tested, among them 2-octanone, which gave 2-octanol in 87% ee. Further details of the method were examined, for example, temperature, solvent composition, amount of molecular sieves (4 A), and catecholborane quality, as well as the sensitivity of the ligands towards acids. NMR spectroscopic methods were used to gain some insight into the complexes formed between the ligands and [Ti(OiPr)4]. A dimeric structure is proposed for the pre-catalyst.

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

NASA Astrophysics Data System (ADS)

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-09-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

Acetylcholinesterase and Acetylcholine Receptor

DTIC Science & Technology

1989-01-30

trimethyl analogue, neopentyl alcohol, (CH 3 ) 3 CCH20H, Ki(comi - 29 mM, Ki(nonc)’ = 74 mM, and to the ether isomer of the latter, =-butyl methyl ether, (CH...Trietrylene glycol di-tert-butylether is being prepared from the glycol via the di-p-toluenesulfonate, mp 80-81"C from methanol, lit. 80-810C (60). 2-N,N

On copper peroxide

NASA Technical Reports Server (NTRS)

Moser, L.

1988-01-01

The action of hydrogen superoxide on copper salts in alcoholic solutions is studied. The action of hydrogen peroxide on copper hydroxide in alcoholic suspensions, and the action of ethereal hydrogen peroxide on copper hydroxide are discussed. It is concluded that using the procedure proposed excludes almost entirely the harmful effect of hydrolysis.

High-strength, surface-porous polyether-ether-ketone for load-bearing orthopedic implants.

PubMed

Evans, Nathan T; Torstrick, F Brennan; Lee, Christopher S D; Dupont, Kenneth M; Safranski, David L; Chang, W Allen; Macedo, Annie E; Lin, Angela S P; Boothby, Jennifer M; Whittingslow, Daniel C; Carson, Robert A; Guldberg, Robert E; Gall, Ken

2015-02-01

Despite its widespread clinical use in load-bearing orthopedic implants, polyether-ether-ketone (PEEK) is often associated with poor osseointegration. In this study, a surface-porous PEEK material (PEEK-SP) was created using a melt extrusion technique. The porous layer was 399.6±63.3 μm thick and possessed a mean pore size of 279.9±31.6 μm, strut spacing of 186.8±55.5 μm, porosity of 67.3±3.1% and interconnectivity of 99.9±0.1%. Monotonic tensile tests showed that PEEK-SP preserved 73.9% of the strength (71.06±2.17 MPa) and 73.4% of the elastic modulus (2.45±0.31 GPa) of as-received, injection-molded PEEK. PEEK-SP further demonstrated a fatigue strength of 60.0 MPa at one million cycles, preserving 73.4% of the fatigue resistance of injection-molded PEEK. Interfacial shear testing showed the pore layer shear strength to be 23.96±2.26 MPa. An osseointegration model in the rat revealed substantial bone formation within the pore layer at 6 and 12 weeks via microcomputed tomography and histological evaluation. Ingrown bone was more closely apposed to the pore wall and fibrous tissue growth was reduced in PEEK-SP when compared to non-porous PEEK controls. These results indicate that PEEK-SP could provide improved osseointegration while maintaining the structural integrity necessary for load-bearing orthopedic applications. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Increasing the proton conductivity of sulfonated polyether ether ketone by incorporating graphene oxide: Morphology effect on proton dynamics

NASA Astrophysics Data System (ADS)

Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

2018-03-01

We synthesized graphene oxide-sulfonated polyether ether ketone (GO-SPEEK) composite membrane and compare its proton conductivity with that of Nafion® 117 and SPEEK membranes. From experimental measurements, we found that GO-SPEEK has better proton conductivity (σGO-SPEEK = 3.8 × 10-2 S cm-1) when compared to Nafion® 117 (σNafion = 2.4 × 10-2 S cm-1) and SPEEK (σSPEEK = 2.9 × 10-3 S cm-1). From density functional theory (DFT-) based total energy calculations, we found that GO-SPEEK has the shortest proton diffusion distance among the three membranes, yielding the highest tunneling probability. Hence, GO-SPEEK exhibits the highest conductivity. The short proton diffusion distance in GO-SPEEK, as compared to Nafion® 117 and SPEEK, can be attributed to the presence of oxygenated functional groups of GO in the polymer matrix. This also explains why GO-SPEEK requires the lowest hydration level to reach its maximum conductivity. Moreover, we have successfully shown that the proton conductivity σ is related to the tunneling probability T, i.e., σ = σ‧ exp(-1/T). We conclude that the proton diffusion distance and hydration level are the two most significant factors that determine the membrane’s good conductivity. The distance between ionic sites of the membrane should be small to obtain good conductivity. With this short distance, lower hydration level is required. Thus, a membrane with short separation between the ionic sites can have enhanced conductivity, even at low hydration conditions.

A study to compare the efficacy of polyether ether ketone rod device with titanium devices in posterior spinal fusion in a canine model.

PubMed

Wang, Nanxiang; Xie, Huanxin; Xi, Chunyang; Zhang, Han; Yan, Jinglong

2017-03-09

The benefits of posterior lumbar fusion surgery with orthotopic paraspinal muscle-pediculated bone flaps are well established. However, the problem of non-union due to mechanical support is not completely resolved. The aim of the study was to compare the efficacy of polyether ether ketone (PEEK) rod device with conventional titanium devices in the posterior lumbar fusion surgery with orthotopic paraspinal muscle-pediculated bone flaps. This was a randomized controlled study with an experimental animal model. Thirty-two mongrel dogs were randomly divided into two groups-control group (n = 16), which received the titanium device and the treatment group (n = 16), which received PEEK rods. The animals were sacrificed 8 or 16 weeks after surgery. Lumbar spines of dogs in both groups were removed, harvested, and assessed for radiographic, biomechanical, and histological changes. Results in the current study indicated that there was no significant difference in the lumbar spine of the control and treatment groups in terms of radiographic, manual palpation, and gross examination. However, certain parameters of biomechanical testing showed significant differences (p < 0.05) in stiffness and displacement, revealing a better fusion (treatment group showed decreased stiffness with decreased displacement) of the bone graft. Similarly, the histological analysis also revealed a significant fusion mass in both treatment and control groups (p < 0.05). These findings revealed that fixation using PEEK connecting rod could improve the union of the bone graft in the posterior lumbar spine fusion surgery compared with that of the titanium rod fixation.

Bio-functionalisation of polyether ether ketone using plasma immersion ion implantation

NASA Astrophysics Data System (ADS)

Wakelin, Edgar; Yeo, Giselle; Kondyurin, Alexey; Davies, Michael; McKenzie, David; Weiss, Anthony; Bilek, Marcela

2015-12-01

Plasma immersion ion implantation (PIII) is used here to improve the surface bioactivity of polyether ether ketone (PEEK) by modifying the chemical and mechanical properties and by introducing radicals. Modifications to the chemical and mechanical properties are characterised as a function of ion fluence (proportional to treatment time) to determine the suitability of the treated surfaces for biological applications. Radical generation increases with treatment time, where treatments greater than 400 seconds result in a high concentration of long-lived radicals. Radical reactions are responsible for oxidation of the surface, resulting in a permanent increase in the polar surface energy. The nano-scale reduced modulus was found to increase with treatment time at the surface from 4.4 to 5.2 GPa. The macromolecular Young's modulus was also found to increase, but by an amount corresponding to the volume fraction of the ion implanted region. The treated surface layer exhibited cracking under cyclical loads, associated with an increased modulus due to dehydrogenation and crosslinking, however it did not show any sign of delamination, indicating that the modified layer is well integrated with the substrate - a critical factor for bioactive surface coatings to be used in-vivo. Protein immobilisation on the PIII treated surfaces was found to saturate after 240 seconds of treatment, indicating that there is room to tune surface mechanical properties for specific applications without affecting the protein coverage. Our findings indicate that the modification of the chemical and mechanical properties by PIII treatments as well as the introduction of radicals render PEEK well suited for use in orthopaedic implantable devices.

Catalytic Arylation and Vinylation Reactions Directed by Anionic Oxygen Functions via Cleavage of C - H and C - C Bonds

NASA Astrophysics Data System (ADS)

Satoh, Tetsuya; Miura, Masahiro

Aromatic compounds having oxygen-containing substituents such as phenols, phenyl ketones, benzyl alcohols, and benzoic acids undergo regioselective arylation and vinylation via C-H bond cleavage in the presence of transition-metal catalysts. The latter two substrates are also arylated and vinylated via C-C bond cleavage accompanied by liberation of ketones and CO2, respectively. Coordination of their anionic oxygen to the metal center is the key to activate the inert bonds effectively and regioselectively. The recent progress of these oxygen-directed reactions is summarized herein.

Oxidation of Secondary Alcohols by Duckweed: A Biotransformation Experiment for Undergraduate Students.

ERIC Educational Resources Information Center

Karfarski, Pawel; And Others

1988-01-01

Describes an experiment designed to use the ability of duckweed to convert the secondary hydroxyl moieties into ketone groups. Discusses the preparation of plant material, materials, procedures, and results for this biotransformation experiment for undergraduate students. (CW)

FACTORS CONTROLLING THE EMISSIONS OF MONOTERPENES AND OTHER VOLATILE ORGANIC COMPOUNDS

EPA Science Inventory

Plants contain a number of volatile organic compounds, including isoprene, mono- and sesquiterpenes, alcohols, aldehydes, ketones, and esters. ndividual plant species have unique combinations of these compounds; consequently, the emission pattern for each species is also specific...

26 CFR 1.40-1 - Questions and answers relating to the meaning of the term “qualified mixture” in section 40(b)(1).

Code of Federal Regulations, 2014 CFR

2014-04-01

...) if such product is produced in a chemical reaction between alcohol and either gasoline or a special... ether (ETBE), a compound derived from ethanol (a qualified alcohol), in a chemical reaction in which... the alcohol is no longer present as a separate chemical in the final product, provided that there is...

26 CFR 1.40-1 - Questions and answers relating to the meaning of the term “qualified mixture” in section 40(b)(1).

Code of Federal Regulations, 2010 CFR

2010-04-01

...) if such product is produced in a chemical reaction between alcohol and either gasoline or a special... ether (ETBE), a compound derived from ethanol (a qualified alcohol), in a chemical reaction in which... the alcohol is no longer present as a separate chemical in the final product, provided that there is...

26 CFR 1.40-1 - Questions and answers relating to the meaning of the term “qualified mixture” in section 40(b)(1).

Code of Federal Regulations, 2011 CFR

2011-04-01

...) if such product is produced in a chemical reaction between alcohol and either gasoline or a special... ether (ETBE), a compound derived from ethanol (a qualified alcohol), in a chemical reaction in which... the alcohol is no longer present as a separate chemical in the final product, provided that there is...

26 CFR 1.40-1 - Questions and answers relating to the meaning of the term “qualified mixture” in section 40(b)(1).

Code of Federal Regulations, 2012 CFR

2012-04-01

...) if such product is produced in a chemical reaction between alcohol and either gasoline or a special... ether (ETBE), a compound derived from ethanol (a qualified alcohol), in a chemical reaction in which... the alcohol is no longer present as a separate chemical in the final product, provided that there is...

26 CFR 1.40-1 - Questions and answers relating to the meaning of the term “qualified mixture” in section 40(b)(1).

Code of Federal Regulations, 2013 CFR

2013-04-01

...) if such product is produced in a chemical reaction between alcohol and either gasoline or a special... ether (ETBE), a compound derived from ethanol (a qualified alcohol), in a chemical reaction in which... the alcohol is no longer present as a separate chemical in the final product, provided that there is...

Reductive Etherification of Fatty Acids or Esters with Alcohols using Molecular Hydrogen.

PubMed

Erb, Benjamin; Risto, Eugen; Wendling, Timo; Gooßen, Lukas J

2016-06-22

In the presence of a catalyst system consisting of a ruthenium/triphos complex and the Brønsted acid trifluoromethanesulfonimide, mixtures of fatty acids and aliphatic alcohols are converted into the corresponding ethers at 70 bar H2 . The protocol allows the sustainable one-step synthesis of valuable long-chain ether fragrances, lubricants, and surfactants from renewable sources. The reaction protocol is extended to various fatty acids and esters both in pure form and as mixtures, for example, tall oil acids or rapeseed methyl ester (RME). Even the mixed triglyceride rapeseed oil was converted in one step. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes

NASA Astrophysics Data System (ADS)

Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

2016-06-01

We have demonstrated large enhancements of CH bond acidities in alcohol, ether, and amine cations through infrared predissociation spectroscopy based on the vacuum ultraviolet photoionization detection. In this study, we investigate for the cationic alkanes (pentane, hexane, and heptane) with different alkyl chain lengths. The σ electrons are ejected in the ionization of alkanes, while nonbonding electrons are ejected in ionization of alcohols, ethers, and amines. Nevertheless, the acidity enhancements of CH in these cationic alkanes have also been demonstrated by infrared spectroscopy. The correlations of their CH bond acidities with the alkyl chain lengths as well as the mechanisms of their acidity enhancements will be discussed by comparison of infrared spectra and theoretical calculations.

Enzymatic Addition of Alcohols to Terpenes by Squalene Hopene Cyclase Variants.

PubMed

Kühnel, Lisa C; Nestl, Bettina M; Hauer, Bernhard

2017-11-16

Squalene-hopene cyclases (SHCs) catalyze the polycyclization of squalene into a mixture of hopene and hopanol. Recently, amino-acid residues lining the catalytic cavity of the SHC from Alicyclobacillus acidocaldarius were replaced by small and large hydrophobic amino acids. The alteration of leucine 607 to phenylalanine resulted in increased enzymatic activity towards the formation of an intermolecular farnesyl-farnesyl ether product from farnesol. Furthermore, the addition of small-chain alcohols acting as nucleophiles led to the formation of non-natural ether-linked terpenoids and, thus, to significant alteration of the product pattern relative to that obtained with the wild type. It is proposed that the mutation of leucine at position 607 may facilitate premature quenching of the intermediate by small alcohol nucleophiles. This mutagenesis-based study opens the field for further intermolecular bond-forming reactions and the generation of non-natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

MICROWAVE-ASSISTED PREPARATION OF DIALKYLIMIDAZOLIUM TETRACHLOROALUMINATES AND THEIR USE AS CATALYSTS IN THE SOLVENT-FREE TETRAHYDROPYRANYLATION OF ALCOHOLS AND PHENOLS

EPA Science Inventory

Microwave-assisted preparation of dialkylimidazolium tetrachloroaluminates and their application as recyclable catalysts for the efficient and eco-friendly protection of alcohols as tetrahydropyranyl (THP) ethers are described; the same catalyst can also be utilized for the depro...

Synthetic approach to the AB ring system of ouabain.

PubMed

Jung, Michael E; Piizzi, Grazia

2003-04-04

Several novel hydroxylated cis-decalin derivatives, potential intermediates for the synthesis of the AB ring system of the important cardiotonic steroid ouabain, have been synthesized from commercially available starting materials. The first step in the preparation of these highly functionalized intermediates is a Robinson annulation of the beta-keto ester 6 and the 4-silyl-3-buten-2-one 5 to furnish the octalone 4 with good diastereoselectivity in fair yield (due to competition with a novel silicon-to-carbon phenyl migration). Reduction of the epoxy alcohol 3 (derived from 4 in two high-yielding steps) with LiAlH(4) gave a mixture of the desired triol 11 along with the product of an unusual reductive opening at the tertiary carbon, namely the triol 12. A plausible mechanism for this unusual reduction is presented as are possible methods for avoiding it. In particular, reduction of the corrresponding epoxy ketone 15 with aluminum amalgam proceeded in good yield to give the hydroxy ketone 16. Also reduction of the epoxide ester having the inverted stereochemistry at C3 afforded the desired tertiary alcohol 33 in good yield. Another approach using the beta,gamma-unsaturated ketal 38 permitted the formation of the tertiary alcohol 40. Fleming oxidation of the related, very functionalized silane 39 afforded the desired 1beta-alcohol 41 in fair yield. Finally a novel rearrangement was observed when the epoxy alcohol 24 was treated with DIBAL to effect loss of the angular hydroxymethyl group to produce the tetrasubstitued alkene 29 in high yield.

MEASUREMENT OF EXHALED BREATH AND VENOUS BLOOD TO DEVELOP A PHYSIOLOGICALLY BASED PHARMACOKINETIC MODEL FOR HUMAN EXPOSURE TO METHYL TERTIARY-BUTYL ETHER AND THE PRODUCTION OF THE BIOMARKER TERTIARY-BUTYL ALCOHOL

EPA Science Inventory

Methyl tertiary-butyl ether (MTBE) is a common fuel additive used to increase the availability of oxygen in gasoline to reduce winter-time carbon monoxide emissions from automobiles. Also, MTBE boosts gasoline "octane" rating and, as such, allows reduction of benzene...

[Alcoholic ketoacidosis and reversible neurological complications due to hypophosphataemia].

PubMed

Fernández López, Ma T; García Bargo, Ma D; Rivero Luis, Ma T; Álvarez Vázquez, P; Saenz Fernández, C A; Mato Mato, J A

2012-01-01

A 57-year-old man with chronic alcoholism was admitted to our hospital due to disturbance of consciousness and polyradiculitis. Laboratory examination revealed metabolic acidosis, hypokalemia and hypophosphataemia. Alcoholic ketoacidosis is a common disorder in alcoholic patients. All patients present with a history of heavy alcohol misuse, preceding a bout of particularly excesive intake, which had been terminated by nausea, vomiting and abdominal pain. The most important laboratory results are: normal or low glucose level, metabolic acidosis with a raised anion GAP, low or absent blood alcohol level and urinary ketones. The greatest threats to patients are: hypovolemia, hypokaliemia, hypoglucemia and acidosis. Alcohol abuse may result in a wide range of electrolyte and acid-base disorders including hypophosphataemia, hypomagnesemia, hypocalcemia, hypokalemia, metabolic acidosis and respiratory alkalosis. Disturbance of consciousness in alcoholic patients is observed in several disorders, such drunkenness, Wernicke encephalopathy, alcohol withdrawal syndrome, central pontine myelinolysis, hepatic encephalopathy, hypoglucemia and electrolyte disorders.

A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C-C Multiple Bonds.

PubMed

Hossein Bagi, Amin; Khaledi, Yousef; Ghari, Hossein; Arndt, Sebastian; Hashmi, A Stephen K; Yates, Brian F; Ariafard, Alireza

2016-11-09

The gold-catalyzed direct functionalization of aromatic C-H bonds has attracted interest for constructing organic compounds which have application in pharmaceuticals, agrochemicals, and other important fields. In the literature, two major mechanisms have been proposed for these catalytic reactions: inner-sphere syn-addition and outer-sphere anti-addition (Friedel-Crafts-type mechanism). In this article, the AuCl 3 -catalyzed hydrofurylation of allenyl ketone, vinyl ketone, ketone, and alcohol substrates is investigated with the aid of density functional theory calculations, and it is found that the corresponding functionalizations are best rationalized in terms of a novel mechanism called "concerted electrophilic ipso-substitution" (CEIS) in which the gold(III)-furyl σ-bond produced by furan auration acts as a nucleophile and attacks the protonated substrate via an outer-sphere mechanism. This unprecedented mechanism needs to be considered as an alternative plausible pathway for gold(III)-catalyzed arene functionalization reactions in future studies.

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

PubMed Central

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-01-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions. PMID:27671606

The mechanism of enantioselective ketone reduction with Noyori and Noyori–Ikariya bifunctional catalysts

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

Dub, Pavel A.; Gordon, John C.

2016-03-21

The catalytic hydrogenation of prochiral ketones with second and third-row transition metal complexes bearing chelating chiral ligands containing at least one N–H functionality has achieved unparalleled performance, delivering, in the best cases, chiral alcohols with up to 99.9% ee using extremely small catalyst loadings (~10 -5 mol%). Hence the efficacy of this reaction has closely approached that of natural enzymatic systems and the reaction itself has become one of the most efficient artificial catalytic reactions developed to date. This paper describes the current level of understanding of the mechanism of enantioselective hydrogenation and transfer hydrogenation of aromatic ketones with pioneeringmore » prototypes of bifunctional catalysts, the Noyori and Noyori–Ikariya complexes. Finally, analysis presented herein expands the concept of “metal–ligand cooperation”, redefines the term “cooperative ligand” and introduces “H –/H + outer-sphere hydrogenation” as a novel paradigm in outer-sphere hydrogenation.« less

Photopyroelectric response of PTCa∕PEEK composite.

PubMed

Estevam, Giuliano Pierre; de Melo, Washington Luiz Barros; Sakamoto, Walter Katsumi

2011-02-01

A pyroelectric composite made of calcium modified lead titanate ceramic and polyether-ether-ketone high performance polymer was obtained in the film form by hot pressing the ceramic/polymer mixture into the desired composition. After polarization with a suitable electric field, a ceramic composite film (60% vol.) exhibited a pyroelectric figure of merit three times higher than that of a lead zirconate titanate ceramic. The material was used as infrared radiation sensor. The voltage responsivity decreases with the inverse of the frequency showing the same behavior of the thermally thick sensor. The reproducibility of the sensor responses was observed.

SEPARATION OF INORGANIC SALTS FROM ORGANIC SOLUTIONS

DOEpatents

Katzin, L.I.; Sullivan, J.C.

1958-06-24

A process is described for recovering the nitrates of uranium and plutonium from solution in oxygen-containing organic solvents such as ketones or ethers. The solution of such salts dissolved in an oxygen-containing organic compound is contacted with an ion exchange resin whereby sorption of the entire salt on the resin takes place and then the salt-depleted liquid and the resin are separated from each other. The reaction seems to be based on an anion formation of the entire salt by complexing with the anion of the resin. Strong base or quaternary ammonium type resins can be used successfully in this process.

Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

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

Klier, Kamil; Herman, Richard G

2005-11-30

This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. Themore » latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.« less

Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

DOEpatents

Stahl, Shannon S; Rahimi, Alireza

2015-03-03

Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

Research on precise control of 3D print nozzle temperature in PEEK material

NASA Astrophysics Data System (ADS)

Liu, Zhichao; Wang, Gong; Huo, Yu; Zhao, Wei

2017-10-01

3D printing technology has shown more and more applicability in medication, designing and other fields for its low cost and high timeliness. PEEK (poly-ether-ether-ketone), as a typical high-performance special engineering plastic, become one of the most excellent materials to be used in 3D printing technology because of its excellent mechanical property, good lubricity, chemical resistance, and other properties. But the nozzle of 3D printer for PEEK has also a series of very high requirements. In this paper, we mainly use the nozzle temperature control as the research object, combining with the advantages and disadvantages of PID control and fuzzy control. Finally realize a kind of fuzzy PID controller to solve the problem of the inertia of the temperature system and the seriousness of the temperature control hysteresis in the temperature control of the nozzle, and to meet the requirements of the accuracy of the nozzle temperature control and rapid reaction.

Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

PubMed

Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G

2013-05-23

Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

Calculating pKa values for substituted phenols and hydration energies for other compounds with the first-order Fuzzy-Border continuum solvation model

PubMed Central

Sharma, Ity; Kaminski, George A.

2012-01-01

We have computed pKa values for eleven substituted phenol compounds using the continuum Fuzzy-Border (FB) solvation model. Hydration energies for 40 other compounds, including alkanes, alkenes, alkynes, ketones, amines, alcohols, ethers, aromatics, amides, heterocycles, thiols, sulfides and acids have been calculated. The overall average unsigned error in the calculated acidity constant values was equal to 0.41 pH units and the average error in the solvation energies was 0.076 kcal/mol. We have also reproduced pKa values of propanoic and butanoic acids within ca. 0.1 pH units from the experimental values by fitting the solvation parameters for carboxylate ion carbon and oxygen atoms. The FB model combines two distinguishing features. First, it limits the amount of noise which is common in numerical treatment of continuum solvation models by using fixed-position grid points. Second, it employs either second- or first-order approximation for the solvent polarization, depending on a particular implementation. These approximations are similar to those used for solute and explicit solvent fast polarization treatment which we developed previously. This article describes results of employing the first-order technique. This approximation places the presented methodology between the Generalized Born and Poisson-Boltzmann continuum solvation models with respect to their accuracy of reproducing the many-body effects in modeling a continuum solvent. PMID:22815192

Intramolecular Hydroamination of Unbiased and Functionalized Primary Aminoalkenes Catalyzed by a Rhodium Aminophosphine Complex

PubMed Central

Julian, Lisa D.; Hartwig, John F.

2010-01-01

We report a rhodium catalyst that exhibits high reactivity for the hydroamination of primary aminoalkenes that are unbiased toward cyclization and that possess functional groups that would not be tolerated in hydroaminations catalyzed by more electrophilic systems. This catalyst contains an unusual diaminophosphine ligand that binds to rhodium in a κ3-P,O,P mode. The reactions catalyzed by this complex typically proceed at mild temperatures (room temperature to 70 °C), occur with primary aminoalkenes lacking substituents on the alkyl chain that bias the system toward cyclization, occur with primary aminoalkenes containing chloride, ester, ether, enolizable ketone, nitrile, and unprotected alcohol functionality, and occur with primary aminoalkenes containing internal olefins. Mechanistic data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late transition metal complexes of Pd, Pt, and Ir. This change in the turnover-limiting step and resulting high activity of the catalyst stem from favorable relative rates for protonolysis of the M-C bond to release the hydroamination product vs reversion of the aminoalkyl intermediate to regenerate the acyclic precursor. Probes for the origin of the reactivity of the rhodium complex of L1 imply that the aminophosphine groups lead to these favorable rates by effects beyond steric demands and simple electron donation to the metal center. PMID:20839807

Identification of chemical components in Baidianling Capsule based on gas chromatography-mass spectrometry and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Wu, Wenying; Chen, Yu; Wang, Binjie; Sun, Xiaoyang; Guo, Ping; Chen, Xiaohui

2017-08-01

Baidianling Capsule, which is made from 16 Chinese herbs, has been widely used for treating vitiligo clinically. In this study, the sensitive and rapid method has been developed for the analysis of chemical components in Baidianling Capsule by gas chromatography-mass spectrometry in combination with retention indices and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Firstly, a total of 110 potential volatile compounds obtained from different extraction procedures including alkanes, alkenes, alkynes, ketones, ethers, aldehydes, alcohols, phenols, organic acids, esters, furans, pyrrole, acid amides, heterocycles, and oxides were detected from Baidianling Capsule by gas chromatography-mass spectrometry, of which 75 were identified by mass spectrometry in combination with the retention index. Then, a total of 124 components were tentatively identified by high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Fifteen constituents from Baidianling Capsule were accurately identified by comparing the retention times with those of reference compounds, others were identified by comparing the retention times and mass spectrometry data, as well as retrieving the reference literature. This study provides a practical strategy for rapidly screening and identifying the multiple constituents of a complex traditional Chinese medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Dual Antimelanogenic and Antioxidant Activities of the Essential Oil Extracted from the Leaves of Acorus macrospadiceus (Yamamoto) F. N. Wei et Y. K. Li

PubMed Central

Huang, Huey-Chun; Wang, Hsiao-Fen; Yih, Kuang-Hway; Chang, Long-Zen; Chang, Tsong-Min

2012-01-01

The antimelanogenic and antioxidant activities of the essential oil extracted from the leaves of Acorus macrospadiceus (Yamamoto) F. N. Wei et Y. K. Li have never been explored. The essential oil effectively inhibited mushroom tyrosinase activity (EC50 = 1.57 mg/mL) and B16F10 tyrosinase activity (IC50 = 1.01 mg/mL), decreased the melanin content (EC50 = 1.04 mg/mL), and depleted the cellular level of the reactive oxygen species (ROS) (EC50 = 1.87 mg/mL). The essential oil effectively scavenged 2,2-diphenyl-1-picryl-hydrazyl (DPPH) (EC50 = 0.121 mg/mL) and 2,2′-azino-bis (3-ethylbenzthiazoline-6-sulphonic acid) ABTS+ radicals (EC50 = 0.122 mg/mL). It also exhibited an apparent reducing power (EC50 = 0.021 mg/mL) and metal-ion chelating activity (EC50 = 0.029 mg/mL). The chemical constituents of the essential oil are ethers (55.73%), ketones (19.57%), monoterpenes (7.82%), alcohols (3.85%), esters (3.77%), sesquiterpenes (3.72%), and aromatic compounds (2.85%). The results confirm that A. macrospadiceus essential oil is a natural antioxidant and inhibitor of melanogenesis. PMID:23304214

Optimisation of supercritical carbon dioxide extraction of essential oil of flowers of tea (Camellia sinensis L.) plants and its antioxidative activity.

PubMed

Chen, Zhenchun; Mei, Xin; Jin, Yuxia; Kim, Eun-Hye; Yang, Ziyin; Tu, Youying

2014-01-30

To extract natural volatile compounds from tea (Camellia sinensis) flowers without thermal degradation and residue of organic solvents, supercritical fluid extraction (SFE) using carbon dioxide was employed to prepare essential oil of tea flowers in the present study. Four important parameters--pressure, temperature, static extraction time, and dynamic extraction time--were selected as independent variables in the SFE. The optimum extraction conditions were the pressure of 30 MPa, temperature of 50°C, static time of 10 min, and dynamic time of 90 min. Based on gas chromatography-mass spectrometry analysis, 59 compounds, including alkanes (45.4%), esters (10.5%), ketones (7.1%), aldehydes (3.7%), terpenes (3.7%), acids (2.1%), alcohols (1.6%), ethers (1.3%) and others (10.3%) were identified in the essential oil of tea flowers. Moreover, the essential oil of tea flowers showed relatively stronger DPPH radical scavenging activity than essential oils of geranium and peppermint, although its antioxidative activity was weaker than those of essential oil of clove, ascorbic acid, tert-butylhydroquinone, and butylated hydroxyanisole. Essential oil of tea flowers using SFE contained many types of volatile compounds and showed considerable DPPH scavenging activity. The information will contribute to the future application of tea flowers as raw materials in health-care food and food flavour industries. © 2013 Society of Chemical Industry.

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.

Health assessment of gasoline and fuel oxygenate vapors: developmental toxicity in rats.

PubMed

Roberts, Linda G; Gray, Thomas M; Trimmer, Gary W; Parker, Robert M; Murray, F Jay; Schreiner, Ceinwen A; Clark, Charles R

2014-11-01

Gasoline-vapor condensate (BGVC) or condensed vapors from gasoline blended with methyl t-butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME) diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA) were evaluated for developmental toxicity in Sprague-Dawley rats exposed via inhalation on gestation days (GD) 5-20 for 6h/day at levels of 0 (control filtered air), 2000, 10,000, and 20,000mg/m(3). These exposure durations and levels substantially exceed typical consumer exposure during refueling (<1-7mg/m(3), 5min). Dose responsive maternal effects were reduced maternal body weight and/or weight change, and/or reduced food consumption. No significant malformations were seen in any study. Developmental effects occurred at 20,000mg/m(3) of G/TAME (reduced fetal body weight, increased incidence of stunted fetuses), G/TBA (reduced fetal body weight, increased skeletal variants) and G/DIPE (reduced fetal weight) resulting in developmental NOAEL of 10,000mg/m(3) for these materials. Developmental NOAELs for other materials were 20,000mg/m(3) as no developmental toxicity was induced in those studies. Developmental NOAELs were equal to or greater than the concurrent maternal NOAELs which ranged from 2000 to 20,000mg/m(3). There were no clear cut differences in developmental toxicity between vapors of gasoline and gasoline blended with the ether or alcohol oxygenates. Copyright © 2014 Elsevier Inc. All rights reserved.

Fire extinguishing tests -80 with methyl alcohol gasoline

NASA Astrophysics Data System (ADS)

Holmstedt, G.; Ryderman, A.; Carlsson, B.; Lennmalm, B.

1980-10-01

Large scale tests and laboratory experiments were carried out for estimating the extinguishing effectiveness of three alcohol resistant aqueous film forming foams (AFFF), two alcohol resistant fluoroprotein foams and two detergent foams in various poolfires: gasoline, isopropyl alcohol, acetone, methyl-ethyl ketone, methyl alcohol and M15 (a gasoline, methyl alcohol, isobutene mixture). The scaling down of large scale tests for developing a reliable laboratory method was especially examined. The tests were performed with semidirect foam application, in pools of 50, 11, 4, 0.6, and 0.25 sq m. Burning time, temperature distribution in the liquid, and thermal radiation were determined. An M15 fire can be extinguished with a detergent foam, but it is impossible to extinguish fires in polar solvents, such as methyl alcohol, acetone, and isopropyl alcohol with detergent foams, AFFF give the best results; and performances with small pools can hardly be correlated with results from large scale fires.

Corona-discharge air-purification system

NASA Technical Reports Server (NTRS)

Wydeven, T. J.; Flamm, D. L.

1979-01-01

Plasma reaction chamber removes trace contaminants from spacecraft, submarines, and other closed environments by oxidizing contaminants to produce carbon dioxide and water. Contaminants are alcohols, esters, hydrogen sulfide, and ammonia. Others are lubricant solvents such as Freons, aromatics, and Ketones. Contaminants are removed from chamber by scrubber.

Fourier transform infrared analysis of aerosol formed in the photooxidation of 1-octene

NASA Astrophysics Data System (ADS)

Palen, Edward J.; Allen, David T.; Pandis, Spyros N.; Paulson, Suzanne; Seinfeld, John H.; Flagan, Richard C.

The chemical composition of aerosol generated in the photooxidation of 1-octene was examined using infrared microscopy interfaced with a low pressure impactor. The low pressure impactor segregated the aerosol into eight size fractions and deposited the aerosol onto ZnSe impaction substrates. The ZnSe surfaces were transparent in the mid-infrared region and therefore allowed direct analysis of the aerosol, with no extraction, using infrared microscopy. Infrared spectra of the size segregated aerosol showed strong absorbances due to ketone, alcohol, carboxylic acid and organonitrate functional groups. Absorbance features were relatively independent of particle size, with the exception of the carboxylic acid absorbances, which were found only in the largest aerosol size fractions. Molar loadings for each of the groups were estimated, based on model compound calibration standards. The molar loadings indicate that most aerosol species are multifunctional, with an average of one ketone group per molecule, an alcohol group in two of every three molecules and an organonitrate group in one of every three molecules.

A biphasic oxidation of alcohols to aldehydes and ketones using a simplified packed-bed microreactor

PubMed Central

Bogdan, Andrew

2009-01-01

Summary We demonstrate the preparation and characterization of a simplified packed-bed microreactor using an immobilized TEMPO catalyst shown to oxidize primary and secondary alcohols via the biphasic Anelli-Montanari protocol. Oxidations occurred in high yields with great stability over time. We observed that plugs of aqueous oxidant and organic alcohol entered the reactor as plugs but merged into an emulsion on the packed-bed. The emulsion coalesced into larger plugs upon exiting the reactor, leaving the organic product separate from the aqueous by-products. Furthermore, the microreactor oxidized a wide range of alcohols and remained active in excess of 100 trials without showing any loss of catalytic activity. PMID:19478910

Structure of alcohol cluster ions in the gas phase, according to spectrometry and ab initio calculations

NASA Astrophysics Data System (ADS)

Krisilov, A. V.; Lantsuzskaya, E. V.; Levina, A. M.

2017-01-01

Reduced ion mobility and scattering cross sections are calculated from experimentally obtained spectra of the ion mobility of linear aliphatic alcohols with carbon atom numbers from 2 to 9. A linear increase in the scattering cross sections as the molecular weight grows is found. According to the results from experiments and quantum chemical calculations, alcohol cluster ions do not form a compact structure. Neither are dipole moments compensated for during dimerization, in contrast to the aldehydes and ketones described earlier. It was concluded from ab initio calculations that charge delocalization in monomeric and dimeric ions of alcohols increases the dipole moment many times over.

Methyl t-Butyl Ether Mineralization in Surface-Water Sediment Microcosms under Denitrifying Conditions

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.; Landmeyer, J.E.

2001-01-01

Mineralization of [U-14C] methyl t-butyl ether (MTBE) to 14CO2 without accumulation of t-butyl alcohol (TBA) was observed in surface-water sediment microcosms under denitrifying conditions. Methanogenic activity and limited transformation of MTBE to TBA were observed in the absence of denitrification. Results indicate that bed sediment microorganisms can effectively degrade MTBE to nontoxic products under denitrifying conditions.

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study.

PubMed

Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2015-09-21

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Spider monkeys (Ateles geoffroyi) are less sensitive to the odor of aliphatic ketones than to the odor of other classes of aliphatic compounds.

PubMed

Eliasson, Moa; Hernandez Salazar, Laura Teresa; Laska, Matthias

2015-10-01

Aliphatic ketones are widely present in body-borne and food odors of primates. Therefore, we used an operant conditioning paradigm and determined olfactory detection thresholds in four spider monkeys for a homologous series of aliphatic 2-ketones (2-butanone to 2-nonanone) and two of their isomers (3- and 4-heptanone). We found that, with the exception of the two shortest-chained ketones, all animals detected concentrations <1 ppm (parts per million), and with five odorants individual animals even reached threshold values <0.1 ppm. Further, we found a significant correlation between olfactory sensitivity of the spider monkeys and carbon chain length of the 2-ketones which can best be described as a U-shaped function. In contrast, no significant correlation was found between olfactory sensitivity and position of the functional carbonyl group. Across-odorant and across-species comparisons revealed the following: spider monkeys are significantly less sensitive to the odors of aliphatic ketones than to the odor of other classes of aliphatic compounds (1-alcohols, n-aldehydes, n-acetic esters, and n-carboxylic acids) sharing the same carbon length. Spider monkeys do not differ significantly in their olfactory sensitivity for aliphatic ketones from squirrel monkeys and pigtail macaques, but are significantly less sensitive to these odorants compared to human subjects and mice. These findings support the notion that neuroanatomical and genetic properties do not allow for reliable predictions with regard to a species' olfactory sensitivity. Further, we conclude that the frequency of occurrence of a class of odorants in a species' chemical environment does not allow for reliable predictions of the species' olfactory sensitivity. Copyright © 2015 Elsevier Ireland Ltd and the Japan Neuroscience Society. All rights reserved.

High-efficiency preparation of poly(2-methacryloyloxyethyl phosphorylcholine) grafting layer on poly(ether ether ketone) by photoinduced and self-initiated graft polymerization in an aqueous solution in the presence of inorganic salt additives.

PubMed

Shiojima, Taro; Inoue, Yuuki; Kyomoto, Masayuki; Ishihara, Kazuhiko

2016-08-01

A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Photoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic salt. The salt itself did not show any adverse effects on the radical polymerization; however, the apparent concentration of the monomer in feed may be increased due to the hydration of ions attributed to salt additives. We could obtain PMPC-grafted PEEK with sufficient PMPC thickness to obtain good functionality with only 5-min photoirradiation by using 2.5mol/L NaCl in the feed solution. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A Series of Synthetic Organic Experiments Demonstrating Physical Organic Principles.

ERIC Educational Resources Information Center

Sayed, Yousry; And Others

1989-01-01

Describes several common synthetic organic transformations involving alkenes, alcohols, alkyl halides, and ketones. Includes concepts on kinetic versus thermodynamic control of reaction, rearrangement of a secondary carbocation to a tertiary cation, and the effect of the size of the base on orientation during elimination. (MVL)

GALLIUM-MEDIATED ALLYLATION OF CARBONYL COMPOUNDS IN WATER. (R828129)

EPA Science Inventory

Ga-mediated allylation of aldehydes or ketones in distilled or tap water generated the corresponding homoallyl alcohols in high yields without the assistance of either acidic media or sonication.

Infrared Analysis of Gasoline/Alcohol Blends.

DTIC Science & Technology

1981-02-01

in storage, routine handling and distribution. As a result, other oxygenates such as methanol , iso-propanol, t-butanoA, methyl -t- butyl ether, and...Table 1 lists TABLE 1. ALCOHOL ANALYTE BAND NUMBERS -1 Component Analytical Frequency, cm Gasoline 967 Methanol 1030 Ethanol 882 iso-propanol 952 t...of varying concen- trations of each alcohol in a gasoline were obtained, with Figure 4 showing a low and high standard for methanol . The net peak

Structural investigation of the β-cyclodextrin complexes with chiral bicyclic monoterpenes - Influence of the functionality group on the host-guest stoichiometry

NASA Astrophysics Data System (ADS)

Ceborska, Magdalena

2017-10-01

The crystal structures of the complexes of β-cyclodextrin with (+)- and (-)-camphors are presented. The comparison of the obtained crystal structures with available data for other complexes of β-cyclodextrin with chiral bicyclic monoterpenes (hydrocarbon (+)-fenchene and alcohols: (-)-isopinocampheol, and (+)-, and (-)-borneols) obtained from Cambridge Structural Database (CSD) shows the trend of alcohols to form dimeric complexes of 2:3 stoichiometry, while hydrocarbons and ketones prefer to form 2:2 host-guest inclusion complexes.

Stereoselective oxidation of racemic 1-arylethanols by basil cultured cells of Ocimum basilicum cv. Purpurascens.

PubMed

Itoh, Ken-ichi; Nakamura, Kaoru; Utsukihara, Takamitsu; Sakamaki, Hiroshi; Horiuchi, C Akira

2008-05-01

The biotransformation of racemic 1-phenylethanol (30 mg) with plant cultured cells of basil (Ocimum basilicum cv. Purpurascens, 5 g wet wt) by shaking 120 rpm at 25 degrees C for 7 days in the dark gave (R)-(+)-1-phenylethanol and acetophenone in 34 and 24% yields, respectively. The biotransformation can be applied to other 1-arylethanols and basil cells oxidized the (S)-alcohols to the corresponding ketones remaining the (R)-alcohols in excellent ee.

Enhanced Proton Conductivity of Sulfonated Hybrid Poly(arylene ether ketone) Membranes by Incorporating an Amino-Sulfo Bifunctionalized Metal-Organic Framework for Direct Methanol Fuel Cells.

PubMed

Ru, Chunyu; Li, Zhenhua; Zhao, Chengji; Duan, Yuting; Zhuang, Zhuang; Bu, Fanzhe; Na, Hui

2018-03-07

Novel side-chain-type sulfonated poly(arylene ether ketone) (SNF-PAEK) containing naphthalene and fluorine moieties on the main chain was prepared in this work, and a new amino-sulfo-bifunctionalized metal-organic framework (MNS, short for MIL-101-NH 2 -SO 3 H) was synthesized via a hydrothermal technology and postmodification. Then, MNS was incorporated into a SNF-PAEK matrix as an inorganic nanofiller to prepare a series of organic-inorganic hybrid membranes (MNS@SNF-PAEK-XX). The mechanical property, methanol resistance, electrochemistry, and other properties of MNS@SNF-PAEK-XX hybrid membranes were characterized in detail. We found that the mechanical strength and methanol resistances of these hybrid membranes were improved by the formation of an ionic cross-linking structure between -NH 2 of MNS and -SO 3 H on the side chain of SNF-PAEK. Particularly, the proton conductivity of these hybrid membranes increased obviously after the addition of MNS. MNS@SNF-PAEK-3% exhibited the proton conductivity of 0.192 S·cm -1 , which was much higher than those of the pristine membrane (0.145 S·cm -1 ) and recast Nafion (0.134 S·cm -1 ) at 80 °C. This result indicated that bifunctionalized MNS rearranged the microstructure of hybrid membranes, which could accelerate the transfer of protons. The hybrid membrane (MNS@SNF-PAEK-3%) showed a better direct methanol fuel cell performance with a higher peak power density of 125.7 mW/cm 2 at 80 °C and a higher open-circuit voltage (0.839 V) than the pristine membrane.

Effects of wear particles of polyether-ether-ketone and cobalt-chromium-molybdenum on CD4- and CD8-T-cell responses

PubMed Central

Du, Zhe; Wang, Shujun; Yue, Bing; Wang, Ying; Wang, You

2018-01-01

T-cells, second only to macrophages, are often considered as the potential cells involved in debris-related failure of arthroplasty. Here, we assessed the effects of particulate wear debris on T-cells and inflammatory reactions. Blood samples from 25 donors were incubated with polyether-ether-ketone (PEEK) and cobalt-chromium-molybdenum (CoCrMo) particles generated by custom cryo-milling and pulverization. The T-cell phenotypes were assessed using immunostaining and flow cytometry. For the in vivo study, 0.1 mL of each particle suspension (approximately 1.0 × 108 wear particles) was injected into murine knee joints; the synovium and spleen were collected one week after the operation for histological examination and immunofluorescence staining. The T-cell responses observed included low-level activation of Th1, Th2, Th17, and CD8+ pathways after 72 h of co-culture of the particles with peripheral blood mononuclear cells. Obvious CD8+ T-cell responses were observed in local synovium and peripheral spleen, with higher inflammatory cytokine expression in the CoCrMo group. Relatively minor cytotoxic and immunological reactions were observed in vitro, with PEEK and CoCrMo particle-induced immune responses being primarily mediated by CD8+ T-cells, rather than CD4+ T-cells, in vivo. Overall, PEEK wear particles induced fewer inflammatory reactions than CoCrMo particles. This study verified that PEEK was suitable as a potential alternative for metals in total knee replacements in terms of the immunological reaction to PEEK particles, and shed light on the effects of wear particles from polymer and metal-based implants on immune responses. PMID:29541407

Computed-tomography modeled polyether ether ketone (PEEK) implants in revision cranioplasty.

PubMed

O'Reilly, Eamon B; Barnett, Sam; Madden, Christopher; Welch, Babu; Mickey, Bruce; Rozen, Shai

2015-03-01

Traditional cranioplasty methods focus on pre-operative or intraoperative hand molding. Recently, CT-guided polyether ether ketone (PEEK) plate reconstruction enables precise, time-saving reconstruction. This case series aims to show a single institution experience with use of PEEK cranioplasty as an effective, safe, precise, reusable, and time-saving cranioplasty technique in large, complex cranial defects. We performed a 6-year retrospective review of cranioplasty procedures performed at our affiliated hospitals using PEEK implants. A total of nineteen patients underwent twenty-two cranioplasty procedures. Pre-operative, intra-operative, and post-operative data was collected. Nineteen patients underwent twenty-two procedures. Time interval from injury to loss of primary cranioplasty averaged 57.7 months (0-336 mo); 4.0 months (n=10, range 0-19) in cases of trauma. Time interval from primary cranioplasty loss to PEEK cranioplasty was 11.8 months for infection (n=11, range 6-25 mo), 12.2 months for trauma (n=5, range 2-27 mo), and 0.3 months for cosmetic or functional reconstructions (n=3, range 0-1). Similar surgical techniques were used in all patients. Drains were placed in 11/22 procedures. Varying techniques were used in skin closure, including adjacent tissue transfer (4/22) and free tissue transfer (1/22). The PEEK plate required modification in four procedures. Three patients had reoperation following PEEK plate reconstruction. Cranioplasty utilizing CT-guided PEEK plate allows easy inset, anatomic accuracy, mirror image aesthetics, simplification of complex 3D defects, and potential time savings. Additionally, it's easily manipulated in the operating room, and can be easily re-utilized in cases of intraoperative course changes or infection. Copyright © 2014 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

The interaction of adipose-derived human mesenchymal stem cells and polyether ether ketone.

PubMed

Wang, Weiwei; Kratz, Karl; Behl, Marc; Yan, Wan; Liu, Yue; Xu, Xun; Baudis, Stefan; Li, Zhengdong; Kurtz, Andreas; Lendlein, Andreas; Ma, Nan

2015-01-01

Polyether ether ketone (PEEK) as a high-performance, thermoplastic implant material entered the field of medical applications due to its structural function and commercial availability. In bone tissue engineering, the combination of mesenchymal stem cells (MSCs) with PEEK implants may accelerate the bone formation and promote the osseointegration between the implant and the adjacent bone tissue. In this concept the question how PEEK influences the behaviour and functions of MSCs is of great interest. Here the cellular response of human adipose-derived MSCs to PEEK was evaluated and compared to tissue culture plate (TCP) as the reference material. Viability and morphology of cells were not altered when cultured on the PEEK film. The cells on PEEK presented a high proliferation activity in spite of a relatively lower initial cell adhesion rate. There was no significant difference on cell apoptosis and senescence between the cells on PEEK and TCP. The inflammatory cytokines and VEGF secreted by the cells on these two surfaces were at similar levels. The cells on PEEK showed up-regulated BMP2 and down-regulated BMP4 and BMP6 gene expression, whereas no conspicuous differences were observed in the committed osteoblast markers (BGLAP, COL1A1 and Runx2). With osteoinduction the cells on PEEK and TCP exhibited a similar osteogenic differentiation potential. Our results demonstrate the biofunctionality of PEEK for human MSC cultivation and differentiation. Its clinical benefits in bone tissue engineering may be achieved by combining MSCs with PEEK implants. These data may also provide useful information for further modification of PEEK with chemical or physical methods to regulate the cellular processes of MSCs and to consequently improve the efficacy of MSC-PEEK based therapies.

A tricalcium phosphate/polyether ether ketone anchor bionic fixation device for anterior cruciate ligament reconstruction: Safety and efficacy in a beagle model.

PubMed

Mao, Genwen; Qin, Zili; Li, Zheng; Li, Xiang; Qiu, Yusheng; Bian, Weiguo

2018-05-02

The goal of this study was to develop a bionic fixation device based on the use of a tricalcium phosphate/polyether ether ketone anchor and harvesting of the ulnar carpal flexor muscle tendon for application as a ligament graft in a beagle anterior cruciate ligament (ACL) reconstruction model, with the goal of accelerating the ligament graft-to-bone tunnel healing and providing a robust stability through exploration of this new kind of autologous ligament graft. The safety and efficacy of this fixation device were explored 3 and 6 months after surgery in a beagle ACL reconstruction model using biomechanical tests and comprehensive histological observation. The data were compared using a two-tailed Student's t test and a paired t test. A p value <0.05 was defined as statistically significant. All the models were successfully established. This fixation device possessed the excellent mechanical properties for ACL reconstruction. A comprehensive histological observation revealed that a cartilage layer was visible in the transition zone between the tendon and bone interface at both 3 and 6 months postoperation. The trabecular of the new bone was observed six months after surgery and was found to be similar to a direct connection. This fixation technique provided not only a robust primary mechanical fixation but also a bionic fixation for long-term knee joint stability by accelerating the healing of the tendon to the bone tunnel, showing a high potential for use in clinical practice. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2018. © 2018 Wiley Periodicals, Inc.

Effects of wear particles of polyether-ether-ketone and cobalt-chromium-molybdenum on CD4- and CD8-T-cell responses.

PubMed

Du, Zhe; Wang, Shujun; Yue, Bing; Wang, Ying; Wang, You

2018-02-16

T-cells, second only to macrophages, are often considered as the potential cells involved in debris-related failure of arthroplasty. Here, we assessed the effects of particulate wear debris on T-cells and inflammatory reactions. Blood samples from 25 donors were incubated with polyether-ether-ketone (PEEK) and cobalt-chromium-molybdenum (CoCrMo) particles generated by custom cryo-milling and pulverization. The T-cell phenotypes were assessed using immunostaining and flow cytometry. For the in vivo study, 0.1 mL of each particle suspension (approximately 1.0 × 10 8 wear particles) was injected into murine knee joints; the synovium and spleen were collected one week after the operation for histological examination and immunofluorescence staining. The T-cell responses observed included low-level activation of Th1, Th2, Th17, and CD8+ pathways after 72 h of co-culture of the particles with peripheral blood mononuclear cells. Obvious CD8+ T-cell responses were observed in local synovium and peripheral spleen, with higher inflammatory cytokine expression in the CoCrMo group. Relatively minor cytotoxic and immunological reactions were observed in vitro , with PEEK and CoCrMo particle-induced immune responses being primarily mediated by CD8+ T-cells, rather than CD4+ T-cells, in vivo . Overall, PEEK wear particles induced fewer inflammatory reactions than CoCrMo particles. This study verified that PEEK was suitable as a potential alternative for metals in total knee replacements in terms of the immunological reaction to PEEK particles, and shed light on the effects of wear particles from polymer and metal-based implants on immune responses.

Computational and experimental study of the interactions between ionic liquids and volatile organic compounds.

PubMed

Gao, Tingting; Andino, Jean M; Alvarez-Idaboy, J Raul

2010-09-07

Computational chemistry calculations were performed to investigate the interactions of ionic liquids with different classes of volatile organic compounds (VOCs), including alcohols, aldehydes, ketones, alkanes, alkenes, alkynes and aromatic compounds. At least one VOC was studied to represent each class. Initially, 1-butyl-3-methylimindazolium chloride (abbreviated as C(4)mimCl) was used as the test ionic liquid compound. Calculated interaction lengths between atoms in the ionic liquid and the VOC tested as well as thermodynamic data suggest that C(4)mimCl preferentially interacts with alcohols as compared to other classes of volatile organic compounds. The interactions of methanol with different kinds of ionic liquids, specifically 1-butyl-3-methylimidazolium bromine (C(4)mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (C(4)mimBF(4)) were also studied. In comparing C(4)mimCl, C(4)mimBr, and C(4)mimBF(4), the computational results suggest that C(4)mimCl is more likely to interact with methanol. Laboratory experiments were performed to provide further evidence for the interaction between C(4)mimCl and different classes of VOCs. Fourier transform infrared spectroscopy was used to probe the ionic liquid surface before and after exposure to the VOCs that were tested. New spectral features were detected after exposure of C(4)mimCl to various alcohols. The new features are characteristic of the alcohols tested. No new IR features were detected after exposure of the C(4)mimCl to the aldehyde, ketone, alkane, alkene, alkyne or aromatic compounds studied. In addition, after exposing the C(4)mimCl to a multi-component mixture of various classes of compounds (including an alcohol), the only new peaks that were detected were characteristic of the alcohol that was tested. These experimental results demonstrated that C(4)mimCl is selective to alcohols, even in complex mixtures. The findings in this work provide information for future gas-phase alcohol sensor design.

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.

Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls

PubMed Central

Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D.; Krische, Michael J.

2015-01-01

The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo- and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k and 6m, respectively. Primary alcohols 2a, 2l and 2p were converted to the siloxy-crotylation products 3a, 3l and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes. PMID:26418572

Purification of a toxic metalloprotease produced by the pathogenic Photobacterium damselae subsp. piscicida isolated from cobia (Rachycentron canadum).

PubMed

Liu, Ping-Chung; Chuang, Wen-Hsiao; Lee, Kuo-Kau

2011-01-01

The aim of the present study was to purify and characterize a toxic protease secreted by the pathogenic Photobacterium damselae subsp. piscicida strain CP1 originally isolated from diseased cobia (Rachycentron canadum). The toxin isolated by anion exchange chromatography, was a metalloprotease, inhibited by L-cysteine, ethylenediaminetetraacetic acid (EDTA), ethylene glycol-bis(beta-aminoethyl ether)N,N,N',N'-tetraacetic acid (EGTA), 1,10-phenanthroline, N-tosyl-L-phenylalanine-chloromethyl ketone (TPCK), and N-alpha-p-tosyl-L-lysine-chloromethyl ketone (TLCK), and showed maximal activity at pH 6.0-8.0 and an apparent molecular mass of about 34.3 kDa. The toxin was also completely inhibited by HgCl2, and partially by sodium dodecyl sulfate (SDS) and CuCl2. The extracellular products and the partially purified protease were lethal to cobia with LD50 values of 1.26 and 6.8 microg protein/g body weight, respectively. The addition of EDTA completely inhibited the lethal toxicity of the purified protease, indicating that this metalloprotease was a lethal toxin produced by the bacterium.

Ethanol exposure induces the cancer-associated fibroblast phenotype and lethal tumor metabolism

PubMed Central

Sanchez-Alvarez, Rosa; Martinez-Outschoorn, Ubaldo E.; Lin, Zhao; Lamb, Rebecca; Hulit, James; Howell, Anthony; Sotgia, Federica; Rubin, Emanuel; Lisanti, Michael P.

2013-01-01

Little is known about how alcohol consumption promotes the onset of human breast cancer(s). One hypothesis is that ethanol induces metabolic changes in the tumor microenvironment, which then enhances epithelial tumor growth. To experimentally test this hypothesis, we used a co-culture system consisting of human breast cancer cells (MCF7) and hTERT-immortalized fibroblasts. Here, we show that ethanol treatment (100 mM) promotes ROS production and oxidative stress in cancer-associated fibroblasts, which is sufficient to induce myofibroblastic differentiation. Oxidative stress in stromal fibroblasts also results in the onset of autophagy/mitophagy, driving the induction of ketone body production in the tumor microenvironment. Interestingly, ethanol has just the opposite effect in epithelial cancer cells, where it confers autophagy resistance, elevates mitochondrial biogenesis and induces key enzymes associated with ketone re-utilization (ACAT1/OXCT1). During co-culture, ethanol treatment also converts MCF7 cells from an ER(+) to an ER(-) status, which is thought to be associated with “stemness,” more aggressive behavior and a worse prognosis. Thus, ethanol treatment induces ketone production in cancer-associated fibroblasts and ketone re-utilization in epithelial cancer cells, fueling tumor cell growth via oxidative mitochondrial metabolism (OXPHOS). This “two-compartment” metabolic model is consistent with previous historical observations that ethanol is first converted to acetaldehyde (which induces oxidative stress) and then ultimately to acetyl-CoA (a high-energy mitochondrial fuel), or can be used to synthesize ketone bodies. As such, our results provide a novel mechanism by which alcohol consumption could metabolically convert “low-risk” breast cancer patients to “high-risk” status, explaining tumor recurrence or disease progression. Hence, our findings have clear implications for both breast cancer prevention and therapy. Remarkably, our results also show that antioxidants [such as N-acetyl cysteine (NAC)] can effectively reverse or prevent ethanol-induced oxidative stress in cancer-associated fibroblasts, suggesting a novel strategy for cancer prevention. We also show that caveolin-1 and MCt4 protein expression can be effectively used as new biomarkers to monitor oxidative stress induced by ethanol. PMID:23257780

Ethanol exposure induces the cancer-associated fibroblast phenotype and lethal tumor metabolism: implications for breast cancer prevention.

PubMed

Sanchez-Alvarez, Rosa; Martinez-Outschoorn, Ubaldo E; Lin, Zhao; Lamb, Rebecca; Hulit, James; Howell, Anthony; Sotgia, Federica; Rubin, Emanuel; Lisanti, Michael P

2013-01-15

Little is known about how alcohol consumption promotes the onset of human breast cancer(s). One hypothesis is that ethanol induces metabolic changes in the tumor microenvironment, which then enhances epithelial tumor growth. To experimentally test this hypothesis, we used a co-culture system consisting of human breast cancer cells (MCF7) and hTERT-immortalized fibroblasts. Here, we show that ethanol treatment (100 mM) promotes ROS production and oxidative stress in cancer-associated fibroblasts, which is sufficient to induce myofibroblastic differentiation. Oxidative stress in stromal fibroblasts also results in the onset of autophagy/mitophagy, driving the induction of ketone body production in the tumor microenvironment. Interestingly, ethanol has just the opposite effect in epithelial cancer cells, where it confers autophagy resistance, elevates mitochondrial biogenesis and induces key enzymes associated with ketone re-utilization (ACAT1/OXCT1). During co-culture, ethanol treatment also converts MCF7 cells from an ER(+) to an ER(-) status, which is thought to be associated with "stemness," more aggressive behavior and a worse prognosis. Thus, ethanol treatment induces ketone production in cancer-associated fibroblasts and ketone re-utilization in epithelial cancer cells, fueling tumor cell growth via oxidative mitochondrial metabolism (OXPHOS). This "two-compartment" metabolic model is consistent with previous historical observations that ethanol is first converted to acetaldehyde (which induces oxidative stress) and then ultimately to acetyl-CoA (a high-energy mitochondrial fuel), or can be used to synthesize ketone bodies. As such, our results provide a novel mechanism by which alcohol consumption could metabolically convert "low-risk" breast cancer patients to "high-risk" status, explaining tumor recurrence or disease progression. Hence, our findings have clear implications for both breast cancer prevention and therapy. Remarkably, our results also show that antioxidants [such as N-acetyl cysteine (NAC)] can effectively reverse or prevent ethanol-induced oxidative stress in cancer-associated fibroblasts, suggesting a novel strategy for cancer prevention. We also show that caveolin-1 and MCT4 protein expression can be effectively used as new biomarkers to monitor oxidative stress induced by ethanol.

SYNTHESIZING ALCOHOLS AND KETONES BY PHOTOINDUCED CATALYTIC PARTIAL-OXIDATION OF HYDROCARBONS IN TI02 FILM REACTORS PREPARED BY THREE DIFFERENT METHODS

EPA Science Inventory

The partial oxidation of cyclohexane to cyclohexanol and cyclohexanone on UV irradiated titanium dioxide films in the presence of molecular oxygen at ambient temperatures and pressures was studied. Three different coating methodologies (dip coating using titanium isopropoxide an...

Extraction spectrophotometric determination of niobium in rocks with sulfochlorophenol S

USGS Publications Warehouse

Childress, A.E.; Greenland, L.P.

1980-01-01

After acid decomposition and potassium pyrosulfate fusion, niobium (1-26 ppm) is separated from interfering elements by extraction into methyl isobutyl ketone from 6 M H2SO4-2 M HF and back-extracted into water. The niobium-sulfochloro-phenol S complex is extracted into amyl alcohol. ?? 1980.

The Nitric Acid Oxidation of Selected Alcohols and Ketones.

ERIC Educational Resources Information Center

Field, Kurt W.; And Others

1985-01-01

Shows that nitric acid can be used as a rapid, versatile, and economical oxidant for selected organic substances. The experiments (with background information, procedures, and results provided) require one three-hour laboratory period but could serve as open-ended projects since substrates not described could be oxidized. (JN)

Application of Novel Method to Measure Endogenous VOCs in Exhaled Breath Condensate Before and After Exposure to Diesel Exhaust

EPA Science Inventory

Polar volatile organic compounds (PVOCs) such as aldehydes, ketones, and alcohols are byproducts of normal human metabolism and are present in exhaled breath and blood. Environmental exposures, individual activities, and disease states can perturb normal metabolic processes and ...

VANADIA CATALYZED VAPOR PHASE OXIDATION OF METHANOL IN THE PRESENCE OF OZONE

EPA Science Inventory

Catalytic oxidation of methanol was carried out in the presence of ozone using vanadia based catalysts. The process can be used to selectively convert alcohols to aldehydes or ketones. It can also be used to control emissions of volatile organic compounds from Kraft mill and ot...

Preparation of Solid Derivatives by Differential Scanning Calorimetry.

ERIC Educational Resources Information Center

Crandall, E. W.; Pennington, Maxine

1980-01-01

Describes the preparation of selected aldehydes and ketones, alcohols, amines, phenols, haloalkanes, and tertiaryamines by differential scanning calorimetry. Technique is advantageous because formation of the reaction product occurs and the melting point of the product is obtained on the same sample in a short time with no additional purification…

Characterization of volatile aroma compounds in different brewing barley cultivars.

PubMed

Dong, Liang; Hou, Yingmin; Li, Feng; Piao, Yongzhe; Zhang, Xiao; Zhang, Xiaoyu; Li, Cheng; Zhao, Changxin

2015-03-30

Beer is a popular alcoholic malt beverage resulting from fermentation of the aqueous extract of malted barley with hops. The aroma of brewing barley impacts the flavor of beer indirectly, because some flavor compounds or their precursors in beer come from the barley. The objectives of this research were to study volatile profiles and to characterize odor-active compounds of brewing barley in order to determine the variability of the aroma composition among different brewing barley cultivars. Forty-one volatiles comprising aldehydes, ketones, alcohols, organic acids, aromatic compounds and furans were identified using solid phase microextraction combined with gas chromatography/mass spectrometry, among which aldehydes, alcohols and ketones were quantitatively in greatest abundance. Quantitative measurements performed by means of solvent extraction and calculation of odor activity values revealed that acetaldehyde, 2-methylpropanal, 3-methylbutanal, 2-methylbutanal, hexanal, heptanal, octanal, nonanal, 3-methyl-1-butanol, cyclopentanol, 2,3-butanedione, 2,3-pentanedione, 2-heptanone, acetic acid, ethyl acetate, 2-pentylfuran and benzeneacetaldehyde, whose concentrations exceeded their odor thresholds, could be considered as odor-active compounds of brewing barley. Principal component analysis was employed to evaluate the differences among cultivars. The results demonstrated that the volatile profile based on the concentrations of aroma compounds enabled good differentiation of most barley cultivars. © 2014 Society of Chemical Industry.

Production of Biomass-Based Automotive Lubricants by Reductive Etherification.

PubMed

Jadhav, Deepak; Grippo, Adam M; Shylesh, Sankaranarayanapillai; Gokhale, Amit A; Redshaw, John; Bell, Alexis T

2017-06-09

Growing concern with the effects of CO 2 emissions due to the combustion of petroleum-based transportation fuels has motivated the search for means to increase engine efficiency. The discovery of ethers with low viscosity presents an important opportunity to improve engine efficiency and fuel economy. We show here a strategy for the catalytic synthesis of such ethers by reductive etherification/O-alkylation of alcohols using building blocks that can be sourced from biomass. We find that long-chain branched ethers have several properties that make them superior lubricants to the mineral oil and synthetic base oils used today. These ethers provide a class of potentially renewable alternatives to conventional lubricants produced from petroleum and may contribute to the reduction of greenhouse gases associated with vehicle emissions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis

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

Casey, Charles P

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis Charles P. Casey, Principal Investigator Department of Chemistry, University of Wisconsin - Madison, Madison, Wisconsin 53706 Phone 608-262-0584 FAX: 608-262-7144 Email: casey@chem.wisc.edu http://www.chem.wisc.edu/main/people/faculty/casey.html Executive Summary. Our goal was to learn the intimate mechanistic details of reactions involved in homogeneous catalysis and to use the insight we gain to develop new and improved catalysts. Our work centered on the hydrogenation of polar functional groups such as aldehydes and ketones and on hydroformylation. Specifically, we concentrated on catalysts capable of simultaneously transferring hydride from a metal center and a proton frommore » an acidic oxygen or nitrogen center to an aldehyde or ketone. An economical iron based catalyst was developed and patented. Better understanding of fundamental organometallic reactions and catalytic processes enabled design of energy and material efficient chemical processes. Our work contributed to the development of catalysts for the selective and mild hydrogenation of ketones and aldehydes; this will provide a modern green alternative to reductions by LiAlH4 and NaBH4, which require extensive work-up procedures and produce waste streams. (C5R4OH)Ru(CO)2H Hydrogenation Catalysts. Youval Shvo described a remarkable catalytic system in which the key intermediate (C5R4OH)Ru(CO)2H (1) has an electronically coupled acidic OH unit and a hydridic RuH unit. Our efforts centered on understanding and improving upon this important catalyst for reduction of aldehydes and ketones. Our mechanistic studies established that the reduction of aldehydes by 1 to produce alcohols and a diruthenium bridging hydride species occurs much more rapidly than regeneration of the ruthenium hydride from the diruthenium bridging hydride species. Our mechanistic studies require simultaneous transfer of hydride from ruthenium to the aldehyde carbon and of a proton from the CpOH unit to the aldehyde oxygen and support reduction of the aldehyde without its prior coordination to ruthenium. Another important step in the catalysis is the regeneration of 1 from reaction of H2 with the stable diruthenium bridging hydride complex 2. Studies of the microscopic reverse of this process (hydrogen evolution from 1 which occurs at 80°C) in the presence of alcohol (the product of aldehyde hydrogenation) have shown that a dihydrogen complex is formed reversibly at a rate much faster than hydrogen evolution. Kinetic and theoretical studies in collaboration with Professor Qiang Cui of Wisconsin indicated an important role for alcohol in mediating transfer of hydrogen to ruthenium. One key to developing more active catalysts was to destabilize the bridging hydride intermediate 2 to prevent its formation or to speed its conversion to a reactive monohydride 1 by reaction with H2. We found several successful ways to destabilize the bridging hydride and to obtain more active catalysts. Most recently, we discovered related iron catalysts for hydrogenation that do not form dimers; the cost advantage of iron catalysts is spectacular. Iron Catalysts. In an exciting development, we found that a related iron complex is also a very active ketone hydrogenation catalyst. This hydrogenation catalyst shows high chemoselectivity for aldehydes, ketones, and imines and isolated C=C, CºC, C-X, -NO2, epoxides, and ester functions are unaffected by the hydrogenation conditions. Mechanistic studies have established a reversible hydrogen transfer step followed by rapid dihydrogen activation. The same iron complex also catalyzes transfer hydrogenation of ketones.« less

Development of time projection chamber for precise neutron lifetime measurement using pulsed cold neutron beams

NASA Astrophysics Data System (ADS)

Arimoto, Y.; Higashi, N.; Igarashi, Y.; Iwashita, Y.; Ino, T.; Katayama, R.; Kitaguchi, M.; Kitahara, R.; Matsumura, H.; Mishima, K.; Nagakura, N.; Oide, H.; Otono, H.; Sakakibara, R.; Shima, T.; Shimizu, H. M.; Sugino, T.; Sumi, N.; Sumino, H.; Taketani, K.; Tanaka, G.; Tanaka, M.; Tauchi, K.; Toyoda, A.; Tomita, T.; Yamada, T.; Yamashita, S.; Yokoyama, H.; Yoshioka, T.

2015-11-01

A new time projection chamber (TPC) was developed for neutron lifetime measurement using a pulsed cold neutron spallation source at the Japan Proton Accelerator Research Complex (J-PARC). Managing considerable background events from natural sources and the beam radioactivity is a challenging aspect of this measurement. To overcome this problem, the developed TPC has unprecedented features such as the use of polyether-ether-ketone plates in the support structure and internal surfaces covered with 6Li-enriched tiles to absorb outlier neutrons. In this paper, the design and performance of the new TPC are reported in detail.

Automated Tow Placement Processing and Characterization of Composites

NASA Technical Reports Server (NTRS)

Prabhakaran, R.

2004-01-01

The project had one of the initial objectives as automated tow placement (ATP), in which a robot was used to place a collimated band of pre-impregnated ribbons or a wide preconsolidated tape onto a tool surface. It was proposed to utilize the Automated Tow Placement machine that was already available and to fabricate carbon fiber reinforced PEEK (polyether-ether-ketone) matrix composites. After initial experiments with the fabrication of flat plates, composite cylinders were to be fabricated. Specimens from the fabricated parts were to be tested for mechanical characterization. A second objective was to conduct various types of tests for characterizing composite specimens cured by different fabrication processes.