Temperature influence on mixing properties of {ethyl tert-butyl ether (ETBE) + gasoline additives}

International Nuclear Information System (INIS)

Gonzalez-Olmos, R.; Iglesias, M.

2007-01-01

The densities and ultrasonic velocity of {ethyl tert-butyl ether (ETBE) + (benzene, toluene, ethylbenzene, isooctane, tert-butyl alcohol, and ethanol)} over the temperature range (288.15 to 323.15) K and atmospheric pressure, have been measured over the whole concentration range. The experimental excess volumes and deviation of isentropic compressibilities data have been analysed in terms of different theoretical models. The gathered data improve open literature related to gasoline additives, and help to understand the ETBE volumetric and acoustic trend into different chemical environment

Poly(ether ester amide)s for tissue engineering

NARCIS (Netherlands)

Deschamps, A.A.; van Apeldoorn, Aart A.; de Bruijn, Joost Dick; Grijpma, Dirk W.; Feijen, Jan

2003-01-01

Poly(ether ester amide) (PEEA) copolymers based on poly(ethylene glycol) (PEG), 1,4-butanediol and dimethyl-7,12-diaza-6,13-dione-1,18-octadecanedioate were evaluated as scaffold materials for tissue engineering. A PEEA copolymer based on PEG with a molecular weight of 300 g/mol and 25 wt% of soft

Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters

Directory of Open Access Journals (Sweden)

Yoshinori Yamamoto

2011-05-01

Full Text Available Unprecedented alkylation of silyl enol ethers has been developed by the use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents in the presence of a gold catalyst. The reaction probably proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack on the silyl enol ethers. The generated leaving compound abstracts a proton to regenerate the silyl enol ether structure.

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

Science.gov (United States)

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

DERMAL, ORAL, AND INHALATION PHARMACOKINETICS OF METHYL TERTIARY BUTYL ETHER (MTBE) IN HUMAN VOLUNTEERS

Science.gov (United States)

Methyl tertiary butyl ether (MTBE), a gasoline additive, used to increase octane and reduce carbon monoxide emissions and ozone precursors has contaminated drinking water leading to exposure by oral, inhalation, and dermal routes. To determine its dermal, oral, and inhalation ki...

Simultaneous determination of triacetin, acetic ether, butyl acetate and amorolfine hydrochloride in amorolfine liniment by HPLC.

Science.gov (United States)

Gao, Yuan; Li, Li; Zhang, Jianjun; Shu, Wenjuan; Gao, Liqiong

2012-04-01

A simple, rapid, specific and precise reversed-phase high-performance liquid chromatographic method was developed for simultaneous estimation of triacetin, acetic ether, butyl acetate and amorolfine in marketed pharmaceutical liniment. Chromatographic separation was performed on a Shimadzu VP-ODS C(18) column using the mixture of citric acid-hydrochloric acid-sodium hydrate buffer (pH 3.0), acetonitrile and methanol (32:30:38) as the mobile phase at a flow rate of 1.0 mL/min with UV-detection at 215 nm. The method separated the four components simultaneously in less than 10 min. The validation of the method was performed with respect to specificity, linearity, accuracy, and precision. The calibration curves were linear in the range of 35.1-81.9 μ/mL for triacetin, 431.1-1005.9 μ/mL for acetic ether, 167.0-389.7 μ/mL for butyl acetate and 151.0-352.3 μ/mL for amorolfine. The mean 100% spiked recovery for triacetin, acetic ether, butyl acetate and amorolfine is 99.43 ± 0.42, 101.5 ± 1.09, 101.4 ± 1.02 and 100.8 ± 0.69, respectively. The intra-day and inter-day relative standard deviation values were liniment.

DERMAL, ORAL AND INHALATION PHARMACOKINETICS OF METHYL TERTIARY-BUTYL ETHER (MTBE) IN HUMAN VOLUNTEERS

Science.gov (United States)

Methyl tertiary butyl ether (MTBE), a gasoline additive used to increase octane and reduce carbon monoxide emissions and ozone precursors, has contaminated drinking water and can lead to exposure by oral, inhalation, and dermal routes. To determine its dermal, oral, and inhal...

Risicogrenzen voor MTBE (Methyl tertiair-Butyl Ether) in bodem, sediment, grondwater, oppervlaktewater en voor drinkwaterbereiding

NARCIS (Netherlands)

Swartjes FA; Baars AJ; Fleuren RHLJ; Otte PF; LER

2004-01-01

Recentelijk is politieke commotie ontstaan ten gevolge van de mogelijke schadelijke gezondheidseffecten van Methyl tertiair-Butyl Ether (MTBE). Dit was reden voor het ministerie van VROM om het RIVM te verzoeken risicogrenzen voor MTBE in bodem, sediment, grondwater, oppervlaktewater, drinkwater en

INHALATION EXPOSURE TO METHYL TERT-BUTYL ETHER (MTBE) AND DIBROMOCHLOROMETHANE (DBCM) USING CONTINUOUS BREATH ANALYSIS

Science.gov (United States)

The oxygenate methyl tert-butyl ether (MTBE) has been added to gasoline to help meet national ambient air quality standards in those parts of the U.S. that are non-compliant for carbon monoxide. Although MTBE has provided important health benefits in terms of reduced haza...

Synchrotron Photoionization Investigation of the Oxidation of Ethyl tert-Butyl Ether.

Science.gov (United States)

Winfough, Matthew; Yao, Rong; Ng, Martin; Catani, Katherine; Meloni, Giovanni

2017-02-23

The oxidation of ethyl tert-butyl ether (ETBE), a widely used fuel oxygenated additive, is investigated using Cl atoms as initiators in the presence of oxygen. The reaction is carried out at 293, 550, and 700 K. Reaction products are probed by a multiplexed chemical kinetics photoionization mass spectrometer coupled with the synchrotron radiation produced at the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory. Products are identified on the basis of mass-to-charge ratio, ionization energies, and shape of photoionization spectra. Reaction pathways are proposed together with detected primary products.

Neutral lipid biosynthesis in engineered Escherichia coli: jojoba oil-like wax esters and fatty acid butyl esters.

Science.gov (United States)

Kalscheuer, Rainer; Stöveken, Tim; Luftmann, Heinrich; Malkus, Ursula; Reichelt, Rudolf; Steinbüchel, Alexander

2006-02-01

Wax esters are esters of long-chain fatty acids and long-chain fatty alcohols which are of considerable commercial importance and are produced on a scale of 3 million tons per year. The oil from the jojoba plant (Simmondsia chinensis) is the main biological source of wax esters. Although it has a multitude of potential applications, the use of jojoba oil is restricted, due to its high price. In this study, we describe the establishment of heterologous wax ester biosynthesis in a recombinant Escherichia coli strain by coexpression of a fatty alcohol-producing bifunctional acyl-coenzyme A reductase from the jojoba plant and a bacterial wax ester synthase from Acinetobacter baylyi strain ADP1, catalyzing the esterification of fatty alcohols and coenzyme A thioesters of fatty acids. In the presence of oleate, jojoba oil-like wax esters such as palmityl oleate, palmityl palmitoleate, and oleyl oleate were produced, amounting to up to ca. 1% of the cellular dry weight. In addition to wax esters, fatty acid butyl esters were unexpectedly observed in the presence of oleate. The latter could be attributed to solvent residues of 1-butanol present in the medium component, Bacto tryptone. Neutral lipids produced in recombinant E. coli were accumulated as intracytoplasmic inclusions, demonstrating that the formation and structural integrity of bacterial lipid bodies do not require specific structural proteins. This is the first report on substantial biosynthesis and accumulation of neutral lipids in E. coli, which might open new perspectives for the biotechnological production of cheap jojoba oil equivalents from inexpensive resources employing recombinant microorganisms.

Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

Energy Technology Data Exchange (ETDEWEB)

Francois, A

2002-11-01

Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

Energy Technology Data Exchange (ETDEWEB)

Francois, A.

2002-11-01

Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

Process Intensification of Enzymatic Fatty Acid Butyl Ester Synthesis Using a Continuous Centrifugal Contactor Separator

NARCIS (Netherlands)

Ilmi, Miftahul; Abduh, Muhammad Yusuf; Hommes, Arne; Winkelman, Jozef; Hidayat, C.; Heeres, Hero

2018-01-01

Fatty acid butyl esters were synthesized from sunflower oil with 1-butanol using a homogeneous Rhizomucor miehei lipase in a biphasic organic (triglyceride, 1-butanol, hexane)– water (with enzyme) system in a continuous setup consisting of a cascade of a stirred tank reactor and a continuous

Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

Science.gov (United States)

Finneran, K T; Lovley, D R

2001-05-01

The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

SYNTHESIS OF METHYL TERT-BUTYL ETHER CATALYZED BY ACIDIC ION-EXCHANGE RESINS - INFLUENCE OF THE PROTON ACTIVITY

NARCIS (Netherlands)

PANNEMAN, HJ; BEENACKERS, AACM

1995-01-01

The catalytic activity of various strong acid ion-exchange resins on the synthesis of methyl tert-butyl ether (MtBE) from methanol and isobutene has been investigated. Relative to Amberlyst 15, Kastel CS 381 and Amberlyst CSP have similar rate constants, whereas Duolite ES 276 and Amberlyst XE 307

DEVELOPMENT OF PHYSIOLOGICAL-BASED PHARMACOKINETIC MODEL FOR DERMAL ABSORPTION NAD PENETRATION OF METHYL TERTIARY BUTYL ETHER IN HUMANS

Science.gov (United States)

Background: Methyl tertiary butyl ether (MTBE) is a volatile organic chemical that is added to gasoline as an octane booster and to reduce vehicular emissions of carbon monoxide. MTBE is introduced into the environment through fuel spills, leakage of storage tanks, and evaporat...

Simultaneous clostridial fermentation, lipase-catalyzed esterification, and ester extraction to enrich diesel with butyl butyrate

NARCIS (Netherlands)

Berg, C. van den; Heeres, A.S.; Wielen, L.A.M. van der; Straathof, A.J.J.

2013-01-01

The recovery of 1-butanol from fermentation broth is energy-intensive since typical concentrations in fermentation broth are below 20gL -1. To prevent butanol inhibition and high downstream processing costs, we aimed at producing butyl esters instead of 1-butanol. It is shown that it is possible to

U.S. Geological Survey laboratory method for methyl tert-Butyl ether and other fuel oxygenates

Science.gov (United States)

Raese, Jon W.; Rose, Donna L.; Sandstrom, Mark W.

1995-01-01

Methyl tert-butyl ether (MTBE) was found in shallow ground-water samples in a study of 8 urban and 20 agricultural areas throughout the United States in 1993 and 1994 (Squillace and others, 1995, p. 1). The compound is added to gasoline either seasonally or year round in many parts of the United States to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL), near Denver, uses state-of-the-art technology to analyze samples for MTBE as part of the USGS water-quality studies. In addition, the NWQL offers custom analyses to determine two other fuel oxygenates--ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME). The NWQL was not able to obtain a reference standard for tert-amyl ethyl ether (TAEE), another possible fuel oxygenate (Shelley and Fouhy, 1994, p. 63). The shallow ground-water samples were collected as part of the USGS National Water-Quality Assessment Program. These samples were collected from 211 urban wells or springs and 562 agricultural wells sampled by the USGS in 1993 and 1994. The wells were keyed to specific land-use areas to assess the effects of different uses on ground-water quality (Squillace and others, 1995, p. 2). Ground-water samples were preserved on site to pH less than or equal to 2 with a solution of 1:1 hydrochloric acid. All samples were analyzed at the NWQL within 2 weeks after collection. The purpose of this fact sheet is to explain briefly the analytical method implemented by the USGS for determining MTBE and other fuel oxygenates. The scope is necessarily limited to an overview of the analytical method (instrumentation, sample preparation, calibration and quantitation, identification, and preservation of samples) and method performance (reagent blanks, accuracy, and precision).

Volumetric Behaviour of the Ternary System (Methyl Tert-butyl ether + Methylbenzene + Butan-1-ol) and Its Binary sub-System (Methyl Tert-Butyl Ether + Butan-1-ol) within the Temperature Range (298.15–328.15) K

Czech Academy of Sciences Publication Activity Database

Morávková, Lenka; Troncoso, J.; Škvorová, M.; Havlica, Jaromír; Petrus, P.; Sedláková, Zuzana

2015-01-01

Roč. 90, NOV 2015 (2015), s. 59-70 ISSN 0021-9614 R&D Projects: GA ČR(CZ) GAP105/12/0664; GA MŠk(CZ) LD14094 Grant - others:GNIL(IT) 408 REGALIs (CN2012/120) Institutional support: RVO:67985858 Keywords : methylbenzene * density * methyl-tert-butyl ether Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.196, year: 2015

INTERACTION OF METHYL-TERT BUTYL ETHER AND WATER STRESS ON SEED GERMINATION AND SEEDLING GROWTH IN SOIL MICROCOSMS

Science.gov (United States)

Methyl tert-butyl ether (MTBE) is a widespread contaminant in surface and ground water in the United States. Frequently irrigation is used to water fields to germinate planted seeds and sustain plant growth. A likely possibility exists that water used may have some MTBE. Our s...

Overview of technologies for removal of methyl tert-butyl ether (MTBE) from water.

Science.gov (United States)

Levchuk, Irina; Bhatnagar, Amit; Sillanpää, Mika

2014-04-01

Wide use of methyl tert-butyl ether (MTBE) as fuel oxygenates leads to worldwide environment contamination with this compound basically due to fuel leaks from storage or pipelines. Presence of MTBE in drinking water is of high environmental and social concern. Existing methods for MTBE removal from water have a number of limitations which can be possibly overcome in the future with use of emerging technologies. This work aims to provide an updated overview of recent developments in technologies for MTBE removal from water. Copyright © 2014. Published by Elsevier B.V.

Enhancement of methyl tert-butyl ether degradation by the addition of readily metabolizable organic substrates

International Nuclear Information System (INIS)

Chen Dongzhi; Chen Jianmeng; Zhong Weihong

2009-01-01

Supplements with readily metabolizable organic substrates were investigated to increase the biomass and enhance degradation of methyl tert-butyl ether (MTBE) due to the low biomass yield of MTBE which has been one of the factors for low-rate MTBE degradation. The influence of various organic substrates on the rate of aerobic degradation of methyl tert-butyl ether (MTBE) by Methylibium petroleiphilum PM1 was investigated, and only yeast extract (YE), beef extract and tryptone exhibited stimulatory effect. With the concentration of each substrate being 100 mg/L, the average MTBE removal rate could increase to 1.29, 1.20 and 1.04 mg/(L h), respectively, in comparison with 0.71 mg/(L h) when carried out in medium without addition. The stimulatory effects of YE addition, as well as induction period required by MTBE degradation, varied dramatically with the storage conditions, pre-culture medium and concentrations of the inoculums. The extent of stimulatory effects of YE might be closely related to the proportion of induction period in the total time of MTBE-degradation. The removal efficiency increased from about 50% to 90.5% with the addition of YE in a packed-bed reactor loaded with calcium alginate immobilized cells.

Two-year drinking water carcinogenicity study of methyl tertiary-butyl ether (MTBE) in Wistar rats.

Science.gov (United States)

Dodd, Darol; Willson, Gabrielle; Parkinson, Horace; Bermudez, Edilberto

2013-07-01

Methyl tertiary-butyl ether (MTBE) has been used as a gasoline additive to reduce tailpipe emissions and its use has been discontinued. There remains a concern that drinking water sources have been contaminated with MTBE. A two-year drinking water carcinogenicity study of MTBE was conducted in Wistar rats (males, 0, 0.5, 3, 7.5 mg ml(-1); and females, 0, 0.5, 3, and 15 mg ml(-1)). Body weights were unaffected and water consumption was reduced in MTBE-exposed males and females. Wet weights of male kidneys were increased at the end of two years of exposure to 7.5 mg ml(-1) MTBE. Chronic progressive nephropathy was observed in males and females, was more severe in males, and was exacerbated in the high MTBE exposure groups. Brain was the only tissue with a statistically significant finding of neoplasms. One astrocytoma (1/50) was found in a female rat (15 mg ml(-1)). The incidence of brain astrocytomas in male rats was 1/50, 1/50, 1/50 and 4/50 for the 0, 0.5, 3 and 7.5 mg ml(-1) exposure groups, respectively. This was a marginally significant statistical trend, but not statistically significant when pairwise comparisons were made or when multiple comparisons were taken into account. The incidence of astrocytoma fell within historical control ranges for Wistar rats, and the brain has not been identified as a target organ following chronic administration of MTBE, ethyl tert-butyl ether, or tertiary butyl alcohol (in drinking water) to mice and rats. We conclude that the astrocytomas observed in this study are not associated with exposure to MTBE. Copyright © 2011 John Wiley & Sons, Ltd.

Analysis of Oxygenated Component (butyl Ether) and Egr Effect on a Diesel Engine

Science.gov (United States)

Choi, Seung-Hun; Oh, Young-Taig

Potential possibility of the butyl ether (BE, oxygenates of di-ether group) was analyzed as an additives for a naturally aspirated direct injection diesel engine fuel. Engine performance and exhaust emission characteristics were analyzed by applying the commercial diesel fuel and oxygenates additives blended diesel fuels. Smoke emission decreased approximately 26% by applying the blended fuel (diesel fuel 80 vol-% + BE 20vol-%) at the engine speed of 25,000 rpm and with full engine load compared to the diesel fuel. There was none significant difference between the blended fuel and the diesel fuel on the power, torque, and brake specific energy consumption rate of the diesel engine. But, NOx emission from the blended fuel was higher than the commercial diesel fuel. As a counter plan, the EGR method was employed to reduce the NOx. Simultaneous reduction of the smoke and the NOx emission from the diesel engine was achieved by applying the BE blended fuel and the cooled EGR method.

Synthesis of [11C]-labelled methyl esters: transesterification of enol esters versus BF3 etherate catalysed esterification - a comparative study

International Nuclear Information System (INIS)

Ackermann, U.; Falzon, C.; Issa, W.; Tochon-Danguy, H.J.; Sachinidis, J.I.; Blanc, P.; White, J.; Scott, A.M.

2005-01-01

An important issue in Positron Emission Tomography (PET) is the development of labelling techniques to incorporate positron emitting radionuclides into biologically active compounds. When labelling with 11C, the short 20 minutes half-life of the radionuclide significantly limits the number of synthetic protocols available to the radiochemist. C-l synthons such as [HCJ-methyl iodide (1) or methyl triflate (2) are readily available and are frequently used as alkylating agents for the preparation of radiopharmaceuticals. However, the use of these alkylating agents often makes it necessary to introduce protecting groups in order to prevent labelling at unwanted sites on the molecule. Since the removal of protecting groups is a time-consuming process, a more direct synthesis strategy is desirable. This has prompted us to investigate the esterification of carboxylic acids using [1 lC]-mcthanol and BF3 etherate as Lewis acid catalyst. Our results have demonstrated that the reaction conditions necessary to promote the esterification can cleave functional groups such as ethers. We have therefore shifted our attention towards the irreversible transesterification of enol esters using [HCl-methanol and a tin catalyst as an alternative strategy to [HC]-methyl ester formation. We have prepared a series of 5 aromatic ethoxy vinyl esters bearing various functional groups. The transesterification (radiolabelling) was carried out in DMSO at 150 Degrees C for 7 minutes in the presence of [HQMeOH and 1.3-dichlo-rotetrabutyldistannoxane as catalyst. We have found that the transesterification of enol esters is a mild and efficient labelling method for the formation of [HCl-methyl esters. The reaction proceeds smoothly and leaves functional groups intact. It requires only one synthesis step compared to two steps for the conventional method, and gives a radiochemical yields of 25%

Observation on the biodegradation and bioremediation potential of methyl t-butyl ether

International Nuclear Information System (INIS)

Salanitro, J.; Wisniewski, H.; McAllister, P.

1995-01-01

There have been few reports documenting evidence for the biodegradation of the fuel oxygenate alkyl ether, methyl t-butyl ether (MTBE) in groundwater, soils, and biosludges. Partial (or complete) microbial breakdown of MTBE has been observed in an anaerobic subsoil, a river sediment under methanogenic conditions, a cyclohexane-degrading bacterial consortium and a pure culture of the methylotroph, Methylisnus trichosporium OB3b. An aerobic bacterial enrichment (BC-1) isolated from an industrial transient (non-accumulating) metabolic intermediate. The studies suggest that MTBE is cleaved by BC-1 to TBA which is then metabolized via isopropanol and acetone. There is little information on the occurrence of indigenous MTBE-degraders in groundwater, soils and activated sludges. Preliminary evidence has been obtained, however, from a marketing terminal groundwater site that naturally-occurring MTBE-degraders are present in some monitoring wells. Microcosm experiments with groundwater from this aquifer show that MTBE is aerobically degraded (no TBA formed) with a first-order decay rate (0.31/day) similar to BTEX. Also, MTBE did not inhibit the intrinsic biodegradation potential of BTEX in groundwater microcosms. In summary, the data presented indicate that MTBE biodegradation has been observed in some environmental media. Further work is needed to assess the feasibility of using indigenous or derived aerobic and anaerobic MTBE-degrading cultures for treating fuel ethers in groundwaters or wastewater with in-situ or ex-situ bioremediation technologies

UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

DEFF Research Database (Denmark)

Nielsen, O.J.; Sehested, J.; Langer, S.

1995-01-01

Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

Biodegradation of methyl tert-butyl ether by Kocuria sp.

Directory of Open Access Journals (Sweden)

Kiković Dragan D.

2012-01-01

Full Text Available Methyl tert-butyl ether (MTBE has been used to replace the toxic compounds from gasoline and to reduce emission of air pollutants. Due to its intensive use, MTBE has become one of the most important environment pollutants. The aim of this paper is isolation and identification of the bacteria from wastewater sample of “HIP Petrohemija” Pančevo (Serbia, capable of MTBE biodegradation. The results of the investigation showed that only the bacterial isolate 27/1 was capable of growth on MTBE. The result of sequence analyzes of 16S rDNA showed that this bacterial isolate belongs to the Kocuria sp. After the incubation period of 86 days, the degradation rates of initial MTBE concentration of 25 and 125 μg/ml were 55 and 36%, respectively. These results indicated that bacteria Kocuria sp. is successfully adapted on MTBE and can be potentially used in bioremediation of soils and waters contaminated with MTBE.

Mechanistic Study of the sPLA2 Mediated Hydrolysis of a Thio-ester Pro Anticancer Ether Lipid

DEFF Research Database (Denmark)

Linderoth, Lars; Fristrup, Peter; Hansen, Martin

2009-01-01

Secretory phospholipase A2 (sPLA2) is an interesting enzyme for triggered liposomal drug delivery to tumor tissue due the overexpression of sPLA2 in cancerous tissue. A drug delivery system based on the triggered release of therapeutics from sPLA2-sensitive liposomes constituted of pro anticancer...... ether lipids, which become cytotoxic upon sPLA2-catalyzed hydrolysis has previously been established. To optimize the hydrolysis rate of the lipids and thereby optimizing the release profile of the drugs from the liposomes, we have synthesized a thio-ester pro anticancer ether lipid. Liposomes...... constituted of this lipid showed an altered rate of hydrolysis by sPLA2. We have tested the cytotoxicity of the thio-ester pro anticancer ether lipids toward cancer cells, and the results showed that the cytotoxicity is indeed maintained upon sPLA2 exposure. To further understand the origin for the observed...

Sorption of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) to synthetic resins.

Science.gov (United States)

Bi, Erping; Haderlein, Stefan B; Schmidt, Torsten C

2005-10-01

Methyl tert-butyl ether (MTBE) is a widely used gasoline oxygenate. Contamination of MTBE and its major degradation product tert-butyl alcohol (TBA) in groundwater and surface water has received great attention. However, sorption affinity and sorption mechanisms of MTBE and TBA to synthetic resins, which can be potentially used in removal of these contaminants from water, in passive sampling, or in enrichment of bacteria, have not been studied systemically. In this study, kinetic and equilibrium sorption experiments (single solute and binary mixtures) on four synthetic resins were conducted. The sorption affinity of the investigated sorbents for MTBE and TBA decreases in the order Ambersorb 563>Optipore L493>Amberlite XAD4>Amberlite XAD7, and all show higher sorption affinity for MTBE than for TBA. Binary experiments with o-xylene, a major compound of gasoline as co-contaminant, imply that all resins preferentially sorb o-xylene over MTBE or TBA, i.e., there is sorption competition. In the equilibrium aqueous concentration (Ceq) range (0.1-139.0 mg/L for MTBE, and 0.01-48.4 mg/L for TBA), experimental and modeling results as well as sorbent characteristics indicate that micropore filling and/or some other type of adsorption process (e.g., adsorption to specific sites of high sorption potential at low concentrations) rather than partitioning were the dominant sorption mechanisms. Optipore L493 has favourable sorption and desorption characteristics, and is a suitable sorbent, e.g., in bacteria enrichment or passive sampling for moderately polar compounds. However, for highly polar compounds such as TBA, Ambersorb 563 might be a better choice, especially in water treatment.

Tissue engineering of bovine articular cartilage within porous poly(ether ester) copolymer scaffolds with different structures

NARCIS (Netherlands)

Mahmood, Tahir A.; Shastri, V. Prasad; van Blitterswijk, Clemens; Langer, Robert; Riesle, J.U.

2005-01-01

The potential of porous poly(ether ester) scaffolds made from poly(ethylene glycol) terephthalate: poly(butylene terephthalate) (PEGT:PBT) block copolymers produced by various methods to enable cartilaginous tissue formation in vitro was studied. Scaffolds were fabricated by two different processes:

Chemical kinetic study of a novel lignocellulosic biofuel: Di-n-butyl ether oxidation in a laminar flow reactor and flames

KAUST Repository

Cai, Liming; Sudholt, Alena; Lee, Dongjoon; Egolfopoulos, Fokion N.; Pitsch, Heinz G.; Westbrook, Charles K.; Sarathy, Mani

2014-01-01

The combustion characteristics of promising alternative fuels have been studied extensively in the recent years. Nevertheless, the pyrolysis and oxidation kinetics for many oxygenated fuels are not well characterized compared to those of hydrocarbons. In the present investigation, the first chemical kinetic study of a long-chain linear symmetric ether, di-n-butyl ether (DBE), is presented and a detailed reaction model is developed. DBE has been identified recently as a candidate biofuel produced from lignocellulosic biomass. The model includes both high temperature and low temperature reaction pathways with reaction rates generated using appropriate rate rules. In addition, experimental studies on fundamental combustion characteristics, such as ignition delay times and laminar flame speeds have been performed. A laminar flow reactor was used to determine the ignition delay times of lean and stoichiometric DBE/air mixtures. The laminar flame speeds of DBE/air mixtures were measured in the stagnation flame configuration for a wide rage of equivalence ratios at atmospheric pressure and an unburned reactant temperature of 373. K. All experimental data were modeled using the present kinetic model. The agreement between measured and computed results is satisfactory, and the model was used to elucidate the oxidation pathways of DBE. The dissociation of keto-hydroperoxides, leading to radical chain branching was found to dominate the ignition of DBE in the low temperature regime. The results of the present numerical and experimental study of the oxidation of di-n-butyl ether provide a good basis for further investigation of long chain linear and branched ethers. © 2013 The Combustion Institute.

Chemical kinetic study of a novel lignocellulosic biofuel: Di-n-butyl ether oxidation in a laminar flow reactor and flames

KAUST Repository

Cai, Liming

2014-03-01

The combustion characteristics of promising alternative fuels have been studied extensively in the recent years. Nevertheless, the pyrolysis and oxidation kinetics for many oxygenated fuels are not well characterized compared to those of hydrocarbons. In the present investigation, the first chemical kinetic study of a long-chain linear symmetric ether, di-n-butyl ether (DBE), is presented and a detailed reaction model is developed. DBE has been identified recently as a candidate biofuel produced from lignocellulosic biomass. The model includes both high temperature and low temperature reaction pathways with reaction rates generated using appropriate rate rules. In addition, experimental studies on fundamental combustion characteristics, such as ignition delay times and laminar flame speeds have been performed. A laminar flow reactor was used to determine the ignition delay times of lean and stoichiometric DBE/air mixtures. The laminar flame speeds of DBE/air mixtures were measured in the stagnation flame configuration for a wide rage of equivalence ratios at atmospheric pressure and an unburned reactant temperature of 373. K. All experimental data were modeled using the present kinetic model. The agreement between measured and computed results is satisfactory, and the model was used to elucidate the oxidation pathways of DBE. The dissociation of keto-hydroperoxides, leading to radical chain branching was found to dominate the ignition of DBE in the low temperature regime. The results of the present numerical and experimental study of the oxidation of di-n-butyl ether provide a good basis for further investigation of long chain linear and branched ethers. © 2013 The Combustion Institute.

Amphiphilic poly(ether ester amide) multiblock copolymers as biodegradable matrices for the controlled release of proteins

NARCIS (Netherlands)

Bezemer, J.M.; Oude Weme, P.; Grijpma, Dirk W.; Dijkstra, Pieter J.; van Blitterswijk, Clemens; Feijen, Jan

2000-01-01

Amphiphilic poly(ether ester amide) (PEEA) multiblock copolymers were synthesized by polycondensation in the melt from hydrophilic poly(ethylene glycol) (PEG), 1,4-dihydroxybutane and short bisester-bisamide blocks. These amide blocks were prepared by reaction of 1,4-diaminobutane with dimethyl

Palladium-catalysed arylation of acetoacetate esters to yield 2-arylacetic acid esters

CSIR Research Space (South Africa)

Zeevaart, JG

2004-05-24

Full Text Available , was developed simultaneously by Hart- wig and Buchwald.5 Typically the tert-butyl ester of propionic acid is treated with an aryl halide (bromide or chloride) in the presence of a strong base, palladium and a bulky phosphine ligand or a bulky imidazolinium CO2t... novel palladium- catalysed conditions for the arylation of acetoacetate esters resulting in the formation of 2-arylacetic acid esters. When we attempted the arylation of tert-butyl aceto- acetate 1a with bromobenzene 2a using mild reaction conditions (K3...

In vivo and in vitro degradation of poly(ether ester) block copolymers based on poly(ethylene glycol) and poly(butylene terephthalate

NARCIS (Netherlands)

Deschamps, A.A.; van Apeldoorn, Aart A.; Hayen, H.; de Bruijn, Joost Dick; Karst, U.; Grijpma, Dirk W.; Feijen, Jan

2004-01-01

Two in vivo degradation studies were performed on segmented poly(ether ester)s based on polyethylene glycol (PEG) and poly(butylene terephthalate) (PBT) (PEOT/PBT). In a first series of experiments, the in vivo degradation of melt-pressed discs of different copolymer compositions were followed up

Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

DEFF Research Database (Denmark)

Langer, S.; Ljungström, E.; Ellermann, T.

1995-01-01

UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... and the alkylperoxy radicals with NO and NO2 are (9.1 +/- 1.5) X 10(-13), (4.3 +/- 1.6) X 10(-12) and (1.2 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1), respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule....

Biodegradation of Methyl tert-Butyl Ether by Co-Metabolism with a Pseudomonas sp. Strain

Directory of Open Access Journals (Sweden)

Shanshan Li

2016-09-01

Full Text Available Co-metabolic bioremediation is supposed to be an impressive and promising approach in the elimination technology of methyl tert-butyl ether (MTBE, which was found to be a common pollutant worldwide in the ground or underground water in recent years. In this paper, bacterial strain DZ13 (which can co-metabolically degrade MTBE was isolated and named as Pseudomonas sp. DZ13 based on the result of 16S rRNA gene sequencing analysis. Strain DZ13 could grow on n-alkanes (C5-C8, accompanied with the co-metabolic degradation of MTBE. Diverse n-alkanes with different carbon number showed a significant influence on the degradation rate of MTBE and accumulation of tert-butyl alcohol (TBA. When Pseudomonas sp. DZ13 co-metabolically degraded MTBE with n-pentane as the growth substrate, a higher MTBE-degrading rate (Vmax = 38.1 nmol/min/mgprotein, Ks = 6.8 mmol/L and lower TBA-accumulation was observed. In the continuous degradation experiment, the removal efficiency of MTBE by Pseudomonas sp. Strain DZ13 did not show an obvious decrease after five times of continuous addition.

The thermal degradation of poly(iso-butyl methacrylate and poly(sec-butyl methacrylate

Directory of Open Access Journals (Sweden)

IVANKA G. POPOVIC

2000-12-01

Full Text Available The non-oxidative thermal degradation of poly(iso-butyl methacrylate and poly(sec-butyl methacrylate was investigated by studying changes in the polymer residue. Due to the different number of b-hydrogens in their ester substituents, these two polymeric isomers behave differently when subjected to elevated temperatures. Poly(iso-butyl methacrylate degrades quantitatively by depolymerisation with zip lengths of the same order of magnitude as those of poly(methyl methacrylate. Poly(sec-butyl methacrylate degrades by a combined degradation mechanism of depolymerisation and de-esterification. De-esterification becomes a significant thermolysis route at temperatures higher than 240°C.

Detection and Quantification of Methyl tert-Butyl Ether-Degrading Strain PM1 by Real-Time TaqMan PCR

OpenAIRE

Hristova, Krassimira R.; Lutenegger, Christian M.; Scow, Kate M.

2001-01-01

The fuel oxygenate methyl tert-butyl ether (MTBE), a widely distributed groundwater contaminant, shows potential for treatment by in situ bioremediation. The bacterial strain PM1 rapidly mineralizes and grows on MTBE in laboratory cultures and can degrade the contaminant when inoculated into groundwater or soil microcosms. We applied the TaqMan quantitative PCR method to detect and quantify strain PM1 in laboratory and field samples. Specific primers and probes were designed for the 16S ribos...

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

Science.gov (United States)

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.

Solubility investigation of ether and ester essential oils in water using spectrometry and GC/MS

Directory of Open Access Journals (Sweden)

B. Khodabandeloo

2017-11-01

Full Text Available Background and objectives: Essential oils (volatiles are aromatic oily liquids prepared from different parts of plants and demonstrate various therapeutic and cosmetic properties. The dissolution of essential oils are not desirable in water, therefore the aim of this research was evaluation and selection the best co-solvents for increasing their solubility and bio availability. Methods:The solubility of six  plants essential oils were investigated in presence of propylene glycol (PG, polyethylene glycol 300 (PEG, glycerin and ethanol as solvent and tween 80 or lecithin as co-solvent by observation and spectrophotometric assay. Chemical composition of the essential oils and supersaturated 50% ethanol (SSE and 50% PG or PEG (SSP solutions were analyzed by GC/MS, too. Results: Ester (Lavandula dentata, Heracleum persicum and, Elettaria cardamomum essential oils showed the best solubility in ethanol and PG, respectively. Ether (Foeniculum vulgare, Pimpinella anisum and Petroselinum crispum essential oils had the best solubility in ethanol and PEG, respectively. In ester class, mixture of ethanol/water was the best solvent according to solubility and total amounts of major compounds of the essential oils. In ether class, all samples had better solubility in mixtures of ethanol/water than PEG, but the amounts of total phenols or ethers in SSP of some samples were higher than SSE. Therefore selecting the best solvent for these class need more experiments. Conclusion: Selecting the solvent for essential oils changes their chemical composition; therefore the best solvent was different for various purposes.

Effects of a thirteen-week inhalation exposure to ethyl tertiary butyl ether on fischer-344 rats and CD-1 mice.

Science.gov (United States)

Medinsky, M A; Wolf, D C; Cattley, R C; Wong, B; Janszen, D B; Farris, G M; Wright, G A; Bond, J A

1999-09-01

The 1990 Clean Air Act Amendments require that oxygenates be added to automotive fuels to reduce emissions of carbon monoxide and hydrocarbons. One potential oxygenate is the aliphatic ether ethyl tertiary butyl ether (ETBE). Our objective was to provide data on the potential toxic effects of ETBE. Male and female Fisher 344 rats and CD-1 mice were exposed to 0 (control), 500, 1750, or 5000 ppm of ETBE for 6 h/day and 5 days/wk over a 13-week period. ETBE exposure had no effect on mortality and body weight with the exception of an increase in body weights of the female rats in the 5000-ppm group. No major changes in clinical pathology parameters were noted for either rats or mice exposed to ETBE for 6 (rats only) or 13 weeks. Liver weights increased with increasing ETBE-exposure concentration for both sexes of rats and mice. Increases in kidney, adrenal, and heart (females only) weights were noted in rats. Degenerative changes in testicular seminiferous tubules were observed in male rats exposed to 1750 and 5000 ppm but were not seen in mice. This testicular lesion has not been reported previously for aliphatic ethers. Increases in the incidence of regenerative foci, rates of renal cell proliferation, and alpha2u-globulin containing protein droplets were noted in the kidneys of all treated male rats. These lesions are associated with the male rat-specific syndrome of alpha2u-globulin nephropathy. Increases in the incidence of centrilobular hepatocyte hypertrophy and rates of hepatocyte cell proliferation were seen in the livers of male and female mice in the 5000-ppm group, consistent with a mitogenic response to ETBE. These two target organs for ETBE toxicity, mouse liver and male rat kidney, have also been reported for methyl tertiary butyl ether and unleaded gasoline.

Ethyl tertiary-butyl ether: a toxicological review.

Science.gov (United States)

McGregor, Douglas

2007-05-01

A number of oxygenated compounds (oxygenates) are available for use in gasoline to reduce vehicle exhaust emissions, reduce the aromatic compound content, and avoid the use of organo-lead compounds, while maintaining high octane numbers. Ethyl tertiary-butyl ether (ETBE) is one such compound. The current use of ETBE in gasoline or petrol is modest but increasing, with consequently similar trends in the potential for human exposure. Inhalation is the most likely mode of exposure, with about 30% of inhaled ETBE being retained by the lungs and distributed around the body. Following cessation of exposure, the blood concentration of ETBE falls rapidly, largely as a result of its metabolism to tertiary-butyl alcohol (TBA) and acetaldehyde. TBA may be further metabolized, first to 2-methyl-1,2-propanediol and then to 2-hydroxyisobutyrate, the two dominant metabolites found in urine of volunteers and rats. The rapid oxidation of acetaldehyde suggests that its blood concentration is unlikely to rise above normal as a result of human exposure to sources of ETBE. Single-dose toxicity tests show that ETBE has low toxicity and is essentially nonirritant to eyes and skin; it did not cause sensitization in a maximization test in guinea pigs. Neurological effects have been observed only at very high exposure concentrations. There is evidence for an effect of ETBE on the kidney of rats. Increases in kidney weight were seen in both sexes, but protein droplet accumulation (with alpha(2u)-globulin involvement) and sustained increases in cell proliferation occurred only in males. In liver, centrilobular necrosis was induced in mice, but not rats, after exposure by inhalation, although this lesion was reported in some rats exposed to very high oral doses of ETBE. The proportion of liver cells engaged in S-phase DNA synthesis was increased in mice of both sexes exposed by inhalation. ETBE has no specific effects on reproduction, development, or genetic material. Carcinogenicity studies

Chronic Carcinogenicity Study of Gasoline Vapor Condensate (GVC) and GVC Containing Methyl Tertiary-Butyl Ether in F344 Rats

OpenAIRE

Benson, Janet M.; Gigliotti, Andrew P.; March, Thomas H.; Barr, Edward B.; Tibbetts, Brad M.; Skipper, Betty J.; Clark, Charles R.; Twerdok, Lorraine

2011-01-01

Chronic inhalation studies were conducted to compare the toxicity and potential carcinogenicity of evaporative emissions from unleaded gasoline (GVC) and gasoline containing the oxygenate methyl tertiary-butyl ether (MTBE; GMVC). The test materials were manufactured to mimic vapors people would be exposed to during refueling at gas stations. Fifty F344 rats per gender per exposure level per test article were exposed 6 h/d, 5 d/wk for 104 wk in whole body chambers. Target total vapor concentra...

Effect of external mass transfer on activation energy of butyl oleate ester synthesis using a whole cell bio catalyst

International Nuclear Information System (INIS)

Shahhoseini, Sh.; Nasernejad, B.; Vahabzadeh, F.

2016-01-01

In the present research, synthesis of butyl oleate ester from oleic acid and butanol using loofa-immobilized Rhizopus oryzae as a whole cell biocatalyst (LIC) was studied in which hexane was used as the hydrophobic solvent. Decrease of mass transfer limitations as result of the interface formation between the two immiscible substrates, positively affected on the reaction progress (87% as the ester product yielded within 10 h). By applying Arrhenius equation, the activation energy of the ester synthesis was determined as Ea=18.2 kJ/mol within temperature range of 15-45°C. It was notable to test appearance of the nonlinearity in Arrhenius plot which was indicative of presence of two sections. The reaction limited region was 15-35°C; Ea=27 kJ/mol and diffusion limited region was >35°C; Ea=6.8 kJ/mol. Eventually, in this research, influence of external mass transfer on activation energy with reference to the catalytic role of the LIC in the ester synthesis was discussed.

Involvement of a novel enzyme, MdpA, in methyl tert-butyl ether degradation in Methylibium petroleiphilum PM1.

Science.gov (United States)

Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R

2008-11-01

Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr(59) distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum.

Analysis of chemical signatures of alkaliphiles using fatty acid methyl ester analysis

Directory of Open Access Journals (Sweden)

Basha Sreenivasulu

2017-01-01

Full Text Available Background: Fatty acids occur in nearly all living organisms as the important predominant constituents of lipids. While all fatty acids have essentially the same chemical nature, they are an extremely diverse group of compounds. Materials and Methods: To test the hypothesis, fatty acids of alkaliphiles isolates, Bacillus subtilis SVUNM4, Bacillus licheniformis SVUNM8, Bacillus methylotrohicus SVUNM9, and Paenibacillus dendritiformis SVUNM11, were characterized compared using gas chromatography-mass spectrometry (GC-MS analysis. Results: The content of investigated ten fatty acids, 1, 2-benzenedicarboxylic acid butyl 2-methylpropyl ester, phthalic acid, isobutyl 2-pentyl ester, dibutyl phthalate, cyclotrisiloxane, hexamethyl, cyclotetrasiloxane, octamethyl, dodecamethyl, heptasiloxane 1,1,3,3,5,5,7,7,9,9,11,11,13,13-etradecamethyl, 7,15-dihydroxydehydroabietic acid, methyl ester, di (trimethylsilyl ether, hentriacontane, 2-thiopheneacetic acid, undec-2-enyl ester, obviously varied among four species, suggesting each species has its own fatty acid pattern. Conclusions: These findings demonstrated that GC-MS-based fatty acid profiling analysis provides the reliable platform to classify these four species, which is helpful for ensuring their biotechnological interest and novel chemotaxonomic.

Gene mdpC plays a regulatory role in the methyl-tert-butyl ether degradation pathway of Methylibium petroleiphilum strain PM1.

Science.gov (United States)

Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

2015-04-01

Among the few bacteria known to utilize methyl tert-butyl ether (MTBE) as a sole carbon source, Methylibium petroleiphilum PM1 is a well-characterized organism with a sequenced genome; however, knowledge of the genetic regulation of its MTBE degradation pathway is limited. We investigated the role of a putative transcriptional activator gene, mdpC, in the induction of MTBE-degradation genes mdpA (encoding MTBE monooxygenase) and mdpJ (encoding tert-butyl alcohol hydroxylase) of strain PM1 in a gene-knockout mutant mdpC(-). We also utilized quantitative reverse transcriptase PCR assays targeting genes mdpA, mdpJ and mdpC to determine the effects of the mutation on transcription of these genes. Our results indicate that gene mdpC is involved in the induction of both mdpA and mdpJ in response to MTBE and tert-butyl alcohol (TBA) exposure in PM1. An additional independent mechanism may be involved in the induction of mdpJ in the presence of TBA. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

A new, direct analytical method using LC-MS/MS for fatty acid esters of 3-chloro-1,2-propanediol (3-MCPD esters) in edible oils.

Science.gov (United States)

Yamazaki, K; Ogiso, M; Isagawa, S; Urushiyama, T; Ukena, T; Kibune, N

2013-01-01

A new, direct analytical method for the determination of 3-chloro-1,2-propanediol fatty acid esters (3-MCPD esters) was developed. The targeted 3-MCPD esters included five types of monoester and 25 [corrected] types of diester. Samples (oils and fats) were dissolved in a mixture of tert-butyl methyl ether and ethyl acetate (4:1), purified using two solid-phase extraction (SPE) cartridges (C(18) and silica), then analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Five monoesters and five diesters with the same fatty acid group could be separated and quantified. Pairs of 3-MCPD diesters carrying the same two different fatty acid groups, but at reversed positions (sn-1 and sn-2), could not be separated and so were expressed as a sum of both compounds. The limits of quantification (LOQs) were estimated to be between 0.02 to 0.08 mg kg(-1), depending on the types of 3-MCPD ester. Repeatability expressed as relative standard deviation (RSD(r)%) varied from 5.5% to 25.5%. The new method was shown to be applicable to various commercial edible oils and showed levels of 3-MCPD esters varying from 0.58 to 25.35 mg kg(-1). The levels of mono- and diesters ranged from 0.10 to 0.69 mg kg(-1) and from 0.06 to 16 mg kg(-1), respectively.

Involvement of a Novel Enzyme, MdpA, in Methyl tert-Butyl Ether Degradation in Methylibium petroleiphilum PM1 ▿

Science.gov (United States)

Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R.

2008-01-01

Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr59 distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum. PMID:18791002

Tactical Fuel and Energy Strategy for The Future Modular Force

Science.gov (United States)

2009-05-18

Environmental Protection Agency ESSP Energy Strategic Security Plan EV Electric Vehicle FAME Fatty Acid Methyl Ester Appendix...1992. Methanol can be used to make methyl tertiary-butyl ether (MTBE), oxygenate that is blended with gasoline to enhance octane and create cleaner...Military Occupation Specialty MTBE Methyl Tertiary Butyl Ether MW Megawatt NASA National Aeronautics and Space Administration NATO North

Radiochemical study of isomerization of free butyl cations

International Nuclear Information System (INIS)

Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

1987-01-01

Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

Radiation chemistry of alternative fuel oxygenates - substituted ethers

International Nuclear Information System (INIS)

Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

1999-01-01

The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

Segmented poly(ether ester)s and poly(ether ester amide)s for use in tissue engineering

OpenAIRE

Deschamps, A.A.

2002-01-01

The objective of the studies described in this thesis is to investigate the applicability of these slowly degradable thermoplastic elastomers as scaffolds for tissue engineering, with emphasis on their phase separation and degradation properties. A second thermoplastic elastomer in which the terephthalic moieties have been replaced by ester-amide segments, is also investigated for use in scaffolding.

Use of experimental design for the purge-and-trap-gas chromatography-mass spectrometry determination of methyl tert.-butyl ether, tert.-butyl alcohol and BTEX in groundwater at trace level.

Science.gov (United States)

Bianchi, F; Careri, M; Marengo, E; Musci, M

2002-10-25

An efficient method for the simultaneous determination of methyl tert.-butyl ether, tert.-butyl alcohol, benzene, toluene, ethylbenzene and xylene isomers in groundwater by purge-and-trap-gas chromatography-mass spectrometry was developed and validated. Experimental design was used to investigate the effects of temperature of extraction, time of extraction and percentage of salt added to the water samples. Regression models and desirability functions were applied to find the experimental conditions providing the highest global extraction yield. Validation was carried out in terms of limits of detection (LOD), limits of quantitation (LOQ), linearity and precision. LOD values ranging from 2.6 to 23 ng l(-1) were achieved, whereas linearity was statistically verified over two orders of magnitude for each compound. Precision was evaluated testing two concentration levels. Good results were obtained both in terms of intra-day repeatability and intermediate precision: RSD% lower than 4.5% at the highest concentration and lower than 13% at the lowest one were calculated for intra-day repeatability. A groundwater sample suspected of contamination by leaking underground petroleum storage tanks was analysed and some of the analytes were detected and quantitated.

Study of an aquifer contaminated by ethyl tert-butyl ether (ETBE): Site characterization and on-site bioremediation

International Nuclear Information System (INIS)

Fayolle-Guichard, Françoise; Durand, Jonathan; Cheucle, Mathilde; Rosell, Mònica; Michelland, Rory Julien; Tracol, Jean-Philippe; Le Roux, Françoise; Grundman, Geneviève; Atteia, Olivier; Richnow, Hans H.; Dumestre, Alain

2012-01-01

Highlights: ► Ethyl tert-butyl ether (ETBE) (>300 mg L −1 ) found in a groundwater (gas-station). ► No significant carbon or hydrogen isotopic fractionation of ETBE along the plume. ► MC-IFP culture degraded ETBE (0.91 mg L −1 h −1 ) and BTEX (0.64 mg L −1 h −1 ). ► A pilot plant (2 m 3 ) inoculated with MC-IFP degraded ETBE in groundwater (15 °C). ► ethB gene (ETBE biodegradation) amplified during bioaugmentation (5 × 10 6 ethB gene copies L −1 ). - Abstract: Ethyl tert-butyl ether (ETBE) was detected at high concentration (300 mg L −1 ) in the groundwater below a gas-station. No significant carbon neither hydrogen isotopic fractionation of ETBE was detected along the plume. ETBE and BTEX biodegradation capacities of the indigenous microflora Pz1-ETBE and of a culture (MC-IFP) composed of Rhodococcus wratislaviensis IFP 2016, Rhodococcus aetherivorans IFP 2017 and Aquincola tertiaricarbonis IFP 2003 showed that ETBE and BTEX degradation rates were in the same range (ETBE: 0.91 and 0.83 mg L −1 h −1 and BTEX: 0.64 and 0.82 mg L −1 h −1 , respectively) but tert-butanol (TBA) accumulated transiently at a high level using Pz1-ETBE (74 mg L −1 ). An on-site pilot plant (2 m 3 ) filled with polluted groundwater and inoculated by MC-IFP, successfully degraded four successive additions of ETBE and gasoline. However, an insignificant ETBE isotopic fractionation was also accompanying this decrease which suggested the involvement of low fractionating-strains using EthB enzymes, but required of additional proofs. The ethB gene encoding a cytochrome P450 involved in ETBE biodegradation (present in R. aetherivorans IFP 2017) was monitored by quantitative real-time polymerase chain reaction (q-PCR) on DNA extracted from water sampled in the pilot plant which yield up to 5 × 10 6 copies of ethB gene per L −1 .

Gamma-aminobutyric acid esters. 1. Synthesis, brain uptake, and pharmacological studies of aliphatic and steroid esters of gamma-aminobutyric acid

International Nuclear Information System (INIS)

Shashoua, V.E.; Jacob, J.N.; Ridge, R.; Campbell, A.; Baldessarini, R.J.

1984-01-01

Labeled and unlabeled aliphatic and steroid esters of gamma-amino[U- 14 C]butyric acid (GABA) were synthesized and tested for their capacity to penetrate the blood-brain barrier and for evidence of central neuropharmacological activity in rodents. The uptake of the labeled 9,12,15-octadecatrienyl (linolenyl), 3-cholesteryl, 1-butyl, and the 9-fluoro-11 beta,17-dihydroxy-16 alpha-methyl-3,20-dioxopregna -1,4-dien-21-yl (dexamethasone) esters of GABA into mouse brain increased 2-, 25-, 74-, and 81-fold over GABA, respectively. The cholesteryl ester of GABA depressed the general motor activity of mice and rats in a dose-dependent manner, whereas the 1-butyl, linolenyl, and dexamethasone esters were inactive by this test. Studies of the rates of hydrolysis, GABA receptor binding capacity, and octanol/water partition coefficients indicated that pharmacological activity of the esters after entry into the central nervous system (CNS) was dependent on their capacity to release GABA by enzymatic hydrolysis and their lipid solubility

Carcinogenicity of methyl-tertiary butyl ether in gasoline.

Science.gov (United States)

Mehlman, Myron A

2002-12-01

Methyl tertiary butyl ether (MTBE) was added to gasoline on a nationwide scale in 1992 without prior testing of adverse, toxic, or carcinogenic effects. Since that time, numerous reports have appeared describing adverse health effects of individuals exposed to MTBE, both from inhalation of fumes in the workplace and while pumping gasoline. Leakage of MTBE, a highly water-soluble compound, from underground storage tanks has led to contamination of the water supply in many areas of the United States. Legislation has been passed by many states to prohibit the addition of MTBE to gasoline. The addition of MTBE to gasoline has not accomplished its stated goal of decreasing air pollution, and it has posed serious health risks to a large portion of the population, particularly the elderly and those with respiratory problems, asthma, and skin sensitivity. Reports of animal studies of carcinogenicity of MTBE began to appear in the 1990s, prior to the widespread introduction of MTBE into gasoline. These reports were largely ignored. In ensuing years, further studies have shown that MTBE causes various types of malignant tumors in mice and rats. The National Toxicology Program (NTP) Board of Scientific Counselors' Report on Carcinogens Subcommittee met in December 1998 to consider listing MTBE as "reasonably anticipated to be a human carcinogen." In spite of recommendations from Dr. Bailer, the primary reviewer, and other scientists on the committee, the motion to list MTBE in the report was defeated by a six to five vote, with one abstention. On the basis of animal studies, it is widely accepted that if a chemical is carcinogenic in appropriate laboratory animal test systems, it must be treated as though it were carcinogenic in humans. In the face of compelling evidence, NTP Committee members who voted not to list MTBE as "reasonably anticipated to be a human carcinogen" did a disservice to the general public; this action may cause needless exposure of many to health risks

Degradation of methyl tert-butyl ether by gel immobilized Methylibium petroleiphilum PM1.

Science.gov (United States)

Chen, Dongzhi; Chen, Jianmeng; Zhong, Weihong; Cheng, Zhuowei

2008-07-01

Cells of Methylibium petroleiphilum PM1 were immobilized in gel beads to degrade methyl tert-butyl ether (MTBE). Calcium alginate, agar, polyacrylamide and polyvinvyl alcohol were screened as suitable immobilization matrices, with calcium alginate demonstrating the fastest MTBE-degradation rate. The rate was accelerated by 1.8-fold when the beads had been treated in physiological saline for 24h at 28 degrees C. MTBE degradation in mineral salts medium (MSM) was accompanied by the increase of biomass. The half-life of MTBE-degradation activity for the encapsulated cells stored at 28 degrees C was about 120 h, which was obviously longer than that of free cells (approximately 36 h). Efficient reusability of the beads up to 30 batches was achieved in poor nutrition solution as compared to only 6 batches in MSM. The immobilized cells could be operated in a packed-bed reactor for degradation of 10 mg L(-1) MTBE in groundwater with more than 99% removal efficiency at hydraulic retention time of 20 min. These results suggested that immobilized cells of PM1 in bioreactor might be applicable to a groundwater treatment system for the removal of MTBE.

The preparation and intramolecular radical cyclisation reactions of chiral oxyme ethers

International Nuclear Information System (INIS)

Booth, Susan E.; Jenkins, Paul R.

1998-01-01

Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethyl azo dicarboxylate, the two product were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3,8 and 12. (author)

The Preparation and Intramolecular Radical Cyclisation Reactions of Chiral Oxime Ethers

Directory of Open Access Journals (Sweden)

Booth Susan E.

1998-01-01

Full Text Available Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethylazodicarboxylate, the two products were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3, 8 and 12.

Butylated caffeic acid: An efficient novel antioxidant

Directory of Open Access Journals (Sweden)

G. Shi

2017-09-01

Full Text Available A novel antioxidant, butylated caffeic acid (BCA was rationally designed by adding a tert-butyl group to caffeic acid, which was synthesized at a high yield (36.2% from 2-methoxy-4-methylphenol by a four-step reaction including Friedel-Crafts alkylation, bromine oxidation, ether bond hydrolysis and Knoevenagel condensation. Its antioxidant capacity was much stronger than common commercial antioxidant tert-butyl hydroquinone (TBHQ and its mother compound, caffeic acid, in both rancimat and deep frying tests. When investigated via the DPPH method, the antioxidant capacity of BCA was almost equal to TBHQ, but lower than caffeic acid. BCA could be a potentially strong antioxidant, especially for food processing at high temperatures such as deep frying and baking.

Butylated caffeic acid: An efficient novel antioxidant

International Nuclear Information System (INIS)

Shi, G.; Liao, X.; Olajide, T.M.; Liu, J.; Jiang, X.; Weng, X.

2017-01-01

A novel antioxidant, butylated caffeic acid (BCA) was rationally designed by adding a tert-butyl group to caffeic acid, which was synthesized at a high yield (36.2%) from 2-methoxy-4-methylphenol (1) by a four-step reaction including Friedel-Crafts alkylation, bromine oxidation, ether bond hydrolysis and Knoevenagel condensation. Its antioxidant capacity was much stronger than common commercial antioxidant tert-butyl hydroquinone (TBHQ) and its mother compound, caffeic acid, in both rancimat and deep frying tests. When investigated via the DPPH method, the antioxidant capacity of BCA was almost equal to TBHQ, but lower than caffeic acid. BCA could be a potentially strong antioxidant, especially for food processing at high temperatures such as deep frying and baking. [es

Association between content in serum in 2, 4-D butyl ester and behavior-intelligence quotient of children%儿童血清中2,4-D丁酯水平与行为、智力的关系

Institute of Scientific and Technical Information of China (English)

鲁彦; 祝丽玲; 姚嵩坡; 杜宁; 关宝生; 张艺滢; 张媛媛; 李美玲; 李京

2013-01-01

目的:探讨儿童血清中2,4-D丁酯与行为及智力的关系.方法:分层整群抽取黑龙江省某市农业发达的农村321例6～10岁儿童为研究对象,气相色谱法测定血清2,4-D丁酯含量,根据血清2,4-D丁酯浓度将儿童分为2,4-D丁酯低暴露组(＜0.0345Jg/L)和2,4-D丁酯高暴露组 (≥0.0345μg/L),Conners儿童行为量表 (父母问卷)评价儿童行为,瑞文推理测验联合型(CRT)量表评价儿童智力.结果:在275名(85.67％)儿童血清中检出2,4-D丁酯(检出限0.0044 μg/L),59名(18.38％)儿童有行为问题.高暴露组行为问题总发生率高于低暴露组(P＜0.05),高暴露组品行问题、学习困难、心身问题、行为问题发生率高于低暴露组(P＜0.05),高暴露组智商(IQ)低于低暴露组(P＜0.05)；2,4-D丁酯含量与品行问题、学习困难、心身问题、冲动-多动行为因子评分呈正相关(P＜0.05),与IQ值呈负相关(P＜0.05).结论:2,4-D丁酯影响6～10岁儿童行为和智力.%Objective:To explore the association between the content of serum 2,4-D butyl ester and behavior-intelligence quotient of children.Methods:321 children aged 6-10 years old peasants were investigated with stratifler cluster sampling in rural developed areas in a city of Heilongjiang province.Content of 2,4-D butyl ester in serum was analyzed by gas chromatography.According to concentrations of 2,4-D butyl ester in serum were studied as lower exposure group (＜ 0.034 5μg/L) and higher exposure group (≥0.034 5 μg/L).Behaviors of children were evaluated by Conners Behavior Checklist questionnaire.Combined Raven's Test (CRT) are used to assess the children's intelligence quotient (IQ).Results:In the study,the 2,4-D butyl ester (detection limit 0.004 4 μg/L)were detected in serum of 275 (85.67％) children and 59 (18.38％) of them had behavior problems.The rates of behavior problem in high-exposure group was higher than those rates of behavior problem in low-exposure group (P �

Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

Energy Technology Data Exchange (ETDEWEB)

Fayolle-Guichard, F

2005-04-01

Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

Energy Technology Data Exchange (ETDEWEB)

Tang, G.H. [Xian Medical Univ. (China); Shen, Y.; Shen, H.M. [National Univ. of Singapore (Singapore)] [and others

1996-12-31

Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

Study of an aquifer contaminated by ethyl tert-butyl ether (ETBE): Site characterization and on-site bioremediation

Energy Technology Data Exchange (ETDEWEB)

Fayolle-Guichard, Francoise, E-mail: francoise.fayolle@ifpen.fr [IFP Energies nouvelles, 1 et 4 avenue de Bois-Preau, 92852 Rueil-Malmaison (France); Durand, Jonathan [Institut EGID Bordeaux 3, 1 Allee Daguin 33607 Pessac Cedex (France); SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Cheucle, Mathilde [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Rosell, Monica [Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research - UFZ, Permoserstrasse 15, 04318 Leipzig (Germany); Michelland, Rory Julien [Universite de Lyon, F-69622 Lyon (France); Universite Lyon 1, Villeurbanne (France); CNRS, UMR5557, Ecologie Microbienne (France); Tracol, Jean-Philippe [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Le Roux, Francoise [IFP Energies nouvelles, 1 et 4 avenue de Bois-Preau, 92852 Rueil-Malmaison (France); Grundman, Genevieve [Universite de Lyon, F-69622 Lyon (France); Universite Lyon 1, Villeurbanne (France); CNRS, UMR5557, Ecologie Microbienne (France); Atteia, Olivier [Institut EGID Bordeaux 3, 1 Allee Daguin 33607 Pessac Cedex (France); Richnow, Hans H. [Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research - UFZ, Permoserstrasse 15, 04318 Leipzig (Germany); Dumestre, Alain [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); and others

2012-01-30

Highlights: Black-Right-Pointing-Pointer Ethyl tert-butyl ether (ETBE) (>300 mg L{sup -1}) found in a groundwater (gas-station). Black-Right-Pointing-Pointer No significant carbon or hydrogen isotopic fractionation of ETBE along the plume. Black-Right-Pointing-Pointer MC-IFP culture degraded ETBE (0.91 mg L{sup -1} h{sup -1}) and BTEX (0.64 mg L{sup -1} h{sup -1}). Black-Right-Pointing-Pointer A pilot plant (2 m{sup 3}) inoculated with MC-IFP degraded ETBE in groundwater (15 Degree-Sign C). Black-Right-Pointing-Pointer ethB gene (ETBE biodegradation) amplified during bioaugmentation (5 Multiplication-Sign 10{sup 6}ethB gene copies L{sup -1}). - Abstract: Ethyl tert-butyl ether (ETBE) was detected at high concentration (300 mg L{sup -1}) in the groundwater below a gas-station. No significant carbon neither hydrogen isotopic fractionation of ETBE was detected along the plume. ETBE and BTEX biodegradation capacities of the indigenous microflora Pz1-ETBE and of a culture (MC-IFP) composed of Rhodococcus wratislaviensis IFP 2016, Rhodococcus aetherivorans IFP 2017 and Aquincola tertiaricarbonis IFP 2003 showed that ETBE and BTEX degradation rates were in the same range (ETBE: 0.91 and 0.83 mg L{sup -1} h{sup -1} and BTEX: 0.64 and 0.82 mg L{sup -1} h{sup -1}, respectively) but tert-butanol (TBA) accumulated transiently at a high level using Pz1-ETBE (74 mg L{sup -1}). An on-site pilot plant (2 m{sup 3}) filled with polluted groundwater and inoculated by MC-IFP, successfully degraded four successive additions of ETBE and gasoline. However, an insignificant ETBE isotopic fractionation was also accompanying this decrease which suggested the involvement of low fractionating-strains using EthB enzymes, but required of additional proofs. The ethB gene encoding a cytochrome P450 involved in ETBE biodegradation (present in R. aetherivorans IFP 2017) was monitored by quantitative real-time polymerase chain reaction (q-PCR) on DNA extracted from water sampled in the pilot plant

Artificial Neural Network Approach to Predict Biodiesel Production in Supercritical tert-Butyl Methyl Ether

Directory of Open Access Journals (Sweden)

Obie Farobie

2016-05-01

Full Text Available In this study, for the first time artificial neural network was used to predict biodiesel yield in supercritical tert-butyl methyl ether (MTBE. The experimental data of biodiesel yield conducted by varying four input factors (i.e. temperature, pressure, oil-to-MTBE molar ratio, and reaction time were used to elucidate artificial neural network model in order to predict biodiesel yield. The main goal of this study was to assess how accurately this artificial neural network model to predict biodiesel yield conducted under supercritical MTBE condition. The result shows that artificial neural network is a powerful tool for modeling and predicting biodiesel yield conducted under supercritical MTBE condition that was proven by a high value of coefficient of determination (R of 0.9969, 0.9899, and 0.9658 for training, validation, and testing, respectively. Using this approach, the highest biodiesel yield was determined of 0.93 mol/mol (corresponding to the actual biodiesel yield of 0.94 mol/mol that was achieved at 400 °C, under the reactor pressure of 10 MPa, oil-to-MTBE molar ratio of 1:40 within 15 min of reaction time.

Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

Energy Technology Data Exchange (ETDEWEB)

Fayolle-Guichard, F.

2005-04-01

Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

Biofuels for transportation. From R and D to market

Energy Technology Data Exchange (ETDEWEB)

Pilo, C [comp.

1996-11-01

The aim of the Workshop was to bring together stakeholders in industry, government and science to identify technical, economic and institutional opportunities and/or barriers to the market penetration of biofuels and to tackle these issues jointly in an international environment. The Workshop was to cover the role of biofuels in replacing fossil fuels and achieving sustainable transportation. It was to be more oriented towards policy issues than towards analyses of scientific and technical details. The Workshop was focused on the conditions in Northern Europe and North America. Three main themes were chosen: THEME 1. Biomass Feedstocks. How do we produce them cost-effectively and for what purpose? THEME 2. Biofuels for Transportation. What will make them technically and economically competitive? THEME 3. Market Penetration of Biofuels. How do we remove barriers? The following biofuels were considered during the Workshop: Alcohols, such as ethanol and methanol. Ethers, such as MTBE (methyl-tertio-butyl-ether) and ETBE (ethyl-tertio-butyl-ether). Vegetable oils and esters, such as VME (vegetable-oil-methylester), RME (rape-oil-methyl-ester) and REE (rape-oil-ethyl-ester)

Temperature-Induced Desorption of Methyl tert-Butyl Ether Confined on ZSM-5: An In Situ Synchrotron XRD Powder Diffraction Study

Directory of Open Access Journals (Sweden)

Elisa Rodeghero

2017-02-01

Full Text Available The temperature-induced desorption of methyl tert-butyl ether (MTBE from aqueous solutions onto hydrophobic ZSM-5 was studied by in situ synchrotron powder diffraction and chromatographic techniques. This kind of information is crucial for designing and optimizing the regeneration treatment of such zeolite. The evolution of the structural features monitored by full profile Rietveld refinements revealed that a monoclinic (P21/n to orthorhombic (Pnma phase transition occurred at about 100 °C. The MTBE desorption process caused a remarkable change in the unit-cell parameters. Complete MTBE desorption was achieved upon heating at about 250 °C. Rietveld analysis demonstrated that the desorption process occurred without any significant zeolite crystallinity loss, but with slight deformations in the channel apertures.

Synthesis, Characterization and Biocompatibility of Biodegradable Elastomeric Poly(ether-ester urethane)s Based on Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and Poly(ethylene glycol) via Melting Polymerization

DEFF Research Database (Denmark)

Li, Zibiao; Yang, Xiaodi; Wu, Linping

2009-01-01

Poly(ether-ester urethane)s (PUs) multiblock co-polymers were synthesized from telechelic hydroxylated poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and poly(ethylene glycol) (PEG) via a melting polymerization (MP) process using 1,6-hexamethylene diisocyanate (HDI) as a non-toxic couplin...

Synthesis of water-soluble poly [acrylic acid-co-vinyl butyl ether] and its applications in cement admixtures

International Nuclear Information System (INIS)

Negim, S.M.; Mun, G.A.; Nurkeeva, Z.S.; Danveesh, H.H.M.

2005-01-01

Three composition ratios of poly[acrylic acid (AA)-co-vinyl butyl ether)] were prepared in alcoholic solution using azo-bis-isobutyro-nitrile as initiator (ABIN). The water-soluble copolymers were characterized through FT-IR, 1 H NMR, Mass spectra, ESEM as well as viscosity. The effect of water-soluble copolymers and their sodium salts on the physico-mechanical properties of Ordaniary Portland Cement (O.P.C) pastes was investigated. The results showed that the addition of aqueous solutions from the prepared copolymers and their sodium salts to the cement improve most of the specific characteristics of (O.P.C). As the concentration of the water-soluble copolymer increases, the setting time increases. The combined water content enhances the addition of copolymer to the mixing water. The compressive strength was she increased at all any hydration. The results of the solution of the prepared sodium salt copolymers are better than its copolymers. (author)

The rapid detection of methyl tert-butyl ether (MtBE) in water using a prototype gas sensor system.

Science.gov (United States)

de Lacy Costello, B P J; Sivanand, P S; Ratcliffe, N M; Reynolds, D M

2005-01-01

The gasoline additive Methyl-tertiary-Butyl Ether (MtBE) is the second most common contaminant of groundwater in the USA and represents an important soil contaminant. This compound has been detected in the groundwater in at least 27 states as a result of leaking underground storage facilities (gasoline storage tanks and pipelines). Since the health effects of MtBE are unclear the potential threat to drinking water supplies is serious. Therefore, the ability to detect MtBE at low levels (ppb) and on-line at high-risk groundwater sites would be highly desirable. This paper reports the use of 'commercial' and metal oxide sensor arrays for the detection of MtBE in drinking and surface waters at low ppb level (microg.L(-1) range). The output responses from some of the sensors were found to correlate well with MtBE concentrations under laboratory conditions.

Tandem Carbocupration/Oxygenation of Terminal Alkynes

Science.gov (United States)

Zhang, Donghui; Ready, Joseph M.

2008-01-01

A direct and general synthesis of α-branched aldehydes and their enol derivatives is described. Carbocupration of terminal alkynes and subsequent oxygenation with lithium tert-butyl peroxide generates a metallo-enolate. Trapping with various electrophiles provides α-branched aldehydes or stereo-defined trisubstituted enol esters or silyl ethers. The tandem carbocupration/oxygenation tolerates alkyl and silyl ethers, esters and tertiary amines. The reaction is effective with organocopper complexes derived from primary, secondary and tertiary Grignard reagents and from n-butyllithium. PMID:16321021

Viscosities of binary mixtures of some n-ethoxyethanols with ethyl tert-butyl ether at T = (293.15, 298.15, and 303.15) K

International Nuclear Information System (INIS)

Cwiklinska, Aneta; Dzikowski, Tomasz; Szychowski, Dariusz; Kinart, Wojciech J.; Kinart, Cezary M.

2007-01-01

Viscosities at T = (293.15, 298.15, and 303.15) K in the binary mixtures of ethyl tert-butyl ether with 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, and 2-[2-(2-ethoxyethoxy)ethoxy]ethanol have been measured over the entire range of mixture compositions. From the experimental data, deviations in the viscosity (Δln η) and excess energies of activation for viscous flow (ΔG *E ) have been calculated. The viscosity data were correlated with equations of Hind et al., Grunberg and Nissan, Auslaender, and McAllister. The results for Δln η and ΔG *E are discussed in terms of intermolecular interactions and structure of studied binary mixtures

High-pressure phase behavior of propyl lactate and butyl lactate in supercritical carbon dioxide

International Nuclear Information System (INIS)

Cho, Dong Woo; Shin, Jungin; Shin, Moon Sam; Bae, Won; Kim, Hwayong

2012-01-01

Highlights: ► The phase behavior of propyl lactate and butyl lactate in scCO 2 was measured. ► Experimental data were correlated by the PR-EOS. ► The critical constants were estimated by the three group contribution methods. ► Acentric factor was estimated by the Lee–Kesler method. ► The Nannoolal–Rarey and Lee–Kesler method shows the best correlation results. - Abstract: Lactate esters synthesized with lactic acid and ester are used as solvents and reactants in various industries, including agricultural chemistry, pharmaceuticals, electronics, and fine chemicals. Among lactate esters, high purity propyl lactate and butyl lactate are used to produce fine chemicals and in the synthesis of chiral intermediates for use in pesticides and drugs. However, distillation for the removal of propyl lactate and butyl lactate alters or degenerates products due the high boiling points of these two lactate esters. This problem can be solved by supercritical fluid extraction (SCFE) at lower temperatures. SCFE process requires high-pressure phase behavior data on CO 2 and lactates for its design and operation. In this study, high-pressure phase behavior of propyl lactate and butyl lactate in CO 2 was measured from (323.2 to 363.2) K using a variable-volume view cell apparatus. Experimental data were well correlated by the Peng–Robinson equation of state using the van der Waals one-fluid mixing rules. The critical constants were estimated by the Joback method, the Constantinou–Gani method, and the Nannoolal–Rarey method. Acentric factor was estimated by the Lee–Kesler method.

Neutral Lipid Biosynthesis in Engineered Escherichia coli: Jojoba Oil-Like Wax Esters and Fatty Acid Butyl Esters

OpenAIRE

Kalscheuer, Rainer; Stöveken, Tim; Luftmann, Heinrich; Malkus, Ursula; Reichelt, Rudolf; Steinbüchel, Alexander

2006-01-01

Wax esters are esters of long-chain fatty acids and long-chain fatty alcohols which are of considerable commercial importance and are produced on a scale of 3 million tons per year. The oil from the jojoba plant (Simmondsia chinensis) is the main biological source of wax esters. Although it has a multitude of potential applications, the use of jojoba oil is restricted, due to its high price. In this study, we describe the establishment of heterologous wax ester biosynthesis in a recombinant E...

Assessment of genotoxicity of methyl-tert-butyl ether, benzene, toluene, ethylbenzene, and xylene to human lymphocytes using comet assay

International Nuclear Information System (INIS)

Chen, Colin S.; Hseu, You C.; Liang, Shih H.; Kuo, J.-Y.; Chen, Ssu. C.

2008-01-01

Methyl-tert-butyl ether (MTBE) is a gasoline oxygenate and antiknock additive substituting for lead alkyls currently in use worldwide. Benzene, toluene, ethylbenzene, and xylene (BTEX) are volatile monoaromatic hydrocarbons which are commonly found together in crude petroleum and petroleum products such as gasoline. The aim of this study is to evaluate the genotoxic effects of these tested chemicals in human lymphocytes. Using the alkaline comet assay, we showed that all of the tested chemicals induce DNA damage in isolated human lymphocytes. This effect could follow from the induction of DNA strands breaks. The neutral version of the test revealed that MTBE, benzene, and xylenes induce DNA double-strand breaks at 200 μM. Apart from MTBE, the spin traps, 5,5-dimethyl-pyrroline-N-oxide (DMPO) and N-tert-butyl-α-phenylnitrone (PBN) can decrease the level of DNA damage in BTEX at 200 μM. This indicated that DNA damage could result from the participation of free radicals in DNA-damaging effect, which was further supported by the fact that post-treatment of formamidopyrimidine-DNA glycosylase (Fpg), enzyme recognizing oxidized DNA purines, gave rise to a significant increase in the extent of DNA damage in cells treated with benzene, and xylene at 200 μM. The results obtained suggested that MTBE and BTEX could induce a variety type of DNA damage such as single-strand breaks (SSBs), double-strand breaks (DSBs), and oxidative base modification

Atomic Force Microscopy Based Thermal Lithography of Poly(tert-butyl acrylate) Block Copolymer Films for Bioconjugation

NARCIS (Netherlands)

Duvigneau, Joost; Schönherr, Holger; Vancso, Gyula J.

2008-01-01

In this paper, we report on the local thermal activation of thin polymer films for area-selective surface chemical modification on micrometer and nanometer length scales. The thermally induced activation of tert-butyl ester moieties in polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) block

Antioxidants Inhibit Formation of 3-Monochloropropane-1,2-diol Esters in Model Reactions.

Science.gov (United States)

Li, Chang; Jia, Hanbing; Shen, Mingyue; Wang, Yuting; Nie, Shaoping; Chen, Yi; Zhou, Yongqiang; Wang, Yuanxing; Xie, Mingyong

2015-11-11

The capacities of six antioxidants to inhibit the formation of 3-monochloropropane-1,2 diol (3-MCPD) esters were examined in this study. Inhibitory capacities of the antioxidants were investigated both in chemical models containing the precursors (tripalmitoyl glycerol, 1,2-dipalmitoyl-sn-glycerol, monopalmitoyl glycerol, and sodium chloride) of 3-MCPD esters and in oil models (rapeseed oil and sodium chloride). Six antioxidants, butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), tert-butyl hydroquinone (TBHQ), propyl gallate (PG), L-ascorbyl palmitate (AP), and α-tocopherol (VE), were found to exhibit inhibiting capacities on 3-MCPD ester formation both in chemical models and in oil models. TBHQ provided the highest inhibitory capacity both in chemical models and in oil models; 44% of 3-MCPD ester formation was inhibited in the presence of TBHQ (66 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min, followed by PG and AP. BHT, BHA, and VE appeared to have weaker inhibitory abilities in both models. VE exhibited the lowest inhibition rate; 22% of 3-MCPD esters were inhibited in the presence of VE (172 mg/kg of oil) after heating of rapeseed oil at 230 °C for 30 min. In addition, the inhibition rates of PG and VE decreased dramatically with an increase in temperature or heating time. The results suggested that some antioxidants, such as TBHQ, PG, and AP, could be the potential inhibitors of 3-MCPD esters in practice.

Mutagenic activity of phthalate esters in bacterial liquid suspension assays.

OpenAIRE

Seed, J L

1982-01-01

The mutagenic activities of several phthalate esters have been evaluated in an 8-azaguanine resistance assay in Salmonella typhimurium. Three phthalate esters were found to be mutagenic: dimethyl phthalate, diethyl phthalate and di-n-butyl phthalate. A number of other phthalate esters were not found to be mutagenic, including di(2-ethylhexyl) phthalate, di-n-octyl phthalate, diallyl phthalate, diisobutyl phthalate and diisodecyl phthalate. A metabolite of di(2-ethylhexyl) phthalate, 2-ethylhe...

Effect of benzene and ethylbenzene on the transcription of methyl-tert-butyl ether degradation genes of Methylibium petroleiphilum PM1.

Science.gov (United States)

Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

2016-09-01

Methyl-tert-butyl ether (MTBE) and its degradation by-product, tert-butyl alcohol (TBA), are widespread contaminants detected frequently in groundwater in California. Since MTBE was used as a fuel oxygenate for almost two decades, leaking underground fuel storage tanks are an important source of contamination. Gasoline components such as BTEX (benzene, toluene, ethylbenzene and xylenes) are often present in mixtures with MTBE and TBA. Investigations of interactions between BTEX and MTBE degradation have not yielded consistent trends, and the molecular mechanisms of BTEX compounds' impact on MTBE degradation are not well understood. We investigated trends in transcription of biodegradation genes in the MTBE-degrading bacterium, Methylibium petroleiphilum PM1 upon exposure to MTBE, TBA, ethylbenzene and benzene as individual compounds or in mixtures. We designed real-time quantitative PCR assays to target functional genes of strain PM1 and provide evidence for induction of genes mdpA (MTBE monooxygenase), mdpJ (TBA hydroxylase) and bmoA (benzene monooxygenase) in response to MTBE, TBA and benzene, respectively. Delayed induction of mdpA and mdpJ transcription occurred with mixtures of benzene and MTBE or TBA, respectively. bmoA transcription was similar in the presence of MTBE or TBA with benzene as in their absence. Our results also indicate that ethylbenzene, previously proposed as an inhibitor of MTBE degradation in some bacteria, inhibits transcription of mdpA, mdpJ and bmoAgenes in strain PM1.

Temperature effect on tert-butyl alcohol (TBA) biodegradation kinetics in hyporheic zone soils.

Science.gov (United States)

Greenwood, Mark H; Sims, Ronald C; McLean, Joan E; Doucette, William J

2007-09-19

Remediation of tert-butyl alcohol (TBA) in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-butyl formate (TBF). The effect of temperature on TBA biodegradation has not been not been published in the literature. Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. First order mineralization rate constants of TBA at 5 degrees C, 15 degrees C and 25 degrees C were 7.84 +/- 0.14 x 10-3, 9.07 +/- 0.09 x 10-3, and 15.3 +/- 0.3 x 10-3 days-1, respectively (or 2.86 +/- 0.05, 3.31 +/- 0.03, 5.60 +/- 0.14 years-1, respectively). Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A) and activation energy (Ea) of 154 day-1 and 23,006 mol/J, respectively. Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature.

Synthesis of Poly(vinyl ether) Thermoplastic Elastomers Having Functional Soft Segments

OpenAIRE

今枝, 嗣人; 漆崎, 美智遠; 阪口, 壽一; 橋本, 保; Tsuguto, IMAEDA; Michio, URUSHISAKI; Toshikazu, SAKAGUCHI; Tamotsu, HASHIMOTO

2013-01-01

The ABA-type triblock copolymers consisting of poly(2-adarnantyl vinyl ether) [poly(2-AdVE) as outer hard segments and poly(6-acetoxyhexyl vinyl ether) [poly(AcHVE)] poly(6-hydroxyhexyl vinyl ether) [poly(H HVE)], or poly(2-(2-methoxyethoxy)ethyl vinyl ether [poly(MOEOVE)] as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxy, and oxyethylene units in their soft segments, the two polymer seg...

Effects of diethylene glycol butyl ether and butoxyethoxyacetic acid on rat and human erythrocytes.

Science.gov (United States)

Udden, M M

2005-03-28

The toxicity of diethylene glycol butyl ether (DGBE), and its principal metabolite, butoxyethoxyacetic acid (BEAA), were assessed in vitro for rat and human red blood cells. Rat erythrocytes showed evidence of mild hemolysis when exposed to BEAA at concentrations of 5 or 10 mM for 4 h. BEAA treated rat red blood cells also showed evidence of sub-hemolytic damage: increased spherocytosis, a shift in distribution of cell size to larger cells, a significant increase in mean cellular volume, and a decrease in cellular deformability. However, DGBE had no effect on rat red blood cell morphology, cell size, hemolysis or deformability. There was no hemolysis when human red blood cells were exposed to DGBE or BEAA at the same concentrations. No changes in mean cellular volume, distribution of cell size, or morphologic appearance of human red blood cells were observed. No evidence for decreased deformability of human red blood cells exposed to DGBE or BEAA was found. In conclusion, BEAA has weak hemolytic activity and sub-hemolytic effects in vitro on rat erythrocytes, which is consistent with the finding of mild hemolysis when the parent compound DGBE is administered to rats by gavage. The absence of hemolysis or sub-hemolytic damage when human red blood cells were exposed to BEAA or DGBE in vitro indicates that it is unlikely that hemolysis will occur as a result of human exposure to DGBE.

Williamson alkylation approach to the synthesis of poly(alkyl vinyl ether) copolymers

International Nuclear Information System (INIS)

Markova, D.; Christova, D.; Velichkova, R.

2008-01-01

A method for synthesis of poly(alkyl vinyl ether-co-vinyl alcohol) copolymers was developed based on the Williamson's alkylation of poly(vinyl acetate) (PVAc) with alkyl iodides. The influence of the alkylating agent and the reaction conditions on the efficiency of the modification reaction was investigated. The copolymers obtained were characterized by means of 1 H NMR and GPC. It was proved that by applying the proposed method copolymers of different composition and properties containing methyl vinyl ether, ethyl vinyl ether as well as n-butyl vinyl ether units could be prepared. Poly(methyl vinyl ether-co-vinyl alcohol)s of high degree of methylation exhibit sharp temperature response at 38-39 deg C in aqueous solution typical of the so-called smart polymers. (authors)

Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions

Science.gov (United States)

Landmeyer, J.E.; Chapelle, F.H.; Herlong, H.H.; Bradley, P.M.

2001-01-01

Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert-butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were > 1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/L to a depth of 1.5 m, and MTBE concentrations decreased to CO2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.

Risk characterization of methyl tertiary butyl ether (MTBE) in tap water.

Science.gov (United States)

Stern, B R; Tardiff, R G

1997-12-01

Methyl tertiary butyl ether (MTBE) can enter surface water and groundwater through wet atmospheric deposition or as a result of fuel leaks and spills. About 30% of the U.S. population lives in areas where MTBE is in regular use. Ninety-five percent of this population is unlikely to be exposed to MTBE in tap water at concentrations exceeding 2 ppb, and most will be exposed to concentrations that are much lower and may be zero. About 5% of this population may be exposed to higher levels of MTBE in tap water, resulting from fuel tank leaks and spills into surface or groundwater used for potable water supplies. This paper describes the concentration ranges found and anticipated in surface and groundwater, and estimates the distribution of doses experienced by humans using water containing MTBE to drink, prepare food, and shower/bathe. The toxic properties (including potency) of MTBE when ingested, inhaled, and in contact with the skin are summarized. Using a range of human toxic potency values derived from animal studies, margins of exposure (MOE) associated with alternative chronic exposure scenarios are estimated to range from 1700 to 140,000. Maximum concentrations of MTBE in tap water anticipated not to cause adverse health effects are determined to range from 700 to 14,000 ppb. The results of this analysis demonstrate that no health risks are likely to be associated with chronic and subchronic human exposures to MTBE in tap water. Although some individuals may be exposed to very high concentrations of MTBE in tap water immediately following a localized spill, these exposures are likely to be brief in duration due to large-scale dilution and rapid volatilization of MTBE, the institution of emergency response and remediation measures to minimize human exposures, and the low taste and odor thresholds of MTBE which ensure that its presence in tap water is readily detected at concentrations well below the threshold for human injury.

Effect of benzene, toluene, ethylbenzene, and p-xylene (BTEX) mixture on biodegradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) by pure culture UC1.

Science.gov (United States)

Pruden, Amy; Suidan, Makram

2004-08-01

The effect of a BTEX mixture on the biodegradation of methyl tert-butyl ether (MTBE) and its degradation intermediate, tert-butyl alcohol (TBA) was investigated in the pure bacterial culture UC1, which has been identified to be a strain of the known MTBE-degrader PM1 based on greater than 99% 16S rDNA similarity. Several degradation studies were carried out on UC1 at three initial concentration levels of MTBE or TBA: 6-7; 15-17; and 40-45 mg/l, both with and without BTEX present cumulatively at about half of the MTBE or TBA molar mass in the system. The BTEX mixture was observed not to affect either the rate or the degradation lag period of MTBE or TBA degradation, except that the TBA degradation rate actually increased when BTEX was present initially in the highest concentration studies. When serving as the sole substrate, the MTBE degradation rate ranged from 48 +/- 1.2 to 200 +/- 7.0 mg(MTBE)/g(dw) h, and the TBA degradation rate from 140 +/- 18 to 530 +/- 70 mg(TBA)/g(dw) h. When present with BTEX, MTBE and TBA rates ranged from 46 +/- 2.2 to 210 +/- 14 and 170 +/- 28 to 780 +/- 43 mg(TBA)/g(dw) h, respectively. In studies where varying concentrations of TBA were present with 5 mg/l MTBE, both compounds were degraded simultaneously with no obvious preference for either substrate. In the highest concentration study of TBA with 5 mg/l MTBE, BTEX was also observed to increase the ultimate rate of TBA degradation. In addition to exploring the affect of BTEX, this study also provides general insight into the metabolism of MTBE and TBA by pure culture UC1.

Temperature effect on tert-butyl alcohol (TBA biodegradation kinetics in hyporheic zone soils

Directory of Open Access Journals (Sweden)

Sims Ronald C

2007-09-01

Full Text Available Abstract Background Remediation of tert-butyl alcohol (TBA in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE, ethyl tert-butyl ether (ETBE, and tert-butyl formate (TBF. The effect of temperature on TBA biodegradation has not been not been published in the literature. Methods Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. Results First order mineralization rate constants of TBA at 5°C, 15°C and 25°C were 7.84 ± 0.14 × 10-3, 9.07 ± 0.09 × 10-3, and 15.3 ± 0.3 × 10-3 days-1, respectively (or 2.86 ± 0.05, 3.31 ± 0.03, 5.60 ± 0.14 years-1, respectively. Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A and activation energy (Ea of 154 day-1 and 23,006 mol/J, respectively. Conclusion Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature.

Synthesis of Novel Bibrachial Lariat Ethers (BiBLEs) Containing [1,2 ...

African Journals Online (AJOL)

NICO

A practical and regioselective method for the synthesis of cis-diastereomers of bibrachial lariat ethers (BiBLEs) bearing ester and amide groups is reported. The novel bibrachial lariat ethers (BiBLEs) 3a–d with neutral side chains were prepared by reaction of the corresponding aza-crown macrocycles 1a–b with ethyl ...

[Biodegradation of methyl tert-butyl ether by stabilized immobilized Methylibium petroleiphilum PM1 cells and its biodegradation kinetics analysis].

Science.gov (United States)

Cheng, Zhuo-wei; Fu, Ling-xiao; Jiang, Yi-feng; Chen, Jian-meng; Zhang, Rong

2011-05-01

Methylibium petroleiphilum PM1, which is capable of degrading methyl tert-butyl ether (MTBE) , was immobilized in calcium alginate gel beads. Several methods were explored to increase the strength of these gel beads. The central composite design analysis indicated that the introduction of 0.2 mol x L(-1) Ca2+ into the crosslinking solution, 1.38 mmol x L(-1) Ca2+ into the growth medium and 0.1% polyethyleneimine (PEI) as the chemical crosslinking agent could increase the stability of the Ca-alginate gel beads with no loss of biodegradation activity. The stabilized immobilized cells could be used 400 h continuously with no breakage and no bioactivity loss. Examination of scanning electron microscope demonstrated that a membrane surrounding the gel beads was formed and the cells could grow and breed well in the stabilized calcium alginate gel beads. Kinetic analysis of the gel bead-degradation indicated that the rate-limiting step was biochemical process instead of intraparticle diffusion process. The diameter of 3 mm affected the biodegradability less while high concentration of PEI induced much more serious mass transfer restraint.

Critical properties of some aliphatic symmetrical ethers

International Nuclear Information System (INIS)

Nikitin, Eugene D.; Popov, Alexander P.; Bogatishcheva, Nataliya S.

2014-01-01

Highlights: • Critical properties of simple aliphatic ethers were measured. • The ethers decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. -- Abstract: The critical temperatures T c and the critical pressures p c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T c = (665 ± 7) K, p c = (1.44 ± 0.04) MPa for dihexyl ether, T c = (723 ± 7) K, p c = (1.19 ± 0.04) MPa for dioctyl ether, and T c = (768 ± 8) K, p c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson

Percutaneous Dissolution of Gallstones using Methyl Tert-Butyl Ether

OpenAIRE

1990-01-01

Radiolucent cholesterol gallstones can be dissolved rapidly by methyl terc-buryl ether (MTBE) introduced directly into the gallbladder. Percutaneous transhepatic catheter placement is a well established interventional radiology procedure and is the preferred route for MTBE administration. A small number of patients have been treated using nasobiliary placement of a gallbladder catheter. Rapid stirring automatic pump systems allow dissolution of most cholesterol stones, but s...

Application of Computational Methods Mm2 and Gussian for Studing Unimolecular Decomposition of Vinil Ethers based on the Mechanism of Hydrogen Bonding

OpenAIRE

Behnaz Shahrokh; Garnik N. Sargsyan; Arkadi B. Harutyunyan

2012-01-01

Investigations of the unimolecular decomposition of vinyl ethyl ether (VEE), vinyl propyl ether (VPE) and vinyl butyl ether (VBE) have shown that activation of the molecule of a ether results in formation of a cyclic construction - the transition state (TS), which may lead to the displacement of the thermodynamic equilibrium towards the reaction products. The TS is obtained by applying energy minimization relative to the ground state of an ether under the program MM2 when...

Lack of micronucleus induction activity of ethyl tertiary-butyl ether in the bone marrow of F344 rats by sub-chronic drinking-water treatment, inhalation exposure, or acute intraperitoneal injection.

Science.gov (United States)

Noguchi, Tadashi; Kamigaito, Tomoyuki; Katagiri, Taku; Kondou, Hitomi; Yamazaki, Kazunori; Aiso, Shigetoshi; Nishizawa, Tomoshi; Nagano, Kasuke; Fukushima, Shoji

2013-01-01

Ethyl tertiary-butyl ether (ETBE) is an oxygenated gasoline additive synthesized from ethanol and isobutene that is used to reduce CO2 emissions. To support the Kyoto Protocol, the production of ETBE has undergone a marked increase. Previous reports have indicated that exposure to ETBE or methyl tertiary-butyl ether resulted in liver and kidney tumors in rats and/or mice. These reports raise concern about the effects of human exposure being brought about by the increased use of ETBE. The present study was conducted to evaluate the genotoxicity of ETBE using micronucleus induction of polychromatic erythrocytes in the bone marrow of male and female rats treated with ETBE in the drinking-water at concentrations of 0, 1,600, 4,000 or 10,000 ppm or exposed to ETBE vapor at 0, 500, 1,500 or 5,000 ppm for 13 weeks. There were no significant increases in micronucleus induction in either the drinking water-administered or inhalation-administered groups at any concentration of ETBE; although, in both groups red blood cells and hemoglobin concentration were slightly reduced in the peripheral blood in rats administered the highest concentration of ETBE. In addition, two consecutive daily intraperitoneal injections of ETBE at doses of 0, 250, 500 or 1,000 mg/kg did not increase the frequency of micronucleated bone marrow cells in either sex; all rats receiving intraperitoneal injections of ETBE at a dose of 2,000 mg/kg died after treatment day 1. These data suggest that ETBE is not genotoxic in vivo.

Enhancement of the Biodegradability of Methyl tert- Butyl Ether (MTBE by Advanced Oxidation

Directory of Open Access Journals (Sweden)

Mehraban Sadeghi

2006-06-01

Full Text Available The effectiveness of ozone treatment for improving the biodegradability of recalcitrant pollutants has been proved by investigating the ozonation reaction of Methyl tert-Butyl Ether (MTBE as a bioresistant gasoline oxygenate. Laboratory scale experiments have been carried out at room temperature by bubbling for 120 minutes ozonated air (3.4 ppm/min into 3 liter of an alkaline (pH=11.5 aqueous solution (100 mg/L of MTBE. The experimental results indicated that during the ozonation, complete MTBE degradation occurs in 100 minutes and after this time, ozone consumption goes on very slowly. At the end of the ozonation, after 100 minutes, the initial value of COD (256 mg O2/L is 98 and corresponds to a relative removal of about 62%. As for MTBE solution biodegradability expressed as (BOD5 / (COD ratio, during the first 90 minutes, its value regularly increases from lowest 0.01 up to a maximum of 0.68 that corresponds to an ozone consumption of 1.25 mg per each mg of COD initially present in the solution. The research showed that partial degradation of MTBE in the advanced oxidation processes results an increase in its biological degradation. But more oxidation results lower  (BOD5 / (COD ratio. Also the research showed that for idealization of the chemical oxidation conditions of MTBE, it needs to decrease COD to 46-68% before the biological degradation. The experimental results for determining the rate of MTBE removal due to stripping showed that about 14% of MTBE strips out after an hour of sparging with oxygen gas. The fraction of MTBE oxidized and/or striped increases to about 28% (in pH=7 and 70% (in pH=11.5 with ozonation over the same time period.

MONITORED NATURAL ATTENUATION OF TERTIARY BUTYL ALCOHOL (TBA) IN GROUND WATER AT GASOLINE SPILL SITES

Science.gov (United States)

The state agencies that implement the Underground Storage Tank program rely heavily on Monitored Natural Attenuation (MNA) to clean up contaminants such as benzene and methyl tertiary butyl ether (MTBE) at gasoline spill sites. This is possible because the contaminants are biolo...

Gasoline ether oxygenate occurrence in Europe, and a review of their fate and transport characteristics in the environment

Energy Technology Data Exchange (ETDEWEB)

Stupp, D.; Gass, M.; Leiteritz, H. [Dr. Stupp Consulting DSC, Tauw, Bergisch Gladbach (Germany); Pijls, C. [TAUW, Apeldoorn (Netherlands); Thornton, S. [University of Sheffield, Sheffield (United Kingdom); Smith, J.; Dunk, M.; Grosjean, T.; Den Haan, K. [CONCAWE, Brussels (Belgium)

2012-06-15

Ether oxygenates are added to certain gasoline (petrol) formulations to improve combustion efficiency and to increase the octane rating. In this report the term gasoline ether oxygenates (GEO) refers collectively to methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), diisopropyl ether (DIPE), tertiary amyl ethyl ether (TAEE), tertiary hexyl methyl ether (THxME), and tertiary hexyl ethyl ether (THxEE), as well as the associated tertiary butyl alcohol (TBA). This report presents newly collated data on the production capacities and use of MTBE, ETBE, TAME, DIPE and TBA in 30 countries (27 EU countries and Croatia, Norway and Switzerland) to inform continued and effective environmental management practices for GEO by CONCAWE members. The report comprises data on gasoline use in Europe that were provided by CONCAWE and obtained from the European Commission. Furthermore Societe Generale de Surveillance (SGS) provided detailed analytical data (more than 1,200 sampling campaigns) on the GEO composition of gasoline in European countries in the period 2000-2010. Another major aspect of this report is the investigation of GEO distribution in groundwater, drinking water, surface water, runoff water, precipitation (rain/snow) and air in the European environment. Apart from the general sources of literature for the study, local environmental authorities and institutes in the 30 European countries have been contacted for additional information. Finally, a review of the international literature on GEO natural attenuation processes was undertaken with a focus on international reports and peer-reviewed scientific publications to give an overview on the known fate, transport and degradation mechanisms of GEO in the subsurface, to inform risk-management strategies that may rely on natural attenuation processes. The literature reveals that all GEO compounds used in fuels are highly water soluble and weakly retarded by aquifer

An improved synthesis process of calixcrown ethers and synthesis of novel calixcrown ether

International Nuclear Information System (INIS)

Wang Hairong; Zhang Ping; Wang Chunmiao; Wang Jianchen; Chen Jing

2007-01-01

The synthesis method of calixcrown ethers was simplified and improved, and 10 L- scale synthesis was carried out. In the synthesis of the intermediates of the first three steps, the synthesis of 5, 11, 17, 23-tetra-tert-butyl-25, 26, 27, 28-tetrahydroxyl-calix[4] and its dehydroxylation were considered together, the purification procedures of the former, including re-crystallization in toluene and decolorization with activated carbon, were cancelled, and thus these steps were simplified. In the synthesis of oligoethylene glycol ditosylate, the purification method was also improved and the time-consuming column chromatography was left out. In the final step, impurities were removed by repeating stirring-settlement steps, by following recrystallization, the pure product was obtained. With these measures, the whole process could be implemented easily. The industrial scale production of calixcrown ethers could be fulfilled with the improved process. In addition, a new extracant, 25, 27-bis (n-propyloxy)calix[4]-26, 28-crown-6, is prepared and identified. (authors)

Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters

DEFF Research Database (Denmark)

Nguyen, Ngoc-Lan Thi; Vo, Hong-Thom; Duus, Fritz

2017-01-01

The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylim......The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3...

Development of natural rubber membranes for separation of methyl tert-butyl ether and methanol

International Nuclear Information System (INIS)

Nur Azrini Ramlee; Ghazali Mohd Nawawi; Khairul Zaman Dahlan

2010-01-01

As a new commercial process, membrane separation raises significant expectations in the process plant of the future and therefore this research was being initiated to develop and characterize pervaporation membrane based on natural rubber (NR). Natural Rubber SMR-L grade which was supplied by Malaysia Rubber Research Institute (MRRI) was used for the development of the membranes via interpenetrating polymer network (IPN) techniques. Polystyrene (PS) was used to modify the natural rubber to further improve their mechanical and chemical properties. The membranes were prepared with various blend ratios of natural rubber, polystyrene and divinyl benzene as cross linker with constant 1 % of dicumyl peroxide as the initiator. The developed membranes were then characterized to study the functional group presence, membranes morphology, crosslink density, tear strength, adsorption of the membranes and pervaporation separation of Methyl-Tert-Butyl-Ether (MTBE) and Methanol. Pervaporation process was conducted by using varies of MTBE concentration 10, 30, 50 and 70 wt % and at differ operation temperature, 25 degree Celsius and 55 degree Celsius. Separation performance of IPN NR/ PS membranes were based on the presented permeation flux and separation factor. Examination through Fourier Transform Infrared Spectroscopy (FTIR), determined crosslink density and tear strength, 6 series of IPN NR/ PS membranes were successfully developed using natural rubber. Observation from Scanning Electron Microscopy (SEM) showed that the membranes were dense and appropriated for the pervaporation process application. From the pervaporation of MTBE and Methanol, IPN NR/ PS membranes of series D4N30 shown low permeation flux of MTBE but high separation factor while D2N70 membranes was vice versa for both temperature of 25 degree Celsius and 55 degree Celsius. (author)

Oxidative DNA damage in male wistar rats exposed to di-n-butyl phthalate

DEFF Research Database (Denmark)

Wellejus, A.; Dalgaard, Majken; Loft, S.

2002-01-01

Dialkyl phthalate esters are used in the plastic industry and widely distributed in the environment, Previously, it has been shown that di-n-butyl phthalate (DBP) produces testicular atrophy and liver enlargement in rodents, and the mechanisms behind this could involve reactive oxygen species (ROS...

Method detection limit determination and application of a convenient headspace analysis method for methyl tert-butyl ether in water.

Science.gov (United States)

O'Neill, Dennis T; Rochette, Elizabeth A; Ramsey, Philip J

2002-11-15

Methyl tert-butyl ether (MTBE) is a common groundwater contaminant, introduced to the environment by leaking petroleum storage tanks, urban runoff, and motorized watercraft. In this study. a simplified (static) headspace analysis method was adapted for determination of MTBE in water samples and soil water extracts. The MDL of the headspace method was calculated to be 2.0 microg L(-1) by the EPA single-concentration design method(1) and 1.2 microg L(-1) by a calibration method developed by Hubaux and Vos (Hubaux, A.; Vos, G. Anal. Chem. 1970,42, 849-855). The MDL calculated with the Hubaux and Vos method was favored because it considers both a true positive and a false positive. The static headspace method was applied to analysis of a tap water sample and a monitoring well sample from a gasoline service station, a river sample, and aqueous extracts from soil excavated during removal of a leaking underground storage tank (LUST). The water samples examined in this study had MTTBE concentrations ranging from 6 to 19 microg L(-1). Aqueous extracts of a soil sample taken from the LUST site had 8 microg L(-1) MTBE.

Assessing soil ecotoxicity of methyl tert-butyl ether using earthworm bioassay; closed soil microcosm test for volatile organic compounds

International Nuclear Information System (INIS)

An, Youn-Joo

2005-01-01

An earthworm bioassay was conducted to assess ecotoxicity in methyl tert-butyl ether (MTBE)-amended soils. Ecotoxicity of MTBE to earthworms was evaluated by a paper contact method, natural field soil test, and an OECD artificial soil test. All tests were conducted in closed systems to prevent volatilization of MTBE out of test units. Test earthworm species were Perionyx excavatus and Eisenia andrei. Mortality and abnormal morphology of earthworms exposed to different concentrations of MTBE were examined. MTBE was toxic to both earthworm species and the severity of response increased with increasing MTBE concentrations. Perionyx excavatus was more sensitive to MTBE than Eisenia andrei in filter papers and two different types of soils. MTBE toxicity was more severe in OECD artificial soils than in field soils, possibly due to the burrowing behavior of earthworms into artificial soils. The present study demonstrated that ecotoxicity of volatile organic compounds such as MTBE can be assessed using an earthworm bioassay in closed soil microcosm with short-term exposure duration. - Earthworm bioassay can be a good protocol to assess soil ecotoxicity of volatile organic compounds such as MTBE

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

Science.gov (United States)

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.

IRIS Toxicological Review of Ethylene Glycol Mono-Butyl ...

Science.gov (United States)

EPA released the draft report, Toxicological Review for Ethylene Glycol Mono-Butyl Ether , that was distributed to Federal agencies and White House Offices for comment during the Science Discussion step of the IRIS Assessment Development Process. Comments received from other Federal agencies and White House Offices are provided below with external peer review panel comments. EPA is conducting a peer review of the scientific basis supporting the human health hazard and dose-response assessment of EGBE that will appear on the Integrated Risk Information System (IRIS) database.

Final report of the safety assessment of methacrylate ester monomers used in nail enhancement products.

Science.gov (United States)

2005-01-01

Methacrylate ester monomers are used in as artificial nail builders in nail enhancement products. They undergo rapid polymerization to form a hard material on the nail that is then shaped. While Ethyl Methacrylate is the primary monomer used in nail enhancement products, other methacrylate esters are also used. This safety assessment addresses 22 other methacrylate esters reported by industry to be present in small percentages as artificial nail builders in cosmetic products. They function to speed up polymerization and/or form cross-links. Only Tetrahydrofurfuryl Methacrylate was reported to the FDA to be in current use. The polymerization rates of these methacrylate esters are within the same range as Ethyl Methacrylate. While data are not available on all of these methacrylate esters, the available data demonstrated little acute oral, dermal, or i.p. toxicity. In a 28-day inhalation study on rats, Butyl Methacrylate caused upper airway irritation; the NOAEL was 1801 mg/m3. In a 28-day oral toxicity study on rats, t-Butyl Methacrylate had a NOAEL of 20 mg/kg/day. Beagle dogs dosed with 0.2 to 2.0 g/kg/day of C12 to C18 methacrylate monomers for 13 weeks exhibited effects only in the highest dose group: weight loss, emesis, diarrhea, mucoid feces, or salivation were observed. Butyl Methacrylate (0.1 M) and Isobutyl Methacrylate (0.1 M) are mildly irritating to the rabbit eye. HEMA is corrosive when instilled in the rabbit eye, while PEG-4 Dimethacrylate and Trimethylolpropane Trimethacrylate are minimally irritating to the eye. Dermal irritation caused by methacrylates is documented in guinea pigs and rabbits. In guinea pigs, HEMA, Isopropylidenediphenyl Bisglycidyl Methacrylate, Lauryl Methacrylate, and Trimethylolpropane Trimethacrylate are strong sensitizers; Butyl Methacrylate, Cyclohexyl Methacrylate, Hexyl Methacrylate, and Urethane Methacrylate are moderate sensitizers; Hydroxypropyl Methacrylate is a weak sensitizer; and PEG-4 Dimethacrylate and

Long term studies on the anaerobic biodegradability of MTBE and other gasoline ethers

DEFF Research Database (Denmark)

Waul, Christopher Kevin; Arvin, Erik; Schmidt, Jens Ejbye

2009-01-01

to investigate the anaerobic biodegradability of MTBE and other gasoline ethers. Inoculums collected from various environments were used, along with different electron acceptors. Only one set of the batch experiments showed a 30-60% conversion of MTBE to tert-butyl alcohol under Fe(III)-reducing conditions...

Effect of Polyhedral Oligomeric Silsesquioxane (POSS) Substituents on the Rheological Behavior in Butyl Methacrylate/POSS Copolymers

Science.gov (United States)

2008-10-27

was repeated twice, dissolving the product in chloroform and diethyl ether, respectively. The polymer was dried at 60 °C under vacuum overnight...the Tg of the i Bu remains the same. Table 1. Tg for Butyl Methacrylate-co- Propyl Methacryl POSS Polymers with Various POSS Substituents

Polypyrrole-Grafted Coconut Shell Biological Carbon as a Potential Adsorbent for Methyl Tert-Butyl Ether Removal: Characterization and Adsorption Capability

Directory of Open Access Journals (Sweden)

Shanshan Li

2017-01-01

Full Text Available Methyl tert-butyl ether (MTBE has been used as a common gasoline additive worldwide since the late twentieth century, and it has become the most frequently detected groundwater pollutant in many countries. This study aimed to synthesize a novel microbial carrier to improve its adsorptive capacity for MTBE and biofilm formation, compared to the traditional granular activated carbon (GAC. A polypyrrole (PPy-modified GAC composite (PPy/GAC was synthesized, and characterized by Fourier transform infrared spectroscopy (FT-IR and Brunauer-Emmett-Teller (BET surface area analysis. The adsorption behaviors of MTBE were well described by the pseudo-second-order and Langmuir isotherm models. Furthermore, three biofilm reactors were established with PPy/GAC, PPy, and GAC as the carriers, respectively, and the degradation of MTBE under continuous flow was investigated. Compared to the biofilm reactors with PPy or GAC (which both broke after a period of operation, the PPy/GAC biofilm column produced stable effluents under variable treatment conditions with a long-term effluent MTBE concentration <20 μg/L. Pseudomonas aeruginosa and Acinetobacter pittii may be the predominant bacteria responsible for MTBE degradation in these biofilm reactors.

Inhibition of IgE-induced mast cell activation by ethyl tertiary-butyl ether, a bioethanol-derived fuel oxygenate.

Science.gov (United States)

Yamaki, Kouya; Yoshino, Shin

2009-09-01

The effect of ethyl tertiary-butyl ether (ETBE), which is widely used as a fuel oxygenate commonly produced from bioethanol, on immunoglobulin (Ig)E-dependent mast cell activation was investigated. The rat mast cell line RBL2H3 sensitised with monoclonal anti-ovalbumin IgE was challenged with ovalbumin in the presence or absence of ETBE, tert-butanol (TBA), which is the main metabolite of ETBE in humans, and ethanol. Degranulation of RBL2H3 was examined by the release of beta-hexosaminidase. To understand the mechanisms responsible for regulating mast cell function, the effects of ETBE, TBA and ethanol on the levels of intracellular calcium, phosphorylation of Akt (as a marker of phosphatidylinositol 3-kinase) and global tyrosine phosphorylation were also measured as indicators of mast cell activation. In the presence of ETBE, TBA or ethanol, IgE-induced release of beta-hexosaminidase was decreased. These compounds also attenuated the IgE-mediated increase in the levels of intracellular Ca(2+), phosphorylation of Akt and global tyrosine phosphorylation in RBL2H3 cells. ETBE, TBA and ethanol inhibited mast cell degranulation by inhibiting the increase in intracellular calcium ion concentration and activation of phosphatidylinositol 3-kinase and protein tyrosine kinase activation, suggesting that exposure to ETBE might affect immune responses, particularly in allergic diseases.

Health Risk Assessment for Inhalation Exposure to Methyl Tertiary Butyl Ether at Petrol Stations in Southern China.

Science.gov (United States)

Hu, Dalin; Yang, Jianping; Liu, Yungang; Zhang, Wenjuan; Peng, Xiaowu; Wei, Qinzhi; Yuan, Jianhui; Zhu, Zhiliang

2016-02-06

Methyl tertiary butyl ether (MTBE), a well known gasoline additive, is used in China nationwide to enhance the octane number of gasoline and reduce harmful exhaust emissions, yet little is known regarding the potential health risk associated with occupational exposure to MTBE in petrol stations. In this study, 97 petrol station attendants (PSAs) in southern China were recruited for an assessment of the health risk associated with inhalation exposure to MTBE. The personal exposure levels of MTBE were analyzed by Head Space Solid Phase Microextraction GC/MS, and the demographic characteristics of the PSAs were investigated. Cancer and non-cancer risks were calculated with the methods recommended by the United States Environmental Protection Agency. The results showed that the exposure levels of MTBE in operating workers were much higher than among support staff (p < 0.01) and both were lower than 50 ppm (an occupational threshold limit value). The calculated cancer risks (CRs) at the investigated petrol stations was 0.170 to 0.240 per 10⁶ for operating workers, and 0.026 to 0.049 per 10⁶ for support staff, which are below the typical target range for risk management of 1 × 10(-6) to 1 × 10(-4); The hazard quotients (HQs) for all subjects were <1. In conclusion, our study indicates that the MTBE exposure of PSAs in southern China is in a low range which does not seem to be a significant health risk.

Health Risk Assessment for Inhalation Exposure to Methyl Tertiary Butyl Ether at Petrol Stations in Southern China

Directory of Open Access Journals (Sweden)

Dalin Hu

2016-02-01

Full Text Available Methyl tertiary butyl ether (MTBE, a well known gasoline additive, is used in China nationwide to enhance the octane number of gasoline and reduce harmful exhaust emissions, yet  little is known regarding the potential health risk associated with occupational exposure to MTBE in petrol stations. In this study, 97 petrol station attendants (PSAs in southern China were recruited for an assessment of the health risk associated with inhalation exposure to MTBE. The personal exposure levels of MTBE were analyzed by Head Space Solid Phase Microextraction GC/MS, and the demographic characteristics of the PSAs were investigated. Cancer and non-cancer risks were calculated with the methods recommended by the United States Environmental Protection Agency. The results showed that the exposure levels of MTBE in operating workers were much higher than among support staff (p < 0.01 and both were lower than 50 ppm (an occupational threshold limit value. The calculated cancer risks (CRs at the investigated petrol stations was 0.170 to 0.240 per 106 for operating workers, and 0.026 to 0.049 per 106 for support staff, which are below the typical target range for risk management of 1 × 10−6 to 1 × 10−4; The hazard quotients (HQs for all subjects were <1. In conclusion, our study indicates that the MTBE exposure of PSAs in southern China is in a low range which does not seem to be a significant health risk.

Reactions of phenols and alcohols over thoria: mechanism of ether formation

International Nuclear Information System (INIS)

Karuppannasamy, S.; Narayanan, K.; Pillai, C.N.

1980-01-01

The dehydration of phenols and alkylation of phenols by alcohols over thoria were studied at 400 to 500 0 C and atmospheric pressure. Phenol and cresols, when dehydrated gave diaryl ethers as main products. With para-substituted phenols such as p-methoxy, p-t-butyl, p-chloro, and p-nitrophenol no ether formation was noticed. All the reactions were accompanied by considerable amount of coke formation. Alkylation of phenols by alcohols gave a mixture of O- and C-alkylated products under the same reaction conditions. O-alkylation and C-alkylation are parallel reactions. The mechanistic aspects of the reactions are discussed. 3 figures, 3 tables

Transdermal uptake of diethyl phthalate and di(n-butyl) phthalate directly from air: Experimental verification

DEFF Research Database (Denmark)

Weschler, Charles J.; Bekö, Gabriel; Koch, Holger M.

2015-01-01

of phthalate esters. Objectives: This study investigated transdermal uptake, directly from air, of diethyl phthalate (DEP) and di(n-butyl) phthalate (DnBP) in humans. Methods: In a series of experiments, six human participants were exposed for 6 hr in a chamber containing deliberately elevated air...

Use of ELISA Immunoassay Kits as a Complement to HPLC Analysis of lmazapyr and Triclopyr in Water Samples from Forest Watersheds

Science.gov (United States)

J.B. Fischer; J.L. Michael

1997-01-01

The herbicide triclopyr (3,5,6-trichloro-2-pyridinyl)-oxyacetic acid has been marketed by the Dow Chemical Co. since the mid 1970's as the triethylammonium salt (Garlon 3A) and as the ethylene glycol butyl ether ester (Garlon 4). Shortly after its introduction, McKellar (1977) published a method for the extraction, isolation, and electron capture gas...

Feasibility of bio-based lactate esters as extractant for biobutanol recovery: (Liquid + liquid) equilibria

International Nuclear Information System (INIS)

Zheng, Shaohua; Cheng, Hongye; Chen, Lifang; Qi, Zhiwen

2016-01-01

Highlights: • Lactate esters were studied as solvent to remove butanol from aqueous media. • (Liquid + liquid) equilibrium data were measured at T = 298.15 K and 1 atm. • Selectivity and 1-butanol partition coefficient were calculated. • COSMO-based study of separation efficiency on solvent structure was conducted. - Abstract: As bio-based solvents, lactate esters can be used as extractant for removing 1-butanol from the aqueous fermentation broths. In order to evaluate the separation efficiency of butyl lactate and 2-ethylhexyl lactate for the extraction of 1-butanol from its mixture with water, the (liquid + liquid) equilibrium for the ternary systems {water (1) + 1-butanol (2) + lactate ester (3)} were measured at T = 298.15 K. The 1-butanol partition coefficient varied in the range of 4.46 to 10.29, and the solvent selectivity within 32.12 to 108.18. For the separation of low-concentration butanol from fermentation broths, butyl lactate exhibits higher partition coefficient and lower selectivity than 2-ethylhexyl lactate. The NRTL model was employed to correlate the experimental data, and the COSMO-RS theory was utilized to predict the (liquid + liquid) equilibria and to analyze the influence of lactate esters on extraction efficiency.

Phthalate esters in main source water and drinking water of Zhejiang Province (China): Distribution and health risks.

Science.gov (United States)

Wang, Xiaofeng; Lou, Xiaoming; Zhang, Nianhua; Ding, Gangqiang; Chen, Zhijian; Xu, Peiwei; Wu, Lizhi; Cai, Jianmin; Han, Jianlong; Qiu, Xueting

2015-10-01

To evaluate the distributions and health risks of phthalate esters in the main source water and corresponding drinking water of Zhejiang Province, the concentrations of 16 phthalate esters in water samples from 19 sites were measured from samples taken in the dry season and wet season. The concentration of the total phthalate ester congeners in source water ranged from 1.07 μg/L to 7.12 μg/L in the wet season, from 0.01 μg/L to 1.58 μg/L in the dry season, from 1.18 μg/L to 15.28 μg/L from drinking water in the wet season, and from 0.16 μg/L to 1.86 μg/L from drinking water in the dry season. Of the 16 phthalate esters, dimethyl phthalate, dibutyl phthalate, di-(2-ethyl-hexyl) phthalate, di-iso-butyl phthalate, bis-2-n-butoxyethyl phthalate, and dicyclohexyl phthalate were present in the samples analyzed, dominated by di-iso-butyl phthalate and di-(2-ethyl-hexyl) phthalate. The concentrations of phthalate esters in the wet season were all relatively higher than those in the dry season, and the drinking water had higher concentrations of phthalate esters than source water. The phthalate ester congeners studied pose little health risk to nearby citizens. Environ Toxicol Chem 2015;34:2205-2212. © 2015 SETAC. © 2015 SETAC.

Whole-genome analysis of the methyl tert-butyl ether-degrading beta-proteobacterium Methylibium petroleiphilum PM1.

Science.gov (United States)

Kane, Staci R; Chakicherla, Anu Y; Chain, Patrick S G; Schmidt, Radomir; Shin, Maria W; Legler, Tina C; Scow, Kate M; Larimer, Frank W; Lucas, Susan M; Richardson, Paul M; Hristova, Krassimira R

2007-03-01

Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C(5) to C(12)) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an approximately 4-Mb circular chromosome and an approximately 600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (approximately 99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria.

Biofiltration and inhibitory interactions of gaseous benzene, toluene, xylene, and methyl tert-butyl ether.

Science.gov (United States)

Shim, Eun-Hwa; Kim, Jaisoo; Cho, Kyung-Suk; Ryu, Hee Wook

2006-05-01

This study evaluated the individual and combined removal capacities of benzene, toluene, and xylene (B, T, and X) in the presence and absence of methyl tert-butyl ether (MTBE) in a polyurethane biofilter inoculated with a BTX-degrading microbial consortium, and further examined their interactive effects in various mixtures. In addition, Polymerase chain reaction-denaturing gradient gel electrophoresis and phylogenetic analysis of 16S rRNA gene sequences were used to compare the microbial community structures found in biofilters exposed to the various gases and gas mixtures. The maximum individual elimination capacities (MECs) of B, T, and X were 200, 238, and 400 g m(-3) h(-1), respectively. There was no significant elimination of MTBE alone. Addition of MTBE decreased the MECs of B,T, and X to 75, 100, and 300 g m(-3) h(-1), respectively, indicating that benzene was most strongly inhibited by MTBE. When the three gases were mixed (B + T + X), the removal capacities of individual B, T, and X were 50, 90, and 200 g m(-3) h(-1), respectively. These capacities decreased to 40, 50, and 100 g m(-3) h(-1) when MTBE was added to the mix. The MEC of the three-gas mixture (B + T + X) was 340 g m(-3) h(-1), and that of the four-gas mixture was 200 g m(-3) h(-1). Although MTBE alone was not degraded by the biofilter, it could be co-metabolically degraded in the presence of toluene, benzene, or xylene with the MECs of 34, 23, and 14 g m(-3) h(-1), respectively. The microbial community structure analysis revealed that two large groups could be distinguished based on the presence or absence of MTBE, and many of the dominant bacteria in the consortia were closely related to bacteria isolated from aromatic hydrocarbon-contaminated sites and/ or oil wastewaters. These findings provide important new insights into biofiltration and may be used to improve the rational design of biofilters for remediation of petroleum gas-contaminated airstreams according to composition types of mixed

Aldh2 knockout mice were more sensitive to DNA damage in leukocytes due to ethyl tertiary butyl ether exposure.

Science.gov (United States)

Weng, Zuquan; Suda, Megumi; Ohtani, Katsumi; Mei, Nan; Kawamoto, Toshihiro; Nakajima, Tamie; Wang, Rui-Sheng

2011-01-01

To clarify the genotoxicity of ethyl tertiary butyl ether (ETBE), a gasoline additive, male and female C57BL/6 mice of Aldh2+/+ and Aldh2-/- genotypes, aged 8 wk, were exposed to 0, 500, 1,750, or 5,000 ppm ETBE for 6 h/day, 5 d per week for 13 wk. DNA damage in leukocytes was measured by the alkaline comet assay and expressed quantitatively as Tail Intensity (TI). For male mice, TI was significantly higher in all three groups exposed to ETBE than in those without exposure within Aldh2-/- mice, whereas within Aldh2+/+ mice, TI increased only in those exposed to 5,000 ppm of ETBE as compared with mice without exposure. For female mice, a significant increase in TI values was observed in the group exposed to 5,000 ppm of ETBE as compared with those without exposure within Aldh2-/- mice; TI in Aldh2-/- mice exposed to 1,750 and 5,000 ppm was significantly higher than in Aldh2+/+ mice without exposure. TI did not significantly increase in any of the groups exposed to ETBE within female Aldh2+/+ mice. Based on the results we suggest that Aldh2-/- mice are more sensitive to DNA damage caused by ETBE than Aldh2+/+ mice and that males seem more susceptible to this effect than females.

Functionalization of epoxy esters with alcohols as stoichiometric reagents.

Science.gov (United States)

Pavlović, Dona; Modec, Barbara; Dolenc, Darko

2015-01-01

Glycidyl esters, frequently employed as reactive groups on polymeric supports, were functionalized with alcohols as stoichiometric reagents, yielding β-alkoxyalcohols. Among the solvents studied, best results were obtained in ethers in the presence of a strong proton acid as a catalyst. Alcohols include simple alkanols, diols, protected polyols, 3-butyn-1-ol 3-hydroxypropanenitrile and cholesterol. This protocol represents a convenient way for introduction of various functionalities onto epoxy-functionalized polymers. Under the reaction conditions, some side reactions take place, mostly due to the reactive ester group and water present in the reaction mixture.

Poly(ether amide) segmented block copolymers with adipicacid based tetra amide segments

NARCIS (Netherlands)

Biemond, G.J.E.; Feijen, Jan; Gaymans, R.J.

2007-01-01

Poly(tetramethylene oxide)-based poly(ether ester amide)s with monodisperse tetraamide segments were synthesized. The tetraamide segment was based on adipic acid, terephthalic acid, and hexamethylenediamine. The synthesis method of the copolymers and the influence of the tetraamide concentration,

n-Alkane assimilation and tert-butyl alcohol (TBA) oxidation capacity in Mycobacterium austroafricanum strains.

Science.gov (United States)

Lopes Ferreira, Nicolas; Mathis, Hugues; Labbé, Diane; Monot, Frédéric; Greer, Charles W; Fayolle-Guichard, Françoise

2007-06-01

Mycobacterium austroafricanum IFP 2012, which grows on methyl tert-butyl ether (MTBE) and on tert-butyl alcohol (TBA), the main intermediate of MTBE degradation, also grows on a broad range of n-alkanes (C2 to C16). A single alkB gene copy, encoding a non-heme alkane monooxygenase, was partially amplified from the genome of this bacterium. Its expression was induced after growth on n-propane, n-hexane, n-hexadecane and on TBA but not after growth on LB. The capacity of other fast-growing mycobacteria to grow on n-alkanes (C1 to C16) and to degrade TBA after growth on n-alkanes was compared to that of M. austroafricanum IFP 2012. We studied M. austroafricanum IFP 2012 and IFP 2015 able to grow on MTBE, M. austroafricanum IFP 2173 able to grow on isooctane, Mycobacterium sp. IFP 2009 able to grow on ethyl tert-butyl ether (ETBE), M. vaccae JOB5 (M. austroaafricanum ATCC 29678) able to degrade MTBE and TBA and M. smegmatis mc2 155 with no known degradation capacity towards fuel oxygenates. The M. austroafricanum strains grew on a broad range of n-alkanes and three were able to degrade TBA after growth on propane, hexane and hexadecane. An alkB gene was partially amplified from the genome of all mycobacteria and a sequence comparison demonstrated a close relationship among the M. austroafricanum strains. This is the first report suggesting the involvement of an alkane hydroxylase in TBA oxidation, a key step during MTBE metabolism.

Product analyses and kinetic studies on gas phase oxidation of the fuel additive ethyl tert-butyl ether and its products; Produktanalysen und Kinetikuntersuchungen der Gasphasenoxidation des Kraftstoffadditivs Ethyl-tert-butylether und seiner Produkte

Energy Technology Data Exchange (ETDEWEB)

Becker, K H; Thuener, L

1997-04-01

The widespread use of the additive ETBE in gasoline leads to an increased release of this compound into the atmosphere via evaporation or exhaust fumes. In order to determine the influence of this additive on trace gas cycles it is first necessary to carry out studies on the degradation mechanisms and pertinent kinetic properties of this substance. The aim of the present study was to examine the degradation mechanisms of the fuel additive t-butyl ethyl ether under atmospheric conditions. The reactions of the main degradation products (t-butyl formiate and t-butyl acetate, together ca. 80%) were also studied in order to obtain as complete a picture of the degradation paths as possible. This was to permit an assessment of the influence of ETBE and its products on tropospheric trace gas cycles and ozone formation. [Deutsch] Bei haeufigem Zusatz von ETBE in Benzin wird diese Verbindung durch Verdampfung oder als Abgas verstaerkt in die Atmosphaere abgegeben. Um den Einfluss des Additivs auf die Spurengas-Kreislaeufe zu bestimmen, sind daher Untersuchungen noetig, um die Abbau-Mechanismen und die zugehoerigen kinetischen Daten zu ermitteln. Das Ziel dieser Arbeit ist die Untersuchung der Abbaumechanismen des Kraftstoffadditivs t-Butylethylether unter atmosphaerischen Bedingungen. Fuer eine moeglichst vollstaendige Analyse des Abbauweges werden auch die Reaktionen der Hauptabbauprodukte (t-Butylformiat und t-Butylacetat, zusammen etwa 80%) untersucht. Dadurch soll der Einfluss auf troposphaerische Spurengas-Kreislaeufe und auf die Ozonbildung von ETBE und seinen Produkten abgeschaetzt werden. (orig./SR)

Effects of Poly(cyclohexanedimethylene terephthalate on Microstructures, Crystallization Behavior and Properties of the Poly(ester ether Elastomers

Directory of Open Access Journals (Sweden)

Yi-Cheng Feng

2017-06-01

Full Text Available To understand the role of molecular structure on the crystallization behavior of copolyester in thermoplastic poly(ether ester elastomers (TPEEs, series of poly(butylene-co-1,4-cyclohexanedimethylene terephthalate (P(BT-co-CT-b-poly(tetramethylene glycol (PTMG are synthesized through molten polycondensation process. The effects of poly(cyclohexanedimethylene terephthalate (PCT content on the copolymer are investigated by Fourier transform infrared spectroscopy (FT-IR, 1H and 13C nuclear magnetic resonance (NMR, gel permeation chromatographs (GPC, wide-angle X-ray diffraction (WAXD, differential scanning calorimetry (DSC, thermogravimetric analysis (TGA, mechanical, and visible light transmittance tests. FT-IR and NMR results confirm the incorporation of PCT onto the copolymer. WAXD and DSC indicate that the crystalline structure of the copolymers changed from α-PBT lattice to trans-PCT lattice when the molar fraction of PCT (MPCT is above 30%, while both crystallization and melting temperatures reach the minima. An increase in MPCT led to an increase in the number sequence length of PCT, the thermal stability and the visible light transmittance of the copolymer, but to a slight decrease in tensile strength and elastic modulus.

Study on separation of methanol-butyl methylether-1-chlorobutane system

International Nuclear Information System (INIS)

Zhang Weijiang; Cao Tianhong

2006-01-01

The separation of mixture plays an important role in chemical, petrochemical, medical biochemical industries and environmental protection engineering. Liquid mixture with azeotropic phenomenon cannot be separated by conventional distillation as well as extractive distillation. But the combination of extraction and distillation can be effective for them. This paper includes many experiments with the ternary mixture of methanol butyl methyl ether and 1-chlorobytane, which shows that the system is not ternary azeotrope and can be separated by the combination of extraction and rectification using water as extractive solvent. (authors)

IRIS Toxicological Review of Ethylene Glycol Mono-Butyl Ether (Egbe) (External Review Draft)

Science.gov (United States)

EPA has conducted a peer review of the scientific basis supporting the human health hazard and dose-response assessment of ethylene glycol monobutyl ether that will appear on the Integrated Risk Information System (IRIS) database.

Impact of di-n-butyl phthalate on reproductive system development in European pikeperch (Sander lucioperca

Directory of Open Access Journals (Sweden)

Sylwia Jarmołowicz

2013-01-01

Full Text Available Phthalic acid, di-n-butyl ester known as di-n-butyl phthalate, is an organic chemical compound that belongs to the group of endocrine disruptor compounds that have a documented negative impact on mammalian endocrine systems. Di-n-butyl phthalate is used widely as a plasticizer in the manufacture of artificial materials, which is why it is found in all types of environmental samples including those from water basins. The aim of the study was to describe the impact of di-n-butyl phthalate on the development of the reproductive system of European pikeperch (Sander lucioperca during the sex differentiation period (age 61–96 days post hatch. A total of 240 fish were divided into 6 groups (40 fish per tank. Treatments consisted of a control group (0 g di-n-butyl phthalate·kg-1 feed and five trial groups with 0.125, 0.25, 0.5, 1, and 2 g di-n-butyl phthalate·kg-1 feed, respectively. Histological changes of the fish gonads, sex ratio, survival and growth of fish were evaluated. Di-n-butyl phthalate seriously disturbed sex differentiation process of pikeperch. Histopathological analyses revealed that the administration of 2 g di-n-butyl phthalate·kg-1 significantly affected the sex ratio. The feminization process (intersex gonads at concentrations of 1 g and 2 g di-n-butyl phthalate·kg-1 were observed. All analyzed concentrations delayed testicular development. Phthalate did not have a significant impact on the survival or growth rates of the pikeperch. This is the first report of disruption sex differentiation processes in fish by di-n-butyl phthalate.

TOXICITY OF METHYL-TERT BYTYL ETHER (MTBE) TO PLANTS (AVENA SATIVA, ZEA MAYS, TRITICUM AESTIVUM, AND LACTUCA SATIVA)

Science.gov (United States)

Effects of Methyl tert-butyl ether (MTBE) on the germination of seeds and growth of the plant were studied in some laboratory experiments. Test plants were wild oat (Avena sative), sweet corn (Zea mays), wheat (Triticum aestivum), and lettuce (Lactuca sativa). Seed germination,...

Recovery of slaughterhouse Animal Fatty Wastewater Sludge by conversion into Fatty Acid Butyl Esters by acid-catalyzed esterification.

Science.gov (United States)

Wallis, Christopher; Cerny, Muriel; Lacroux, Eric; Mouloungui, Zéphirin

2017-02-01

Two types of Animal Fatty Wastewater Sludges (AFWS 1 and 2) were analyzed and fully characterized to determine their suitability for conversion into biofuel. AFWS 1 was determined to be unsuitable as it contains 68.8wt.% water and only 32.3wt.% dry material, of which only around 80% is lipids to be converted. AFWS 2 has only 15.7wt.% water and 84.3wt.% dry material of which is assumed to 100% lipids as the protein and ash contents were determined to be negligible. The 4-dodecylbenzenesulfonic acid (DBSA) catalyzed esterification of AFWS with 1-butanol was performed in a novel batch reactor fitted with a drying chimney for the "in situ" removal of water and optimized using a non-conventional Doehlert surface response methodology. The optimized condition was found to be 1.66mol equivalent of 1-butanol (with respect to total fatty acid chains), 10wt.% of DBSA catalyst (with respect to AFWS) at 105°C for 3h. Fatty Acid Butyl Esters (FABEs) were isolated in good yields (95%+) as well as a blend of FABEs with 1-butanol (16%). The two potential biofuels were analyzed in comparison with current and analogous biofuels (FAME based biodiesel, and FABE products made from vegetable oils) and were found to exhibit high cetane numbers and flash point values. Copyright © 2016 Elsevier Ltd. All rights reserved.

Structure and reactivity of boron-ate complexes derived from primary and secondary boronic esters.

Science.gov (United States)

Feeney, Kathryn; Berionni, Guillaume; Mayr, Herbert; Aggarwal, Varinder K

2015-06-05

Boron-ate complexes derived from primary and secondary boronic esters and aryllithiums have been isolated, and the kinetics of their reactions with carbenium ions studied. The second-order rate constants have been used to derive nucleophilicity parameters for the boron-ate complexes, revealing that nucleophilicity increased with (i) electron-donating aromatics on boron, (ii) neopentyl glycol over pinacol boronic esters, and (iii) 12-crown-4 ether.

Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

Science.gov (United States)

Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

2010-01-01

In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

The Effect of Water Contaminated with Methyl Tertiary Butyl Ether (MTBE) on the Rat's Weight and Tissue

International Nuclear Information System (INIS)

Backer, Wadiah Saleh; AboKhatwa, Ahmed Nabil; Katouah, Hanadi Ahmed

2008-01-01

Lead is known to cause deleterious effects on health and environment. Therefore, it was removed from car-fuel, in the United States since 1979. In January 2001, Saudi Arabia and other Arabian Gulf States, replaced lead with a synthetic organic substance called methyl tertiary-butyl ether (MTBE). MTBE is added to gasoline at 12-15%. It dissolves readily in water and evaporates quickly. This study was focused on the possible health hazards of MTBE in drinking water as manifested by changes in weight and vital tissues (heart, liver, kidney, lung, and testis) of rat. This study also aimed to establish a quantitative relationship between MTBE concentration and changes that occur to these tissues. One hundred and twenty male Wistar rats were exposed to five different MTBE concentrations (0.0, 1,000, 1,500, 2,000, 2,500 ppm) for 60 days. The results showed that most of MTBE-treated animals have revealed significant weight loss and the maximum weight loss (nearly 10 %) was achieved at the highest concentration (2,500 ppm) after 60 days of treatment. Also, both liver and heart weights were significantly reduced by almost 9%, and kidneys by 8% of MTBE concentration of 2,000 ppm. At a higher concentration (2,500 ppm), liver weight was reduced by 12%. The weight of other tissues (lungs and testes) remained unchanged. The outcome of the results may lead to hepatic disorder. This disorder could reduce plasma glucose, or increase some hepatic markers like ALT, AST, and GGT activity, or elevate the levels of sodium and chloride in plasma and may have other side effects. (author)

Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol in Water by Solid-Phase Microextraction/Head Space Analysis in Comparison to EPA Method 5030/8260B

Energy Technology Data Exchange (ETDEWEB)

Oh, Keun-Chan; Stringfellow, William T.

2003-10-02

Methyl tert-butyl ether (MTBE) is now one of the most common groundwater contaminants in the United States. Groundwater contaminated with MTBE is also likely to be contaminated with tert-butyl alcohol (TBA), because TBA is a component of commercial grade MTBE, TBA can also be used as a fuel oxygenate, and TBA is a biodegradation product of MTBE. In California, MTBE is subject to reporting at concentrations greater than 3 {micro}g/L. TBA is classified as a ''contaminant of current interest'' and has a drinking water action level of 12 {micro}g/L. In this paper, we describe the development and optimization of a simple, automated solid phase microextraction (SPME) method for the analysis of MTBE and TBA in water and demonstrate the applicability of this method for monitoring MTBE and TBA contamination in groundwater, drinking water, and surface water. In this method, the headspace (HS) of a water sample is extracted with a carboxen/polydimethylsiloxane SPME fiber, the MTBE and TBA are desorbed into a gas chromatograph (GC), and detected using mass spectrometry (MS). The method is optimized for the routine analysis of MTBE and TBA with a level of quantitation of 0.3 {micro}g/L and 4 {micro}g/L, respectively, in water. MTBE quantitation was linear for over two orders of concentration (0.3 {micro}g/L -80 {micro}g/L). TBA was found to be linear within the range of 4 {micro}g/L-7,900 {micro}g/L. The lower level of detection for MTBE is 0.03 {micro}g/L using this method. This SPME method using headspace extraction was found to be advantageous over SPME methods requiring immersion of the fiber into the water samples, because it prolonged the life of the fiber by up to 400 sample analyses. This is the first time headspace extraction SPME has been shown to be applicable to the measurement of both MTBE and TBA at concentrations below regulatory action levels. This method was compared with the certified EPA Method 5030/8260B (purge-and-trap/GC/MS) using split

Biofuels - the UFIP position; Biocarburants - la position de l'UFIP

Energy Technology Data Exchange (ETDEWEB)

NONE

2004-07-01

Since 2003 a directive promote the biofuels use. The industry is then using them in ETBE (Ethyl Tertio Butyl Ether) fuels and in diesel oil of vegetal oils esters EMHV. Meanwhile some of them present technical difficulties and must free themselves from fiscal incentives which make them competitive. For these reasons, the UFIP (french union of petroleum industries) do not agree their obligatory incorporation. (A.L.B.)

Biofuels - the UFIP position

International Nuclear Information System (INIS)

2004-01-01

Since 2003 a directive promote the biofuels use. The industry is then using them in ETBE (Ethyl Tertio Butyl Ether) fuels and in diesel oil of vegetal oils esters EMHV. Meanwhile some of them present technical difficulties and must free themselves from fiscal incentives which make them competitive. For these reasons, the UFIP (french union of petroleum industries) do not agree their obligatory incorporation. (A.L.B.)

Fundamental Characterization of the Micellar Self-Assembly of Sophorolipid Esters.

Science.gov (United States)

Koh, Amanda; Todd, Katherine; Sherbourne, Ezekiel; Gross, Richard A

2017-06-13

Surfactants are ubiquitous constituents of commercial and biological systems that function based on complex structure-dependent interactions. Sophorolipid (SL) n-alkyl esters (SL-esters) comprise a group of modified naturally derived glycolipids from Candida bombicola. Herein, micellar self-assembly behavior as a function of SL-ester chain length was studied. Surface tensions as low as 31.2 mN/m and critical micelle concentrations (CMCs) as low as 1.1 μM were attained for diacetylated SL-decyl ester (dASL-DE) and SL-octyl ester, respectively. For deacetylated SL-esters, CMC values reach a lower limit at SL-ester chains above n-butyl (SL-BE, 1-3 μM). This behavior of SL-esters with increasing hydrophobic tail length is unlike other known surfactants. Diffusion-ordered spectroscopy (DOSY) and T 1 relaxation NMR experiments indicate this behavior is due to a change in intramolecular interactions, which impedes the self-assembly of SL-esters with chain lengths above SL-BE. This hypothesis is supported by micellar thermodynamics where a disruption in trends occurs at n-alkyl ester chain lengths above those of SL-BE and SL-hexyl ester (SL-HE). Diacetylated (dA) SL-esters exhibit an even more unusual trend in that CMC increases from 1.75 to 815 μM for SL-ester chain lengths of dASL-BE and dASL-DE, respectively. Foaming studies, performed to reveal the macroscopic implications of SL-ester micellar behavior, show that the observed instability in foams formed using SL-esters are due to coalescence, which highlights the importance of understanding intermicellar interactions. This work reveals that SL-esters are an important new family of green high-performing surfactants with unique structure-property relationships that can be tuned to optimize micellar characteristics.

Forensic analysis of tertiary-butyl alcohol (TBA) detections in a hydrocarbon-rich groundwater basin.

Science.gov (United States)

Quast, Konrad W; Levine, Audrey D; Kester, Janet E; Fordham, Carolyn L

2016-04-01

Tertiary-butyl alcohol (TBA), a high-production volume (HPV) chemical, was sporadically detected in groundwater and coalbed methane (CBM) wells in southeastern Colorado's hydrocarbon-rich Raton Basin. TBA concentrations in shallow water wells averaged 75.1 μg/L, while detections in deeper CBM wells averaged 14.4 μg/L. The detection of TBA prompted a forensic investigation to try to identify potential sources. Historic and recent data were reviewed to determine if there was a discernable pattern of TBA occurrence. Supplemental samples from domestic water wells, monitor wells, CBM wells, surface waters, and hydraulic fracturing (HF) fluids were analyzed for TBA in conjunction with methyl tertiary-butyl ether (MTBE) and ethyl tertiary-butyl ether (ETBE), proxies for evidence of contamination from reformulated gasoline or associated oxygenates. Exploratory microbiological sampling was conducted to determine if methanotrophic organisms co-occurred with TBA in individual wells. Meaningful comparisons of historic TBA data were limited due to widely varying reporting limits. Mapping of TBA occurrence did not reveal any spatial patterns or physical associations with CBM operations or contamination plumes. Additionally, TBA was not detected in HF fluids or surface water samples. Given the widespread use of TBA in industrial and consumer products, including water well completion materials, it is likely that multiple diffuse sources exist. Exploratory data on stable isotopes, dissolved gases, and microbial profiling provide preliminary evidence that methanotrophic activity may be producing TBA from naturally occurring isobutane. Reported TBA concentrations were significantly below a conservative risk-based drinking water screening level of 8000 μg/L derived from animal toxicity data.

Glycerol etherification with TBA: high yield to poly-ethers using a membrane assisted batch reactor.

Science.gov (United States)

Cannilla, Catia; Bonura, Giuseppe; Frusteri, Leone; Frusteri, Francesco

2014-05-20

In this work, a novel approach to obtain high yield to poly-tert-butylglycerolethers by glycerol etherification reaction with tert-butyl alcohol (TBA) is proposed. The limit of this reaction is the production of poly-ethers, which inhibits the formation of poly-ethers potentially usable in the blend with conventional diesel for transportation. The results herein reported demonstrate that the use of a water permselective membrane offers the possibility to shift the equilibrium toward the formation of poly-ethers since the water formed during reaction is continuously and selectively removed from the reaction medium by the recirculation of the gas phase. Using a proper catalyst and optimizing the reaction conditions, in a single experiment, a total glycerol conversion can be reached with a yield to poly-ethers close to 70%, which represents data never before reached using TBA as reactant. The approach here proposed could open up new opportunities for all catalytic reactions affected by water formation.

γ-Rays-induced synthesis of hydrogels of vinyl ethers with stimuli-sensitive behavior

International Nuclear Information System (INIS)

Nam, I.K.; Mun, G.A.; Urkimbaeva, P.I.; Nurkeeva, Z.S.

2003-01-01

γ-Radiation method was applied to synthesize novel water-soluble and water-swelling polymers. Vinyl ether of ethylene glycol (VEEG), vinyl butyl (VBE) and vinyl isobutyl (VIBE) ethers were used as monomers. The synthesis of VEEG-VBE and VEEG-VIBE copolymers was carried out in a wide range of feed composition and absorbed dose. It was found that the hydrophobic-hydrophilic balance of the copolymers could be delicately varied by the copolymer composition as well as by the chemical structure of the alkyl substitute in the hydrophobic moiety. The copolymers exhibit thermo-sensitive behavior in water solutions. The value of transition temperature is considerably decreased at a higher concentration of the hydrophobic component in the copolymer composition

Synthetic Methods for Ester Bond Formation and Conformational Analysis of Ester-Containing Carbohydrates

Science.gov (United States)

Hackbusch, Sven

This dissertation encompasses work related to synthetic methods for the formation of ester linkages in organic compounds, as well as the investigation of the conformational influence of the ester functional group on the flexibility of inter-saccharide linkages, specifically, and the solution phase structure of ester-containing carbohydrate derivatives, in general. Stereoselective reactions are an important part of the field of asymmetric synthesis and an understanding of their underlying mechanistic principles is essential for rational method development. Here, the exploration of a diastereoselective O-acylation reaction on a trans-2-substituted cyclohexanol scaffold is presented, along with possible reasons for the observed reversal of stereoselectivity dependent on the presence or absence of an achiral amine catalyst. In particular, this work establishes a structure-activity relationship with regard to the trans-2-substituent and its role as a chiral auxiliary in the reversal of diastereoselectivity. In the second part, the synthesis of various ester-linked carbohydrate derivatives, and their conformational analysis is presented. Using multidimensional NMR experiments and computational methods, the compounds' solution-phase structures were established and the effect of the ester functional group on the molecules' flexibility and three-dimensional (3D) structure was investigated and compared to ether or glycosidic linkages. To aid in this, a novel Karplus equation for the C(sp2)OCH angle in ester-linked carbohydrates was developed on the basis of a model ester-linked carbohydrate. This equation describes the sinusoidal relationship between the C(sp2)OCH dihedral angle and the corresponding 3JCH coupling constant that can be determined from a J-HMBC NMR experiment. The insights from this research will be useful in describing the 3D structure of naturally occurring and lab-made ester-linked derivatives of carbohydrates, as well as guiding the de novo-design of

Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

DEFF Research Database (Denmark)

Ambrogio, I.; Fabrizi, G.; Cacchi, S.

2008-01-01

The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction...... tolerates a variety of functional groups, including ether, amide, alcohol, aldehyde, ketone, ester, cyano, carboxylic acid, and nitro groups. Ortho-substituted arylating agents afforded moderate yields in some cases, though good to high yields were obtained with o-iodotoluene, iodovanillin, and 1...

Microreactors—A Powerful Tool to Synthesize Peroxycarboxylic Esters

Directory of Open Access Journals (Sweden)

Tobias Illg

2015-12-01

Full Text Available The synthesis of peroxycarboxylic esters, as one subgroup of organic peroxides, is characterized by a high thermal hazard potential regarding process safety. In case of failure in the production process, e.g., if the heat of reaction cannot be removed sufficiently fast, decomposition reactions can be triggered, and as a result, remarkable amounts of heat and gas can be released and can cause a high extent of damage. Multifarious technical and organizational measures are necessary to ensure the safe industrial production of peroxides. With the introduction of microreaction technology plenty of possibilities have been opened to carry out highly exothermic reactions in smaller volumes and with more efficient heat removal. In this paper we report the application of three different microstructured reactors, representing different mixing strategies, to synthesize two peroxymonocarboxylic esters, namely tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate. The following reactor types were considered: an orifice microreactor, a split and recombine microreactor and a capillary tube reactor in combination with ultrasonication. The efficiency of the two phase liquid/liquid reaction is expressed in comparison of conversion and selectivity. With microreaction technology a remarkable increase in space-time-yield, ranging from 12,500 kg·m−3·h−1 to 414,000 kg·m−3·h−1, is achieved.

Whole-Genome Analysis of the Methyl tert-Butyl Ether-Degrading Beta-Proteobacterium Methylibium petroleiphilum PM1▿ †

Science.gov (United States)

Kane, Staci R.; Chakicherla, Anu Y.; Chain, Patrick S. G.; Schmidt, Radomir; Shin, Maria W.; Legler, Tina C.; Scow, Kate M.; Larimer, Frank W.; Lucas, Susan M.; Richardson, Paul M.; Hristova, Krassimira R.

2007-01-01

Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C5 to C12) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an ∼4-Mb circular chromosome and an ∼600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (∼99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria. PMID:17158667

Chronic carcinogenicity study of gasoline vapor condensate (GVC) and GVC containing methyl tertiary-butyl ether in F344 rats.

Science.gov (United States)

Benson, Janet M; Gigliotti, Andrew P; March, Thomas H; Barr, Edward B; Tibbetts, Brad M; Skipper, Betty J; Clark, Charles R; Twerdok, Lorraine

2011-01-01

Chronic inhalation studies were conducted to compare the toxicity and potential carcinogenicity of evaporative emissions from unleaded gasoline (GVC) and gasoline containing the oxygenate methyl tertiary-butyl ether (MTBE; GMVC). The test materials were manufactured to mimic vapors people would be exposed to during refueling at gas stations. Fifty F344 rats per gender per exposure level per test article were exposed 6 h/d, 5 d/wk for 104 wk in whole body chambers. Target total vapor concentrations were 0, 2, 10, or 20 g/m³ for the control, low-, mid-, and high-level exposures, respectively. Endpoints included survival, body weights, clinical observations, organs weights, and histopathology. GVC and GMVC exerted no marked effects on survival or clinical observations and few effects on organ weights. Terminal body weights were reduced in all mid- and high-level GVC groups and high-level GMVC groups. The major proliferative lesions attributable to gasoline exposure with or without MTBE were renal tubule adenomas and carcinomas in male rats. GMV exposure led to elevated testicular mesothelioma incidence and an increased trend for thyroid carcinomas in males. GVMC inhalation caused an increased trend for testicular tumors with exposure concentration. Mid- and high-level exposures of GVC and GMVC led to elevated incidences of nasal respiratory epithelial degeneration. Overall, in these chronic studies conducted under identical conditions, the health effects in F344 rats following 2 yr of GVC or GMVC exposure were comparable in the production of renal adenomas and carcinomas in male rats and similar in other endpoints.

Chronic Carcinogenicity Study of Gasoline Vapor Condensate (GVC) and GVC Containing Methyl Tertiary-Butyl Ether in F344 Rats

Science.gov (United States)

Benson, Janet M.; Gigliotti, Andrew P.; March, Thomas H.; Barr, Edward B.; Tibbetts, Brad M.; Skipper, Betty J.; Clark, Charles R.; Twerdok, Lorraine

2011-01-01

Chronic inhalation studies were conducted to compare the toxicity and potential carcinogenicity of evaporative emissions from unleaded gasoline (GVC) and gasoline containing the oxygenate methyl tertiary-butyl ether (MTBE; GMVC). The test materials were manufactured to mimic vapors people would be exposed to during refueling at gas stations. Fifty F344 rats per gender per exposure level per test article were exposed 6 h/d, 5 d/wk for 104 wk in whole body chambers. Target total vapor concentrations were 0, 2, 10, or 20 g/m3 for the control, low-, mid-, and high-level exposures, respectively. Endpoints included survival, body weights, clinical observations, organs weights, and histopathology. GVC and GMVC exerted no marked effects on survival or clinical observations and few effects on organ weights. Terminal body weights were reduced in all mid- and high-level GVC groups and high-level GMVC groups. The major proliferative lesions attributable to gasoline exposure with or without MTBE were renal tubule adenomas and carcinomas in male rats. GMV exposure led to elevated testicular mesothelioma incidence and an increased trend for thyroid carcinomas in males. GVMC inhalation caused an increased trend for testicular tumors with exposure concentration. Mid- and high-level exposures of GVC and GMVC led to elevated incidences of nasal respiratory epithelial degeneration. Overall, in these chronic studies conducted under identical conditions, the health effects in F344 rats following 2 yr of GVC or GMVC exposure were comparable in the production of renal adenomas and carcinomas in male rats and similar in other endpoints. PMID:21432714

Prediction methods for the calculation of the flammability properties of gases and vapors: CHETAH and ASTM software. Part 1. Esters and Ethers

International Nuclear Information System (INIS)

Gigante, L.; Dellavedova, M.; Pasturenzi, C.; Lunghi, A.; Cardillo, P.

2008-01-01

After the law by decree of the 12. June 2003, N 233 (ATEX Directive) and REACH regulation (Regulation EC n. 2907/2006 of the European Parliament), several industrial fields, also not chemical, need the flammability data for the substances used. Perhaps, many of these data, especially for compounds with not common uses, are not easy to collect. It would be helpful to provide prediction methods in order to calculate these data without any experimentation that sometimes results time consuming, expensive and practically impossible for all the commercial compounds. In this research the ASTM software CHETAH (CHEmical Thermodynamic And Hazard evaluation) has been used in order to compute the lower flammability limit (L i ), the limiting oxygen concentration (LOC, using nitrogen as inert gas) as a function of temperature, the adiabatic flame temperature T flame , the fundamental burning velocity (S u ), the quenching distance (Q d ), the minimum ignition energy (MIE) for esters and ethers, substances highly used in industry. [it

Densities and derived thermodynamic properties of the binary systems of 1,1-dimethylethyl methyl ether with allyl methacrylate, butyl methacrylate, methacrylic acid, and vinyl acetate at T = (298.15 and 308.15) K

International Nuclear Information System (INIS)

Wisniak, Jaime; Peralta, Rene D.; Infante, Ramiro; Cortez, Gladis

2005-01-01

Densities of the binary systems of 1,1-dimethylethyl methyl ether (MTBE) with allyl methacrylate, butyl methacrylate, methacrylic acid, and vinyl acetate have been measured as a function of the composition, at 298.15 and 308.15 K and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densimeter. The calculated excess molar volumes were correlated with the Redlich-Kister equation and with a series of Legendre polynomials. The excess molar volumes are negative for the binaries of MTBE + methacrylates; the system MTBE with vinyl acetate presents near ideal behavior. The excess coefficient of thermal expansion is positive for all the systems studied here; the value of the coefficient for the system MTBE + allyl methacrylate is at least three times larger than that for the other systems

A poly(ether-ester) copolymer for the preparation of nanocarriers with improved degradation and drug delivery kinetics

International Nuclear Information System (INIS)

Gagliardi, M.; Bertero, A.; Bardi, G.; Bifone, A.

2016-01-01

This paper reports the synthesis and the physicochemical, functional and biological characterisations of nanocarriers made of a novel di-block biodegradable poly(ether-ester) copolymer. This material presents tunable, fast biodegradation rates, but its products are less acidic than those of other biosorbable polymers like PLGA, thus presenting a better biocompatibility profile and the possibility to carry pH-sensitive payloads. A method for the production of monodisperse and spherical nanoparticles is proposed; drug delivery kinetics and blood protein adsorption were measured to evaluate the functional properties of these nanoparticles as drug carriers. The copolymer was labelled with a fluorescent dye for internalisation tests, and rhodamine B was used as a model cargo to study transport and release inside cultured cells. Biological tests demonstrated good cytocompatibility, significant cell internalisation and the possibility to vehiculate non-cell penetrating moieties into endothelial cells. Taken together, these results support the potential use of this nanoparticulate system for systemic administration of drugs. - Highlights: • We propose a novel biodegradable nanocarrier for intracellular drug delivery. • Biodegradation rates can be finely tuned by controlling copolymer composition. • Degradation products are less acidic, thus enabling delivery of pH-sensitive cargoes. • We demonstrate intracellular delivery of a non-cell-penetrating model drug. • No significant membrane damage by the polymer nanocarriers is observed.

A poly(ether-ester) copolymer for the preparation of nanocarriers with improved degradation and drug delivery kinetics

Energy Technology Data Exchange (ETDEWEB)

Gagliardi, M., E-mail: mariacristina.gagliardi@iit.it [Center for Micro Bio-Robotics @SSSA, Istituto Italiano di Tecnologia, Viale Rinaldo Piaggio 34, 56025 Pontedera (Italy); Bertero, A. [Department of Biology, Unit of Cellular and Developmental Biology, University of Pisa, S.S.12 Abetone e Brennero 4, 56127 Pisa (Italy); Center for Neuroscience and Cognitive Systems @UNITN, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068 Rovereto (Italy); Bardi, G. [Center for Bio-Molecular Nanotechnologies @UniLe, Istituto Italiano di Tecnologia, Via Barsanti, 73010 Arnesano (Italy); Bifone, A. [Center for Neuroscience and Cognitive Systems @UNITN, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068 Rovereto (Italy)

2016-02-01

This paper reports the synthesis and the physicochemical, functional and biological characterisations of nanocarriers made of a novel di-block biodegradable poly(ether-ester) copolymer. This material presents tunable, fast biodegradation rates, but its products are less acidic than those of other biosorbable polymers like PLGA, thus presenting a better biocompatibility profile and the possibility to carry pH-sensitive payloads. A method for the production of monodisperse and spherical nanoparticles is proposed; drug delivery kinetics and blood protein adsorption were measured to evaluate the functional properties of these nanoparticles as drug carriers. The copolymer was labelled with a fluorescent dye for internalisation tests, and rhodamine B was used as a model cargo to study transport and release inside cultured cells. Biological tests demonstrated good cytocompatibility, significant cell internalisation and the possibility to vehiculate non-cell penetrating moieties into endothelial cells. Taken together, these results support the potential use of this nanoparticulate system for systemic administration of drugs. - Highlights: • We propose a novel biodegradable nanocarrier for intracellular drug delivery. • Biodegradation rates can be finely tuned by controlling copolymer composition. • Degradation products are less acidic, thus enabling delivery of pH-sensitive cargoes. • We demonstrate intracellular delivery of a non-cell-penetrating model drug. • No significant membrane damage by the polymer nanocarriers is observed.

The uptake, distribution, metabolism, and excretion of methyl tertiary-butyl ether inhaled alone and in combination with gasoline vapor.

Science.gov (United States)

Benson, Janet M; Tibbetts, Brad M; Barr, Edward B

2003-06-13

The purpose of these studies was to evaluate the tissue uptake, distribution, metabolism, and excretion of methyl tertiary-butyl ether (MTBE) in rats and to determine the effects of coinhalation of the volatile fraction of unleaded gasoline on these parameters. Male F344 rats were exposed nose-only once for 4 h to 4, 40, or 400 ppm 14C-MTBE and to 20 and 200 ppm of the light fraction of unleaded gasoline (LFG) containing 4 and 40 ppm 14C-MTBE, respectively. To evaluate the effects of repeated inhalation of LFG on the fate of inhaled MTBE, rats were exposed for 7 consecutive days to 20 and 200 ppm LFG followed on d 8 by exposure to LFG containing 14C-MTBE. Three subgroups of rats were included for evaluation of respiratory parameters, rates and routes of excretion, and tissue distribution and elimination. MTBE and its chief metabolite, tertiary-butyl alcohol, were quantitated in blood and kidney (immediately after exposure), and the major urinary metabolites, 2-hydroxyisobutyric acid and 2-methyl-1,2- propanediol, were identified and quantified in urine. Inhalation of MTBE alone or as a component of LFG had no concentration-dependent effect on respiratory minute volume. The initial body burdens (IBBs) of MTBE equivalents achieved after 4 h of exposure to MTBE did not increase linearly with exposure concentration. MTBE equivalents rapidly distributed to all tissues examined, with the largest percentages distributed to liver. Between 40 and 400 ppm, there was a significant reduction in percentage of the IBB present in the major organs examined, both immediately and 72 h after exposure. At 400 ppm, the elimination rates of MTBE equivalents from tissues changed significantly. Furthermore, at 400 ppm there was a significant decrease in the elimination half-time of volatile organic compounds (VOCs) in breath and a significant increase in the percentage of the IBB of MTBE equivalents eliminated as VOCs in breath. LFG coexposure significantly decreased the percentage of the

Effect of Anion on Behaviour of Li-S Battery Electrolyte Solutions Based on N-Methyl-N-Butyl-Pyrrolidinium Ionic Liquids

International Nuclear Information System (INIS)

Barghamadi, Marzieh; Best, Adam S.; Bhatt, Anand I.; Hollenkamp, Anthony F.; Mahon, Peter J.; Musameh, Mustafa; Rüther, Thomas

2015-01-01

The electrochemical behaviour and electrical performance are investigated for a series of lithium-sulfur (Li-S) cells in which the electrolyte solutions are organic solvent-ionic liquid mixtures that are based on the 1-butyl-1-methylpyrrolidinium (C 4 mpyr) cation with a range of anions. In each case, performance is compared with cells that are based on a standard mixed-ether organic electrolyte. The capacity of cells assembled with electrolytes containing 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate (C 4 mpyr-FAP), 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate (C 4 mpyr-OTf), or 1-butyl-1-methylpyrrolidinium tricyanomethanide (C 4 mpyr-TCM) decline rapidly due to low conductivity, high polysulfide solubility and side reaction of electrolyte with electrodes, respectively. Our results confirm that polysulfide solubility is strongly controlled by the anion of the ionic liquid and verify that not all ionic liquids decrease polysulfide solubility. In agreement with previous reports, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (C 4 mpyr-TFSI) shows the best compatibility in Li-S batteries and has a higher coulombic efficiency of greater than 99% over 100 cycles. Furthermore, impedance spectroscopy confirms that electrolyte composition influences the SEI layer formed on the lithium anode and its subsequent impedance.

Contamination of phthalate esters, organochlorine pesticides and polybrominated diphenyl ethers in agricultural soils from the Yangtze River Delta of China.

Science.gov (United States)

Sun, Jianteng; Pan, Lili; Zhan, Yu; Lu, Hainan; Tsang, Daniel C W; Liu, Wenxin; Wang, Xilong; Li, Xiangdong; Zhu, Lizhong

2016-02-15

To reveal the pollution status associated with rapid urbanization and economic growth, extensive areas of agricultural soils (approximately 45,800 km(2)) in the Yangtze River Delta of China were investigated with respect to selected endocrine disruptor compounds (EDCs), including phthalate esters (PAEs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs). The residues of sum of 15 PAEs, sum of 15 OCPs and sum of 13 PBDEs were in the range of 167-9370 ng/g, 1.0-3520 ng/g, and usage and recent input. Agricultural plastic film was considered to be an important source of PAEs. Discharge from furniture industry was potential major source of PBDEs in this region. The selected pollutants showed quite different spatial distributions within the studied region. It is worth noting that much higher concentrations of the EDCs were found on the borders between Shanghai and the two neighboring provinces, where agriculture and industry developed rapidly in recent years. Contaminants from both agricultural and industrial activities made this area a pollution hotspot, which should arouse more stringent regulation to safeguard the environment and food security. Copyright © 2015 Elsevier B.V. All rights reserved.

Thermodynamics and activity coefficients at infinite dilution for organic solutes and water in the ionic liquid 1-butyl-1-methylmorpholinium tricyanomethanide

International Nuclear Information System (INIS)

Domańska, Urszula; Lukoshko, Elena Vadimovna

2014-01-01

Highlights: • Measurements of activity coefficients at infinite dilution using GLC. • Sixty one organic solvents in the ionic liquid 1-butyl-1-methylmorpholinium tricyanomethanide. • High selectivity for heptane/thiophene, or pyridine, or 1-nitropropane. • The excess thermodynamic functions and the gas–liquid partition coefficients were presented. • Possible entrainer for the extraction of sulphur and nitrogen-compounds from alkanes. -- Abstract: The activity coefficients at infinite dilution, γ 13 ∞ , for 61 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, ethers, ketones, esters, aldehyde, acetonitrile, pyridine and 1-nitropropane in the ionic liquid (IL) 1-butyl-1-methylmorpholinium tricyanomethanide, [BMMOR][TCM] were determined by gas–liquid chromatography at six temperatures within the range of (318.15 to 368.15) K. The thermodynamic functions at infinite dilution as partial molar excess Gibbs free energy ΔG 1 E,∞ , enthalpy ΔH 1 E,∞ , and entropy term T ref ΔS 1 E,∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The density of [BMMOR][TCM] was measured over the temperature range (288.15 to 368.15) K. The gas–liquid partition coefficient K L was calculated for all solutes. The values of selectivity and capacity for a few separation problems such as hexane/benzene, cyclohexane/benzene, heptane/thiophene at T = 328.15 K were calculated from γ 13 ∞ and compared to literature values for similar ionic liquids, viz. N-methyl-2-pyrrolidinone (NMP), and sulfolane. In comparison with the previously measured values for [BMPYR][TCM], the morpholinium IL presents high selectivity for the separation of aromatic hydrocarbons from aliphatic hydrocarbons, and especially thiophene, or piridine from heptane with a slightly lower capacity. New data show that [BMMOR][TCM] IL may be proposed as an alternative solvent for the separation of

γ-aminobutyric acidA (GABAA) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of Methyl Tert-Butyl Ether (MTBE)-induced impairment of spatial memory

International Nuclear Information System (INIS)

Zheng Gang; Zhang Wenbin; Zhang Yun; Chen Yaoming; Liu Mingchao; Yao Ting; Yang Yanxia; Zhao Fang; Li Jingxia; Huang Chuanshu; Luo Wenjing; Chen Jingyuan

2009-01-01

Experimental and occupational exposure to Methyl Tert-Butyl Ether (MTBE) has been reported to induce neurotoxicological and neurobehavioral effects, such as headache, nausea, dizziness, and disorientation, etc. However, the molecular mechanisms involved in MTBE-induced neurotoxicity are still not well understood. In the present study, we investigated the effects of MTBE on spatial memory and the expression and function of GABA A receptor in the hippocampus. Our results demonstrated that intraventricular injection of MTBE impaired the performance of the rats in a Morris water maze task, and significantly increased the expression of GABA A receptor α1 subunit in the hippocampus. The phosphorylation of ERK1/2 decreased after the MTBE injection. Furthermore, the decreased ability of learning and the reduction of phosphorylated ERK1/2 level of the MTBE-treated rats was partly reversed by bicuculline injected 30 min before the training. These results suggested that MTBE exposure could result in impaired spatial memory. GABA A receptor may play an important role in the MTBE-induced impairment of learning and memory by regulating the phosphorylation of ERK in the hippocampus.

Exposure to methyl tert-butyl ether, benzene, and total hydrocarbons at the Singapore-Malaysia causeway immigration checkpoint

Energy Technology Data Exchange (ETDEWEB)

Tan, C.; Ong, H.Y.; Kok, P.W. [and others

1996-12-31

The primary aim of this study was to determine the extent and levels of exposure to volatile organic compounds (VOCs) from automobile emissions in a group of immigration officers at a busy cross-border checkpoint. A majority (80%) of the workers monitored were exposed to benzene at levels between 0.01 and 0.5 ppm, with only 1.2% exceeding the current Occupational Safety and Health Administration occupational exposure limit of 1 ppm. The geometric mean (GM) concentrations of 8-hr time-weighted average exposure were 0.03 ppm, 0.9 ppm, and 2.46 ppm for methyl-tert-butyl ether (MTBE), benzene, and total hydrocarbons (THC), respectively. The highest time-weighted average concentrations measured were 1.05 ppm for MTBE, 2.01 ppm for benzene, and 34 ppm for THC. It was found that motorbikes emitted a more significant amount of pollutants compared with motor cars. On average, officers at the motorcycle booths were exposed to four to five times higher levels of VOCs (GMs of 0.07 ppm, 0.23 ppm, and 4.7 ppm for MTBE, benzene, and THC) than their counterparts at the motor car booths (GMs of 0.01 ppm, 0.05 ppm, and 1.5 ppm). The airborne concentrations of all three pollutants correlated with the flow of vehicle traffic. Close correlations were also noted for the concentrations in ambient air for the three pollutants measured. Benzene and MTBE had a correlation coefficient of 0.97. The overall findings showed that the concentrations of various VOCs were closely related to the traffic density, suggesting that they were from a common source, such as exhaust emissions from the vehicles. The results also indicated that although benzene, MTBE, and THC are known to be volatile, a significant amount could still be detected in the ambient environment, thus contributing to our exposure to these compounds. 4 refs., 6 figs.

Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate-poly(poly(ethylene glycol methyl ether methacrylate Copolymers

Directory of Open Access Journals (Sweden)

Patcharin Kanhakeaw

2015-01-01

Full Text Available This work presented the surface modification of magnetite nanoparticle (MNP with poly[(t-butyl acrylate-stat-(poly(ethylene glycol methyl ether methacrylate] copolymers (P[(t-BA-stat-PEGMA] via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP. Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp. such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water, can be fine-tuned. The reaction progress in each step of the synthesis was monitored via Fourier transform infrared spectroscopy (FTIR. The studies in the reaction kinetics indicated that PEGMA had higher reactivity than that of t-BA in the copolymerizations. Gel permeation chromatography (GPC indicated that the molecular weights of the copolymers increased with the increase of the monomer conversion. Transmission electron microscopy (TEM revealed that the particles were spherical with averaged size of 8.1 nm in diameter. Dispersibility of the particles in water was apparently improved when the copolymers were coated as compared to P(t-BA homopolymer coating. The percentages of MNP and the copolymer in the composites were determined via thermogravimetric analysis (TGA and their magnetic properties were investigated via vibrating sample magnetometry (VSM.

Recovering/recycling of butyl and halogenated butyl rubber via ionizing radiation

International Nuclear Information System (INIS)

Martin, Sandra Regina Scagliusi

2013-01-01

Polymeric materials (plastics and rubbers) attain a continuous and raising proportion of urban and industrial scraps discarded in landfills; their impact on environment are more and more concerning. The implementation of new technologies in order to reduce impacts of plastic waste on the environment, at an effective cost, proved to be a great problem, due to inherent complexity for polymers re-using. Ionizing radiation is capable to modify structure and properties of polymeric material. Butyl and halobutyl rubbers have been used within a comprehensive scale, applications such as tires spare parts and diverse artifacts. The major high energy photon effect, as gamma-rays in butyl and halo butyl rubbers consists in free-radicals generation along changes in mechanical properties.This work aims to the development of controlled degradation processes (devulcanization) of butyl and halo butyl (chlorine and bromine) rubbers, in order to characterize their availability for transformation and modification of properties. Experimental results obtained showed that butyl and halobutyl rubbers,irradiated at 25 kGy and further sheared, are able to be used as an initial point for mixtures with pristine. (author)

Microbial synthesis of a branched-chain ester platform from organic waste carboxylates

Directory of Open Access Journals (Sweden)

Donovan S. Layton

2016-12-01

Full Text Available Processing of lignocellulosic biomass or organic wastes produces a plethora of chemicals such as short, linear carboxylic acids, known as carboxylates, derived from anaerobic digestion. While these carboxylates have low values and are inhibitory to microbes during fermentation, they can be biologically upgraded to high-value products. In this study, we expanded our general framework for biological upgrading of carboxylates to branched-chain esters by using three highly active alcohol acyltransferases (AATs for alcohol and acyl CoA condensation and modulating the alcohol moiety from ethanol to isobutanol in the modular chassis cell. With this framework, we demonstrated the production of an ester library comprised of 16 out of all 18 potential esters, including acetate, propionate, butanoate, pentanoate, and hexanoate esters, from the 5 linear, saturated C2-C6 carboxylic acids. Among these esters, 5 new branched-chain esters, including isobutyl acetate, isobutyl propionate, isobutyl butyrate, isobutyl pentanoate, and isobutyl hexanoate were synthesized in vivo. During 24 h in situ fermentation and extraction, one of the engineered strains, EcDL208 harnessing the SAAT of Fragaria ananassa produced ~63 mg/L of a mixture of butyl and isobutyl butyrates from glucose and butyrate co-fermentation and ~127 mg/L of a mixture of isobutyl and pentyl pentanoates from glucose and pentanoate co-fermentation, with high specificity. These butyrate and pentanoate esters are potential drop-in liquid fuels. This study provides better understanding of functional roles of AATs for microbial biosynthesis of branched-chain esters and expands the potential use of these esters as drop-in biofuels beyond their conventional flavor, fragrance, and solvent applications. Keywords: Carboxylate platform, Ester platform, Branched-chain ester, Modular cell, Biological upgrading, Organic waste, Lignocellulosic biomass, Isobutyl esters

The synthesis of 1-11C-labelled ethyl, propyl, butyl and isobutyl iodides and examples of alkylation reactions

International Nuclear Information System (INIS)

Laangstroem, B.; Antoni, G.; Gullberg, P.; Halldin, C.; Naagren, K.; Rimland, A.; Svaerd, H.

1986-01-01

New 11 C-labelled precursors [1- 11 C]ethyl,[1- 11 C]propyl, [1- 11 C]butyl, and [1- 11 C]isobutyl iodides have been prepared by a 3-step reaction route using a one-pot system. The labelled iodides were obtained in 20-55#percent# radiochemical yields and 65-95#percent# radiochemical purities, with a total time for synthesis of the order of 10-14 min. The labelled iodides have been used in alkylation reactions with nitrogen, oxygen and carbon nucleophiles. The nitrogen alkylation reactions are exemplified by the synthesis of the analgetics N-[1- 11 C-ethyl]iodocaine and N-[1- 11 C-butyl] bupivacaine. The synthesis of 3-nitrophenyl[1- 11 C]propyl ether is also presented in this paper as an example of an oxygen alkylation. (author)

Evaluation of ethyl tert-butyl ether biodegradation in a contaminated aquifer by compound-specific isotope analysis and in situ microcosms

Energy Technology Data Exchange (ETDEWEB)

Bombach, Petra, E-mail: petra.bombach@ufz.de [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Isodetect GmbH Leipzig, Deutscher Platz 5b, D-04103 Leipzig (Germany); Nägele, Norbert [Kuvier the Biotech Company S.L., Ctra. N-I, p.k. 234–P.E. INBISA 23" a, E-09001 Burgos (Spain); Rosell, Mònica [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristallografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), C/Martí i Franquès s/n, 08028 Barcelona (Spain); Richnow, Hans H. [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Fischer, Anko [Isodetect GmbH Leipzig, Deutscher Platz 5b, D-04103 Leipzig (Germany)

2015-04-09

Highlights: • In situ biodegradation of ETBE was investigated in a fuel contaminated aquifer. • Degradation was studied by CSIA and in situ microcosms in combination with TLFA-SIP. • ETBE was degraded when ETBE was the main groundwater contaminant. • ETBE was also degraded in the presence of BTEX and MTBE. • Hydrochemical analysis indicated aerobic and anaerobic ETBE biodegradation. - Abstract: Ethyl tert-butyl ether (ETBE) is an upcoming groundwater pollutant in Europe whose environmental fate has been less investigated, thus far. In the present study, we investigated the in situ biodegradation of ETBE in a fuel-contaminated aquifer using compound-specific stable isotope analysis (CSIA), and in situ microcosms in combination with total lipid fatty acid (TLFA)-stable isotope probing (SIP). In a first field investigation, CSIA revealed insignificant carbon isotope fractionation, but low hydrogen isotope fractionation of up to +14‰ along the prevailing anoxic ETBE plume suggesting biodegradation of ETBE. Ten months later, oxygen injection was conducted to enhance the biodegradation of petroleum hydrocarbons (PH) at the field site. Within the framework of this remediation measure, in situ microcosms loaded with [{sup 13}C{sub 6}]-ETBE (BACTRAP{sup ®}s) were exposed for 119 days in selected groundwater wells to assess the biodegradation of ETBE by TLFA-SIP under the following conditions: (i) ETBE as main contaminant; (ii) ETBE as main contaminant subjected to oxygen injection; (iii) ETBE plus other PH; (iv) ETBE plus other PH subjected to oxygen injection. Under all conditions investigated, significant {sup 13}C-incorporation into microbial total lipid fatty acids extracted from the in situ microcosms was found, providing clear evidence of ETBE biodegradation.

Evaluation of ethyl tert-butyl ether biodegradation in a contaminated aquifer by compound-specific isotope analysis and in situ microcosms

International Nuclear Information System (INIS)

Bombach, Petra; a, E-09001 Burgos (Spain))" data-affiliation=" (Kuvier the Biotech Company S.L., Ctra. N-I, p.k. 234–P.E. INBISA 23a, E-09001 Burgos (Spain))" >Nägele, Norbert; Rosell, Mònica; Richnow, Hans H.; Fischer, Anko

2015-01-01

Highlights: • In situ biodegradation of ETBE was investigated in a fuel contaminated aquifer. • Degradation was studied by CSIA and in situ microcosms in combination with TLFA-SIP. • ETBE was degraded when ETBE was the main groundwater contaminant. • ETBE was also degraded in the presence of BTEX and MTBE. • Hydrochemical analysis indicated aerobic and anaerobic ETBE biodegradation. - Abstract: Ethyl tert-butyl ether (ETBE) is an upcoming groundwater pollutant in Europe whose environmental fate has been less investigated, thus far. In the present study, we investigated the in situ biodegradation of ETBE in a fuel-contaminated aquifer using compound-specific stable isotope analysis (CSIA), and in situ microcosms in combination with total lipid fatty acid (TLFA)-stable isotope probing (SIP). In a first field investigation, CSIA revealed insignificant carbon isotope fractionation, but low hydrogen isotope fractionation of up to +14‰ along the prevailing anoxic ETBE plume suggesting biodegradation of ETBE. Ten months later, oxygen injection was conducted to enhance the biodegradation of petroleum hydrocarbons (PH) at the field site. Within the framework of this remediation measure, in situ microcosms loaded with [ 13 C 6 ]-ETBE (BACTRAP ® s) were exposed for 119 days in selected groundwater wells to assess the biodegradation of ETBE by TLFA-SIP under the following conditions: (i) ETBE as main contaminant; (ii) ETBE as main contaminant subjected to oxygen injection; (iii) ETBE plus other PH; (iv) ETBE plus other PH subjected to oxygen injection. Under all conditions investigated, significant 13 C-incorporation into microbial total lipid fatty acids extracted from the in situ microcosms was found, providing clear evidence of ETBE biodegradation

Emission Studies in CI Engine using LPG and Palm Kernel Methyl Ester as Fuels and Di-ethyl Ether as an Additive

Science.gov (United States)

Dora, Nagaraju; Jothi, T. J. Sarvoththama

2018-05-01

The present study investigates the effectiveness of using di-ethyl ether (DEE) as the fuel additive in engine performance and emissions. Experiments are carried out in a single cylinder four stroke diesel engine at constant speed. Two different fuels namely liquefied petroleum gas (LPG) and palm kernel methyl ester (PKME) are used as primary fuels with DEE as the fuel additive. LPG flow rates of 0.6 and 0.8 kg/h are considered, and flow rate of DEE is varied to maintain the constant engine speed. In case of PKME fuel, it is blended with diesel in the latter to the former ratio of 80:20, and DEE is varied in the volumetric proportion of 1 and 2%. Results indicate that for the engine operating in LPG-DEE mode at 0.6 kg/h of LPG, the brake thermal efficiency is lowered by 26%; however, NOx is subsequently reduced by around 30% compared to the engine running with only diesel fuel at 70% load. Similarly, results of PKME blended fuel showed a drastic reduction in the NOx and CO emissions. In these two modes of operation, DEE is observed to be significant fuel additive regarding emissions reduction.

Determining the fatty acid composition in plasma and tissues as fatty acid methyl esters using gas chromatography – a comparison of different derivatization and extraction procedures.

Science.gov (United States)

Ostermann, Annika I; Müller, Maike; Willenberg, Ina; Schebb, Nils Helge

2014-12-01

Analysis of the fatty acid (FA) composition in biological samples is commonly carried out using gas liquid chromatography (GC) after transesterification to volatile FA methyl esters (FAME). We compared the efficacy of six frequently used protocols for derivatization of different lipid classes as well as for plasma and tissue samples. Transesterification with trimethylsulfonium hydroxide (TMSH) led to insufficient derivatization efficacies for polyunsaturated FAs (PUFA, ester (CE) as well as triacylglycerols (TGs). In contrast, methanolic hydrochloric acid (HCl) as well as a combination of BF3 with methanolic sodium hydroxide (NaOH+BF3) were suitable for the derivatization of FFAs, polar lipids, TGs, and CEs (derivatization rate >80% for all tested lipids). Regarding plasma samples, all methods led to an overall similar relative FA pattern. However, significant differences were observed, for example, for the relative amount of EPA+DHA (n3-index). Absolute FA plasma concentrations differed considerably among the methods, with low yields for KOH and BF3. We also demonstrate that lipid extraction with tert-butyl methyl ether/methanol (MTBE/MeOH) is as efficient as the classical method according to Bligh and Dyer, making it possible to replace (environmentally) toxic chloroform.We conclude that HCl-catalyzed derivatization in combination with MeOH/MTBE extraction is the most appropriate among the methods tested for the analysis of FA concentrations and FA pattern in small biological samples. A detailed protocol for the analysis of plasma and tissues is included in this article.

Identification of tertiary butyl alcohol (TBA)-utilizing organisms in BioGAC reactors using 13C-DNA stable isotope probing.

Science.gov (United States)

Aslett, Denise; Haas, Joseph; Hyman, Michael

2011-09-01

Biodegradation of the gasoline oxygenates methyl tertiary-butyl ether (MTBE) and ethyl tertiary-butyl ether (ETBE) can cause tertiary butyl alcohol (TBA) to accumulate in gasoline-impacted environments. One remediation option for TBA-contaminated groundwater involves oxygenated granulated activated carbon (GAC) reactors that have been self-inoculated by indigenous TBA-degrading microorganisms in ground water extracted from contaminated aquifers. Identification of these organisms is important for understanding the range of TBA-metabolizing organisms in nature and for determining whether self-inoculation of similar reactors is likely to occur at other sites. In this study (13)C-DNA-stable isotope probing (SIP) was used to identify TBA-utilizing organisms in samples of self-inoculated BioGAC reactors operated at sites in New York and California. Based on 16S rRNA nucleotide sequences, all TBA-utilizing organisms identified were members of the Burkholderiales order of the β-proteobacteria. Organisms similar to Cupriavidus and Methylibium were observed in both reactor samples while organisms similar to Polaromonas and Rhodoferax were unique to the reactor sample from New York. Organisms similar to Hydrogenophaga and Paucibacter strains were only detected in the reactor sample from California. We also analyzed our samples for the presence of several genes previously implicated in TBA oxidation by pure cultures of bacteria. Genes Mpe_B0532, B0541, B0555, and B0561 were all detected in (13)C-metagenomic DNA from both reactors and deduced amino acid sequences suggested these genes all encode highly conserved enzymes. One gene (Mpe_B0555) encodes a putative phthalate dioxygenase-like enzyme that may be particularly appropriate for determining the potential for TBA oxidation in contaminated environmental samples.

Catalytic Upgrading of Biomass-Derived Furfuryl Alcohol to Butyl Levulinate Biofuel over Common Metal Salts

Directory of Open Access Journals (Sweden)

Lincai Peng

2016-09-01

Full Text Available Levulinate ester has been identified as a promising renewable fuel additive and platform chemical. Here, the use of a wide range of common metal salts as acid catalysts for catalytic upgrading of biomass-derived furfuryl alcohol to butyl levulinate was explored by conventional heating. Both alkali and alkaline earth metal chlorides did not lead effectively to the conversion of furfuryl alcohol, while several transition metal chlorides (CrCl3, FeCl3, and CuCl2 and AlCl3 exhibited catalytic activity for the synthesis of butyl levulinate. For their sulfates (Cr(III, Fe(III, Cu(II, and Al(III, the catalytic activity was low. The reaction performance was correlated with the Brønsted acidity of the reaction system derived from the hydrolysis/alcoholysis of cations, but was more dependent on the Lewis acidity from the metal salts. Among these investigated metal salts, CuCl2 was found to be uniquely effective, leading to the conversion of furfuryl alcohol to butyl levulinate with an optimized yield of 95%. Moreover, CuCl2 could be recovered efficiently from the resulting reaction mixture and remained with almost unchanged catalytic activity in multiple recycling runs.

Structure and properties of oil palm-based nanocellulose reinforced chitosan nanocomposite for efficient synthesis of butyl butyrate.

Science.gov (United States)

Elias, Nursyafiqah; Chandren, Sheela; Attan, Nursyafreena; Mahat, Naji Arafat; Razak, Fazira Ilyana Abdul; Jamalis, Joazaizulfazli; Wahab, Roswanira Abdul

2017-11-15

In this study, nanocellulose (NC) was successfully extracted from oil palm frond leaves (OPFL) using a combination of bleaching, alkaline treatment and acid hydrolysis. X-ray diffractogram revealed the extracted NC was crystalline with a crystallinity index of 70.2%. This indicates its suitability as nano-fillers for preparing the chitosan/nanocellulose (CS-NC) supports to immobilize Candida rugosa lipase (CRL) to produce the CRL/CS-NC biocatalysts. FTIR, FESEM and TGA characterizations of the CRL/CS-NC confirm the CRLs were successfully conjugated to the CS-NC supports. The air-dried CS-NC supports gave satisfactory immobilization of the CRLs (5.2mg/g) with the resultant CRL/CS-NCs catalysed conversions of ≥80% of butyl butyrate within 6h. Time course reaction profile revealed that 76.3% butyl butyrate conversion was achieved at 4h immobilization time using 3mg/mL of CRL/CS-NCs. NMR analyses on the purified butyl butyrate confirmed that the ester was successfully synthesized. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

Energy Technology Data Exchange (ETDEWEB)

Lopes Ferreira, N

2005-11-15

Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

Energy Technology Data Exchange (ETDEWEB)

Lopes Ferreira, N.

2005-11-15

Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

Aerobic degradation of methyl tert-butyl ether in a closed symbiotic system containing a mixed culture of Chlorella ellipsoidea and Methylibium petroleiphilum PM1.

Science.gov (United States)

Zhong, Weihong; Li, Yixiao; Sun, Kedan; Jin, Jing; Li, Xuanzhen; Zhang, Fuming; Chen, Jianmeng

2011-01-30

The contamination of groundwater by methyl tert-butyl ether (MTBE) is one of the most serious environmental problems around the world. MTBE degradation in a closed algal-bacterial symbiotic system, containing a mixed culture of Methylibium petroleiphilum PM1 and Chlorella ellipsoidea, was investigated. The algal-bacterial symbiotic system showed increased MTBE degradation. The MTBE-degradation rate in the mixed culture (8.808 ± 0.007 mg l(-1) d(-1)) was higher than that in the pure bacterial culture (5.664 ± 0.017 mg l(-1) d(-1)). The level of dissolved oxygen was also higher in the mixed culture than that in the pure bacterial culture. However, the improved efficiency of MTBE degradation was not in proportional to the biomass of the alga. The optimal ratio of initial cell population of bacteria to algae was 100:1. An immobilized culture of mixed bacteria and algae also showed higher MTBE degradation rate than the immobilized pure bacterial culture. A mixed culture with algae and PM1 immobilized separately in different gel beads showed higher degradation rate (8.496 ± 0.636 mg l(-1) d(-1)) than that obtained with algae and PM1 immobilized in the same gel beads (5.424 ± 0.010 mg l(-1) d(-1)). Copyright © 2010 Elsevier B.V. All rights reserved.

Synthesis of thermoplastic poly(ester-olefin elastomers

Directory of Open Access Journals (Sweden)

Tanasijević Branka

2004-01-01

Full Text Available A series of thermoplastic poly(ester-olefin elastomers, based on poly(ethylene-stat-butylene, HO-PEB-OH, as the soft segment and poly (butylene terephthalate, PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol with 1,4-butanediol (BD and dimethyl terephthalate (DMT in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu4, and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD, as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu4 for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylenes were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefins were investigated by differential scanning calorimetry (DSC. The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA. The rheological properties of poly(ester-olefins were investigated by dynamic mechanical spectroscopy in the melt and solid state.

Sonolytic and Silent Polymerization of Methacrlyic Acid Butyl Ester Catalyzed by a New Onium Salt with bis-Active Sites in a Biphasic System — A Comparative Investigation

Directory of Open Access Journals (Sweden)

Perumberkandgai A. Vivekanand

2013-02-01

Full Text Available Currently, ingenious new analytical and process experimental techniques which are environmentally benign techniques, viz., ultrasound irradiation, have become immensely popular in promoting various reactions. In this work, a novel soluble multi-site phase transfer catalyst (PTC viz., 1,4-bis-(propylmethyleneammounium chloridebenzene (BPMACB was synthesized and its catalytic efficiency was assessed by observing the kinetics of sonolytic polymerization of methacrylic acid butyl ester (MABE using potassium persulphate (PPS as an initiator. The ultrasound–multi-site phase transfer catalysis (US-MPTC-assisted polymerization reaction was compared with the silent (non-ultrasonic polymerization reaction. The effects of the catalyst and various reaction parameters on the catalytic performance were in detail investigated by following the kinetics of polymerization of MABE in an ethyl acetate-water biphasic system. From the detailed kinetic investigation we propose a plausible mechanism. Further the kinetic results demonstrate clearly that ultrasound-assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Notably, this environmentally benign and cost-effective process has great potential to be applied in various polymer industries.

Synthesis of 1-/sup 11/C-labelled ethyl, propyl, butyl and isobutyl iodides and examples of alkylation reactions

Energy Technology Data Exchange (ETDEWEB)

Laangstroem, B.; Antoni, G.; Gullberg, P.; Halldin, C.; Naagren, K.; Rimland, A.; Svaerd, H.

1986-01-01

New /sup 11/C-labelled precursors (1-/sup 11/C)ethyl,(1-/sup 11/C)propyl, (1-/sup 11/C)butyl, and (1-/sup 11/C)isobutyl iodides have been prepared by a 3-step reaction route using a one-pot system. The labelled iodides were obtained in 20-55% radiochemical yields and 65-95% radiochemical purities, with a total time for synthesis of the order of 10-14 min. The labelled iodides have been used in alkylation reactions with nitrogen, oxygen and carbon nucleophiles. The nitrogen alkylation reactions are exemplified by the synthesis of the analgetics N-(1-/sup 11/C-ethyl)iodocaine and N-(1-/sup 11/C-butyl) bupivacaine. The synthesis of 3-nitrophenyl(1-/sup 11/C)propyl ether is also presented in this paper as an example of an oxygen alkylation.

Synthesis and characterization of thermoplastic copolyester elastomers modified with fumaric moieties

Directory of Open Access Journals (Sweden)

JASNA DJONLAGIC

2001-03-01

Full Text Available A series of poly(ether-esters derived from dimethyl terephthalate (DMT, dimethyl fumarate (DMF, 1,4-butandiol (BD and poly(tetramethylene oxide (PTMO,Mn = 1000 g/mol was synthesized in a two stage process involving transesterification and polycondensation in the melt. The mole ratio of the starting components was selected to result in copolymers with a constant hard:soft segment wieght ratio (56:44. The amount of DMF was 10 mol %, referred to the total amount of the esters used. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate, Ti(OBu4 and thermal stabilizer N,N’-diphenyl-p-phenylenediamine, DPPD, as well as the temperature. The composition and structure of the synthesized poly(ether-esters were characterized by 1H-NMR. The number average molecular weights of the polymers calculated from the 1H-NMR spectra were compared with the corresponding values of the inherent viscosity (hinh in m-cresol and the complex dynamic viscosity (h *. The effect of the content of fumaric residues on the thermal properties of the synthesized copolyesters was also investigated using differential scanning calorimetry (DSC and thermal gravimetric analysis (TGA.

Physiologically based pharmacokinetic rat model for methyl tertiary-butyl ether; comparison of selected dose metrics following various MTBE exposure scenarios used for toxicity and carcinogenicity evaluation

International Nuclear Information System (INIS)

Borghoff, Susan J.; Parkinson, Horace; Leavens, Teresa L.

2010-01-01

There are a number of cancer and toxicity studies that have been carried out to assess hazard from methyl tertiary-butyl ether (MTBE) exposure via inhalation and oral administration. MTBE has been detected in surface as well as ground water supplies which emphasized the need to assess the risk from exposure via drinking water contamination. This model can now be used to evaluate route-to-route extrapolation issues concerning MTBE exposures but also as a means of comparing potential dose metrics that may provide insight to differences in biological responses observed in rats following different routes of MTBE exposure. Recently an updated rat physiologically based pharmacokinetic (PBPK) model was published that relied on a description of MTBE and its metabolite tertiary-butyl alcohol (TBA) binding to α2u-globulin, a male rat-specific protein. This model was used to predict concentrations of MTBE and TBA in the kidney, a target tissue in the male rat. The objective of this study was to use this model to evaluate the dosimetry of MTBE and TBA in rats following different exposure scenarios, used to evaluate the toxicity and carcinogenicity of MTBE, and compare various dose metrics under these different conditions. Model simulations suggested that although inhalation and drinking water exposures show a similar pattern of MTBE and TBA exposure in the blood and kidney (i.e. concentration-time profiles), the total blood and kidney levels following exposure of MTBE to 7.5 mg/ml MTBE in the drinking water for 90 days is in the same range as administration of an oral dose of 1000 mg/kg MTBE. Evaluation of the dose metrics also supports that a high oral bolus dose (i.e. 1000 mg/kg MTBE) results in a greater percentage of the dose exhaled as MTBE with a lower percent metabolized to TBA as compared to dose of MTBE that is delivered over a longer period of time as in the case of drinking water.

Solubilization of meso-carbon microbeads by potassium- or dibutylzinc-promoted butylation and structural analysis of the butylated products; Mesocarbon microbeads no butyl ka ni yoru kayoka to erareta butyl kabutsu no kozo kaiseki

Energy Technology Data Exchange (ETDEWEB)

Murata, S.; Zhang, Y.; Kidena, K.; Nomura, M. [Osaka University, Osaka (Japan). Faculty of Engineering

1996-10-28

Tetrahydrofuran (THF) solubility and structure of the butylated products of meso-carbon microbeads (MCMB) were studied experimentally. In experiment, MCMB-A and MCMB-B obtained from two kinds of coal-tar pitch were used as specimens. MCMBs were butylated by BZ method using dibutylzinc-butyl iodide and KT method using K-butyl iodide-THF, and the butylated products were successfully obtained. The butylated products were investigated through THF solubility test, {sup 13}C-NMR measurement and gel permeation chromatography (GPC) measurement. As the experimental result, a BZ method produced the butylated products at a yield of nearly 170%, while a KT method produced them at a yield of nearly 130%. The THF solubility was estimated to be 89-97%. As the study result of molecular weight distributions by GPC measurement of solvent solubles, the molecular weight of raw material MCMB was estimated to be 590-770 in terms of polystyrene. 6 refs., 2 figs., 1 tab.

Isolate PM1 populations are dominant and novel methyl tert-butyl ether-degrading bacterial in compost biofilter enrichments.

Science.gov (United States)

Bruns, M A; Hanson, J R; Mefford, J; Scow, K M

2001-03-01

The gasoline additive MTBE, methyl tert-butyl ether, is a widespread and persistent groundwater contaminant. MTBE undergoes rapid mineralization as the sole carbon and energy source of bacterial strain PM1, isolated from an enrichment culture of compost biofilter material. In this report, we describe the results of microbial community DNA profiling to assess the relative dominance of isolate PM1 and other bacterial strains cultured from the compost enrichment. Three polymerase chain reaction (PCR)-based profiling approaches were evaluated: denaturing gradient gel electrophoresis (DGGE) analysis of 230 bp 16S rDNA fragments; thermal gradient gel electrophoresis (TGGE) analysis of 575 bp 16S rDNA fragments; and non-denaturing polyacrylamide gel electrophoresis of 300-1,500 bp fragments containing 16S/23S ribosomal intergenic transcribed spacer (ITS) regions. Whereas all three DNA profiling approaches indicated that PM1-like bands predominated in mixtures from MTBE-grown enrichments, ITS profiling provided the most abundant and specific sequence data to confirm strain PM1's presence in the enrichment. Moreover, ITS profiling did not produce non-specific PCR products that were observed with T/DGGE. A further advantage of ITS community profiling over other methods requiring restriction digestion (e.g. terminal restriction fragment length polymorphisms) was that it did not require an additional digestion step or the use of automated sequencing equipment. ITS bands, excised from similar locations in profiles of the enrichment and PM1 pure culture, were 99.9% identical across 750 16S rDNA positions and 100% identical across 691 spacer positions. BLAST comparisons of nearly full-length 16S rDNA sequences showed 96% similarity between isolate PM1 and representatives of at least four different genera in the Leptothrix subgroup of the beta-Proteobacteria (Aquabacterium, Leptothrix, Rubrivivax and Ideonella). Maximum likelihood and parsimony analyses of 1,249 nucleotide

Optimization of reactive simulated moving bed systems with modulation of feed concentration for production of glycol ether ester.

Science.gov (United States)

Agrawal, Gaurav; Oh, Jungmin; Sreedhar, Balamurali; Tie, Shan; Donaldson, Megan E; Frank, Timothy C; Schultz, Alfred K; Bommarius, Andreas S; Kawajiri, Yoshiaki

2014-09-19

In this article, we extend the simulated moving bed reactor (SMBR) mode of operation to the production of propylene glycol methyl ether acetate (DOWANOL™ PMA glycol ether) through the esterification of 1-methoxy-2-propanol (DOWANOL™ PM glycol ether) and acetic acid using AMBERLYST™ 15 as a catalyst and adsorbent. In addition, for the first time, we integrate the concept of modulation of the feed concentration (ModiCon) to SMBR operation. The performance of the conventional (constant feed) and ModiCon operation modes of SMBR are analyzed and compared. The SMBR processes are designed using a model based on a multi-objective optimization approach, where a transport dispersive model with a linear driving force for the adsorption rate has been used for modeling the SMBR system. The adsorption equilibrium and kinetics parameters are estimated from the batch and single column injection experiments by the inverse method. The multiple objectives are to maximize the production rate of DOWANOL™ PMA glycol ether, maximize the conversion of the esterification reaction and minimize the consumption of DOWANOL™ PM glycol ether which also acts as the desorbent in the chromatographic separation. It is shown that ModiCon achieves a higher productivity by 12-36% over the conventional operation with higher product purity and recovery. Copyright © 2014 Elsevier B.V. All rights reserved.

Lipid oxidation. Part 2. Oxidation products of olive oil methyl esters.

Science.gov (United States)

Pokorný, J; Tài, P; Parízková, H; Smidrkalová, E; El-Tarras, M F; Janícek, G

1976-01-01

Olive oil was converted into methyl esters which were autoxidized at 60 degrees C. The composition of oxidized products was determined by the comparison of infrared spectra and NMR spectra of the original and acetylated samples, the sample reduced with potassium iodide and the acetylated reduced sample. Oxidized products were separated by preparative thin layer chromatography on silica gel and characterized by selective detection and by infrared spectrometry of the fractions. The oxidation products consisted of hydroperoxido butyl oleate, substituted hydroperoxides, mono- and disubstituted monomeric derivatives and a small amount of oligomers.

Thermophysical properties of ionic liquid {1-butyl-3-methylimidazolium bromide [bmim][Br] in alkoxyalkanols + water} mixtures at different temperatures

International Nuclear Information System (INIS)

Pal, Amalendu; Kumar, Harsh; Kumar, Bhupinder; Sharma, Pooja; Kaur, Kirtanjot

2013-01-01

Highlights: ► Densities and speeds of sound of alkoxyalkanols in [bmim][Br]. ► Synthesis of room temperature ionic liquid [bmim][Br]. ► Partial molar volumes and compressibility of transfer. ► Apparent molar expansivities and the Hepler’s constant were calculated. ► Solute–solute and solute–solvent interactions and the structural changes of the solutes. - Abstract: The interactions of alkoxyalkanols with the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim][Br] as a function of temperature were investigated by combination of volumetric and acoustic methods. The density, ρ, and speed of sound, u, of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether (0.00–1.01 mol·kg −1 ) in aqueous 1-butyl-3-methylimidazolium bromide solutions ranging from pure water to 0.29 mass% of ionic liquid have been measured at T = (288.15, 298.15 and 308.15) K and atmospheric pressure. The apparent molar volume (V φ ) and adiabatic compressibility (K φ,S ) of alkoxyalkanols in aqueous ionic liquid solution were determined at the measured temperatures. The partial molar volume (V φ 0 ) and partial molar adiabatic compressibility (K φ 0 ) of alkoxyalkanols at infinite dilution were evaluated. Transfer volumes (ΔV φ 0 ) and transfer adiabatic compressibility (ΔK φ 0 ) at infinite dilution from water to aqueous ionic liquid solution were also calculated. The temperature dependence of the apparent molar volume was used to calculate apparent molar expansivity (φ E 0 ) and the Hepler’s constant values, (∂ 2 V φ 0 /∂T 2 ). The results were explained on the basis of competing patterns of interactions of co-solvent and the solute.

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

Science.gov (United States)

Ensminger, M P; Hess, F D

1985-05-01

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

Radiation curable coatings containing hydroxy functional polyethers and polyesters of monoethylenic acids or hydroxy esters thereof

International Nuclear Information System (INIS)

Kaufman, M.L.

1978-01-01

Relatively water insoluble hydroxy functional monoethylenic polyethers or polyesters of monoethylenic carboxylic acids or hydroxy alkyl esters thereof are formed by adducting the monoethylenic acid or its hydroxy ester with an anhydride selected from monoepoxides, lactones, or mixtures thereof in the presence of a Lewis acid catalyst, such as BF 3 etherate, at a temperature below that at which the unsaturation is consumed, typically about 30 to 70 0 C. These adducts are of low volatility and of low toxicity and can be radiation cured in admixture with polyacrylates to form coatings having improved resistance to elevated temperature exposure

Health assessment of gasoline and fuel oxygenate vapors: Neurotoxicity evaluation

OpenAIRE

O?Callaghan, James P.; Daughtrey, Wayne C.; Clark, Charles R.; Schreiner, Ceinwen A.; White, Russell

2014-01-01

Sprague?Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess potential neurotoxicity of evaporative emissions. Test articles included vapor condensates prepared from ?baseline gasoline? (BGVC), or gasoline combined with methyl tertiary 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). Target concentrati...

Development of solvent-free offset ink using vegetable oil esters and high molecular-weight resin.

Science.gov (United States)

Park, Jung Min; Kim, Young Han; Kim, Sung Bin

2013-01-01

In the development of solvent-free offset ink, the roles of resin molecular weight and used solvent on the ink performance were evaluated by examining the relationship between the various properties of resin and solvent and print quality. To find the best performing resin, the soy-oil fatty acid methyl ester (FAME) was applied to the five modified-phenolic resins having different molecular weights. It is found from the experimental results that the ink made of higher molecular weight and better solubility resin gives better printability and print quality. It is because larger molecular weight resin with better solubility gives higher rate of ink transfer. From the ink application of different esters to high molecular weight resin, the best printing performance was yielded from the soy-oil fatty acid butyl ester (FABE). It is due to its high kinematic viscosity resulting in the smallest change of ink transfer weight upon multiple number of printing, which improves the stability of ink quality.

STABILITY OF EMULSIFIER-FREE EMULSION COPOLYMERIZATION OF METHYL METHACRYLATE/ BUTYL ACRYLATE/SODIUM MONO(ETHYL POLYOXYETHYLENE) MALEATE

Institute of Scientific and Technical Information of China (English)

Mao-gen Zhang; Zhi-xue Weng; Zhi-ming Huang; Zu-ren Pan

1999-01-01

A series of new water-soluble bifunctional comonomers having both carboxyl and alkyl polyoxyethylene groups, such as sodium mono(ethyl polyoxyethylene) maleate (ZE series) with various molecular weights of polyoxyethylene ethyl ether, were synthesized and characterized. The effects of the structural factor, the amount and feeding mode of the comonomers, the initiator concentration and polymerization temperature on the stability of emulsifier-free emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of a small amount of ZE with potassium persulfate as initiator were investigated. Stable, almost monodispersed MMA/BA/ZE emulsifier-free latex particles were prepared.

Tetrabutylammonium Bromide Media Aza-Michael Addition of 1,2,3,6-Tetrahydrophthalimide to Symmetrical Fumaric Esters and Acrylic Esters under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Mohammadreza Zamanloo

2010-10-01

Full Text Available The aza-Michael addition of 1,2,3,6-tetrahydrophthalimide with symmetrical fumaric esters has been performed efficiently in a solvent-free system at 100 °C and using 1,4-diazabicyclo[2.2.2]octane (DABCO as a base in the presence of tetrabutylammonium bromide (TBAB. The products were obtained in good to high yields within 2.5-7.0 h. This reaction worked well on linear alkyl fumarates and was not effective with nonlinear alkyl fumarates. Although the reaction was also applicable to acrylates such as n-butyl acrylate, methacrylates and crotonates were not suitable Michael acceptors for this reaction.

Design and Control of Glycerol-tert-Butyl Alcohol Etherification Process

Directory of Open Access Journals (Sweden)

Elena Vlad

2012-01-01

Full Text Available Design, economics, and plantwide control of a glycerol-tert-butyl alcohol (TBA etherification plant are presented. The reaction takes place in liquid phase, in a plug flow reactor, using Amberlyst 15 as a catalyst. The products' separation is achieved by two distillation columns where high-purity ethers are obtained and a section involving extractive distillation with 1,4-butanediol as solvent, which separates TBA from the TBA/water azeotrope. Details of design performed in AspenPlus and an economic evaluation of the process are given. Three plantwide control structures are examined using a mass balance model of the plant. The preferred control structure fixes the fresh glycerol flow rate and the ratio glycerol + monoether : TBA at reactor-inlet. The stability and robustness in the operation are checked by rigorous dynamic simulation in AspenDynamics.

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

Science.gov (United States)

Ensminger, Michael P.; Hess, F. Dan

1985-01-01

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

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

2014-01-01

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda

2014-03-25

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

Microbial dynamics in anaerobic enrichment cultures degrading di-n-butyl phthalic acid ester

DEFF Research Database (Denmark)

Trably, Eric; Batstone, Damien J.; Christensen, Nina

2008-01-01

losses were observed in the sterile controls (20-22%), substantial DBP biodegradation was found in the enrichment cultures (90-99%). In addition, significant population changes were observed. The dominant bacterial species in the DBP-degrading cultures was affiliated to Soehngenia saccharolytica...... in enrichment cultures degrading phthalic acid esters under methanogenic conditions. A selection pressure was applied by adding DBP at 10 and 200 mg L(-1) in semi-continuous anaerobic reactors. The microbial dynamics were monitored using single strand conformation polymorphism (SSCP). While only limited abiotic...

SIRT1 exhibits antioxidative effects in HT22 cells induced by tert-butyl alcohol.

Science.gov (United States)

Ma, Junxiang; Song, Dongmei; Zhang, Yuanyuan; Chen, Li; Zhang, Shixuan; Jia, Jiaxin; Chen, Tian; Guo, Caixia; Tian, Lin; Gao, Ai; Niu, Piye

2018-02-01

Tertiary butyl alcohol (TBA) is a principal metabolite of methyl tertiary-butyl ether (MTBE), a common pollutant worldwide in the ground or underground water, which is found to produce nervous system damage. Nevertheless, few data regarding the effects of TBA has been reported. Studies indicated that oxidative stress plays a pivotal role in MTBE neurotoxic mechanism. Sirtuin 1 (SIRT1) has been reported to exert a neuroprotective effect on various neurologic diseases via resistance to oxidative stress by deacetylating its substrates. In this study, we examined levels of oxidative stress after exposure to TBA for 6 h in HT22 cells and HT22 cells with SIRT1 silencing (transfected with SIRT1 siRNA) or high expression (preconditioned with agonists SRT1720). We found that TBA activated oxidative stress by increasing generation of intracellular reactive oxygen species (ROS), malondialdehyde (MDA) and Oxidized glutathione (GSSG), and decreasing contents of superoxide dismutase (SOD) and glutathione reductase (GSH). In additional, levels of TBA-induced oxidative stress were aggravated when SIRT1 silenced but alleviated when SIRT1 enhanced. Our study indicated that SIRT1 mitigated oxidative stress induced by TBA. © 2017 Wiley Periodicals, Inc.

Construction of wettability gradient surface on copper substrate by controlled hydrolysis of poly(methyl methacrylate–butyl acrylate) films

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yong, E-mail: Yong.Z@mail.scut.edu.cn [Guangzhou Panyu Polytechnic, Guangzhou 511483 (China); Cheng, Jiang; Yang, Zhuo-ru [School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640 (China)

2014-10-01

We report a gradient wettability surface on copper slide prepared by a simple controlled ester group hydrolysis procedure of poly(methyl methacrylate–butyl acrylate) [P (MMA-BA)] films coated on the copper substrate. In the method, sodium hydroxide solutions are selected to prepare surface gradient wettability on P (MMA-BA) films. The P (MMA-BA) copolymers with different MMA contents are first synthesized by a conventional free atom radical solution polymerization method. The transfer of surface chemical composition from the ester group to acid salt is achieved by hydrolysis in NaOH solution. The effects of different concentrations of NaOH solution and reaction times on the physicochemical properties of the resulting surfaces are studied. The field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) results show that the varying concentration along the substrate length is only attributed to the hydrolysis reaction of ester groups. The hydrolysis causes insignificant change on the morphology of the original film on the copper substrate. In addition, it is found that the MMA copolymer content has a significant influence on the concentration of ester groups on the outermost surface and thus important for forming the slope gradients.

An investigation of 2,5-di-tertbutyl-1,4-bis(methoxyethoxy)benzene in ether-based electrolytes

Energy Technology Data Exchange (ETDEWEB)

Su, Liang; Ferrandon, Magali; Barton, John L.; de la Rosa, Noel Upia; Vaughey, John T.; Brushett, Fikile R.

2017-08-01

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

Measurement of critical temperatures and critical pressures for binary mixtures of methyl tert-butyl ether (MTBE) + alcohol and MTBE + alkane

International Nuclear Information System (INIS)

Han, Kewei; Xia, Shuqian; Ma, Peisheng; Yan, Fangyou; Liu, Tao

2013-01-01

Highlights: • The critical properties of seven binary mixtures related to gasoline were measured. • The critical properties of the five systems containing MTBE were reported for the first time. • Binary interaction parameters were fitted by experimental data using PR EOS with Wong–Sandler mixing rule. • Redlich–Kister equation was used to correlate the experimental data. -- Abstract: A set of high-pressure view apparatus was designed for determining the critical properties of chemicals. In order to check the reliability of the apparatus, the critical temperatures (T c ) and critical pressures (P c ) of pure n-heptane, cyclohexane, methanol, ethanol, 1-propanol, methyl tert-butyl ether (MTBE), and binary mixture n-hexane + ethanol were measured. The experimental data were in good agreement with the literature data, which proves the reliability of the apparatus used in the work. The critical temperatures and critical pressures of five binary mixtures containing gasoline additive (MTBE + n-heptane, MTBE + cyclohexane, MTBE + methanol, MTBE + ethanol, MTBE + 1-propanol) were measured using the high-pressure view cell with visual observation. The critical temperatures and critical pressures for the five binary mixtures were all reported for the first time. In addition, the critical temperatures and critical pressures of the binary mixture n-heptane + cyclohexane (two of main components in gasoline) were also measured. All the critical lines for the mixtures studied are continuous which connect the critical points of the two pure components, indicating their phase diagrams belong to type I proposed by Scott and van Konynenburg. The critical points of these systems were calculated by the Peng–Robinson equation of state with the Wong–Sandler mixing rule. This model could calculate the critical properties of the mixtures well with the binary interaction parameter k ij obtained by fitting the experimental critical data. And the experimental data were all

Thermal and enzymatic pretreatment of sludge containing phthalate esters prior to mesophilic anaerobic digestion

DEFF Research Database (Denmark)

Gavala, Hariklia N.; Yenal, U.; Ahring, Birgitte Kiær

2004-01-01

The present study aimed at investigating the effect of thermal pretreatment of sludge at 70degreesC on the anaerobic degradation of three commonly found phthalic acid esters (PAE): di-ethyl phthalate (DEP), di-butyl phthalate (DBP), and di-ethylhexyl phthalate (DEHP). Also, the enzymatic treatment...... at 28degreesC with a commercial lipase was studied as a way to enhance PAE removal. Pretreatment at 70degreesC of the sludge containing PAE negatively influenced the anaerobic biodegradability of phthalate esters at 37degreesC. The observed reduction of PAE biodegradation rates after the thermal...... pretreatment was found to be proportional to the PAE solubility in water: the higher the solubility, the higher the percentage of the reduction (DEP > DBP > DEHP). PAE were slowly degraded during the pretreatment at 70degreesC, yet this was probably due to physicochemical reactions than to microbial...

Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions

NARCIS (Netherlands)

Waals, van der Marcelle J.; Pijls, Charles; Sinke, Anja J.C.; Langenhoff, Alette A.M.; Smidt, Hauke; Gerritse, Jan

2018-01-01

The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl

Effects of ethylene glycol ethers on diesel fuel properties and emissions in a diesel engine

Energy Technology Data Exchange (ETDEWEB)

Gomez-Cuenca, F.; Gomez-Marin, M. [Compania Logistica de Hidrocarburos (CLH), Central Laboratory, Mendez Alvaro 44, 28045 Madrid (Spain); Folgueras-Diaz, M.B., E-mail: belenfd@uniovi.es [Department of Energy, University of Oviedo, Independencia 13, 33004 Oviedo (Spain)

2011-08-15

Highlights: {yields} Effect of ethylene glycol ethers on diesel fuel properties. {yields} Effect of ethylene glycol ethers on diesel engine specific consumption and emissions. {yields} Blends with {<=}4 wt.% of oxygen do not change substantially diesel fuel quality. {yields} Blends with 1 and 2.5 wt.% of oxygen reduce CO and HC emissions, but not smoke. - Abstract: The effect of ethylene glycol ethers on both the diesel fuel characteristics and the exhaust emissions (CO, NO{sub x}, smoke and hydrocarbons) from a diesel engine was studied. The ethers used were monoethylene glycol ethyl ether (EGEE), monoethylene glycol butyl ether (EGBE), diethylene glycol ethyl ether (DEGEE). The above effect was studied in two forms: first by determining the modification of base diesel fuel properties by using blends with oxygen concentration around 4 wt.%, and second by determining the emission reductions for blends with low oxygen content (1 wt.%) and with 2.5 wt.% of oxygen content. The addition of DEGEE enhances base diesel fuel cetane number, but EGEE and EGBE decrease it. For concentrations of {>=}4 wt.% of oxygen, EGEE and diesel fuel can show immiscibility problems at low temperatures ({<=}0 {sup o}C). Also, every oxygenated compound, according to its boiling point, modifies the distillation curve at low temperatures and the distillate percentage increases. These compounds have a positive effect on diesel fuel lubricity, and slightly decrease its viscosity. Blends with 1 and 2.5 wt.% oxygen concentrations were used in order to determine their influence on emissions at both full and medium loads and different engine speeds. Generally, all compounds help to reduce CO, and hydrocarbon emissions, but not smoke. The best results were obtained for blends with 2.5 wt.% of oxygen. At this concentration, the additive efficiency in decreasing order was EGEE > DEGEE > EGBE for CO emissions and DGEE > EGEE > EGBE for hydrocarbon emissions. For NO{sub x}, both its behaviour and the

Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

Directory of Open Access Journals (Sweden)

Atsushi Morikawa

2016-02-01

Full Text Available Poly(ether ether ketone dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4′-(4-fluorobenzoyldiphenyl ether and 3,5-dihydroxy-4′-(4-fluorobenzoyldiphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy-3,5-bis(4-fluorobenzoylbenzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketones having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

Phthalate esters in the environment: A critical review of their occurrence, biodegradation, and removal during wastewater treatment processes.

Science.gov (United States)

Gao, Da-Wen; Wen, Zhi-Dan

2016-01-15

Phthalate esters are one of the most frequently detected persistent organic pollutants in the environment. A better understanding of their occurrence and degradation in the environment and during wastewater treatment processes will facilitate the development of strategies to reduce these pollutants and to bioremediate contaminated freshwater and soil. Phthalate esters occur at measurable levels in different environments worldwide. For example, the concentrations of dimethyl phthalate (DMP) in atmospheric particulate matter, fresh water and sediments, soil, and landfills are N.D.-10.4 ng/m(3), N.D.-31.7 μg/L, N.D.-316 μg/kg dry weight, and N.D.-200 μg/kg dry weight, N.D.-43.27 μg/L, respectively. Bis(2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DBP) are primary phthalate ester pollutants. Urbanization has increased the discharge of phthalate esters to atmospheric and aquatic environments, and the use of agricultural plastics has exacerbated soil contamination by phthalate esters in rural areas. Aerobic biodegradation is the primary manner of phthalate ester mineralization in the environment, and this process has been widely studied. Phthalate esters can be removed during wastewater treatment processes. The combination of different wastewater treatment technologies showed greater efficiency in the removal of phthalate esters than individual treatment steps, such as the combination of anaerobic wastewater treatment with a membrane bioreactor would increase the efficiency of phthalate ester removal from 65%-71% to 95%-97%. This review provides a useful framework to identify future research objectives to achieve the mineralization and elimination of phthalate esters in the environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Numerical analysis of spray characteristics of dimethyl ether and diethyl ether fuel

International Nuclear Information System (INIS)

Mohan, Balaji; Yang, Wenming; Yu, Wenbin; Tay, Kun Lin

2017-01-01

Highlights: • Thermo-physical properties of liquid DME and DEE are reported. • Ether fuels tend to cavitate higher compared to that of diesel fuel. • Spray tip penetration and SMD are found to be lesser for ether fuels. • Ether fuels shows excellent atomization behavior. - Abstract: In this work, the spray characteristics of ether fuels such as dimethyl ether (DME) and diethyl ether (DEE) have been numerically investigated using KIVA-4 CFD code. A new hybrid spray model developed by coupling the standard KHRT model to cavitation sub model was used. The detailed thermo-physical properties of ether fuels have been predicted and validated with experimental results available from literature. The cavitation inception inside the injector nozzle hole has been studied for ether fuels in comparison with diesel fuel. It was found that ether fuels cavitates higher compared to that of conventional diesel fuel because of its low viscosity. The spray tip penetration of diesel fuel was longer than that of ether fuels due to high viscosity and density of diesel fuel. Ether fuels characterized by low Ohnesorge number and high Reynolds number showed better atomization behavior compared to that of the diesel fuel.

Structure of pyridine and quinoline vinyl ethers according to data from 1H and 13C NMR spectra and quantum-chemical calculations

International Nuclear Information System (INIS)

Afonin, A.V.; Voronov, V.K.; Andriankov, M.A.; Danovich, D.K.

1987-01-01

A systematic investigation of the structure of the vinyl ethers of heterocyclic compounds has not been undertaken. The present work was devoted to investigation of the stereochemical and electronic structure of the vinyl ethers of pyridine and quinoline. The PMR spectra of the samples were recorded for 5% solutions in deuterochloroform on a Tesla BS-497 spectrometer at 100 MHz. The 13 C NMR spectra were recorded on a Tesla BS-567A spectrometer at 25.1 MHz in deuterochloroform with the samples at concentrations of 30%. The internal standard was HMDS. The vinyl ethers of pyridine and quinoline exist preferentially in the nonplanar S-trans conformation. In the vinyl esters of pyridine and quinoline the p-π conjugation is concurrent in nature and depends on the position of the vinyloxy group in the heterocycle

Compound list: butylated hydroxyanisole [Open TG-GATEs

Lifescience Database Archive (English)

Full Text Available butylated hydroxyanisole BHA 00156 ftp://ftp.biosciencedbc.jp/archive/open-tggates/...LATEST/Human/in_vitro/butylated_hydroxyanisole.Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/o...pen-tggates/LATEST/Rat/in_vivo/Liver/Single/butylated_hydroxyanisole.Rat.in_vivo.Liver.Single.zip ftp://ftp....biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/butylated_hydroxyanisole.Rat.in_vivo.Liver.Repeat.zip ...

Dietary exposure and human risk assessment of phthalate esters based on total diet study in Cambodia

International Nuclear Information System (INIS)

Cheng, Zhang; Li, Han-Han; Wang, Hong-sheng; Zhu, Xue-Mei; Sthiannopkao, Suthipong; Kim, Kyoung-Woong; Yasin, Mohamed Salleh Mohamed; Hashim, Jamal Hisham; Wong, Ming-Hung

2016-01-01

Phthalate esters are used in a wide variety of consumer products, and human exposure to this class of compounds is widespread. Nevertheless, studies on dietary exposure of human to phthalates are limited. In this study, to assess the daily intakes of phthalate esters and the possible adverse health impacts, different food samples were collected from three areas of Cambodia, one of the poorest countries in the world. The ∑phthalate ester concentrations in Kampong Cham, Kratie and Kandal provinces ranged from 0.05 to 2.34 (median 0.88) μg g −1 , 0.19–1.65 (median 0.86) μg g −1 and 0.24–3.05 (median 0.59) μg g −1 wet weight (ww), respectively. Di-2-Ethylhexyl phthalate (DEHP) and diisobutyl phthalate (DiBP) were the predominant compounds among all foodstuffs. The estimated daily intake (EDI) of phthalate esters for the general population in Kampong Cham, Kratie and Kandal was 34.3, 35.6 and 35.8 μg kg −1 bw d −1 , respectively. The dietary daily intake of DEHP, benzylbutyl phthalate (BBP) and di-n-butyl phthalate (DBP) in Kampong Cham, Kratie and Kandal were below the tolerable daily intakes (TDI) imposed by the European Food Safety Authority (EFSA) and reference doses (RfD) imposed by The United States Environmental Protection Agency (USEPA). Rice contributed the greatest quantity of DEHP to the daily intake in Cambodia so may deserve further exploration. To our knowledge, this is the first study to investigate the occurrence and the daily intakes of phthalate esters in Cambodia. - Highlights: • Phthalate esters concentration in daily foodstuffs collected from Cambodia. • Investigate the bioaccessbility of phthalate esters via the foodstuffs consumption. • Health risk evaluation of dietary exposure to phthalate esters.

Dietary exposure and human risk assessment of phthalate esters based on total diet study in Cambodia

Energy Technology Data Exchange (ETDEWEB)

Cheng, Zhang; Li, Han-Han [College of Environment, Sichuan Agricultural University, Chengdu 611130 (China); Wang, Hong-sheng [Department of Microbial and Biochemical Pharmacy, School of Pharmaceutical Sciences, Sun Yat-sen University, No.132 Waihuandong Road, University Town, Guangzhou 510006 (China); Zhu, Xue-Mei [College of Environment, Sichuan Agricultural University, Chengdu 611130 (China); Sthiannopkao, Suthipong [Department of Environmental and Occupational Health, National Cheng Kung University, Tainan City, Taiwan (China); Kim, Kyoung-Woong [School of Environmental Science and Engineering, Gwangju Institute of Science and Technology, Gwangju (Korea, Republic of); Yasin, Mohamed Salleh Mohamed; Hashim, Jamal Hisham [United Nations University-International Institute for Global Health, Kuala Lumpur (Malaysia); Wong, Ming-Hung, E-mail: minghwong@ied.edu.hk [Consortium on Health, Environment, Education and Research (CHEER), and Department of Science and Environmental Studies, Hong Kong Institute of Education, Tai Po, Hong Kong (China); School of Environment, Jinan University, Guangzhou (China)

2016-10-15

Phthalate esters are used in a wide variety of consumer products, and human exposure to this class of compounds is widespread. Nevertheless, studies on dietary exposure of human to phthalates are limited. In this study, to assess the daily intakes of phthalate esters and the possible adverse health impacts, different food samples were collected from three areas of Cambodia, one of the poorest countries in the world. The ∑phthalate ester concentrations in Kampong Cham, Kratie and Kandal provinces ranged from 0.05 to 2.34 (median 0.88) μg g{sup −1}, 0.19–1.65 (median 0.86) μg g{sup −1} and 0.24–3.05 (median 0.59) μg g{sup −1} wet weight (ww), respectively. Di-2-Ethylhexyl phthalate (DEHP) and diisobutyl phthalate (DiBP) were the predominant compounds among all foodstuffs. The estimated daily intake (EDI) of phthalate esters for the general population in Kampong Cham, Kratie and Kandal was 34.3, 35.6 and 35.8 μg kg{sup −1} bw d{sup −1}, respectively. The dietary daily intake of DEHP, benzylbutyl phthalate (BBP) and di-n-butyl phthalate (DBP) in Kampong Cham, Kratie and Kandal were below the tolerable daily intakes (TDI) imposed by the European Food Safety Authority (EFSA) and reference doses (RfD) imposed by The United States Environmental Protection Agency (USEPA). Rice contributed the greatest quantity of DEHP to the daily intake in Cambodia so may deserve further exploration. To our knowledge, this is the first study to investigate the occurrence and the daily intakes of phthalate esters in Cambodia. - Highlights: • Phthalate esters concentration in daily foodstuffs collected from Cambodia. • Investigate the bioaccessbility of phthalate esters via the foodstuffs consumption. • Health risk evaluation of dietary exposure to phthalate esters.

Cosmic Ether

CERN Document Server

Tomaschitz, R

1998-01-01

A prerelativistic approach to particle dynamics is explored in an expanding Robertson-Walker cosmology. The receding galactic background provides a distinguished frame of reference and a unique cosmic time. In this context the relativistic, purely geometric space-time concept is criticized. Physical space is regarded as a permeable medium, the cosmic ether, which effects the world-lines of particles and rays. We study in detail a Robertson-Walker universe with linear expansion factor and negatively curved, open three-space; we choose the permeability tensor of the ether in such a way that the semiclassical approximation is exact. Galactic red-shifts depend on the refractive index of the ether. In the local Minkowskian limit the ether causes a time variation of mass, which scales inversely proportional to cosmic time. In the globally geodesic rest frames of galactic observers the ether manifests itself in an unbounded speed of signal transfer, in bifurcations of world-lines, and in time inversion effects.

The effects of pH in profile of lipid and ester accumulation of arthrospira platensis (spirulina) as a potential source of biodiesel

International Nuclear Information System (INIS)

Reyes, Patrick A.; Ybañez, Manolito G. Jr.; Avilla, Ruel A.

2013-01-01

This study aimed to produce biodiesel (ester-based fuel) using the extracts of microalgae Arthrospira platensis (Spirulina). Specifically, the research focused in determining effect of pH in culturing the Spirulina and its lipid accumulation; determining the constituents present in the lipid extracts; and determining the methyl esters in the transesterified lipids. The best pH condition in culturing the algal sample was found to be at pH 10 to 11. Analysis of the extracted lipid samples revealed that pH condition in culturing medium has a significant effect on the lipid accumulation in Spirulina. Perkin Elmer Claurus 500 GC-MS system elucidated that the constituents present in the experimental samples were esterified lipids. The esters were derived from butanoic, hexadeanoic and octadecanoic acid. About 19 free fatty acids out of 23 determined compounds present were from the controlled sample which suggests that these were main precursors of the esters found in the sample were butyl, allyl nonyl, propyl tetradecyl, methylpropyl, allyl dodecyl, hexyl pentadecyl, dodecyl propyl, heptyl esters with the parent chain of fatty acids enumerated above. These showed that pH manipulations could be used as a direct transesterification of fatty acids in producing biodiesels. (author)

Occurrence of fatty acid short-chain-alkyl esters in fruits of Celastraceae plants.

Science.gov (United States)

Sidorov, Roman A; Zhukov, Anatoly V; Pchelkin, Vasily P; Vereshchagin, Andrei G; Tsydendambaev, Vladimir D

2013-06-01

Small amounts of a mixture of fatty acid short-chain-alkyl esters (FASCAEs) were obtained from the fruits of twelve plant species of Celastraceae family, and in five of them the FASCAEs were present not only in the arils but also in the seeds. These mixtures contained 32 individual FASCAE species, which formed four separate fractions, viz. FA methyl, ethyl, isopropyl, and butyl esters (FAMEs, FAEEs, FAIPEs, and FABEs, resp.). The FASCAE acyl components included the residues of 16 individual C₁₄-C₂₄ saturated, mono-, di-, and trienoic FAs. Linoleic, oleic, and palmitic acids, and, in some cases, also α-linolenic acid predominated in FAMEs and FAEEs, while myristic acid was predominant in FAIPEs. It can be suggested that, in the fruit arils of some plant species, FAMEs and FAEEs were formed at the expense of a same FA pool characteristic of a given species and were strongly different from FAIPEs and FABEs esters regarding the mechanism of their biosynthesis. However, as a whole, the qualitative and quantitative composition of various FASCAE fractions, as well as their FA composition, varied considerably depending on various factors. Therefore, separate FASCAE fractions seem to be synthesized from different FA pools other than those used for triacylglycerol formation. Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

International Nuclear Information System (INIS)

Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

2016-01-01

A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

GC-ECNICI-MS/MS of eicosanoids as pentafluorobenzyl-trimethylsilyl (TMS) derivatives: Evidence of CAD-induced intramolecular TMS ether-to-ester rearrangement using carboxy-18O-labelled eicosanoids and possible implications in quantitative analysis.

Science.gov (United States)

Tsikas, Dimitrios

2017-03-15

GC-MS and GC-MS/MS of pentafluorobenzyl (PFB) ester trimethylsilyl (TMS) ether (PFB-TMS) derivatives of hydroxylated long-chain fatty acids including arachidonic acid metabolites, the eicosanoids, in the electron-capture negative-ion chemical ionization (ECNICI) mode are the most sensitive and accurate approaches to quantify carboxyl groups-containing compounds in complex biological fluids such as plasma and urine. Under ECNICI conditions, PFB-TMS derivatives of eicosanoids ionize to form very few ions, with the carboxylates [M-PFB] - being typically the most intense. Less intense ions may be additionally formed by consecutive neutral loss (NL) of trimethylsilanol (TMSOH, 90Da) groups ([M-PFB-(TMSOH) n ] - ). By using [1,1- 18 O 2 ]- and [1,ω- 18 O 2 ]-eicosanoids, we studied ion processes following collisionally activated dissociation (CAD) of the precursor ions [M-PFB] - . We found that CAD resulted in formation of product ions due to NL of a TMS 18 OH (92Da) group in monocarboxylic and of a PFB 18 OH (200Da) group in dicarboxylic eicosanoids. TMS 18 OH NL implies an intra-molecular transfer of the TMS group from hydroxyl groups to their carboxylate anions [M-PFB] - . From a mechanistic point of view, this rearrangement may explain formation of unique product ions in GC-MS/MS of eicosanoids under ECNICI conditions. From the quantitative point of view, quantification by GC-MS/MS of product ions due to [M-PFB-(TMSOH) n ] - and [M-PFB-TMS 18 OH-(TMSOH) n-1 ] - would reveal incorrect data, if [1,1- 18 O 2 ]-eicosanoids are used as internal standards and if no correction for the 18 O-loss is performed. In 18 O-labelled dicarboxylic eicosanoids, such as the major urinary metabolite (MUM) of E prostaglandins, i.e., [1,ω- 18 O 2 ]-PGE-MUM), no TMS ester/TMS ether rearrangement was observed. Yet, 18 O-loss occurred upon CAD of [M-PFB] - due to NL of PFB 18 OH (200Da). In both cases the extent of 18 O-loss needs to be determined and considered for accurate quantification

Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model

DEFF Research Database (Denmark)

Frederiksen, Marie; Stapleton, Heather M; Vorkamp, Katrin

2018-01-01

Organophosphate esters (OPEs) are used as flame retardants, plasticizers, and as hydraulic fluids. They are present in indoor environments in high concentrations compared with other flame retardants, and human exposure is ubiquitous. In this study we provide data for estimating dermal uptake...... through the skin. For tris(isobutyl) phosphate (TIBP), tris(n-butyl) phosphate (TNBP), and tris(methylphenyl) phosphate (TMPP) the mass balance was not stable over time indicating possible degradation during the experimental period of 72 h. The rates at which OPEs permeated through the skin decreased...

Butyl Rubber: Compound Development and Characterization

National Research Council Canada - National Science Library

Sloan, James

2000-01-01

...), to develop the standard butyl rubber compound. The strategy of this work was to compound- and compression-mold high-quality, uniform butyl rubber experimental sheets and to evaluate their cure properties, mechanical properties...

Misconceptions about the ether

International Nuclear Information System (INIS)

Duffy, M.C.

1980-01-01

Several misconceptions concerning the ether concept and ether models are reviewed and clarified so that the relationship between modern ether theory and orthodox relativity may be better understood. The question of the ether's supposed superfluidity as a concept, and its status in modern physics remains to be answered. (author)

17O NMR parameters of some substituted benzyl ethers components: Ab initio study

Directory of Open Access Journals (Sweden)

Mahdi Rezaei Sameti

2016-09-01

Full Text Available The 17O NMR chemical shielding tensors and chemical shift for a set of substituted benzyl ethers derivatives containing (methyl, ethyl, isopropyl, t-butyl, brome and lithium have been calculated. The molecular structures were fully optimized using B3LYP/6-31G(d,p. The calculation of the 17O shielding tensors employed the GAUSSIAN 98 implementation of the gauge-including atomic orbital (GIAO and continuous set of gauge transformations (CSGT by using 6-31G (d,p, 6-31++G(d,p and 6-311++G(d,p basis set methods at density functional levels of theories (DFT. The values determined using the GIAO and CSGT were found to give a good agreement with the experimental chemical shielding.

Metabolism of the insecticidally active GABAA receptor antagonist 4-sec-[3,4-3H2]butyl-1-(4-cyanophenyl)-2,6,7-trioxabicyclo[2.2.2]octane

International Nuclear Information System (INIS)

Deng, Yanli; Palmer, C.J.; Toia, R.F.; Casida, J.E.

1990-01-01

4-sec-[3,4- 3 H 2 ]Butyl-1-(4-cyanophenyl)-2,6,7-trioxabicyclo[2.2.2]octane (referred to as [ 3 H]COB) was examined as an example of a new class of insecticidally active compounds that block the γ-aminobutyric acid gated chloride channel. Metabolites were identified by thin-layer cochromatography with standards from synthesis and by consideration of their hydrolytic and oxidative degradation products formed in situ on two-dimensional silica gel chromatoplates. Metabolism of [ 3 H]COB by mouse liver and housefly abdomen microsomes is dependent on fortification with NADPH. The O-methylene and sec-butyl sites are sensitive to oxidation. Each carbon of the sec-butyl group is individually functionalized with strong preference for the methylene site in the mouse but not the housefly microsomal system. O-Methylene hydroxylation initiates spontaneous cage opening to form an aldehyde that undergoes metabolic reduction, ultimately yielding the same cyanobenzoate ester of 2,2-bis-(hydroxymethyl)-3-methylpentan-1-ol formed by direct hydrolysis. Houseflies injected with [ 3 H]COB form many if not all of the same metabolites, with major products being the aforementioned cyanobenzoate, the orthoester oxidized at the sec-butyl methylene site, and polar conjugates

Tailoring the toughness and CTE of high temperature bisphenol E cyanate ester (BECy resin

Directory of Open Access Journals (Sweden)

M. Thunga

2014-05-01

Full Text Available The objective of the present work is to enhancing the toughness and minimizing the CTE of a special class of bisphenol E cyanate ester (BECy resin by blending it with a thermoplastic toughening agent. Poly(ether sulfone was chosen as a high temperature resistant thermoplastic resin to enhance the thermo-mechanical properties of BECy. The influence of poly(ether sulfone/BECy blend composition on the morphology and phase behavior was studied using scanning electron microscopy and dynamic mechanical analysis. The mechanical properties of the blends were evaluated by flexural tests, which demonstrated significant enhancement in the material’s toughness with an increase in PES concentration from 0 to 15 wt%. The coefficient of thermal expansion of pure BECy was reduced from 61 to 48 ppm/°C in the blends with PES, emphasizing the multi-functional benefits of PES as a toughening agent in BECy.

Selective solvation extraction of gold from alkaline cyanide solution by alkyl phosphorus esters

Energy Technology Data Exchange (ETDEWEB)

Miller, J.D.; Wan, R.Y.; Mooiman, M.B.; Sibrell, P.L.

1987-01-01

Research efforts have shown that solvation extraction of gold from alkaline cyanide solution is possible by alkyl phosphorus esters. Both tributyl phosphate (TBP) and dibutyl butyl phosphonate (DBBP) appear to be effective extractants for gold and exhibit high loading capacities exceeding 30 gpl. Selective solvation extraction of gold from alkaline cyanide solution can be achieved with selectivity factors relative to other cyanoanions as high as 1000 under certain circumstances. Variables influencing the selectivity such as ionic strength, temperature, and extractant structure, are discussed in terms of the extraction chemistry, which seems to involve the solvation of a M dot, dot, dot Au(CN)2 ion pair.

Biosynthesis of archaeal membrane ether lipids

Directory of Open Access Journals (Sweden)

Samta eJain

2014-11-01

Full Text Available A vital function of the cell membrane in all living organism is to maintain the membrane permeability barrier and fluidity. The composition of the phospholipid bilayer is distinct in archaea when compared to bacteria and eukarya. In archaea, isoprenoid hydrocarbon side chains are linked via an ether bond to the sn-glycerol-1-phosphate backbone. In bacteria and eukarya on the other hand, fatty acid side chains are linked via an ester bond to the sn-glycerol-3-phosphate backbone. The polar head groups are globally shared in the three domains of life. The unique membrane lipids of archaea have been implicated not only in the survival and adaptation of the organisms to extreme environments but also to form the basis of the membrane composition of the last universal common ancestor (LUCA. In nature, a diverse range of archaeal lipids is found, the most common are the diether (or archaeol and the tetraether (or caldarchaeol lipids that form a monolayer. Variations in chain length, cyclization and other modifications lead to diversification of these lipids. The biosynthesis of these lipids is not yet well understood however progress in the last decade has led to a comprehensive understanding of the biosynthesis of archaeol. This review describes the current knowledge of the biosynthetic pathway of archaeal ether lipids; insights on the stability and robustness of archaeal lipid membranes; and evolutionary aspects of the lipid divide and the last universal common ancestor LUCA. It examines recent advances made in the field of pathway reconstruction in bacteria.

Poly (ether imide sulfone) membranes from solutions in ionic liquids

KAUST Repository

Kim, Dooli

2017-11-20

A membrane manufacture method based on non-volatile solvents and a high performance polymer, poly (ether imide sulfone) (EXTEM™), is proposed, as greener alternative to currently industrial process. We dissolved EXTEM™ in pure ionic liquids: 1-ethyl-3-methylimidalzolium thiocyanate ([EMIM]SCN), 1-butyl-3-methylimidalzolium thiocyanate ([BMIM]SCN), and 1-ethyl-3-methylimidalzolium acetate ([EMIM]OAc). The following polymer solution parameters were evaluated to optimize the manufacture: Gibbs free energy of mixing (G), intrinsic viscosity ([]) and hydrodynamic diameter. Membranes with sponge-like structure and narrow pore size distribution were obtained from solutions in [EMIM]SCN. They were tested for separation of proteins and deoxyribonucleic acids (DNA). Due to the polymer stability, we foresee that applications in more demanding chemical separations would be possible. [EMIM]SCN was 96 % purified and recovered after the membrane fabrication, contributing to the sustainability of the whole manufacturing process.

Thermodynamic study of (alkyl esters+α,ω-alkyl dihalides) III. HmEandVmE for 20 binary mixtures {xCu-1H2u-1CO2C4H9+(1-x)α,ω-ClCH2(CH2)v-2CH2Cl}, where u=1 to 4, α=1 and v=ω=2 to 6

International Nuclear Information System (INIS)

Ortega, J.; Marrero, E.; Toledo, F.J.

2006-01-01

In this article, the experimental data of excess molar enthalpies H m E and excess molar volumes V m E are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The V m E are positive for mixtures of (butyl esters+1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in H m E with the dichloroethane chain length for a same ester is regular although the V m E presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied. To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems' behaviour.

Life cycle analyses applied to first generation bio-fuels consumed in France

International Nuclear Information System (INIS)

2010-01-01

This rather voluminous publication reports detailed life cycle analyses for the different present bio-fuels channels also named first-generation bio-fuels: bio-ethanol, bio-diesel, pure vegetal oils, and oil. After a recall of the general principles adopted for this life-cycle analysis, it reports the modelling of the different channels (agricultural steps, bio-fuel production steps, Ethyl tert-butyl ether or ETBE steps, vehicles, animal fats and used vegetal oils, soil assignment change). It gives synthetic descriptions of the different production ways (methyl ester from different plants, ethanol from different plants). It reports and compares the results obtained in terms of performance

Determination of phthalate esters from environmental water samples by micro-solid-phase extraction using TiO2 nanotube arrays before high-performance liquid chromatography.

Science.gov (United States)

Zhou, Qingxiang; Fang, Zhi; Liao, Xiangkun

2015-07-01

We describe a highly sensitive micro-solid-phase extraction method for the pre-concentration of six phthalate esters utilizing a TiO2 nanotube array coupled to high-performance liquid chromatography with a variable-wavelength ultraviolet visible detector. The selected phthalate esters included dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl)phthalate and dioctyl phthalate. The factors that would affect the enrichment, such as desorption solvent, sample pH, salting-out effect, extraction time and desorption time, were optimized. Under the optimum conditions, the linear range of the proposed method was 0.3-200 μg/L. The limits of detection were 0.04-0.2 μg/L (S/N = 3). The proposed method was successfully applied to the determination of six phthalate esters in water samples and satisfied spiked recoveries were achieved. These results indicated that the proposed method was appropriate for the determination of trace phthalate esters in environmental water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Early steps of biosynthesis of ether lipids in archaebacteria; Eteru shishitsu seigosei no shoki dankai

Energy Technology Data Exchange (ETDEWEB)

Nishino, T. [Tohoku Univ., Sendai (Japan). Faculty of Engineering

1997-05-20

Membrane lipids in archaebacteria are different from those of eubacteria and eukaryote which are fatty acid esters of glycerol. Archaebacterial lipids are mainly ether-linked lipids composed of glycerol linked to two molecules of isoprenoid phytanyl groups or of ether-linked glycerol with phytanyl group. This structural feature is one of the origins of survival and growth of archaebacteria in extreme conditions of high temperature, strong acid or alkali. It is considered that geranylgeranyl phosphate (GGPP) is synthesized and attached to glycerol phosphate, followed by reduction of the double bond in the geranylgeranyl moieties to form the diether lipids while the head-to-heat condensation of the phytanyl groups produces the tetraether lipids. Aiming to elucidate the lipid biosynthesis mechanism in a hyperthermophilic archaebacterium, Sulfolobus acidocaldarius, the gene of GGPP synthase was cloned with the aid of carotenoid synthesis in phytopathogenic Erwinia uredovora and its sequence was studied. 29 refs., 9 figs.

Catalytic hydrolysis of Metil Teret Botil Eter in under ground contaminated water

International Nuclear Information System (INIS)

Nikpey, A.; Mortazavi, B.; Asilian, H.; Khavanin, A.; Rezaee, A.; Soleimanian, A.; Kazemian, H.

2005-01-01

The behavior of ZSM-5 and Mordenite catalyst in the hydrolysis at room temperature of methyl tert-butyl ether was studied with reference to the possibility of its conversion to more biodegradable products in underground water contaminated by methyl tert-butyl ether. Hydrolysis products were determined using a gas chromatograph equipped with a flame ionization detector. The results indicate that acid ZSM-5 catalyst are effective in both adsorption and hydrolysis of methyl tert-butyl ether and may be applied for both in situ underground water remediation and as protection barrier for wells or leaking tanks. However, acid mordenite catalyst completely inactive

Landfills as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

Science.gov (United States)

Weinberg, Ingo; Dreyer, Annekatrin; Ebinghaus, Ralf

2011-02-01

In order to investigate landfills as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two landfills (one active and one closed) and two reference sites using high volume air samplers. Contaminants were accumulated on glass fiber filters (particle phase) and PUF/XAD-2/PUF cartridges (gas phase), extracted by methyl-tert butyl ether/acetone (neutral PFCs), methanol (ionic PFCs) or hexane/acetone (PBDEs, musk fragrances), and detected by GC-MS (neutral PFCs, PBDEs, musk fragrances) or HPLC-MS/MS (ionic PFCs). Total concentrations ranged from 84 to 706 pg m -3 (volatile PFCs, gas phase), from fragrances, gas + particle phase) and from 1 to 11 pg m -3 (PBDEs, gas + particle phase). Observed sum concentrations of PFCs and synthetic musk fragrances and partly PBDE concentrations were elevated at landfill sites compared to corresponding reference sites. Concentrations determined at the active landfill were higher than those of the inactive landfill. Overall, landfills can be regarded as a source of synthetic musk fragrances, several PFCs and potentially of PBDEs to ambient air.

Modeling of the oxidation of methyl esters-Validation for methyl hexanoate, methyl heptanoate, and methyl decanoate in a jet-stirred reactor.

Science.gov (United States)

Glaude, Pierre Alexandre; Herbinet, Olivier; Bax, Sarah; Biet, Joffrey; Warth, Valérie; Battin-Leclerc, Frédérique

2010-11-01

The modeling of the oxidation of methyl esters was investigated and the specific chemistry, which is due to the presence of the ester group in this class of molecules, is described. New reactions and rate parameters were defined and included in the software EXGAS for the automatic generation of kinetic mechanisms. Models generated with EXGAS were successfully validated against data from the literature (oxidation of methyl hexanoate and methyl heptanoate in a jet-stirred reactor) and a new set of experimental results for methyl decanoate. The oxidation of this last species was investigated in a jet-stirred reactor at temperatures from 500 to 1100 K, including the negative temperature coefficient region, under stoichiometric conditions, at a pressure of 1.06 bar and for a residence time of 1.5 s: more than 30 reaction products, including olefins, unsaturated esters, and cyclic ethers, were quantified and successfully simulated. Flow rate analysis showed that reactions pathways for the oxidation of methyl esters in the low-temperature range are similar to that of alkanes.

Reproductive toxicity of the glycol ethers.

Science.gov (United States)

Hardin, B D

1983-06-01

The glycol ethers are an important and widely used class of solvents. Recent studies have demonstrated that ethylene glycol monomethyl ether (EGME), ethylene glycol dimethyl ether (EGdiME), ethylene glycol monoethyl ether (EGEE), and ethylene glycol monoethyl ether acetate (EGEEA) are teratogenic. Other studies have demonstrated that testicular atrophy or infertility follow treatment of males with EGME, ethylene glycol monomethyl ether acetate (EGMEA), EGEE, EGEEA, diethylene glycol dimethyl ether (diEGdiME), and diethylene glycol monoethyl ether (diEGEE). Experimental data are reviewed and structure-activity relationships are speculated upon.

Organophosphate Ester Flame Retardants and Plasticizers in Ocean Sediments from the North Pacific to the Arctic Ocean.

Science.gov (United States)

Ma, Yuxin; Xie, Zhiyong; Lohmann, Rainer; Mi, Wenying; Gao, Guoping

2017-04-04

The presence of organophosphate ester (OPE) flame retardants and plasticizers in surface sediment from the North Pacific to Arctic Ocean was observed for the first time during the fourth National Arctic Research Expedition of China in the summer of 2010. The samples were analyzed for three halogenated OPEs [tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(dichloroisopropyl) phosphate], three alkylated OPEs [triisobutyl phosphate (TiBP), tri-n-butyl phosphate, and tripentyl phosphate], and triphenyl phosphate. Σ 7 OPEs (total concentration of the observed OPEs) was in the range of 159-4658 pg/g of dry weight. Halogenated OPEs were generally more abundant than the nonhalogenated OPEs; TCEP and TiBP dominated the overall concentrations. Except for that of the Bering Sea, Σ 7 OPEs values increased with increasing latitudes from Bering Strait to the Central Arctic Ocean, while the contributions of halogenated OPEs (typically TCEP and TCPP) to the total OPE profile also increased from the Bering Strait to the Central Arctic Ocean, indicating they are more likely to be transported to the remote Arctic. The median budget of 52 (range of 17-292) tons for Σ 7 OPEs in sediment from the Central Arctic Ocean represents only a very small amount of their total production volume, yet the amount of OPEs in Arctic Ocean sediment was significantly larger than the sum of polybrominated diphenyl ethers (PBDEs) in the sediment, indicating they are equally prone to long-range transport away from source regions. Given the increasing level of production and usage of OPEs as substitutes of PBDEs, OPEs will continue to accumulate in the remote Arctic.

Toxicity of phosphor esters: Willy Lange (1900-1976) and Gerda von Krueger (1907-after 1970).

Science.gov (United States)

Petroianu, G A

2010-10-01

In 1851 Williamson serendipitously discovered a new and efficient way to produce ethers using ethyl iodide and potassium salts. Based on this new synthetic approach, the Frenchman Philippe de Clermont and the Muscovite Wladimir Moschnin, both élèves of Adolphe Wurtz in his Paris School of Chemistry, achieved the synthesis of the first ester of pyrophosphoric acid (TEPP). de Clermont "tasted" the new compound and although TEPP is a potent cholinesterase inhibitor he failed to recognize its toxicity. Almost a century later, in 1932, Willy Lange (1900-1976) and his graduate student Gerda v. Krueger (1907-after 1970) described the toxicity of organophosphonates. While the classic paper of the two "Uber Ester der Monofluorphosphorsäure." is cited by almost everybody working in the field, little is known about Lange and almost nothing about v. Krueger. This brief communication attempts to shed some light on the life of both.

Conducting polymers of octanoic acid 2-thiophen-3-yl-ethyl ester and their electrochromic properties

International Nuclear Information System (INIS)

Camurlu, Pinar; Cirpan, Ali; Toppare, Levent

2005-01-01

Octanoic acid 2-thiophen-3-yl-ethyl ester was synthesized via the reaction of 3-thiophene ethanol with octanoyl chloride. The resulting monomer was electrochemically homopolymerized in the presence of tetrabutylammonium tetrafluoroborate as the supporting electrolyte, in the acetonitrile/borontrifluoride ethyl ether solvent system. The resulting polymer was characterized using various experimental techniques. Spectroelectrochemistry analysis of the homopolymer reflects electronic transitions at 434, ∼800 and ∼1100 nm, revealing π-π* transition, polaron and bipolaron band formation, respectively, leading to esthetically pleasing color changes between transmissive yellow and blue, with reasonable switching times

Bioreversible Derivatives of Phenol. 2. Reactivity of Carbonate Esters with Fatty Acid-like Structures Towards Hydrolysis in Aqueous Solutions

Directory of Open Access Journals (Sweden)

Claus Larsen

2007-10-01

Full Text Available A series of model phenol carbonate ester prodrugs encompassing derivatives with fatty acid-like structures were synthesized and their stability as a function of pH (range 0.4 – 12.5 at 37°C in aqueous buffer solutions investigated. The hydrolysis rates in aqueous solutions differed widely, depending on the selected pro-moieties (alkyl and aryl substituents. The observed reactivity differences could be rationalized by the inductive and steric properties of the substituent groups when taking into account that the mechanism of hydrolysis may change when the type of pro-moiety is altered, e.g. n-alkyl vs. t-butyl. Hydrolysis of the phenolic carbonate ester 2-(phenoxycarbonyloxy-acetic acid was increased due to intramolecular catalysis, as compared to the derivatives synthesized from ω-hydroxy carboxylic acids with longer alkyl chains. The carbonate esters appear to be less reactive towards specific acid and base catalyzed hydrolysis than phenyl acetate. The results underline that it is unrealistic to expect that phenolic carbonate ester prodrugs can be utilized in ready to use aqueous formulations. The stability of the carbonate ester derivatives with fatty acid-like structures, expected to interact with the plasma protein human serum albumin, proved sufficient for further in vitro and in vivo evaluation of the potential of utilizing HSA binding in combination with the prodrug approach for optimization of drug pharmacokinetics.

Extraction of phthalate esters from water and beverages using a graphene-based magnetic nanocomposite prior to their determination by HPLC

International Nuclear Information System (INIS)

Wu, Q.; Liu, M.; Ma, X.; Wang, W.; Wang, C.; Zang, X.; Wang, Z.

2012-01-01

We have developed a highly sensitive microextraction method for the preconcentration of some phthalate esters such as diethyl phthalate, di-n-propylphthalate, di-n-butyl-phthalate, dicyclohexyl-phthalate, and diethyl-hexyl phthalate prior to their determination by HPLC. It is based on a magnetic graphene nanocomposite as an effective adsorbent. The effects of the amount of the extractant composite employed, extraction time, pH values, salt concentration and desorption conditions were investigated. Under the optimum conditions, the enrichment factors range from 1574 to 2880. Response is linear in the concentration range from 0. 1 to 50 ng mL -1 . The limits of detection (at S/N = 3) were between 0. 01 and 0. 04 ng mL -1 . The method was successfully applied to the determination of five phthalate esters in water and beverage samples. (author)

Amide and Ester-Functionalized Humic Acid for Fuel Combustion Enhancement

Science.gov (United States)

Riggs, Mark

Humic acid is a class of naturally occurring molecules composed of large sheet-like regions of cyclic aromatic hydrocarbon networks with surface and edge functional groups including phenols, carboxylic acids, and epoxides. These naturally occurring molecules are found in brown coal deposits near lignite formations. Humic acid has gained attention from the scientific community as a precursor for graphene. Graphene is a 2-dimensional honeycomb structure of fully unsaturated carbon atoms that has exceptional material properties and inherent aromaticity. Graphene's incredible properties are matched by the difficulty associated with reproducibly manufacturing it on a large scale. This issue has limited the use of graphene for commercial applications. The polar functional groups of humic acid contribute to the hydrophilic nature of the molecule, limiting its miscibility in any alkyl-based solvent. Surfactants containing long alkyl chains can affect the miscibility of the molecule in an organic solvent. Surfactants are often difficult to remove from the system. It is theorized that alkylation of the functional sites of humic acid can affect the hydrophilic nature of the molecule, and effectively enable its dispersion into organic solvents without simultaneous incorporation of surfactants. This dissertation investigated the amidation and esterification of humic acid molecules extracted from leonardite. The resulting change in the modified humic acid dispersibility in organic solvents and its potential usage as a fuel additive were evaluated. Butyl, hexyl, octyl, and decyl amide-modified and ester-modified humic acids were synthesized. These products were characterized to confirm successful chemical reaction through thermogravimetric analysis, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The decyl-modified humic acids remained suspended in kerosene mixtures for longer than 1 week. Other organo-humic acids showed varying degrees of flocculation

Butylated caffeic acid: An efficient novel antioxidant; Ácido cafeico butilado: un nuevo y eficaz antioxidante.

Energy Technology Data Exchange (ETDEWEB)

Shi, G.; Liao, X.; Olajide, T.M.; Liu, J.; Jiang, X.; Weng, X.

2017-07-01

A novel antioxidant, butylated caffeic acid (BCA) was rationally designed by adding a tert-butyl group to caffeic acid, which was synthesized at a high yield (36.2%) from 2-methoxy-4-methylphenol (1) by a four-step reaction including Friedel-Crafts alkylation, bromine oxidation, ether bond hydrolysis and Knoevenagel condensation. Its antioxidant capacity was much stronger than common commercial antioxidant tert-butyl hydroquinone (TBHQ) and its mother compound, caffeic acid, in both rancimat and deep frying tests. When investigated via the DPPH method, the antioxidant capacity of BCA was almost equal to TBHQ, but lower than caffeic acid. BCA could be a potentially strong antioxidant, especially for food processing at high temperatures such as deep frying and baking. [Spanish] Se diseñó razonadamente un nuevo antioxidante, el ácido cafeico butilado (BCA) mediante la adición de un grupo terc-butilo al ácido cafeico, que se sintetizó con un alto rendimiento (36,2%) a partir de 2-metoxi-4-metilfenol, reacción de Friedel-Crafts, oxidación de bromo, hidrólisis del enlace éter y condensación de Knoevenagel. Su capacidad antioxidante fué mucho más fuerte que la del antioxidante comercial mas común el terc-butil hidroquinona (TBHQ) y la de su compuesto madre el ácido cafeico, tanto en rancimat como en pruebas de fritura. Cuando se investigó mediante el método DPPH, la capacidad antioxidante de BCA fue casi igual a TBHQ, pero menor que la del ácido cafeico. BCA podría ser un fuerte antioxidante potencial, especialmente para el procesamiento de alimentos a alta temperatura, tales como freír y hornear.

Microbial community composition during anaerobic mineralization of tert-butyl alcohol (TBA) in fuel-contaminated aquifer material.

Science.gov (United States)

Wei, Na; Finneran, Kevin T

2011-04-01

Anaerobic mineralization of tert-butyl alcohol (TBA) and methyl tert-butyl ether (MTBE) were studied in sediment incubations prepared with fuel-contaminated aquifer material. Microbial community compositions in all incubations were characterized by amplified ribosomal DNA restriction analysis (ARDRA). The aquifer material mineralized 42.3±9.9% of [U-(14)C]-TBA to 14CO2 without electron acceptor amendment. Fe(III), sulfate, and Fe(III) plus anthraquinone-2,6-disulfonate addition also promoted U-[14C]-TBA mineralization at levels similar to those of the unamended controls. Nitrate actually inhibited TBA mineralization relative to unamended controls. In contrast to TBA, [U-(14)C]-MTBE was not significantly mineralized in 400 days regardless of electron acceptor amendment. Microbial community analysis indicated that the abundance of one dominant clone group correlated closely with anaerobic TBA mineralization. The clone was phylogenetically distinct from known aerobic TBA-degrading microorganisms, Fe(III)- or sulfate-reducing bacteria. It was most closely associated with organisms belonging to the alphaproteobacteria. Microbial communities were different in MTBE and TBA amended incubations. Shannon indices and Simpson indices (statistical community comparison tools) both demonstrated that microbial community diversity decreased in incubations actively mineralizing TBA, with distinct "dominant" clones developing. These data contribute to our understanding of anaerobic microbial transformation of fuel oxygenates in contaminated aquifer material and the organisms that may catalyze the reactions.

Metabolism of the insecticidally active GABA sub A receptor antagonist 4-sec-(3,4- sup 3 H sub 2 )butyl-1-(4-cyanophenyl)-2,6,7-trioxabicyclo(2. 2. 2)octane

Energy Technology Data Exchange (ETDEWEB)

Deng, Yanli; Palmer, C.J.; Toia, R.F.; Casida, J.E. (Univ. of California, Berkeley (USA))

1990-03-01

4-sec-(3,4-{sup 3}H{sub 2})Butyl-1-(4-cyanophenyl)-2,6,7-trioxabicyclo(2.2.2)octane (referred to as ({sup 3}H)COB) was examined as an example of a new class of insecticidally active compounds that block the {gamma}-aminobutyric acid gated chloride channel. Metabolites were identified by thin-layer cochromatography with standards from synthesis and by consideration of their hydrolytic and oxidative degradation products formed in situ on two-dimensional silica gel chromatoplates. Metabolism of ({sup 3}H)COB by mouse liver and housefly abdomen microsomes is dependent on fortification with NADPH. The O-methylene and sec-butyl sites are sensitive to oxidation. Each carbon of the sec-butyl group is individually functionalized with strong preference for the methylene site in the mouse but not the housefly microsomal system. O-Methylene hydroxylation initiates spontaneous cage opening to form an aldehyde that undergoes metabolic reduction, ultimately yielding the same cyanobenzoate ester of 2,2-bis-(hydroxymethyl)-3-methylpentan-1-ol formed by direct hydrolysis. Houseflies injected with ({sup 3}H)COB form many if not all of the same metabolites, with major products being the aforementioned cyanobenzoate, the orthoester oxidized at the sec-butyl methylene site, and polar conjugates.

NIOSH Manual of Analytical Methods (third edition). Fourth supplement

Energy Technology Data Exchange (ETDEWEB)

1990-08-15

The NIOSH Manual of Analytical Methods, 3rd edition, was updated for the following chemicals: allyl-glycidyl-ether, 2-aminopyridine, aspartame, bromine, chlorine, n-butylamine, n-butyl-glycidyl-ether, carbon-dioxide, carbon-monoxide, chlorinated-camphene, chloroacetaldehyde, p-chlorophenol, crotonaldehyde, 1,1-dimethylhydrazine, dinitro-o-cresol, ethyl-acetate, ethyl-formate, ethylenimine, sodium-fluoride, hydrogen-fluoride, cryolite, sodium-hexafluoroaluminate, formic-acid, hexachlorobutadiene, hydrogen-cyanide, hydrogen-sulfide, isopropyl-acetate, isopropyl-ether, isopropyl-glycidyl-ether, lead, lead-oxide, maleic-anhydride, methyl-acetate, methyl-acrylate, methyl-tert-butyl ether, methyl-cellosolve-acetate, methylcyclohexanol, 4,4'-methylenedianiline, monomethylaniline, monomethylhydrazine, nitric-oxide, p-nitroaniline, phenyl-ether, phenyl-ether-biphenyl mixture, phenyl-glycidyl-ether, phenylhydrazine, phosphine, ronnel, sulfuryl-fluoride, talc, tributyl-phosphate, 1,1,2-trichloro-1,2,2-trifluoroethane, trimellitic-anhydride, triorthocresyl-phosphate, triphenyl-phosphate, and vinyl-acetate.

Intake of butylated hydroxyanisole and butylated hydroxytoluene and stomach cancer risk : results from analyses in the Netherlands : cohort study

NARCIS (Netherlands)

Botterweck, A.A.M.; Verhagen, H.; Goldbohm, R.A.; Kleinjans, J.; Brandt, P.A. van den

2000-01-01

Both carcinogenic and anticarcinogenic properties have been reported for the synthetic antioxidants butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT). The association between dietary intake of BHA and BHT and stomach cancer risk was investigated in the Netherlands Cohort Study (NLCS)

Linear free energy relationships in heterogeneous catalysis--13. The dehydration of aliphatic alcohols over silica-alumina. [N-butyl alcohol, sec. -butyl or isopropyl alcohol, tert. -butyl alcolol

Energy Technology Data Exchange (ETDEWEB)

Take, J; Matsumoto, T; Yoneda, Y

1978-01-01

The dehydration of n-butyl alcohol at 120/sup 0/-166/sup 0/C, sec.-butyl or isopropyl alcohol at 100/sup 0/-145/sup 0/C, and tert.-butyl alcohol at 54/sup 0/-80/sup 0/C, over silica/alumina catalyst was zero order in alcohol at 0.01-0.1 atm, and the activation energies were 35.3, 31.7, 32.0, and 29.9 kcal/mol, respectively. The zero-order rate constants were mainly affected by the activation energies since the preexponential factors varied little except for tert.-butyl alcohol. A linear relationship was found between the activation energy or the logarithm of the zero-order rate constant and the heterolytic bond dissociation energy for the carbon-oxygen bond in alcohols D(R/sup +/OH/sup -/). The activation energy increased and the rate constant decreased with increasing D(R/sup +/OH/sup -/). The results indicate that dehydration is E1 over this catalyst, but a similar correlation was observed based on published data for dehydration over alumina, which follows an E2 mechanism, indicating that heterolytic cleavage of the C-O bond is rate-determining in both mechanisms.

Efficacy of oral active ether lipid analogs of cidofovir in a lethal mousepox model

International Nuclear Information System (INIS)

Buller, R. Mark; Owens, Gelita; Schriewer, Jill; Melman, Lora; Beadle, James R.; Hostetler, Karl Y.

2004-01-01

Cidofovir (CDV) is a highly effective inhibitor of orthopoxvirus replication and may be used intravenously to treat smallpox or complications arising from the smallpox vaccine under an investigational new drug application (IND). However, CDV is absorbed poorly following oral administration and is inactive orally. To improve the bioavailability of CDV, others synthesized alkoxyalkanol esters of CDV and observed >100-fold more activity than unmodified CDV against cowpox, vaccinia, and variola virus (VARV) replication. These ether lipid analogs of CDV have high oral bioavailability in mice. In this study, we compared the oral activity of CDV with the hexadecyloxypropyl (HDP)-, octadecyloxyethyl-, oleyloxypropyl-, and oleyloxyethyl-esters of CDV in a lethal, aerosol ectromelia virus (ECTV) challenge model in A/NCR mice. Octadecyloxyethyl-CDV appeared to be the most potent CDV analog as a dose regimen of 5 mg/kg started 4 h following challenge completely blocked virus replication in spleen and liver, and protected 100% of A/NCR mice, although oral, unmodified CDV was inactive. These results suggest that this family of compounds deserves further evaluation as poxvirus antiviral

Exogenous ether lipids predominantly target mitochondria.

Directory of Open Access Journals (Sweden)

Lars Kuerschner

Full Text Available Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high amounts of ether-phosphatidylcholine and ether-phosphatidylethanolamine. Both lipids were specifically labeled using the corresponding lyso-ether lipids, which we established as supreme precursors for lipid tagging. Polyfosine, a fluorescent analogue of the anti-neoplastic ether lipid edelfosine, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria in ether lipid metabolism and intracellular ether lipid trafficking.

Biodegradation of di-n-butyl phthalate by bacterial consortium LV-1 enriched from river sludge.

Directory of Open Access Journals (Sweden)

Yangyang Wang

Full Text Available A stable bacterial consortium (LV-1 capable of degrading di-n-butyl phthalate (DBP was enriched from river sludge. Community analysis revealed that the main families of LV-1 are Brucellaceae (62.78% and Sinobacteraceae (14.83%, and the main genera of LV-1 are Brucella spp. (62.78% and Sinobacter spp. (14.83%. The optimal pH and temperature for LV-1 to degrade DBP were pH 6.0 and 30°C, respectively. Inoculum size influenced the degradation ratio when the incubation time was < 24 h. The initial concentration of DBP also influenced the degradation rates of DBP by LV-1, and the degradation rates ranged from 69.0-775.0 mg/l/d in the first 24 h. Degradation of DBP was best fitted by first-order kinetics when the initial concentration was < 300 mg/l. In addition, Cd2+, Cr6+, and Zn2+ inhibited DBP degradation by LV-1 at all considered concentrations, but low concentrations of Pb2+, Cu2+, and Mn2+ enhanced DBP degradation. The main intermediates (mono-ethyl phthalate [MEP], mono-butyl phthalate [MBP], and phthalic acid [PA] were identified in the DBP degradation process, thus a new biochemical pathway of DBP degradation is proposed. Furthermore, LV-1 also degraded other phthalates with shorter ester chains (DMP, DEP, and PA.

Ether formulations of relativity

International Nuclear Information System (INIS)

Duffy, M.C.

1980-01-01

Contemporary ether theories are surveyed and criticised, especially those formally identical to orthodox Relativity. The historical development of Relativity, Special and General, in terms of an ether, is briefly indicated. Classical interpretations of Generalized Relativity using ether are compared to Euclidean formulations using a background space. The history of a sub-group of theories, formulating a 'new' Relativity involving modified transforms, is outlined. According to the theory with which they agree, recent supposed detections of drift are classified and criticised. Cosmological evidence suggesting an ether is mentioned. Only ether theories formally identical to Relativity have been published in depth. They stand criticised as being contrary to the positivist spirit. The history of mechanical analogues is traced, from Hartley's representing gravitating matter as spherical standing waves, to recent suggestions that vortex-sponge might model electromagnetic, quantum, uncertainty and faster-than-light phenomena. Contemporary theories are particular physical theories, themselves 'second interpretations' of a primary mathematical model. Mechanical analogues are auxiliary, not necessary, to other theory, disclosing relationships between classical and non-classical descriptions of assemblies charging state. The ether-relativity polemic, part of a broader dispute about relativity, is founded on mistaken conceptions of the roles of mathematical and physical models, mechanical analogues; and a distored view of history, which indicates that ether theories have become relativistic. (author)

Sucrose esters from Physalis peruviana calyces with anti-inflammatory activity.

Science.gov (United States)

Franco, Luis A; Ocampo, Yanet C; Gómez, Harold A; De la Puerta, Rocío; Espartero, José L; Ospina, Luis F

2014-11-01

Physalis peruviana is a native plant from the South American Andes and is widely used in traditional Colombian medicine of as an anti-inflammatory medicinal plant, specifically the leaves, calyces, and small stems in poultice form. Previous studies performed by our group on P. peruviana calyces showed potent anti-inflammatory activity in an enriched fraction obtained from an ether total extract. The objective of the present study was to obtain and elucidate the active compounds from this fraction and evaluate their anti-inflammatory activity in vivo and in vitro. The enriched fraction of P. peruviana was purified by several chromatographic methods to obtain an inseparable mixture of two new sucrose esters named peruviose A (1) and peruviose B (2). Structures of the new compounds were elucidated using spectroscopic methods and chemical transformations. The anti-inflammatory activity of the peruvioses mixture was evaluated using λ-carrageenan-induced paw edema in rats and lipopolysaccharide-activated peritoneal macrophages. Results showed that the peruvioses did not produce side effects on the liver and kidneys and significantly attenuated the inflammation induced by λ-carrageenan in a dosage-dependent manner, probably due to an inhibition of nitric oxide and prostaglandin E2, which was demonstrated in vitro. To our knowledge, this is the first report of the presence of sucrose esters in P. peruviana that showed a potent anti-inflammatory effect. These results suggest the potential of sucrose esters from the Physalis genus as a novel natural alternative to treat inflammatory diseases. Georg Thieme Verlag KG Stuttgart · New York.

The effect of sorbic acid and esters of p-hydroxybenzoic acid on the protonmotive force in Escherichia coli membrane vesicles.

Science.gov (United States)

Eklund, T

1985-01-01

The effect of three food preservatives, sorbic acid and methyl and butyl esters of p-hydroxybenzoic acid, on the protonmotive force in Escherichia coli membrane vesicles was investigated. Radioactive chemical probes were used to determine the two components of the protonmotive force: delta pH (pH difference) and delta psi (membrane potential). Both types of compound selectively eliminated delta pH across the membrane, while leaving delta psi much less disturbed indicating that transport inhibition by neutralization of the protonmotive force cannot be the only mechanism of action for the food preservatives tested.

Esters of ricebran oil with short chain alcohols as alternative fuel for diesel engines

Directory of Open Access Journals (Sweden)

F.A. Zaher

2016-06-01

Full Text Available The potential of ricebran oil as a feedstock for the production of a fuel for diesel engines alternative to regular diesel fuel has been assessed. Esterification rate of crude ricebran oil with methyl alcohol was studied using different volumetric ratios of alcohol to oil, different catalyst loads and catalyst types. Catalysts used were sulfuric acid at a concentration of 2% of the oil/alcohol mixture in addition to hydrochloric acid and Amberlite IR-120 cation exchange resin at the same molar concentration of H+ as in case of sulfuric acid. The reaction was fastest using sulfuric acid which has been then used to prepare esters of ricebran oil with methyl, ethyl, propyl and butyl alcohols. The four products have been evaluated as a fuel for diesel engines according to their fuel properties compared to regular diesel fuel. These properties include the calorific value, flash point, viscosity, pour point, cetane number, sulfur content and ASTM distillation characteristics. The results have shown that the methyl as well as the ethyl esters have the closest properties to those of regular diesel fuel. Diesel engine performance using blends of regular diesel fuel with methyl and ethyl esters of ricebran oil have been tested and compared to that using regular diesel fuel. The results have shown that the engine performance using a blend of 50% regular diesel fuel and 50% methyl esters of ricebran oil is better than that using regular diesel fuel. The brake thermal efficiency at full load was 30.2% using the fuel blend compared to 27.5% in case of regular fuel.

Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters

Directory of Open Access Journals (Sweden)

Ngoc-Lan Thi Nguyen

2017-09-01

Full Text Available The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylimidazolium chloride and aluminum chloride were found to be the most efficient and recyclable reaction framework. Ultrasound sonication appeared to be the most useful and green activation method to afford the sulfoxides in yields better than or equivalent to those obtained under the longer-lasting conventional stirring conditions.

Radioiodinated cholesteryl ester analogs as residualizing tracers of lipoproteins disposition

International Nuclear Information System (INIS)

DeForge, L.E.

1989-01-01

Due to the importance of low density lipoprotein (LDL) in lipid metabolism and atherosclerosis, efforts were made to incorporate 125 I-cholesteryl iopanoate ( 125 I-CI), a residualizing cholesteryl ester (CE) analog, into the lipid core of LDL. This preparation is potentially useful as a scintigraphically detectable tracer of LDL uptake into atheroma and tissues such as the adrenal and liver. Initial studies using a cholesterol-fed rabbit model of atherosclerosis validated the use of 125 I-CI as a tracer of CE deposition. However, scintigraphy revealed considerable nonspecific 125 I-CI uptake due to tissue cholesterol loading. An alternative animal model was the guinea pig, which responds moderately to cholesterol feeding and carries the plasma cholesterol predominantly as LDL. Dietary fat and cholesterol, coupled with chronic aortic injury caused by an indwelling catheter, resulted in lipid containing, smooth muscle cell proliferative lesions in many animals. However, further studies are necessary to fully characterize this model. In additional studies, in vitro methods for incorporating 125 I-CI into LDL were examined. These included a reconstitution procedure described by Krieger et al. and a procedure involving incubation of detergent (Tween 20)-solubilized 125 I-CI with plasma. Although both LDL preparations were taken up normally by cultured fibroblasts, the plasma clearance rate of reconstituted LDL was markedly abnormal in guinea pigs. In contrast, LDL labeled by the detergent method cleared from the plasma identically to a radioiodinated LDL control. Therefore, this latter procedure was also used to incorporate two novel radioiodinated cholesteryl ether analogs 125 I-CI cholesteryl m-iodobenzyl ether [ 125 I-CIDE] and 125 I-cholesteryl 12-(miodophenyl)dodecyl ether [ 125 I-CIDE] into LDL

Meso-ester and carboxylic acid substituted BODIPYs with far-red and near-infrared emission for bioimaging applications

KAUST Repository

Ni, Yong

2014-01-21

A series of meso-ester-substituted BODIPY derivatives 1-6 are synthesized and characterized. In particular, dyes functionalized with oligo(ethylene glycol) ether styryl or naphthalene vinylene groups at the α positions of the BODIPY core (3-6) become partially soluble in water, and their absorptions and emissions are located in the far-red or near-infrared region. Three synthetic approaches are attempted to access the meso-carboxylic acid (COOH)-substituted BODIPYs 7 and 8 from the meso-ester-substituted BODIPYs. Two feasible synthetic routes are developed successfully, including one short route with only three steps. The meso-COOH-substituted BODIPY 7 is completely soluble in pure water, and its fluorescence maximum reaches around 650 nm with a fluorescence quantum yield of up to 15 %. Time-dependent density functional theory calculations are conducted to understand the structure-optical properties relationship, and it is revealed that the Stokes shift is dependent mainly on the geometric change from the ground state to the first excited singlet state. Furthermore, cell staining tests demonstrate that the meso-ester-substituted BODIPYs (1 and 3-6) and one of the meso-COOH-substituted BODIPYs (8) are very membrane-permeable. These features make these meso-ester- and meso-COOH-substituted BODIPY dyes attractive for bioimaging and biolabeling applications in living cells. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the characterization and formulation of the decontamination gels

Energy Technology Data Exchange (ETDEWEB)

Park, Youn Bong; Bang, In Bae; Bae, Bong Moon; Oh, Gyu Hwan [Chungnam National University, Daejeon (Korea, Republic of)

2011-04-15

To develop a chemical gel decontamination technology for a removal of non-fixed contaminants during the maintenance and decommissioning works of high radiation hot cells which have been used for a recycling or treatment of spent fuels we have prepare gels with CAB-O-SIL M-5 or Aerosil 380 as viscosifier and some non-ionic surfactants such as diethylene glycol hexyl ether, triethylene glycol dodecyl ether, polyethylene glycol 600, and triethylene glycol butyl ether. Surfactants are playing important roles in manipulating the properties of decontamination the gels. We have found the CAB-O-SIL with triethylene glycol butyl ether and Aerosil with triethylene glycol dodecyl ether systems promising for the decontamination work

Study of the characterization and formulation of the decontamination gels

International Nuclear Information System (INIS)

Park, Youn Bong; Bang, In Bae; Bae, Bong Moon; Oh, Gyu Hwan

2011-04-01

To develop a chemical gel decontamination technology for a removal of non-fixed contaminants during the maintenance and decommissioning works of high radiation hot cells which have been used for a recycling or treatment of spent fuels we have prepare gels with CAB-O-SIL M-5 or Aerosil 380 as viscosifier and some non-ionic surfactants such as diethylene glycol hexyl ether, triethylene glycol dodecyl ether, polyethylene glycol 600, and triethylene glycol butyl ether. Surfactants are playing important roles in manipulating the properties of decontamination the gels. We have found the CAB-O-SIL with triethylene glycol butyl ether and Aerosil with triethylene glycol dodecyl ether systems promising for the decontamination work

A novel technique for the simultaneous determination of 210Pb and 210Po using a crown ether

International Nuclear Information System (INIS)

Vajda, N.; LaRosa, J.; Zeisler, R.; Danesi, P.; Kis-Benedek, Gy.

1997-01-01

A simple radiochemical procedure has been developed to separate lead and polonium simultaneously from different environmental and biological materials. After adding 208 Po tracer and lead carrier, samples are decomposed using mineral acids. Lead and polonium are selectively retained from 2M HCl solution by the bis-4,4'(5')-t-butyl-cyclohexano-18-crown-6-ether; polonium is stripped with 6 M HNO 3 while lead is stripped with 6 M HCL solution. A polonium source is prepared by spontaneous deposition onto a silver disk. The activity concentration of 210 Po is determined by isotope dilution alpha spectrometry. Lead is precipitated as oxalate; the chemical recovery is determined by gravimetry. The activity concentration of 210 Pb is calculated from the liquid scintillation spectrum. (author)

High-k 3D-barium titanate foam/phenolphthalein poly(ether sulfone)/cyanate ester composites with frequency-stable dielectric properties and extremely low dielectric loss under reduced concentration of ceramics

Science.gov (United States)

Zheng, Longhui; Yuan, Li; Guan, Qingbao; Liang, Guozheng; Gu, Aijuan

2018-01-01

Higher dielectric constant, lower dielectric loss and better frequency stability have been the developing trends for high dielectric constant (high-k) materials. Herein, new composites have been developed through building unique structure by using hyperbranched polysiloxane modified 3D-barium titanate foam (BTF) (BTF@HSi) as the functional fillers and phenolphthalein poly(ether sulfone) (cPES)/cyanate ester (CE) blend as the resin matrix. For BTF@HSi/cPES/CE composite with 34.1 vol% BTF, its dielectric constant at 100 Hz is as high as 162 and dielectric loss is only 0.007; moreover, the dielectric properties of BTF@HSi/cPES/CE composites exhibit excellent frequency stability. To reveal the mechanism behind these attractive performances of BTF@HSi/cPES/CE composites, three kinds of composites (BTF/CE, BTF/cPES/CE, BTF@HSi/CE) were prepared, their structure and integrated performances were intensively investigated and compared with those of BTF@HSi/cPES/CE composites. Results show that the surface modification of BTF is good for preparing composites with improved thermal stability; while introducing flexible cPES to CE is beneficial to fabricate composites with good quality through effectively blocking cracks caused by the stress concentration, and then endowing the composites with good dielectric properties at reduced concentration of ceramics.

40 CFR 799.1560 - Diethylene glycol butyl ether and diethylene glycol butyl ether acetate.

Science.gov (United States)

2010-07-01

... of the test cage, temperature, relative humidity, lighting conditions, odors, use of home cage or... following components in all appropriate required samples: Neuronal body (e.g., Einarson's gallocyanin), axon...

Gamma-radiation effect on thermal ageing of butyl rubber compounds

Energy Technology Data Exchange (ETDEWEB)

Scagliusi, Sandra R.; Cardoso, Elizabeth C.L.; Lugao, Ademar B., E-mail: srscagliusi@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2015-07-01

Butyl rubber has a comprehensive use in sealing systems, especially in tires inner tubes, due to their low permeability to gases. So, it is required that butyl rubber compounds show a better performance, more and more. Butyl rubber is provided with excellent mechanical properties and oxidation resistance. Besides showing these properties, radiation exposures impart modifications in physical-chemical and morphological properties on butyl rubber materials. When exposed to gamma-radiation, rubbers suffer changes in their mechanical and physical properties, caused by material degradation. The major radiation effect in butyl rubbers is chain scission; besides, ageing promotes too the same effect with further build-up of free radicals. This work aims to the study of gamma-radiation in physical-chemical properties of butyl rubber subjected to thermal ageing. Doses used herein were: 25 kGy, 50 kGy, 100 kGy, 150 kGy and 200 KGy. Samples were evaluated before and after ageing according to traditional essays, such as: hardness, tensile strength and elongation at break. From accomplished assessments it is possible to affirm that at doses higher than 50 kGy it was observed a sharp decreasing in butyl rubber physical-chemical properties, before and after exposure to ageing. (author)

Gamma-radiation effect on thermal ageing of butyl rubber compounds

International Nuclear Information System (INIS)

Scagliusi, Sandra R.; Cardoso, Elizabeth C.L.; Lugao, Ademar B.

2015-01-01

Butyl rubber has a comprehensive use in sealing systems, especially in tires inner tubes, due to their low permeability to gases. So, it is required that butyl rubber compounds show a better performance, more and more. Butyl rubber is provided with excellent mechanical properties and oxidation resistance. Besides showing these properties, radiation exposures impart modifications in physical-chemical and morphological properties on butyl rubber materials. When exposed to gamma-radiation, rubbers suffer changes in their mechanical and physical properties, caused by material degradation. The major radiation effect in butyl rubbers is chain scission; besides, ageing promotes too the same effect with further build-up of free radicals. This work aims to the study of gamma-radiation in physical-chemical properties of butyl rubber subjected to thermal ageing. Doses used herein were: 25 kGy, 50 kGy, 100 kGy, 150 kGy and 200 KGy. Samples were evaluated before and after ageing according to traditional essays, such as: hardness, tensile strength and elongation at break. From accomplished assessments it is possible to affirm that at doses higher than 50 kGy it was observed a sharp decreasing in butyl rubber physical-chemical properties, before and after exposure to ageing. (author)

Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide

International Nuclear Information System (INIS)

Domanska, Urszula; Marciniak, Andrzej

2009-01-01

The activity coefficients at infinite dilution, γ 13 ∞ for 36 solutes: alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofuran, ethers, acetone, and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide [bmPY][NTf 2 ] were determined by gas-liquid chromatography at temperatures from 298.15 K to 368.15 K. The partial molar excess enthalpies at infinite dilution values ΔH 1 E,∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The selectivity for different separation problems were calculated from the γ 13 ∞ and compared to the literature values for other ionic liquids, N-methyl-2-pyrrolidinone (NMP) and sulfolane.

On the predictive capabilities of CPA for applications in the chemical industry: Mulficomponent mixtures containing methyl-methacrylate, dimethyl-ether or acetic acid

DEFF Research Database (Denmark)

Tsivintzelis, Ioannis; Kontogeorgis, Georgios

2014-01-01

mixtures exhibiting vapor-liquid (VLE) and/or liquid-liquid (LLE) equilibrium. The first two cases include mixtures of methyl-methacrylate with acetone or methanol and dimethyl-ether with ethanol, respectively. In these two cases, the classical form of CPA is used. The third case involves aqueous mixtures...... for the acetic acid-water system for which different parameter sets at different temperatures can be recommended. Even with the use of CPA-HV mixing rules, modeling of the acetic acid-water system with few interaction parameters remains a challenging task. Excellent simultaneous VLE and LLE correlation...... is obtained for complex systems such as aqueous mixtures with ethers and esters. The multicomponent results are, with a few exceptions, very satisfactory, especially for the vapor-liquid equilibrium cases. For the demanding aqueous acetic acid-water containing systems, one parameter set is recommended...

Ether the nothing that connects everything

CERN Document Server

Milutis, Joe

2006-01-01

In Ether, the histories of the unseen merge with discussions of the technology of electromagnetism. Navigating more than three hundred years of the ether''s cultural and artistic history, Joe Milutis reveals its continuous reinvention and tangible impact without ever losing sight of its ephemeral, elusive nature. The true meaning of ether, Milutis suggests, may be that it can never be fully grasped.

Organic Semiconductors and Conductors with tert-Butyl Substituents

Directory of Open Access Journals (Sweden)

Toshiki Higashino

2012-08-01

Full Text Available Tetrathiafulvalene (TTF, pentacene, and quarterthiophene with tert-butyl substituents are synthesized, and the crystal structures and the transistor properties are investigated. The tetracyanoquinodimethane (TCNQ complex of tert-butyl TTF constructs highly one-dimensional segregated columns with tetragonal crystal symmetry.

Usage of the word 'ether'

International Nuclear Information System (INIS)

Duffy, M.C.

1980-01-01

Confusion has been caused by scientists using the one word 'ether' to classify models differing from each other in important respects. Major roles assigned to the word are examined, and the nature of modern ether theories surveyed. The part played by the several meanings attached to the word, in the ether concept, is outlined. (author)

Soil contamination by phthalate esters in Chinese intensive vegetable production systems with different modes of use of plastic film

International Nuclear Information System (INIS)

Wang, Jun; Luo, Yongming; Teng, Ying; Ma, Wenting; Christie, Peter; Li, Zhengao

2013-01-01

The concentrations of six priority phthalic acid esters (PAEs) in intensively managed suburban vegetable soils in Nanjing, east China, were analyzed using gas chromatography–mass spectrometry (GC–MS). The total PAE concentrations in the soils ranged widely from 0.15 to 9.68 mg kg −1 with a median value of 1.70 mg kg −1 , and di-n-butyl phthalate (DnBP), bis-(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DnOP) were the most abundant phthalate esters. Soil PAE concentrations depended on the mode of use of plastic film in which PAEs were incorporated as plasticizing agents and both the plastic film and poultry manure appeared to be important sources of soil PAEs. Vegetables in rotation with flooded rice led to lower concentrations of PAEs in soil. The results indicate that agricultural plastic film can be an important source of soil PAE contamination and further research is required to fully elucidate the mechanisms of PAE contamination of intensive agricultural soils with different use modes of use of plastic film. -- Highlights: •Phthalate esters in soils from suburban intensive vegetable production systems were investigated. •Phthalate levels and risks of the vegetable soils with different plastic film use modes were examined. •Sources of phthalate esters in vegetable production soils were analyzed. -- PAE contamination of intensively managed vegetable soils varied widely depending on the mode of use of plastic film in different production systems

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

Science.gov (United States)

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.

Recovering/recycling of butyl and halogenated butyl rubber via ionizing radiation; Recuperacao/reciclagem de compostos de borrachas butilica e halobutilica por meio de radiacao ionizante

Energy Technology Data Exchange (ETDEWEB)

Martin, Sandra Regina Scagliusi

2013-07-01

Polymeric materials (plastics and rubbers) attain a continuous and raising proportion of urban and industrial scraps discarded in landfills; their impact on environment are more and more concerning. The implementation of new technologies in order to reduce impacts of plastic waste on the environment, at an effective cost, proved to be a great problem, due to inherent complexity for polymers re-using. Ionizing radiation is capable to modify structure and properties of polymeric material. Butyl and halobutyl rubbers have been used within a comprehensive scale, applications such as tires spare parts and diverse artifacts. The major high energy photon effect, as gamma-rays in butyl and halo butyl rubbers consists in free-radicals generation along changes in mechanical properties.This work aims to the development of controlled degradation processes (devulcanization) of butyl and halo butyl (chlorine and bromine) rubbers, in order to characterize their availability for transformation and modification of properties. Experimental results obtained showed that butyl and halobutyl rubbers,irradiated at 25 kGy and further sheared, are able to be used as an initial point for mixtures with pristine. (author)

Recycling of Gamma Irradiated Inner Tubes in Butyl Based Rubber Compound

International Nuclear Information System (INIS)

Karaagac, B.

2006-01-01

Crosslinked elastomeric materials, such as tyres are of great challenge concerning the environmental and ecological reasons. Ionizing radiation seems to offer unique opportunities to tackle the problem of recycling of polymers and rubbers on account of its ability to cause chain scission and/or cross-linking of polymeric materials. There is only limited amount of work reported on the irradiation-induced degradation of rubbers. Unlike the majority of the elastomers with high levels of unsaturation, butyl rubber exhibits significant degradation by ionizing radiation action. In this study, recycling of gamma irradiated inner tubes made of butyl rubber in butyl based rubber compounds was studied. Used inner tubes were irradiated with gamma rays in air at 100 and 120 kGy absorbed doses. The compatibility of irradiated inner tubes with virgin butyl rubber was first investigated. Gamma irradiated inner tube wastes were replaced with butyl rubber up to 15 phr in the compound recipe. Similar recipes were also prepared by using the same quantity of commercial butyl rubber crumbs devulcanized by conventional methods. The rheological and mechanical properties and carbon black dispersion degree for both types of compounds prepared by using inner tubes scraps and commercial butyl crumbs were measured and were compared to the values of virgin butyl rubber compound. It is well known that mechanical properties are deteriorated when rubber crumb is added to the virgin compound. It was observed that the decrease in the mechanical properties was much lower for the compounds prepared from the tubes irradiated at 120 kGy than irradiated at 100 kGy. The better mechanical properties were obtained for the compounds prepared by recycling of irradiated inner tubes at 120 kGy than the compounds prepared by using commercial butyl crumbs. Almost similar carbon black distributions were observed for the all compounds studied. It has been concluded that gamma irradiated inner tubes are compatible

Effect of Di-Tertiary Butyl Peroxide on the performance, combustion and emission characteristics of ethanol blended cotton seed methyl ester fuelled automotive diesel engine

International Nuclear Information System (INIS)

Kumar, K. Senthil; Raj, R. Thundil Karuppa

2016-01-01

Highlights: • Effect of di-tertiary butyl peroxide on ethanol blended biodiesel is investigated. • Cetane enhanced ethanol up to 10% can be blended with cotton seed biodiesel. • Nitrogen oxides emissions are lower for cetane enhanced ethanol biodiesels. • Performance characteristics of cetane improved ethanol biodiesels are reasonable. • Cetane enhanced ethanol blended biodiesel is an promising renewable energy source. - Abstract: An experimental study is carried out to examine and analyze the influence of Di-Tertiary Butyl Peroxide in bioethanol diesel blends on the performance, combustion and emission characteristics in a single cylinder, 4-stroke, naturally aspirated, automotive diesel engine for variable speed at full load conditions. Esterified cotton seed oil of 5% by volume is emulsified with 95% pure diesel to get the base fuel (BE0) for the experiments. Bioethanol diesel blends are produced from base fuel by adding 5% and 10% pure ethanol on a volumetric basis to obtain BE5 and BE10 respectively. The bioethanol fuels are low in Cetane number and hence Di-Tertiary Butyl Peroxide a Cetane enhancer is added by 0.4% by volume to produce BE5CN0.4% and BE10CN0.4% emulsions respectively. It is found from the experiments carried out, that an inverse trend exists between brake thermal efficiency and percentage of ethanol in base fuel. This is due to the lower calorific value of ethanol and an improvement in brake thermal efficiency is observed with ignition improver added blends. The presence of Cetane improver significantly reduced oxides of nitrogen and unburned hydro carbon emissions for overall engine speed and carbon monoxide emissions for low to medium speed range.

NMR analysis of t-butyl-catalyzed deuterium exchange at unactivated arene localities.

Science.gov (United States)

Stack, Douglas E; Eastman, Rachel

2016-10-01

Regioselective labelling of arene rings via electrophilic exchange is often dictated by the electronic environment caused by substituents present on the aromatic system. Previously, we observed the presence of a t-butyl group, either covalently bond or added as an external reagent, could impart deuterium exchange to the unactivated, C1-position of estrone. Here, we provide nuclear magnetic resonance analysis of this exchange in a solvent system composed of 50:50 trifluoroacetic acid and D 2 O with either 2-t-butylestrone or estrone in the presence of t-butyl alcohol has shed insights into the mechanism of this t-butyl-catalyzed exchange. Fast exchange of the t-butyl group concurrent with the gradual reduction of the H1 proton signal in both systems suggest a mechanism involving ipso attack of the t-butyl position by deuterium. The reversible addition/elimination of the t-butyl group activates the H1 proton towards exchange by a mechanism of t-butyl incorporation, H1 activation and exchange, followed by eventual t-butyl elimination. Density functional calculations are consistent with the observation of fast t-butyl exchange concurrent with slower H1 exchange. The σ-complex resulting from ipso attack of deuterium at the t-butyl carbon was 6.6 kcal/mol lower in energy than that of the σ-complex resulting from deuterium attack at C1. A better understanding of the t-butyl-catalyzed exchange could help in the design of labelling recipes for other phenolic metabolites. Copyright © 2016 The Authors. Journal of Labelled Compounds and Radiopharmaceuticals published by John Wiley & Sons, Ltd.

Occurrence and risk assessment of phthalate esters (PAEs) in vegetables and soils of suburban plastic film greenhouses.

Science.gov (United States)

Wang, Jun; Chen, Gangcai; Christie, Peter; Zhang, Manyun; Luo, Yongming; Teng, Ying

2015-08-01

Phthalate esters (PAEs) are suspected of having adverse effects on human health and have been frequently detected in soils and vegetables. The present study investigated their occurrence and composition in plastic film greenhouse soil-vegetable systems and assessed their potential health risks to farmers exposed to these widespread pollutants. Six priority control phthalates, namely dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), butyl benzyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DnOP), were determined in 44 plastic film greenhouse vegetables and corresponding soils. Total PAEs ranged from 0.51 to 7.16mgkg(-1) in vegetables and 0.40 to 6.20mgkg(-1) in soils with average concentrations of 2.56 and 2.23mgkg(-1), respectively. DnBP, DEHP and DnOP contributed more than 90% of the total PAEs in both vegetables and soils but the proportions of DnBP and DnOP in vegetables were significantly (p3.00mgkg(-1) but were plastic film greenhouses. Health risks were mainly by exposure through vegetable consumption and soil ingestion. Copyright © 2015 Elsevier B.V. All rights reserved.

Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

Science.gov (United States)

Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

2009-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

Inducing PLA/starch compatibility through butyl-etherification of waxy and high amylose starch.

Science.gov (United States)

Wokadala, Obiro Cuthbert; Emmambux, Naushad Mohammad; Ray, Suprakas Sinha

2014-11-04

In this study, waxy and high amylose starches were modified through butyl-etherification to facilitate compatibility with polylactide (PLA). Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy and wettability tests showed that hydrophobic butyl-etherified waxy and high amylose starches were obtained with degree of substitution values of 2.0 and 2.1, respectively. Differential scanning calorimetry, tensile testing, and scanning electron microscopy (SEM) demonstrated improved PLA/starch compatibility for both waxy and high amylose starch after butyl-etherification. The PLA/butyl-etherified waxy and high amylose starch composite films had higher tensile strength and elongation at break compared to PLA/non-butyl-etherified composite films. The morphological study using SEM showed that PLA/butyl-etherified waxy starch composites had a more homogenous microstructure compared to PLA/butyl-etherified high amylose starch composites. Thermogravimetric analysis showed that PLA/starch composite thermal stability decreased with starch butyl-etherification for both waxy and high amylose starches. This study mainly demonstrates that PLA/starch compatibility can be improved through starch butyl-etherification. Copyright © 2014 Elsevier Ltd. All rights reserved.

Le biogazole de synthèse : un biodiesel de deuxième génération

Directory of Open Access Journals (Sweden)

Blondy Jacques

2006-03-01

Full Text Available Biofuels have developed for more than ten years in France thanks two products: ETBE (Ethyl Tertio Butyl Ether and FAME (Fatty Acids Methyl Esters. These biofuels, in addition to a positive effect on greenhouse gases emissions, offer favourable characteristics for their use, but their blending rates are however limited due to some of their properties. Diversification of biomass resources and exploration of new ways to obtain even better adapted products as component of modern fuels and matching automotive industy requirements, have oriented research towards second generation biofuels like synthetic biodiesel. A first production unit using the NExBTL process, is due to start in 2007 in Finland, a second, scheduled by 2009, is under study in one of the European TOTAL refinery.

Contribution to the study of uranyl salts in butyl phosphate solutions

International Nuclear Information System (INIS)

Coulon, A.

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from ∼ 1270 cm -1 to ∼ 1180 cm -1 . A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [fr

Thermodynamic and kinetic analysis of phase separation of temperature-sensitive poly(vinyl methyl ether) in the presence of hydrophobic tert-butyl alcohol

Czech Academy of Sciences Publication Activity Database

Velychkivska, Nadiia; Bogomolova, Anna; Filippov, Sergey K.; Starovoytova, Larisa; Labuta, J.

2017-01-01

Roč. 295, č. 8 (2017), s. 1419-1428 ISSN 0303-402X R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : phase separation * coil-globule transition * poly(vinyl methyl ether) Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

Optimisation of flavour ester biosynthesis in an aqueous system of coconut cream and fusel oil catalysed by lipase.

Science.gov (United States)

Sun, Jingcan; Yu, Bin; Curran, Philip; Liu, Shao-Quan

2012-12-15

Coconut cream and fusel oil, two low-cost natural substances, were used as starting materials for the biosynthesis of flavour-active octanoic acid esters (ethyl-, butyl-, isobutyl- and (iso)amyl octanoate) using lipase Palatase as the biocatalyst. The Taguchi design method was used for the first time to optimize the biosynthesis of esters by a lipase in an aqueous system of coconut cream and fusel oil. Temperature, time and enzyme amount were found to be statistically significant factors and the optimal conditions were determined to be as follows: temperature 30°C, fusel oil concentration 9% (v/w), reaction time 24h, pH 6.2 and enzyme amount 0.26 g. Under the optimised conditions, a yield of 14.25mg/g (based on cream weight) and signal-to-noise (S/N) ratio of 23.07 dB were obtained. The results indicate that the Taguchi design method was an efficient and systematic approach to the optimisation of lipase-catalysed biological processes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermodynamic study of (alkyl esters+{alpha},{omega}-alkyl dihalides) III. H{sub m}{sup E}andV{sub m}{sup E} for 20 binary mixtures {l_brace}xC{sub u-1}H{sub 2u-1}CO{sub 2}C{sub 4}H{sub 9}+(1-x){alpha},{omega}-ClCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Cl{r_brace}, where u=1 to 4, {alpha}=1 and v={omega}=2 to 6

Energy Technology Data Exchange (ETDEWEB)

Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria, Canary Islands (Spain)]. E-mail: jortega@dip.ulpgc.es; Marrero, E. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria, Canary Islands (Spain); Toledo, F.J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario Tafira, Universidad de Las Palmas de Gran Canaria, 35071-Las Palmas de Gran Canaria, Canary Islands (Spain)

2006-09-15

In this article, the experimental data of excess molar enthalpies H{sub m}{sup E} and excess molar volumes V{sub m}{sup E} are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five {alpha},{omega}-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The V{sub m}{sup E} are positive for mixtures of (butyl esters+1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in H{sub m}{sup E} with the dichloroethane chain length for a same ester is regular although the V{sub m}{sup E} presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied. To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems' behaviour.

Determining Sorption Rate by a Continuous Gravimetric Method

National Research Council Canada - National Science Library

Hall, Monicia R; Procell, Lawrence R; Bartram, Philip W; Shuely, Wendel J

2003-01-01

... were automatically recorded in an Excel file while CARC coupons were submerged in solvent. Initial sorption rates were determined for butyl acetate, butyl ether, cyclohexane and propylene carbonate...

Synthesis & Characterization of New bis-Symmetrical Adipoyl ...

African Journals Online (AJOL)

Full Title: Synthesis and Characterization of New bis-Symmetrical Adipoyl, Terepthaloyl, Chiral Diimido-di-L-alanine Diesters and Chiral Phthaloyl-L-alanine Ester of Tripropoxy p-tert-Butyl Calix[4]arene and Study of Their Hosting Ability for Alanine and Na+. Bis-symmetrical tripropoxy p-tert-butyl calix[4]arene esters were ...

and triorganotin(IV) complexes of 2-tert-butyl-4-methyl phenol

Indian Academy of Sciences (India)

TECS

-2-Me-4) have been synthesized by the reactions of di-n-butyl and dimethyltin dichlorides and tri-n-butyltin(IV) chloride with 2-tert-butyl-4-methylphenol and triethylamine in tetrahydrofuran. The reaction of triphenyltin chloride with trimethylsilyl-2-t-butyl-4- methylphenoxide in the same solvent however, gives a complex of ...

Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide

Energy Technology Data Exchange (ETDEWEB)

Domanska, Urszula [Physical Chemistry Department, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)], E-mail: ula@ch.pw.edu.pl; Marciniak, Andrzej [Physical Chemistry Department, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland)

2009-12-15

The activity coefficients at infinite dilution, {gamma}{sub 13}{sup {infinity}} for 36 solutes: alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofuran, ethers, acetone, and water in the ionic liquid 4-methyl-N-butyl-pyridinium bis(trifluoromethylsulfonyl)-imide [bmPY][NTf{sub 2}] were determined by gas-liquid chromatography at temperatures from 298.15 K to 368.15 K. The partial molar excess enthalpies at infinite dilution values {delta}H{sub 1}{sup E,{infinity}} were calculated from the experimental {gamma}{sub 13}{sup {infinity}} values obtained over the temperature range. The selectivity for different separation problems were calculated from the {gamma}{sub 13}{sup {infinity}} and compared to the literature values for other ionic liquids, N-methyl-2-pyrrolidinone (NMP) and sulfolane.

Silane Cross-Linked Sulfonted Poly(Ether Ketone/Ether Benzimidazoles for Fuel Cell Applications

Directory of Open Access Journals (Sweden)

Zilu Yao

2017-11-01

Full Text Available γ-(2,3-epoxypropoxy propyltrimethoxysilane (KH-560 was incorporated in various proportions into side-chain-type sulfonated poly(ether ketone/ether benzimidazole (SPEKEBI as a crosslinker, to make membranes with high ion exchange capacities and excellent performance for direct methanol fuel cells (DMFCs. Systematical measurements including Fourier transform infrared (FT-IR, scanning electron microscopy-energy-dispersive and X-ray photoelectron spectroscopy (XPS proved the complete disappearance of epoxy groups in KH-560 and the existence of Si in the membranes. The resulting membranes showed increased mechanical strength and thermal stability compared to the unmodified sulfonated poly(ether ketone/ether benzimidazole membrane in appropriate doping amount. Meanwhile, the methanol permeability has decreased, leading to the increase of relative selectivities of SPEKEBI-x-SiO2 membranes. Furthermore, the H2/O2 cell performance of SPEKEBI-2.5-SiO2 membrane showed a much higher peak power density compared with the pure SPEKEBI memrbrane.

Radiation-induced cationic curing of vinyl ethers

International Nuclear Information System (INIS)

Lapin, S.C.

1992-01-01

Recently there has been an increasing interest in nonacrylate radiation-curable coatings. Vinyl ethers are particularly reactive under cationic polymerization reaction conditions. The high efficiency of the photoacid initiators combined with the high reactivity of vinyl ether monomers makes this a potentially very useful system. This chapter discusses the preparation of vinyl ethers, introduces vinyl ether-functional monomers and oligomers, describes radiation-induced cationic polymerization of vinyl ethers, and discusses various coating systems. Throughout the chapter, an emphasis is placed on radiation-curable coating applications. 64 refs., 5 figs., 11 tabs

Disruption of Retinol (Vitamin A Signaling by Phthalate Esters: SAR and Mechanism Studies.

Directory of Open Access Journals (Sweden)

Yanling Chen

Full Text Available A spectrum of reproductive system anomalies (cryptorchidism, hypospadias, dysgenesis of Wolffian duct-derived tissues and prostate, and reduced sperm production in male rats exposed in utero to phthalate esters (PEs are thought to be caused by PE inhibition of fetal testosterone production. Recently, dibutyl and dipentyl phthalate (DBuP, DPnP were shown to disrupt the retinol signaling pathway (RSP in mouse pluripotent P19 embryonal carcinoma cells in vitro. The RSP regulates the synthesis and cellular levels of retinoic acid (RA, the active metabolite of retinol (vitamin A. In this new study, a total of 26 di- and mono-esters were screened to identify additional phthalate structures that disrupt the RSP and explore their mechanisms of action. The most potent PEs, those causing > 50% inhibition, contained aryl and cycloalkane groups or C4-C6 alkyl ester chains and were the same PEs reported to cause malformations in utero. They shared similar lipid solubility; logP values were between 4 and 6 and, except for PEs with butyl and phenyl groups, were stable for prolonged periods in culture. Mono- and cognate di-esters varied in ability to disrupt the RSP; e.g., DEHP was inactive but its monoester was active while DBuP was active yet its monoester was inactive. DBuP and dibenzyl phthalate both disrupted the synthesis of RA from retinol but not the ability of RA to activate gene transcription. Both PEs also disrupted the RSP in C3H10T1/2 multipotent mesenchymal stem cells. Based on this in vitro study showing that some PEs disrupt retinol signaling and previous in vivo studies that vitamin A/RA deficiency and PEs both cause strikingly similar anomalies in the male rat reproductive system, we propose that PE-mediated inhibition of testosterone and RA synthesis in utero are both causes of malformations in male rat offspring.

Catalytic Ester to Stannane Functional Group Interconversion via Decarbonylative Cross-Coupling of Methyl Esters

KAUST Repository

Yue, Huifeng

2018-01-03

An unprecedented conversion of methyl esters to stannanes was realized, providing access to a series of arylstannanes via nickel catalysis. Various common esters including ethyl, cyclohexyl, benzyl, and phenyl esters can undergo the newly developed decarbonylative stannylation reaction. The reaction shows broad substrate scope, can differentiate between different types of esters, and if applied in consecutive fashion, allows the transformation of methyl esters into aryl fluorides or biaryls via fluororination or arylation.

Catalytic Ester to Stannane Functional Group Interconversion via Decarbonylative Cross-Coupling of Methyl Esters

KAUST Repository

Yue, Huifeng; Zhu, Chen; Rueping, Magnus

2018-01-01

An unprecedented conversion of methyl esters to stannanes was realized, providing access to a series of arylstannanes via nickel catalysis. Various common esters including ethyl, cyclohexyl, benzyl, and phenyl esters can undergo the newly developed decarbonylative stannylation reaction. The reaction shows broad substrate scope, can differentiate between different types of esters, and if applied in consecutive fashion, allows the transformation of methyl esters into aryl fluorides or biaryls via fluororination or arylation.

Effective utilization of B20 blend with diethyl ether and ethanol as oxygenated additives

Directory of Open Access Journals (Sweden)

Upadrasta-Satya Vara-Prasad

2011-01-01

Full Text Available In the recent times' fatty acid methyl ester popularly called as biodiesel has become more prominent alternate fuel for compression ignition engines based on a single fuel concept. Since, use of neat biodiesel on a large scale is raising certain difficulties and is being adopted in a blended form with petro-diesel fuel and B20 blend has become standardized. However, the HC and NOx emissions of B20 are still on the higher side. Present work aims at experimental evaluation of a single cylinder water-cooled diesel engine by adopting various proportions of ethanol and diethyl ether blends in order to improve performance and emission characteristics of B20 blend. Besides employing different amounts of ethanol and diethyl ether, simultaneous influence of injector nozzle hole size and fuel injection pressure are also investigated to arrive at an optimum configuration. Brake specific fuel consumption and hydrocarbon emissions values are lower with B20 and DEE 5 whereas B20 with DEE15 yielded lower NOx emissions. It is observed that addition of oxygenates have improved the combustion process and lower emissions are obtained. The present investigation revealed that blends with oxygenated additives having higher Cetane rating are superior to neat blend.

Analysis of phosphate esters in plant material. Extraction and purification.

Science.gov (United States)

Isherwood, F A; Barrett, F C

1967-09-01

1. A critical study was made of the quantitative extraction of nucleotide and sugar phosphates from plant tissue by either boiling aqueous ethanol or cold trichloroacetic acid. The effect of the extraction technique on the inactivation of the enzymes in the plant tissue and the possibility of adsorption of the phosphate esters on the cell wall were especially considered. 2. In the recommended method the plant tissue was frozen in liquid nitrogen, ground to a powder and then blended with cold aqueous trichloroacetic acid containing 8-hydroxyquinoline to prevent adsorption. 3. The extract contained large amounts of trichloroacetic acid, cations, chloride, sugars, amino acids, hydroxy organic acids, phytic acid, orthophosphoric acid and high-molecular-weight material including some phosphorus-containing compounds. All of these were removed as they were liable to interfere with the chromatographic or enzymic assay of the individual nucleotide or sugar phosphates. 4. The procedure was as follows: the last traces of trichloroacetic acid were extracted with ether after the solution had been passed through a column of Dowex AG 50 in the hydrogen form to remove all cations. High-molecular-weight compounds were removed by ultrafiltration and low-molecular-weight solutes by a two-stage chromatography on cellulose columns with organic solvents. In the first stage, sugars, amino acids, chloride and phytic acid were separated by using a basic solvent (propan-1-ol-water-aqueous ammonia) and, in the second stage, the organic acids and orthophosphoric acid were separated by using an acidic solvent (di-isopropyl ether-formic acid-2-methylpropan-2-ol-water). The final solution of nucleotide and sugar phosphates was substantially free from other solutes and was suitable for the detection of individual phosphate esters by either chromatography or enzymic assay. 5. The recovery of d-glucose 6-phosphate or adenosine 5'-triphosphate added to a trichloroacetic acid extract simulating that

Poly (ether ether ketone) membranes for fuel cells

International Nuclear Information System (INIS)

Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D.; Hui, Wang S.; Oliveira, Vivianna S. de

2015-01-01

Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

Extraction and identification of bioactive components in Sida cordata (Burm.f.) using gas chromatography-mass spectrometry.

Science.gov (United States)

Ganesh, Mani; Mohankumar, Murugan

2017-09-01

Sida cordata (Burm.f.) is a pineal tropical plant in the family Malvaceae that is found throughout India and used to treat various diseases and ailments in many complementary and alternative medicine systems. This study identified the bioactive components present in whole-plant ethanol extracts of S . cordata using gas chromatography-mass spectrometry (GC-MS). Based on their retention times (RT) and mass-to-charge ratios (m/z), 29 bioactive compounds were identified: nonanoic acid, vitamin D 3 , 3-trifluroacetoxypentadecane, α-d-glucopyranoside, O-α-d-glucopyranosyl-(1.fwdarw.3)-α-d-fructofuranosyl,3,7,11,15-tetramethyl-2-hexadecan-1-ol, octadecanoic acid, ethyl ester, phytol, 9,12-octadecadienoic acid, methyl ester (E,E), 9,12,15-octadecadienoic acid, methyl ester (Z,Z,Z), oleic acid, 1,2-15,16-diepoxyhexadecane, 3-hexadecyloxycarbonyl-5-(2-hydroxyethyl)-4-methylimidazolium ion, methoxyacetic acid, 4-tetradecyl ester, 1,2-benzenedicarboxylic acid, mono (2-ethylhexyl) ester, 1-iodo-2-methylundecane, dodecane, 2,6,10-trimethyl-, 2-piperidinone-N-[4-bromo-n-butyl]-, squalene, octadecane-1-(ethenyloxy)-, Z,Z-2,5-pentadecadien-1-ol, 1-hexadecanol, 2-methyl-, spiro[androst-5ene-17,1'-cyclobutan]-2'-one-3-hydroxy-, (3a,17a)-, diethylene glycol monododecyl ether, vitamin E, cholestan-3-ol, 2-methylene-, (3a,5a)-, 2H-pyran, 2-(7-heptadecynyloxy)tetrahydro-, and cis -Z-α-bisabolene epoxide. The presence of various bioactive compounds justifies the use of this plant for treating various ailments by traditional practitioners.

Ion-Selective Ionic Polymer Metal Composite (IPMC) actuator based on crown ether containing sulfonated Poly(Arylene Ether Ketone)

NARCIS (Netherlands)

Tas, S.; Zoetebier, B.; Sukas, O.S.; Bayraktar, M.; Hempenius, M.; Vancso, G.J.; Nijmeijer, K.

2017-01-01

This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

Determination of phthalate esters in physiological saline solution by monolithic silica spin column extraction method

Directory of Open Access Journals (Sweden)

Lu Lu

2011-05-01

Full Text Available Monolithic silica spin column extraction (MonoSpin-SPE was developed as a simple, sensitive, and eco-friendly pretreatment method which combined with ultra-fast liquid chromatography-mass spectrometry (UFLC-MS to determine the levels of six phthalate esters, dimethyl-(DMP, diethyl-(DEP, dipropyl- [DPrP], butyl-benzyl-(BBP, dicyclohexyl(DcHP, and di- n-octyl-(DOP phthalate in physiological saline samples. Under optimized experimental conditions, the method was linear in the following ranges: 0.2- 50 μ/L for DMP, DEP, DPrP, DcHP and DOP; 5 – 100 μ/L for BBP. The correlation coefficients (R2 were in the range of O. 9951 – O. 9995 for all the analytes and the limits of detection (LODs and limits of quantification (LOQs were in the ranges of 0.02 – 0.9 μ/L and 0.08 – 2.7 μ/L, respectively. The pretreatment process showed good reproducibility with inter-day and intra-day relative standard deviations (RSDs below 8.5% and 11.2%, respectively. This method was used to determine the levels of six phthalate esters in physiological saline samples and the recoveries ranged from 71.2% to 107. 3%. DMP and DEP were found in actual physical saline samples (brand A and brand B. Keywords: Monolithic silica spin column, Phthalate esters, Physiological saline samples, Ultra fast liquid chromatographymass spectrometry (UFLC-MS

Solvent effects on the magnetic shielding of tertiary butyl alcohol

African Journals Online (AJOL)

)4 and tetramethyl ammonium cation N(CH3)4(+) have also been presented. KEY WORDS: Solvent effects, Magnetic shielding, Tertiary butyl alcohol, Tertiary butyl amine, Continuum solvation calculations, Chemical shift estimation methods

Synthesis and thermal characterization of CdS nano crystals in previously formed template of maleic anhydride-octene 1-vinyl butyl terpolymer

International Nuclear Information System (INIS)

Akbarov, O.H; Mammadova, R.E; Malikov, E.Y.

2008-01-01

Full text: Nano crystals have dimensions in the range 10100 nm. Crystals in this size range possess unique properties, which enable scientists to manufacture materials and devices capable of performing unimaginable tasks. For that reason synthesis of this semiconductor nano crystals is expedient. Many useful methods have been used for preparing sulphide semiconductor nano crystals, such as colloidal chemistry method, sol-gel method, inverse micelle method, in situ synthesis and assemble on polymer template. The most significant method is in situ synthesis and assemble of sulphide semiconductor nano crystals on polymer. Compared with other methods, the stability of nanoparticles is improved by the protection and confinement of the copolymer. Because of confinement and protection effects of template environmental risk is prevented in this method. On the base of this principles in situ synthesis of CdS nano crystals in maleic anhydride-octene 1-vinyl butyl terpolymer was realized in this scientific work. First of all in specific condition maleic anhydride, octene 1, and vinyl butyl ether were polymerized to form a terpolymer as the result of radical ter polymerization. In second step CdS nano crystals were synthesized in N,N-dimethylformamide solution of maleic anhydride-octene 1-vinyl butyl terpolymer through the reaction of thiourea with cadmium chloride. In this process CdCI 2 x 2.5H 2 O was dissolved in N,N-dimethylformamide solution of previously formed terpolymer and was heated in 90 0 C temperature for 4 hours with vigorous stirring. Then desired amount of thiourea in N,N-dimethylformamide was quickly injected into the reaction flask using a syringe. The reaction continued for another 1 hour, and a yellow clear solution was obtained, which indicated the formation of CdS nano crystals

All solid supercapacitor based on polyaniline and crosslinked sulfonated poly[ether ether ketone

International Nuclear Information System (INIS)

Sivaraman, P.; Kushwaha, R.K.; Shashidhara, K.; Hande, V.R.; Thakur, A.P.; Samui, A.B.; Khandpekar, M.M.

2010-01-01

All solid supercapacitor based on polyaniline (PANI) and crosslinked sulfonated poly[ether ether ketone] (XSPEEK,) is reported in this paper. The crosslinker used for sulfonated poly[ether ether ketone] (SPEEK) is 1,4-bis(hydroxymethyl) benzene. The XSPEEK is used as both solid electrolyte and separator membrane. Supercapacitors are fabricated using various PANI/XSPEEK weight ratios. These are characterized by cyclic voltammetry and galvanostatic charge-discharge studies. The supercapacitor with PANI/XSPEEK weight ratio 1:0.5, exhibit a specific capacitance of 480 F g -1 of PANI. To the best of authors' knowledge, the value reported here is the highest for a supercapacitor based on a proton conducting solid polymer electrolyte and PANI. Detailed electrochemical impedance spectroscopy analysis is carried out. The analysis shows that the complex capacitance of the supercapacitor depends on the XSPEEK content. The time constant (t 0 ), derived from the imaginary part of complex capacitance decreases with increase in the XSPEEK content in the supercapacitor. Cycle life characteristics of the supercapacitor show a decrease in specific capacitance during initial cycles and get stabilized during later cycles.

Hydrogen storage by functionalised Poly(ether ether ketone)

Energy Technology Data Exchange (ETDEWEB)

Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

2010-07-01

In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

Synthesis of Poly (Butyl Methacrylate/Butyl Acrylate) Highly Absorptive Resin Using Glow Discharge Electrolysis

International Nuclear Information System (INIS)

Li Yan; Yao Mengqi; Liao Ruirui; Yang Wu; Gao Jinzhang; Ren Jie

2014-01-01

A highly absorptive resin poly (butyl methacrylate (BMA)-co-butyl acrylate (BA)) was prepared by emulsion polymerization, which was initiated by glow discharge electrolysis plasma (GDEP). The effects of discharge voltage, discharge time, monomer ratio and the amounts of cross-linking agent were examined and discussed in detail. The chemical structure of the obtained resin was characterized by means of attenuated total reflectance Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The optimal conditions were obtained as: discharge voltage was 600 V, discharge time was 8 min, the ratios of BMA:BA being 2:1 for chloroform and 3:1 for xylene, with 2% N, N'-methylenebis. Under optimal conditions, the oil absorbency was 70 g/g for chloroform and 46 g/g for xylene. Moreover, the absorptive dynamical behavior of the resulting resin was also investigated

Aerobic biodegradation of tert-butyl alcohol (TBA) by psychro- and thermo-tolerant cultures derived from granular activated carbon (GAC).

Science.gov (United States)

Reinauer, Kimberly M; Zhang, Yang; Yang, Xiaomin; Finneran, Kevin T

2008-04-01

Tert-butyl alcohol (TBA) is a metabolite of methyl tert-butyl ether and is itself possibly a fuel oxygenate. The goals of this study were to enrich and characterize TBA-degrading micro-organism(s) from a granular activated carbon (GAC) unit currently treating TBA. The results reported herein describe the first aerobic, TBA-degrading cultures derived from GAC. Strains KR1 and YZ1 were enriched from a GAC sample in a bicarbonate-buffered freshwater medium. TBA was degraded to 10% of the initial concentration (2-5 mM) within 5 days after initial inoculation and was continuously degraded within 1 day of each re-amendment. Resting cell suspensions mineralized 70 and 60% of the TBA within 24 h for KR1 and YZ1, respectively. Performance optimization with resting cells was conducted to investigate kinetics and the extent of TBA degradation as influenced by oxygen, pH and temperature. The most favorable temperature was 37 degrees C; however, TBA was degraded from 4 to 60 degrees C, indicating that the culture will sufficiently treat groundwater without heating. This is also the first report of psychrotolerant or thermotolerant TBA biodegradation. The pH range for TBA degradation ran from 5.0 to 9.0. Phylogenetic data using a partial 16S rRNA gene sequence (570 bases) suggest that the primary members of KR1 and YZ1 include uncharacterized organisms within the genera Hydrogenophaga, Caulobacter, and Pannonibacter.

Segmented poly(ether ester)s and poly(ether ester amide)s for use in tissue engineering

NARCIS (Netherlands)

Deschamps, A.A.

2002-01-01

The objective of the studies described in this thesis is to investigate the applicability of these slowly degradable thermoplastic elastomers as scaffolds for tissue engineering, with emphasis on their phase separation and degradation properties. A second thermoplastic elastomer in which the

Catalytic oxidation of butyl acetate over silver-loaded zeolites

International Nuclear Information System (INIS)

Wong, Cheng Teng; Abdullah, Ahmad Zuhairi; Bhatia, Subhash

2008-01-01

The performance of silver-loaded zeolite (HY and HZSM-5) catalysts in the oxidation of butyl acetate as a model volatile organic compound (VOC) was studied. The objective was to find a catalyst with superior activity, selectivity towards deep oxidation product and stability. The catalyst activity was measured under excess oxygen condition in a packed bed reactor operated at gas hourly space velocity (GHSV) = 15,000-32,000 h -1 , reaction temperature between 150 and 500 deg. C and butyl acetate inlet concentration of 1000-4000 ppm. Both AgY and AgZSM-5 catalysts exhibited high activity in the oxidation of butyl acetate. Despite lower silver content, AgY showed better activity, attributed to better metal dispersion, surface characteristics and acidity, and its pore system. Total conversion of butyl acetate was achieved at above 400 deg. C. The oxidation of butyl acetate followed a simple power law model. The reaction orders, n and m were evaluated under differential mode by varying the VOC partial pressure between 0.004 and 0.018 atm and partial pressure of oxygen between 0.05 and 0.20 atm. The reaction rate was independent of oxygen concentration and single order with respect to VOC concentration. The activation energies were 19.78 kJ/mol for AgY and 32.26 kJ/mol for AgZSM-5, respectively

Mode of action of ethyl tertiary-butyl ether hepatotumorigenicity in the rat: Evidence for a role of oxidative stress via activation of CAR, PXR and PPAR signaling pathways

Energy Technology Data Exchange (ETDEWEB)

Kakehashi, Anna, E-mail: anna@med.osaka-cu.ac.jp [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan); Hagiwara, Akihiro; Imai, Norio [DIMS Institute of Medical Science, Inc., 64 Goura, Nishiazai, Azai-cho, Ichinomiya, Aichi 491-0113 (Japan); Nagano, Kasuke [Nagano Toxicologic-Pathology Consulting, Ochiai, Hadano, Kanagawa 257-0025 (Japan); Nishimaki, Fukumi [Biofuel Assessment Group, New Fuels Dept., Japan Petroleum Energy Center (JPEC), 4-3-9 Toranomon, Minato-ku, Tokyo 105-0001 (Japan); Banton, Marcy [Toxicology and Risk Assessment, LyondellBasell Industries, LyondellBasell Corporate HSE/Product Safety, One Houston Center, Suite 700, 1221 McKinney Street, Houston, TX 770 10 (United States); Wei, Min [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan); Fukushima, Shoji [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan); Japan Bioassay Research Center, Japan Industrial Safety and Health Association, 2445 Hirasawa, Hadano, Kanagawa 257-0011 (Japan); Wanibuchi, Hideki [Department of Pathology, Osaka City University Graduate School of Medicine, 1-4-3 Asahi-machi, Abeno-ku, Osaka 545-8585 (Japan)

2013-12-01

To elucidate possible mode of action (MOA) and human relevance of hepatotumorigenicity in rats for ethyl tertiary-butyl ether (ETBE), male F344 rats were administered ETBE at doses of 0, 150 and 1000 mg/kg body weight twice a day by gavage for 1 and 2 weeks. For comparison, non-genotoxic carcinogen phenobarbital (PB) was applied at a dose of 500 ppm in diet. Significant increase of P450 total content and hydroxyl radical levels by low, high doses of ETBE and PB treatments at weeks 1 and 2, and 8-OHdG formation at week 2, accompanied accumulation of CYP2B1/2B2, CYP3A1/3A2 and CYP2C6, and downregulation of DNA oxoguanine glycosylase 1, induction of apoptosis and cell cycle arrest in hepatocytes, respectively. Up-regulation of CYP2E1 and CYP1A1 at weeks 1 and 2, and peroxisome proliferation at week 2 were found in high dose ETBE group. Results of proteome analysis predicted activation of upstream regulators of gene expression altered by ETBE including constitutive androstane receptor (CAR), pregnane-X-receptor (PXR) and peroxisome proliferator-activated receptors (PPARs). These results indicate that the MOA of ETBE hepatotumorigenicity in rats may be related to induction of oxidative stress, 8-OHdG formation, subsequent cell cycle arrest, and apoptosis, suggesting regenerative cell proliferation after week 2, predominantly via activation of CAR and PXR nuclear receptors by a mechanism similar to that of PB, and differentially by activation of PPARs. The MOA for ETBE hepatotumorigenicity in rats is unlikely to be relevant to humans. - Highlights: • We focus on MOA and human relevance of hepatotumorigenicity in rats for ETBE. • ETBE was administered to F344 rats for 1 and 2 weeks. • Oxidative stress formation, proliferation and apoptosis in the liver are analyzed. • ETBE-induced changes of gene and protein expression in the liver are examined. • The effects are compared with those induced by non-genotoxic carcinogen PB.

Activity relationships for aromatic crown ethers

International Nuclear Information System (INIS)

Wilson, Mark James

1998-01-01

This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities from molecular modelling and this rational has been applied to the study of proton ionisable and lariating crown ethers. The incorporation of crown ethers into polyamic acid and polyimide frameworks has also been investigated, where the resulting materials have been found to exhibit unusual cation binding and uptake properties. These results imply that the combination of the crown ethers' macrocycle and adjacent carboxylic acid residues, from the polyamic acids, are conducive to effective cationic binding. NMR measurements, in conjunction with molecular modelling, have been used to explore the geometry changes encountered as the crown ether goes from it's uncomplexed to its complexed state. The energy requirement for these geometry changes has subsequently been used to examine the cation selectivity of these materials. The electronic charge changes associated with the complexation have also been investigated and correlated with the theoretical results. (author)

Esters with water esters 2-c to 6-c

CERN Document Server

Getzen, F W; Hefter, G T; Maczynski, Andrzej

1992-01-01

This volume is the first of two devoted to esters and water. It includes solubility data for binary systems containing an ester and water up to the end of 1988. The critical evaluations were all prepared by one author and an introductory section has been included to elaborate the philosophy and methodology followed in the evaluations.

Biaxial deformation behaviour of poly-ether-ether-ketone

Science.gov (United States)

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).

Transesterification of camelina sativa oil with supercritical alcohol mixtures

International Nuclear Information System (INIS)

Sun, Yingqiang; Ponnusamy, Sundaravadivelnathan; Muppaneni, Tapaswy; Reddy, Harvind K.; Wang, Jun; Zeng, Zheling; Deng, Shuguang

2015-01-01

Highlights: • Transesterification of camelina oil under supercritical methanol/ethanol and 1-butanol mixture conditions. • Chemical composition of fatty acid methyl esters, ethyl esters and butyl esters. • Effect of different alcohol molar ratio on biodiesel yields. • Effect of different alcohol molar ratio on physical properties of biodiesel products. - Abstract: The transesterification of camelina sativa oil with methanol–1-butanol, and ethanol–1-butanol alcohol mixtures under supercritical conditions have been studied in order to maximize biodiesel yield and improve biodiesel quality. The influence of the variation of the molar ratio of methanol–1-butanol and ethanol–1-butanol from 1:0, 3:1, 2:1, 1:1, 1:2, to 0:1 on the yield of free fatty methyl esters/free fatty ethanol esters–free fatty acid butyl esters, the composition of the biodiesel blend mixtures, and the physical properties of the biodiesel have been investigated at the reaction temperature of 290 °C, reaction time of 30 min, and the initial reaction pressure of 500 psi. A maximum yield of 86.14 wt% for free fatty acid methyl esters–free fatty acid butyl esters with the optimum cold property can be obtained at the molar ratio of methanol–1-butanol of 0.5–0.9. Also, a maximum yield of 85.60 wt% for free fatty ethyl esters–free fatty butyl esters with the lowest pour point can be achieved at the molar ratio of ethanol–1-butanol in the range of 0.5–0.7

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

Science.gov (United States)

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.

Preparation and Characterization of Sulfonated Poly (ether ether ...

African Journals Online (AJOL)

NJD

2007-08-10

Aug 10, 2007 ... Preparation and Characterization of Sulfonated Poly (ether ... Currently perfluori- ... with phosphoric acid solution according to the method described earlier.11,12 ... where A is the membrane area available for diffusion; CA is.

Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

2013-10-01

Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

International Nuclear Information System (INIS)

Chiu, K.-F.; Su, S.-H.

2013-01-01

Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

Avocado and olive oil methyl esters

International Nuclear Information System (INIS)

Knothe, Gerhard

2013-01-01

Biodiesel, the mono-alkyl esters of vegetable oils, animal fats or other triacylglycerol-containing materials and an alternative to conventional petroleum-based diesel fuel, has been derived from a variety of feedstocks. Numerous feedstocks have been investigated as potential biodiesel sources, including commodity oils, however, the methyl esters of avocado and olive oil would likely be suitable as biodiesel fuel. In order to expand the database and comprehensive evaluation of the properties of vegetable oil esters, in this work the fuel-related properties of avocado and olive oil methyl esters, which exhibit similar fatty acid profiles including high oleic acid content, are determined. The cetane numbers of avocado oil methyl esters and olive oil methyl esters are relatively high, determined as 59.2 and 62.5, respectively, due to their elevated content of methyl oleate. Other properties are well within the ranges specified in biodiesel standards. The cloud points of both esters are slightly above 0 °C due to their content of saturated esters, especially methyl palmitate. Overall, avocado and olive oil yield methyl esters with fuel properties comparable to methyl esters from other commodity vegetable oils. The 1 H and 13 C NMR spectra of avocado and olive oil methyl esters are reported. -- Highlights: • Methyl esters of avocado and olive oil meet biodiesel fuel standards. • Provides comparison for methyl esters of other vegetable oils with high oleic content. • Discusses and compares present results with prior literature

Hardness and wear properties of boron-implanted poly(ether-ether-ketone) and poly-ether-imide

International Nuclear Information System (INIS)

Lee Youngchul; Lee, E.H.; Mansur, L.K.

1992-01-01

The effects of boron beam irradiation on the hardness, friction, and wear of polymer surfaces were investigated. Typical high-performance thermoplastics, poly(ether-ether-ketone) (PEEK) and a poly-ether-imide (Ultem) were studied after 200 keV boron ion beam treatment at ambient temperature to doses of 2.3x10 14 , 6.8x10 14 , and 2.2x10 15 ions cm -2 . The hardnesses of pristine and boron-implanted materials were characterized by a conventional Knoop method and a load-depth sensing nanoindentation technique. Both measurements showed a significant increase in hardness with increasing dose. The increase in hardness was also found to depend on the penetration depth of the diamond indenter. Wear and friction properties were characterized by a reciprocating sliding friction tester with an SAE 52100 high-carbon, chrome steel ball at 0.5 and 1 N normal loads. Wear and frictional properties varied in a complex fashion with polymer type and dose, but not much with normal load. A substantial reduction in friction coefficient was observed for PEEK at the highest dose but no reduction was observed for Ultem. The wear damage was substantially reduced at the highest dose for both Ultem and PEEK. For the system studied, the highest dose, 2.2x10 15 ions cm -2 , appears to be optimum in improving wear resistance for both PEEK and Ultem. (orig.)

Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

NARCIS (Netherlands)

Koziara, B.T.; Nijmeijer, K.; Benes, N.E.

2015-01-01

The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (≤5 wt%) and not too low spin speeds

Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

NARCIS (Netherlands)

Koziara, Beata; Nijmeijer, Dorothea C.; Benes, Nieck Edwin

2015-01-01

The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (B5 wt%) and not too low spin speeds

Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

Energy Technology Data Exchange (ETDEWEB)

Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail: shinj@kaeri.re.kr

2014-02-15

Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

Simultaneous analysis of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils by normal-phase high performance liquid chromatography.

Science.gov (United States)

Li, Jun; Bi, Yanlan; Sun, Shangde; Peng, Dan

2017-11-01

A normal-phase high performance liquid chromatography method for the simultaneous determination of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils was investigated. A silica column was used to separate the analytes with the gradient elution. An ultraviolet-visible detector was set at dual wavelengths mode (280 and 310nm). The column temperature was 30°C. The analytes were directly extracted with methanol. Results showed that the normal-phase high performance liquid chromatography method performed well with wide liner ranges (0.10∼500.00μg/mL, R 2 >0.9998), low limits of detection and quantitation (below 0.40 and 1.21μg/mL, respectively), and good recoveries (81.38∼102.34% in soybean oils and 83.03∼100.79% in lard, respectively). The reduction of tert-butylquinone caused by the reverse-phase high performance liquid chromatography during the injection was avoided with the current normal-phase method. The two isomers of butylated hydroxyanisole can also be separated with good resolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermal stability of sulfonated Poly(Ether Ether Ketone) films : on the role of Protodesulfonation

NARCIS (Netherlands)

Koziara, B.T.; Kappert, E.J.; Ogieglo, W.; Nijmeijer, Kitty; Hempenius, M.A.; Benes, N.E.

Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material,

Synthesis, Anti-HCV, Antioxidant and Reduction of Intracellular Reactive Oxygen Species Generation of a Chlorogenic Acid Analogue with an Amide Bond Replacing the Ester Bond.

Science.gov (United States)

Wang, Ling-Na; Wang, Wei; Hattori, Masao; Daneshtalab, Mohsen; Ma, Chao-Mei

2016-06-08

Chlorogenic acid is a well known natural product with important bioactivities. It contains an ester bond formed between the COOH of caffeic acid and the 3-OH of quinic acid. We synthesized a chlorogenic acid analogue, 3α-caffeoylquinic acid amide, using caffeic and quinic acids as starting materials. The caffeoylquinc acid amide was found to be much more stable than chlorogenic acid and showed anti-Hepatitis C virus (anti-HCV) activity with a potency similar to chlorogenic acid. The caffeoylquinc acid amide potently protected HepG2 cells against oxidative stress induced by tert-butyl hydroperoxide.

Removal of technetium from alkaline nuclear-waste media by a solvent-extraction process using crown ethers

International Nuclear Information System (INIS)

Bonnesen, P.V.; Presley, D.J.; Haverlock, T.J.; Moyer, B.A.

1995-01-01

Crown ethers dissolved in suitably modified aliphatic kerosene diluents can be employed to extract technetium as pertechnetate anion (TcO 4 - ) with good extraction ratios from realistic simulants of radioactive alkaline nitrate waste. The modifiers utilized are non-halogenated and non-volatile, and the technetium can be removed from the solvent by stripping using water. The crown ethers bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 (di-t-BuCH18C6) and dicyclohexano-18-crown-6 (DCH18C6) provide stronger TcO 4 - extraction than dicyclohexano-21-crown-7 and 4-tert-butylcyclohexano 15-crown-5. Whereas DCH18C6 provides somewhat higher TcO 4 - extraction ratios than the more lipophilic di-t-BuCH18C6 derivative, the latter was selected for further study owing to its lower distribution to the aqueous phase. Particularly good extraction and stripping results were obtained with di-t-BuCH 18C6 at 0.02 M in a 2:1 vol/vol blend of tributyl phosphate and Isopar reg-sign M. Using this solvent, 98.9% of the technetium contained (at 6 x 10 -5 M) in a Double-Shell Slurry Feed (DSSF) Hanford tank waste simulant was removed following two cross-current extraction contacts. Two cross-current stripping contacts with deionized water afforded removal of 99.1% of the technetium from the organic solvent

Synthesis of 4-tert-butyl-1,1-dimethylindan and 7-tert-Butyl-3,3-dimethyl-1-indanone and a comparison of isomers

International Nuclear Information System (INIS)

Eisenbraun, E.J.; Harms, W.M.; Paraniswamy, V.A.; Chen, H.H.; Porcaro, P.J.; Wood, T.F.; Chien, M.

1982-01-01

4-tert-Butyl-1,1-dimethylindan was synthesized to help establish the identity of products (5- and 6-tert-butyl-1,1-dimethylindan as minor and major products, respectively) from the sulfuric acid catalyzed condensation of tert-butylbenzene and isoprene. NMR ( 1 H and 13 C) studies of these hydrocarbons and their corresponding indanones, obtained through chromic acid oxidation, provided structural proof. Gated decoupling experiments were crucial to complete assignment

Soil contamination by phthalate esters in Chinese intensive vegetable production systems with different modes of use of plastic film.

Science.gov (United States)

Wang, Jun; Luo, Yongming; Teng, Ying; Ma, Wenting; Christie, Peter; Li, Zhengao

2013-09-01

The concentrations of six priority phthalic acid esters (PAEs) in intensively managed suburban vegetable soils in Nanjing, east China, were analyzed using gas chromatography-mass spectrometry (GC-MS). The total PAE concentrations in the soils ranged widely from 0.15 to 9.68 mg kg(-1) with a median value of 1.70 mg kg(-1), and di-n-butyl phthalate (DnBP), bis-(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DnOP) were the most abundant phthalate esters. Soil PAE concentrations depended on the mode of use of plastic film in which PAEs were incorporated as plasticizing agents and both the plastic film and poultry manure appeared to be important sources of soil PAEs. Vegetables in rotation with flooded rice led to lower concentrations of PAEs in soil. The results indicate that agricultural plastic film can be an important source of soil PAE contamination and further research is required to fully elucidate the mechanisms of PAE contamination of intensive agricultural soils with different use modes of use of plastic film. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Solvent extraction of technetium from alkaline waste media using bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6

International Nuclear Information System (INIS)

Bonnesen, P.V.; Presley, D.J.; Moyer, B.A.

1995-01-01

The crown ether bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 can be utilized in a solvent-extraction process for the removal of technetium as pertechnetate ion, TcO 4 - from solutions simulating highly radioactive alkaline defense wastes (''tank wastes'') stored at several sites in the United States. The process employs non-halogenated and non-volatile diluents and modifiers and includes an efficient stripping procedure using only water. More than 95% of the pertechnetate present at 6 x 10 -5 M in Melton Valley (Oak Ridge, TN) and Hanford (Washington) tank-waste simulants was removed following two cross-current extraction contacts using 0.02 M bis-4,4'(5')[(tertbutyl)cyclohexano]- 18-crown-6 in 2:1 vol/vol TBP/Isopar reg-sign M diluent at 25 C. Similarly, for both simulants, more than 98% of the pertechnetate contained in the solvent was back-extracted following two cross-current stripping contacts using deionized water

Organophosphate esters and phthalate esters in human hair from rural and urban areas, Chongqing, China: Concentrations, composition profiles and sources in comparison to street dust.

Science.gov (United States)

He, Ming-Jing; Lu, Jun-Feng; Ma, Jing-Ye; Wang, Huan; Du, Xiao-Fan

2018-06-01

Human hair and street dust from rural and urban areas in Chongqing were collected to analyze Organophosphate esters (OPEs) and phthalate esters (PAEs). Concentrations of OPEs in urban hair were significantly higher than those in rural hair, whereas PAEs concentrations in rural hair were significantly higher than those in urban hair. Different composition patterns of OPEs were observed in rural and urban hair, where tris (2-chloroisopropyl) phosphate (TCIPP), tris (butyl) phosphate (TNBP) and triphenyl phosphate (TPHP) were the dominating analogues in rural hair, accounting for 62.1% of the OPEs burden, and tris (methylphenyl) phosphate (TMPP) exhibited a high contribution in urban hair, responsible for 51.3% of total OPEs, which differed from the composition profiles in corresponding street dust. Analogous composition patterns of PAEs were found in hair of both areas. Di-(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP) and diethyl phthalate (DEP) were the most abundant analogues in hair samples, while DEHP was the predominant analogue in dust samples. No clear tendency was obtained between the increasing ages and the concentrations of both compounds. Most OPEs and PAEs congeners showed significantly positive correlation with one another in rural hair. On the contrary, different correlation patterns were observed in urban hair for OPEs and PAEs, indicating multiple or additional sources existed in urban areas. Significant correlations of OPEs and PAEs were found between hair and corresponding street dust samples, but poor correlations of OPEs and PAEs were observed between rural hair and rural indoor dust, suggesting that street dust may be a predominant exogenous source for human exposure to OPEs and PAEs in this area. Copyright © 2018 Elsevier Ltd. All rights reserved.

On the Use of Potential Denaturing Agents for Ethanol in Direct Ethanol Fuel Cells

Directory of Open Access Journals (Sweden)

Domnik Bayer

2011-01-01

Full Text Available Acidic or alkaline direct ethanol fuel cells (DEFCs can be a sustainable alternative for power generation if they are fuelled with bio-ethanol. However, in order to keep the fuel cheap, ethanol has to be exempted from tax on spirits by denaturing. In this investigation the potential denaturing agents fusel oil, tert-butyl ethyl ether, and Bitrex were tested with regard to their compatibility with fuel cells. Experiments were carried out both in sulphuric acid and potassium hydroxide solution. Beside, basic electrochemical tests, differential electrochemical mass spectrometry (DEMS and fuel cell tests were conducted. It was found that fusel oil is not suitable as denaturing agent for DEFC. However, tert-butyl ethyl ether does not seem to hinder the ethanol conversion as much. Finally, a mixture of tert-butyl ethyl ether and Bitrex can be proposed as promising candidate as denaturing agent for use in acidic and alkaline DEFC.

On new physical reality (on ψ-ether)

International Nuclear Information System (INIS)

Isaev, P.S.

2002-01-01

It is shown that there exists a new physical reality - the ψ-ether. All the achievements of quantum mechanics and quantum field theory are due to the fact that both the theories include the influence of ψ-ether on the physical processes occurring in the Universe. Physics of the XX century was first of all the physics of ψ-ether

Mitochondrial toxicity of phthalate esters.

OpenAIRE

Melnick, R L; Schiller, C M

1982-01-01

The effects of mono- and dibutyl phthalate and mono- and di(2-ethylhexyl) phthalate on energy-dependent K+ uptake, respiration rates, and succinate cytochrome c reductase activities of isolated rat liver mitochondria were evaluated. The energy-coupling processes, active K+ transport and oxidative phosphorylation, were affected most by di-n-butyl phthalate and mono(2-ethylhexyl) phthalate. Mono-n-butyl phthalate had a moderate effect on energy coupling and di(2-ethylhexyl) phthalate had no app...

High energy radiation effects on mechanical properties of butyl rubber compounds

International Nuclear Information System (INIS)

Pozenato, Cristina A.; Scagliusi, Sandra R.; Cardoso, Elisabeth C.L.; Lugao, Ademar B.

2013-01-01

The high energy radiation on butyl rubber compounds causes a number of chemical reactions that occur after initial ionization and excitation events. These reactions lead to changes in molecular mass of the polymer through scission and crosslinking of the molecules, being able to affect the physical and mechanical properties. Butyl rubber has excellent mechanical properties and oxidation resistance as well as low gas and water vapor permeability. Due to all these properties butyl rubber is widely used industrially and particularly in tires manufacturing. In accordance with various authors, the major effect of high energy, such as gamma rays in butyl rubber, is the yielding of free-radicals along with changes in mechanical properties. There were evaluated effects imparted from high energy radiation on mechanical properties of butyl rubber compounds, non-irradiated and irradiated with 25 kGy, 50 kGy, 150 kGy and 200 kGy. It was also observed a sharp reducing in stress rupture and elongation at break for doses higher than 50 kGy, pointing toward changes in polymeric chain along build-up of free radicals and consequent degradation. (author)

Sensitive multiresidue method by HS-SPME/GC-MS for 10 volatile organic compounds in urine matrix: a new tool for biomonitoring studies on children.

Science.gov (United States)

Antonucci, Arianna; Vitali, Matteo; Avino, Pasquale; Manigrasso, Maurizio; Protano, Carmela

2016-08-01

A HS-SPME method coupled with GC-MS analysis has been developed for simultaneously measuring the concentration of 10 volatile organic compounds (VOCs) (benzene, toluene, ethylbenzene, o-, m-, and p-xylene, methyl tert-butyl ether, ethyl tert-butyl ether, 2-methyl-2-butyl methyl ether, and diisopropyl ether) in urine matrix as a biomonitoring tool for populations at low levels of exposure to such VOCs. These compounds, potentially toxic for human health, are common contaminants of both outdoor and indoor air, as they are released by autovehicular traffic; some of them are also present in environmental tobacco smoke (ETS). Thus, the exposure to these pollutants cannot be neglected and should be assessed. The low limits of detection and quantification (LODs and LOQs <6.5 and 7.5 ng L(-1), respectively) and the high reproducibility (CVs <4 %) make the developed method suited for biomonitoring populations exposed at low levels such as children. Further, the method is cost-effective and low in time-consumption; therefore, it is useful for investigating large populations. It has been applied to children exposed to traffic pollution and/or ETS; the relevant results are reported, and the relevant implications are discussed.

Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

Directory of Open Access Journals (Sweden)

Kheila N. Silgado-Gómez

2017-11-01

Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.

EFFECT OF BTEX ON THE DEGRADATION OF MTBE AND TBA BY MIXED BACTERIAL CONSORTIUM

Science.gov (United States)

Methyl tert-butyl ether (MTBE) contamination in groundwater often coexists with benzene, toluene, ethylbenzene, and xylene (BTEX) near the source of the plume. Tertiary butyl alcohol (TBA) is a prevalent intermediate of MTBE degradation. Therefore, there is a significant p...

Etherification of Glycerol with Propylene or 1-Butene for Fuel Additives

Directory of Open Access Journals (Sweden)

Chakrapong Saengarun

2017-01-01

Full Text Available The etherification of glycerol with propylene over acidic heterogeneous catalysts, Amberlyst-15, S100, and S200 resins, produced mono-propyl glycerol ethers (MPGEs, 1,3-di- and 1,2-di-propyl glycerol ethers (DPGEs, and tri-propyl glycerol ether (TPGE. The propylation of glycerol over Amberlyst-15 yielded only TPGE. The glycerol etherification with 1-butene over Amberlyst-15 and S200 resins produced 1-mono-, 2-mono-, 1,2-di-, and 1,3-di-butyl glycerol ethers (1-MBGE, 2-MBGE, 1,2-DBGE, and 1,3-DBGE. The use of Amberlyst-15 resulted in the propylation and butylation of glycerol with higher yields than those obtained from the S100 and S200 resins. The PGEs, TPGE, and BGEs were evaluated as cold flow improvers and octane boosters. These alkyl glycerol ethers can reduce the cloud point of blended palm biodiesels with diesel. They can increase the research octane number and the motor octane number of gasoline.

Effect of Naphthalene, Butylated Hydroxytoluene, Dioctyl Phthalate, and Adipic Dioctyl Ester, Chemicals Found in the Nests of the Formosan Subterranean Termite (Isoptera: Rhinotermitidae) on a Saprophytic Mucor sp.

Science.gov (United States)

Fungi are commonly found associated with termites and their nests. Four chemicals that have been isolated from the nests of the Formosan subterranean termite, Coptotermes formosanus Shiraki, were evaluated to determine their effect on a common nest fungus, a saprophytic Mucor sp. Butylated hydroxyto...

Sulfonated poly(ether ether ketone) membranes for electric double layer capacitors

International Nuclear Information System (INIS)

Kim, Wan Ju; Kim, Dong-Won

2008-01-01

Sulfonated poly(ether ether ketone) (S-PEEK) with different degree of sulfonation (DS) has been prepared and evaluated as a proton conducting membrane for electric double layer capacitor (EDLC). The polymer electrolytes prepared with S-PEEK membrane exhibited ionic conductivities about 1.2 x 10 -3 -4.5 x 10 -3 S cm -1 at room temperature, which depended on both soaking solvent and degree of sulfonation. The quasi-solid-state EDLCs consisted of activated carbon electrodes and S-PEEK membrane were assembled, and their electrochemical characteristics were studied by cyclic voltammetry and charge-discharge cycle tests. The effect of DS on the electrochemical performances of EDLCs has been investigated

A comparison of the effect of intranasal desmopressin and intramuscular hyoscine N-butyl bromide combination with intramuscular hyoscine N-butyl bromide alone in acute renal colic

Directory of Open Access Journals (Sweden)

Abdol-Reza Kheirollahi

2010-01-01

Full Text Available Background: Patients with acute renal colic usually require immediate diagnosis and treatment. In this clinical trial analgesic effect of hyoscine N-butyl bromide and desmopressin combination in comparison with hyoscine N-butyl bromide alone in patients with acute renal colic induced by urinary stones was assessed. Methods: The study included 114 patients randomly allocated in two groups (A and B. Patients in group A received 20 mg intramuscular hyoscine N-butyl bromide at admission time and patients in group B received 20 μg of intranasal desmopressin in combination with 20 mg intramuscular hyoscine N-butyl bromide. A visual analogue scale (VAS; a 10-cm horizontal scale ranging from "zero or no pain" to "10 or unbearable pain" was hired to assess the patients′ pain severity at baseline, 30 and 60 minutes after the treatments. Results: On admission, the pain level was similar in both groups (group A: 8.95 ± 0.11 and group B: 8.95 ± 0.12. In group A, the mean of pain level showed a decrease after 30 minutes (group A: 7.26 ± 0.25 and group B: 5.95 ± 0.28 but further decreasing did not occur; however in group B, the pain consistently decreased and the mean after 60 minutes was significantly decreased (group A: 6.80 ± 0.31 and group B: 3.71 ± 0.31. No side effects were detected in this study. Conclusions: The combination of hyoscine N-butyl bromide and desmopressin is more effective than hyoscine N-butyl bromide alone in patients with renal colic. Further studies are recommended to validate these findings and compare the different doses of desmopressin.

Ester Tuiksoo. Proua Suhkru kibedad päevad / Ester Tuiksoo ; interv. Piret Tali

Index Scriptorium Estoniae

Tuiksoo, Ester, 1965-

2005-01-01

Põllumajandusminister Ester Tuiksoo, kellel peagi täitub ministri ametis aasta Euroopa Liidu suhkrutrahvist, maaettevõtlusest, põllumajandusest, Euroopa Liidu toetustest, ministri elu- ja teenistuskäigust. Lisa: Ester Tuiksoo

Environmental effect of rapeseed oil ethyl ester

International Nuclear Information System (INIS)

Makareviciene, V.; Janulis, P.

2003-01-01

Exhaust emission tests were conducted on rapeseed oil methyl ester (RME), rapeseed oil ethyl ester (REE) and fossil diesel fuel as well as on their mixtures. Results showed that when considering emissions of nitrogen oxides (NO x ), carbon monoxide (CO) and smoke density, rapeseed oil ethyl ester had less negative effect on the environment in comparison with that of rapeseed oil methyl ester. When fuelled with rapeseed oil ethyl ester, the emissions of NO x showed an increase of 8.3% over those of fossil diesel fuel. When operated on 25-50% bio-ester mixed with fossil diesel fuel, NO x emissions marginally decreased. When fuelled with pure rapeseed oil ethyl ester, HC emissions decreased by 53%, CO emissions by 7.2% and smoke density 72.6% when compared with emissions when fossil diesel fuel was used. Carbon dioxide (CO 2 ) emissions, which cause greenhouse effect, decreased by 782.87 g/kWh when rapeseed oil ethyl ester was used and by 782.26 g/kWh when rapeseed oil methyl ester was used instead of fossil diesel fuel. Rapeseed oil ethyl ester was more rapidly biodegradable in aqua environment when compared with rapeseed oil methyl ester and especially with fossil diesel fuel. During a standard 21 day period, 97.7% of rapeseed oil methyl ester, 98% of rapeseed oil ethyl ester and only 61.3% of fossil diesel fuel were biologically decomposed. (author)

Promoting environmentally sound management of polybrominated diphenyl ethers in Asia.

Science.gov (United States)

Li, Jinhui; Zhao, Nana; Liu, Xue; Wu, Xiaoyang

2014-06-01

Polybrominated diphenyl ethers with persistent organic pollutant properties are required to be controlled by the Stockholm Convention. Recently, polybrominated diphenyl ether contamination has become widespread in Asia, mainly because of the disposal and recycling processes of polybrominated diphenyl ether-containing wastes. The management status, production, usage, import/export, treatment, and disposal, as well as implementation deficiencies for the environmentally sound management of polybrominated diphenyl ethers and polybrominated diphenyl ether-containing materials in ten Asian countries were investigated and assessed in this study. This information could help the participating countries implement the Stockholm Convention and could promote the regional environmentally sound management of polybrominated diphenyl ether-containing articles and products. The results obtained were as follows. (1) Most of the countries studied lacked environmental policies and regulations, or even standards of polybrominated diphenyl ether pollution management and emission control actions. Accurate data on the consumption and importation of polybrominated diphenyl ether-containing materials, however, were not available for all the participating countries. In addition, there were no special treatment or disposal systems for polybrominated diphenyl ether-containing materials, or emission-cutting measures for the treatment of waste in these countries, owing to the lack of sufficient funding or technologies. (2) The improper dismantling of e-waste is a major source of polybrominated diphenyl ether emissions in these countries. (3) Proper e-waste management could result in a breakthrough in the environmentally sound management of this major polybrominated diphenyl ether-containing material flow, and could significantly reduce polybrominated diphenyl ether emissions. Finally, based on the study results, this article puts forward some recommendations for improving the environmentally

The European source term code ESTER - basic ideas and tools for coupling of ATHLET and ESTER

International Nuclear Information System (INIS)

Schmidt, F.; Schuch, A.; Hinkelmann, M.

1993-04-01

The French software house CISI and IKE of the University of Stuttgart have developed during 1990 and 1991 in the frame of the Shared Cost Action Reactor Safety the informatic structure of the European Source TERm Evaluation System (ESTER). Due to this work tools became available which allow to unify on an European basis both code development and code application in the area of severe core accident research. The behaviour of reactor cores is determined by thermal hydraulic conditions. Therefore for the development of ESTER it was important to investigate how to integrate thermal hydraulic code systems with ESTER applications. This report describes the basic ideas of ESTER and improvements of ESTER tools in view of a possible coupling of the thermal hydraulic code system ATHLET and ESTER. Due to the work performed during this project the ESTER tools became the most modern informatic tools presently available in the area of severe accident research. A sample application is given which demonstrates the use of the new tools. (orig.) [de

Cobalt-catalyzed hydrogenation of esters to alcohols: unexpected reactivity trend indicates ester enolate intermediacy.

Science.gov (United States)

Srimani, Dipankar; Mukherjee, Arup; Goldberg, Alexander F G; Leitus, Gregory; Diskin-Posner, Yael; Shimon, Linda J W; Ben David, Yehoshoa; Milstein, David

2015-10-12

The atom-efficient and environmentally benign catalytic hydrogenation of carboxylic acid esters to alcohols has been accomplished in recent years mainly with precious-metal-based catalysts, with few exceptions. Presented here is the first cobalt-catalyzed hydrogenation of esters to the corresponding alcohols. Unexpectedly, the evidence indicates the unprecedented involvement of ester enolate intermediates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemoselective Deprotection of Triethylsilyl Ethers

Science.gov (United States)

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

Structures of butyl ions formed by electron impact ionization of isomeric butyl halides and alkanes

International Nuclear Information System (INIS)

Shold, D.M.; Ausloos, P.

1978-01-01

Using a pulsed ion cyclotron resonance (ICR) spectrometer, it is demonstrated that at pressures of about 10 -6 Torr and at observation times ranging from 10 -3 to 0.5 s, isobutane, neopentane, 2,2-dimethylbutane, isobutyl halides, and tert-butyl halides form C 4 H 9 + ions having the tertiary structure. In n-alkanes, 2-methylbutane, 3-methylpentane, n-butyl halides, and sec-butyl halides, both sec-C 4 H 9 + and t-C 4 H 9 + ions are observed, the sec-C 4 H 9 + ions surviving without rearrangement for at least 0.1 s. However, in the case of the halides, a collision-induced isomerization of the sec-C 4 H 9 + to the t-C 4 H 9 + ions occurs. The efficiency of this process increases with the basicity of the alkyl halide. Radiolysis experiments carried out at atmospheric pressures indicate, in agreement with ICR and solution experiments, that at times as short as 10 -10 s the majority of the i-C 4 H 9 + ions from isobutyl bromide rearrange to the t-C 4 H 9 + structure. On the other hand, in the radiolysis of both n-hexane and 3-methylpentane, the abundance of t-C 4 H 9 + relative to sec-C 4 H 9 + is substantially smaller than that observed in the ICR experiments, and decreases with decreasing collision interval. It is suggested that about 90% of the i-C 4 H 9 + can rearrange to t-C 4 H 9 + by simple 1,2-hydride shift without involving secondary or protonated methylcyclopropane structures as intermediates. 4 figures, 2 tables

Sodium lauryl ether sulfate (SLES) degradation by nitrate-reducing bacteria.

Science.gov (United States)

Paulo, Ana M S; Aydin, Rozelin; Dimitrov, Mauricio R; Vreeling, Harm; Cavaleiro, Ana J; García-Encina, Pedro A; Stams, Alfons J M; Plugge, Caroline M

2017-06-01

The surfactant sodium lauryl ether sulfate (SLES) is widely used in the composition of detergents and frequently ends up in wastewater treatment plants (WWTPs). While aerobic SLES degradation is well studied, little is known about the fate of this compound in anoxic environments, such as denitrification tanks of WWTPs, nor about the bacteria involved in the anoxic biodegradation. Here, we used SLES as sole carbon and energy source, at concentrations ranging from 50 to 1000 mg L -1 , to enrich and isolate nitrate-reducing bacteria from activated sludge of a WWTP with the anaerobic-anoxic-oxic (A 2 /O) concept. In the 50 mg L -1 enrichment, Comamonas (50%), Pseudomonas (24%), and Alicycliphilus (12%) were present at higher relative abundance, while Pseudomonas (53%) became dominant in the 1000 mg L -1 enrichment. Aeromonas hydrophila strain S7, Pseudomonas stutzeri strain S8, and Pseudomonas nitroreducens strain S11 were isolated from the enriched cultures. Under denitrifying conditions, strains S8 and S11 degraded 500 mg L -1 SLES in less than 1 day, while strain S7 required more than 6 days. Strains S8 and S11 also showed a remarkable resistance to SLES, being able to grow and reduce nitrate with SLES concentrations up to 40 g L -1 . Strain S11 turned out to be the best anoxic SLES degrader, degrading up to 41% of 500 mg L -1 . The comparison between SLES anoxic and oxic degradation by strain S11 revealed differences in SLES cleavage, degradation, and sulfate accumulation; both ester and ether cleavage were probably employed in SLES anoxic degradation by strain S11.

[Early contributions from Erlangen to the theory and practice of ether and chloroform anesthesia. 1. Heyfelder's clinical trial with ether and chloroform].

Science.gov (United States)

Hintzenstern, U v; Schwarz, W

1996-02-01

The era of modern anaesthesia in Germany began on January 24th, 1847. This day, professor in ordinary Johann Ferdinand Heyfelder anaesthetized a patient with sulphuric ether in the clinic of surgery and ophthalmology of the University of Erlangen. By March 17th, 1847, Heyfelder had performed 121 surgical procedures under ether. The operations in majority were teeth-extractions, and a few more complex operations such as the treatment of a harelip or of lip cancer or the resection of the shoulder joint. Heyfelder described in detail 108 of these inhalations in a little book entitled The experiments with sulphuric ether. This monograph published in March, 1847, represents one of the first complete dissertations on sulphuric ether in the German literature. In a special chapter he analyzed the development of various physiological and psychological parameters during etherization. Heyfelder also examined blood and urine of some etherized patients and reported that he did not find any important or specific alterations. In 1847, Heyfelder was probably the first to apply salt-ether in man. After 4 administrations he concluded that salt ether acted more quickly but shorter than sulphuric ether. Advantageous were its application without problems and ease of induction. Disadvantageous were its high volatility, its price and the difficulty of getting it in a pure form. From December, 1847, on Heyfelder started to use chloroform. He was now able to perform more major operations, for example, the total resection of the hip-joint. In his book The experiments with sulphuric ether, salt ether, and chloroform he describes a great number of anaesthetic administrations using these 3 agents. In his summary Heyfelder concluded, that chloroform was undoubtly superior to sulphuric ether mainly because it was a quicker acting and longer lasting agent and leads to deeper narcosis. Moreover its application was much easier for it needed no special apparatus. However, because of its great

Molecular structure impacts on secondary organic aerosol formation from glycol ethers

Science.gov (United States)

Li, Lijie; Cocker, David R.

2018-05-01

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

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

Energy Technology Data Exchange (ETDEWEB)

Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

2018-03-06

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.

Organophosphate Esters in Air, Snow, and Seawater in the North Atlantic and the Arctic.

Science.gov (United States)

Li, Jing; Xie, Zhiyong; Mi, Wenying; Lai, Senchao; Tian, Chongguo; Emeis, Kay-Christian; Ebinghaus, Ralf

2017-06-20

The concentrations of eight organophosphate esters (OPEs) have been investigated in air, snow and seawater samples collected during the cruise of ARK-XXVIII/2 from sixth June to third July 2014 across the North Atlantic and the Arctic. The sum of gaseous and particle concentrations (ΣOPE) ranged from 35 to 343 pg/m 3 . The three chlorinated OPEs accounted for 88 ± 5% of the ΣOPE. The most abundant OPE was tris(2-chloroethyl) phosphate (TCEP), with concentrations ranging from 30 to 227 pg/m 3 , followed by three major OPEs, such as tris(1-chloro-2-propyl) phosphate (TCPP, 0.8 to 82 pg/m 3 ), tri-n-butyl phosphate (TnBP, 2 to 19 pg/m 3 ), and tri-iso-butyl phosphate (TiBP, 0.3 to 14 pg/m 3 ). The ΣOPE concentrations in snow and seawater ranged from 4356 to 10561 pg/L and from 348 to 8396 pg/L, respectively. The atmospheric particle-bound dry depositions of TCEP ranged from 2 to 12 ng/m 2 /day. The air-seawater gas exchange fluxes were dominated by net volatilization from seawater to air for TCEP (mean, 146 ± 239 ng/m 2 /day), TCPP (mean, 1670 ± 3031 ng/m 2 /day), TiBP (mean, 537 ± 581 ng/m 2 /day) and TnBP (mean, 230 ± 254 ng/m 2 /day). This study highlighted that OPEs are subject to long-range transport via both air and seawater from the European continent and seas to the North Atlantic and the Arctic.

Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes

Science.gov (United States)

Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei

2017-09-01

Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.

Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules

Science.gov (United States)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar; Venugopalan, Vijay

2017-06-01

Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 °C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 × 10-5 cm2/V s.

IS YOUR TBA COMING FROM BIODEGRADATION OF MTBE

Science.gov (United States)

MTBE (methyl tertiary butyl ether) is present at high concentrations in ground water at many sites where gasoline has been spilled from underground storage tanks. In addition, TBA (tertiary butyl alcohol) is also present at high concentrations in many of the same ground waters. ...

76 FR 77709 - Butyl acrylate-methacrylic acid-styrene polymer; Tolerance Exemption

Science.gov (United States)

2011-12-14

...This regulation establishes an exemption from the requirement of a tolerance for residues of 2-Propenoic acid, 2-methyl-, polymer with butyl 2-propenoate and ethenylbenzene (CAS Reg. No. 25036-16-2); also known as butyl acrylate-methacrylic acid-styrene polymer when used as an inert ingredient in a pesticide chemical formulation. Momentive Performance Materials submitted a petition to EPA under the Federal Food, Drug, and Cosmetic Act (FFDCA), requesting an exemption from the requirement of a tolerance. This regulation eliminates the need to establish a maximum permissible level for residues of 2-Propenoic acid, 2-methyl-, polymer with butyl 2-propenoate and ethenylbenzene on food or feed commodities.

Microwave sintering of poly-ether-ether-ketone (PEEK) based coatings deposited on metallic substrate

International Nuclear Information System (INIS)

Zhang, G.; Leparoux, S.; Liao, H.; Coddet, C.

2006-01-01

In this paper, the feasibility of microwave (MW) sintering PEEK (poly-ether-ether-ketone) based coatings was investigated. Three coatings were studied: pure PEEK, micron-SiC and nano-SiC particles filled (wt.10%) PEEK coatings. The results indicate that, for the two composite coatings, the SiC particles distributed in the polymer matrix, as a good MW susceptor, could be heated preferentially by MW radiation. Consequently, the polymer matrix was heated by these particles

One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

KAUST Repository

Alamri, Haleema

2016-04-20

A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

KAUST Repository

Alamri, Haleema; Hadjichristidis, Nikolaos

2016-01-01

A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

Carboxylesterase-involved metabolism of di-n-butyl phthalate in pumpkin (Cucurbita moschata) seedlings.

Science.gov (United States)

Lin, Qingqi; Chen, Siyuan; Chao, Yuanqing; Huang, Xiongfei; Wang, Shizhong; Qiu, Rongliang

2017-01-01

Uptake and accumulation by plants is a significant pathway in the migration and transformation of phthalate esters (PAEs) in the environment. However, limited information is available on the mechanisms of PAE metabolism in plants. Here, we investigated the metabolism of di-n-butyl phthalate (DnBP), one of the most frequently detected PAEs, in pumpkin (Cucurbita moschata) seedlings via a series of hydroponic experiments with an initial concentration of 10 mg L -1 . DnBP hydrolysis occurred primarily in the root, and two of its metabolites, mono-n-butyl phthalate (MnBP) and phthalic acid (PA), were detected in all plant tissues. The MnBP concentration was an order of magnitude higher than that of PA in shoots, which indicated MnBP was more readily transported to the shoot than was PA because of the former's dual hydrophilic and lipophilic characteristics. More than 80% of MnBP and PA were located in the cell water-soluble component except that 96% of MnBP was distributed into the two solid cellular fractions (i.e., cell wall and organelles) at 96 h. A 13-20% and 29-54% increase of carboxylesterase (CXE) activity shown in time-dependent and concentration-dependent experiments, respectively, indicated the involvement of CXEs in plant metabolism of DnBP. The level of CXE activity in root subcellular fractions was in the order: the cell water-soluble component (88-94%) > cell wall (3-7%) > cell organelles (3-4%), suggesting that the cell water-soluble component is the dominant locus of CXE activity and also the domain of CXE-catalyzed hydrolysis of DnBP. The addition of triphenyl phosphate, a CXE inhibitor, led to 43-56% inhibition of CXE activity and 16-25% increase of DnBP content, which demonstrated the involvement of CXEs in plant metabolism of DnBP. This study contributes to our understanding of enzymitic mechanisms of PAE transformation in plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of Solvent Additives on the Solution Aggregation of Phenyl-C61-Butyl Acid Methyl Ester (PCBM)

KAUST Repository

Tummala, Naga Rajesh

2015-11-24

High-boiling-point solvent additives, employed during the solution processing of active-layer formulations, impact the efficiency of bulk hetero-junction (BHJ) organic solar cells by influencing the morphological / topological features of the multicomponent thin film. Here, we aim at a better understanding of how these additives change the aggregation landscape in the casting solution prior to film deposition via a multi-scale computational study of the aggregation phenomena of phenyl-C61-butyric-acid methyl ester (PCBM) in various solutions. The energetic landscape of PCBM-solvent / solvent-additive intermolecular interactions is evaluated at the electronic-structure level through symmetry-adapted perturbation theory to determine the nature and strength of non-covalent forces important to aggregation. Molecular dynamics simulations highlight how the choice of solvent and solvent additives control the formation of molecular aggregates. Our results indicate that high-boiling-point solvent additives change the effective interactions among the PCBM and casting-solvent molecules and alter the equilibrium PCBM aggregate sizes in solution.

Actinide/crown ether chemistry

International Nuclear Information System (INIS)

Benning, M.M.

1988-01-01

A structural survey of actinide/crown ether compounds was conducted in order to investigate the solid state chemistry of these complexes. Several parameters - the metal size, crown type, counterion, solvent systems and reaction and crystallization conditions - were varied to correlate their importance in complexation. Under atmospheric conditions, two types of complexes were isolated, those containing only hydrogen-bonded crown interactions and instances where the crown interacts directly with the metal center. In both cases, water seems to play a very important role. When coordinated to the metal, water molecules exhibit the necessary donor properties required for the formation of hydrogen-bonded contacts. The water molecules also provide fierce competition with the crown ethers for metal-binding sites and in most cases prohibit the formation of complexes in which direct metal-ligand association exists. The results of this study indicate that direct interaction between the metal atoms and the crown ethers, in the presence of water, can only occur with polyether conformations which limit the steric replusions within the metal coordination sphere

Rearrangements of Cycloalkenyl Aryl Ethers

Directory of Open Access Journals (Sweden)

Mercedesz Törincsi

2016-04-01

Full Text Available Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Claisen and Cope rearrangements were followed by an alkyl migration. The mechanism of this novel rearrangement reaction is also discussed.

Ether: Bitcoin's competitor or ally?

OpenAIRE

Bouoiyour, Jamal; Selmi, Refk

2017-01-01

Although Bitcoin has long been dominant in the crypto scene, it is certainly not alone. Ether is another cryptocurrency related project that has attracted an intensive attention because of its additional features. This study seeks to test whether these cryptocurrencies differ in terms of their volatile and speculative behaviors, hedge, safe haven and risk diversification properties. Using different econometric techniques, we show that a) Bitcoin and Ether are volatile and relatively more resp...

Poly(ester-anhydride):poly(beta-amino ester) micro- and nanospheres: DNA encapsulation and cellular transfection.

Science.gov (United States)

Pfeifer, Blaine A; Burdick, Jason A; Little, Steve R; Langer, Robert

2005-11-04

Poly(ester-anhydride) delivery devices allow flexibility regarding carrier dimensions (micro- versus nanospheres), degradation rate (anhydride versus ester hydrolysis), and surface labeling (through the anhydride functional unit), and were therefore tested for DNA encapsulation and transfection of a macrophage P388D1 cell line. Poly(l-lactic acid-co-sebacic anhydride) and poly(l-lactic acid-co-adipic anhydride) were synthesized through melt condensation, mixed with 25 wt.% poly(beta-amino ester), and formulated with plasmid DNA (encoding firefly luciferase) into micro- and nanospheres using a double emulsion/solvent evaporation technique. The micro- and nanospheres were then characterized (size, morphology, zeta potential, DNA release) and assayed for DNA encapsulation and cellular transfection over a range of poly(ester-anhydride) copolymer ratios. Poly(ester-anhydride):poly(beta-amino ester) composite microspheres (6-12 microm) and nanospheres (449-1031 nm), generated with copolymers containing between 0 and 25% total polyanhydride content, encapsulated plasmid DNA (>or=20% encapsulation efficiency). Within this polyanhydride range, poly(adipic anhydride) copolymers provided DNA encapsulation at an increased anhydride content (10%, microspheres; 10-25%, nanospheres) compared to poly(sebacic anhydride) copolymers (1%, microspheres and nanospheres) with cellular transfection correlating with the observed DNA encapsulation.

STABLE ISOTOPE ANALYSIS OF MTBE TO EVALUATE THE SOURCE OF TBA IN GROUND WATER

Science.gov (United States)

Although tert-butyl alcohol (TBA) has not been used as a fuel oxygenate in Orange County, California, the concentrations of TBA in ground water at gasoline spill sites are high compared those of the conventional fuel oxygenate methyl tert-butyl ether (MTBE). In the year 2002, th...

ANAEROBIC DEGRADATION OF MTBE TO TBA IN GROUND WATER AT GASOLINE SPILL SITES IN ORANGE COUNTY, CALIFORNIA

Science.gov (United States)

Although tert-Butyl Alcohol (TBA) has not been used as a fuel oxygenate in Orange County, California, the concentrations of TBA in ground water at gasoline spill sites are high compared to the concentrations of the conventional fuel oxygenate Methyl tert-Butyl Ether (MTBE). In t...

Conversion of Lignocellulosic Biomass to Ethanol and Butyl Acrylate

Energy Technology Data Exchange (ETDEWEB)

Binder, Thomas [Archer Daniels Midland Company, Decatur, IL (United States); Erpelding, Michael [Archer Daniels Midland Company, Decatur, IL (United States); Schmid, Josef [Archer Daniels Midland Company, Decatur, IL (United States); Chin, Andrew [Archer Daniels Midland Company, Decatur, IL (United States); Sammons, Rhea [Archer Daniels Midland Company, Decatur, IL (United States); Rockafellow, Erin [Archer Daniels Midland Company, Decatur, IL (United States)

2015-04-10

Conversion of Lignocellulosic Biomass to Ethanol and Butyl Acrylate. The purpose of Archer Daniels Midlands Integrated Biorefinery (IBR) was to demonstrate a modified acetosolv process on corn stover. It would show the fractionation of crop residue to distinct fractions of cellulose, hemicellulose, and lignin. The cellulose and hemicellulose fractions would be further converted to ethanol as the primary product and a fraction of the sugars would be catalytically converted to acrylic acid, with butyl acrylate the final product. These primary steps have been demonstrated.

Catalytic hydroprocessing of lignin β-O-4 ether bond model compound phenethyl phenyl ether over ruthenium catalysts

NARCIS (Netherlands)

Gomez-Monedero, B.; Faria, J.; Bimbela, F.; Ruiz, M.P.

2017-01-01

The catalytic hydroprocessing of phenethyl phenyl ether (PPE), a model compound of one of the most significant ether linkages within lignin structure, β-O-4, has been studied. Reactions were carried out using two ruthenium-based catalysts, supported on different materials: 3.8 wt.% Ru/C and 3.9 wt.%

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use

Directory of Open Access Journals (Sweden)

Denny Joseph Manual Kollareth

2018-03-01

Full Text Available Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [3H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [3H]cholesteryl oleoyl ether and [3H]cholesteryl hexadecyl ether from different suppliers, employing in vitro, in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro, in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments. Keywords: Cholesteryl ether, J774 A2 macrophages, Soy oil emulsion, Thin layer chromatography, triDHA emulsion

Study of liver function and expression of some detoxification genes ...

African Journals Online (AJOL)

Ahmad Ali Badr

2015-10-19

Oct 19, 2015 ... In this study we investigate the effect(s) of MTBE on liver function indices and ... Methyl-tertiary butyl ether (MTBE), a well known gasoline oxygenate, is added to ..... ether (MTBE) in CD-1 mice and F-344 rats. J Appl Toxicol.

Radiolabeled cholesteryl ethers: A need to analyze for biological stability before use.

Science.gov (United States)

Manual Kollareth, Denny Joseph; Chang, Chuchun L; Hansen, Inge H; Deckelbaum, Richard J

2018-03-01

Radiolabeled cholesteryl ethers are widely used as non-metabolizable tracers for lipoproteins and lipid emulsions in a variety of in vitro and in vivo experiments. Since cholesteryl ethers do not leave cells after uptake and are not hydrolyzed by mammalian cellular enzymes, these compounds can act as markers for cumulative cell uptakes of labeled particles. We have employed [ 3 H]cholesteryl oleoyl ether to study the uptake and distribution of triglyceride-rich emulsion particles on animal models. However, questionable unexpected results compelled us to analyze the stability of these ethers. We tested the stability of two commercially available radiolabeled cholesteryl ethers - [ 3 H]cholesteryl oleoyl ether and [ 3 H]cholesteryl hexadecyl ether from different suppliers, employing in vitro , in vivo and chemical model systems. Our results show that, among the two cholesteryl ethers tested, one ether was hydrolyzed to free cholesterol in vitro , in vivo and chemically under alkaline hydrolyzing agent. Free cholesterol, unlike cholesteryl ether, can then re-enter the circulation leading to confounding results. The other ether was not hydrolyzed to free cholesterol and remained as a stable ether. Hence, radiolabeled cholesteryl ethers should be analyzed for biological stability before utilizing them for in vitro or in vivo experiments.

Total costs and benefits of biomass in selected regions of the European Union - BioCosts

Energy Technology Data Exchange (ETDEWEB)

Almeida, A de; Costa, F B [Coimbra Univ. (Portugal). Inst. de Sistemas e Robotica; Bauen, A [London Univ. (United Kingdom). Div. of Life Sciences; and others

1998-11-01

In the BioCosts project, representative biomass-to-electricity and biomass-to-transport-service fuel cycles located at different sites within the European Union have been evaluated concerning their environmental and economic performance. Each case study was compared to a fossil-fuel fired reference case. The case studies examined comprise: utilisation of forestry residues in the Naessjoe circulating fluidized bed combustion plant, Sweden, versus the use of Polish coal in the same plant; utilisation of forestry residues and short-rotation coppice for industrial combined heat and power production in Mangualde, Portugal, versus the use of fuel oil in an engine generating heat and power; production of biogas from manure slurry for municipal combined heat and power generation at Hashoej, Denmark, versus the use of Danish natural gas in the same engine; gasification of woody biomass for combined heat and power generation in Vaernamo, Sweden, and Eggborough, UK, versus the use of coal in the Naessjoe plant mentioned above and a UK power plant; production of cold-pressed rape-seed oil and its use in a cogeneration plant at Weissenburg, Germany, versus the use of diesel fuel in a similar engine; production of rape-seed oil methyl ester and its use for goods transport in Germany, versus the use of diesel fuel in the same fleet of trucks; production of ethyl tertiary butyl ether from sugar beets and sweet sorghum for transport applications in France, versus the use of methyl tertiary butyl ether from fossil sources for the same purpose 130 refs, 25 figs, 42 tabs. Research funded in part by the European Commission in the JOULE III programme

Synthèse d'esters de l'acide benzoïque par catalyse enzymatique en milieu hétérogène microaqueux

OpenAIRE

Leszczak , Jean-Pierre

1998-01-01

171 pages; No english abstract; La synthèse d'esters de l'acide benzoïque par voie enzymatique en milieu hétérogène microaqueux est envisagée. Cette estérification est possible et est catalysée par la lipase de Candida rugosa en suspension dans un mélange hexane/toluène. Le toluène permet la solubilisation de l'acide benzoïque. De nombreux paramètres influencent la synthèse des benzoates de méthyle et de butyle. La teneur en eau initiale agit uniquement sur la cinétique de réaction sans modif...

Temporary diplopia upon hyoscine-N-butyl bromide administration: case report

Directory of Open Access Journals (Sweden)

Migliorini R

2013-05-01

Full Text Available R Migliorini, R Malagola, M Mafrici, R Spena, L ArricoDepartment of Sense Organs, University of Rome "La Sapienza", Rome, ItalyAbstract: Hyoscine-N-butyl bromide is a widely used antispasmodic belonging to the belladonna alkaloid class of semisynthetic quaternary ammonium compounds. These compounds exert a spasmolytic action on the smooth muscles of the bile-gastrointestinal tract, genitourinary tract, salivary glands (xerostomia, and also on the visual apparatus – in particular, the irido-ciliary complex. As a consequence, they provoke collateral effects such as mydriasis and accommodation disturbances. We report the case of a 23-year-old woman who complained of not only "dry mouth" but also "cloudy vision" and a "diplopia", both of temporary type, 2 hours after oral administration of hyoscine-N-butyl bromide.Keywords: hyoscine-N-butyl bromide, accommodation disorders, temporary diplopia, fusion alteration, vertical strabismus

Application conditions for ester cured alkaline phenolic resin sand

Directory of Open Access Journals (Sweden)

Ren-he Huang

2016-07-01

Full Text Available Five organic esters with different curing speeds: propylene carbonate (i.e. high-speed ester A; 1, 4-butyrolactone; glycerol triacetate (i.e. medium-speed ester B; glycerol diacetate; dibasic ester (DBE (i.e. low-speed ester C, were chosen to react with alkaline phenolic resin to analyze the application conditions of ester cured alkaline phenolic resin. The relationships between the curing performances of the resin (including pH value, gel pH value, gel time of resin solution, heat release rate of the curing reaction and tensile strength of the resin sand and the amount of added organic ester and curing temperature were investigated. The results indicated the following: (1 The optimal added amount of organic ester should be 25wt.%-30wt.% of alkaline phenolic resin and it must be above 20wt.%-50 wt.% of the organic ester hydrolysis amount. (2 High-speed ester A (propylene carbonate has a higher curing speed than 1, 4-butyrolactone, and they were both used as high-speed esters. Glycerol diacetate is not a high-speed ester in alkaline phenolic resin although it was used as a high-speed ester in ester cured sodium silicate sand; glycerol diacetate and glycerol triacetate can be used as medium-speed esters in alkaline phenolic resin. (3 High-speed ester A, medium-speed ester B (glycerol triacetate and low-speed ester C (dibasic ester, i.e., DBE should be used below 15 ìC, 35 ìC and 50 ìC, respectively. High-speed ester A or low-speed ester C should not be used alone but mixed with medium-speed ester B to improve the strength of the resin sand. (4 There should be a suitable solid content (generally 45wt.%-65wt.% of resin, alkali content (generally 10wt.%-15wt.% of resin and viscosity of alkaline phenolic resin (generally 50-300 mPa≤s in the preparation of alkaline phenolic resin. Finally, the technique conditions of alkaline phenolic resin preparation and the application principles of organic ester were discussed.

Isothermal Vapour-Liquid Equilibria in the Binary and Ternary Systems Composed of tert-Butyl Methyl Ether, 3,3-Dimethyl-2-butanone and 2,2-Dimethyl-1-propanol

Czech Academy of Sciences Publication Activity Database

Bernatová, Svatoslava; Pavlíček, Jan; Wichterle, Ivan

2009-01-01

Roč. 278, 1-2 (2009), s. 129-134 ISSN 0378-3812 R&D Projects: GA ČR GA104/07/0444 Institutional research plan: CEZ:AV0Z40720504 Keywords : alcohol * ether * ketone Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.857, year: 2009

Numerical investigation on the effect of injection pressure on the internal flow characteristics for diethyl ether, dimethyl ether and diesel fuel injectors using CFD

Directory of Open Access Journals (Sweden)

Vijayakumar Thulasi

2011-01-01

Full Text Available The spray characteristics of the diesel fuel are greatly affected by the cavitation formed inside the injector due to the high pressure differential across the nozzle. Many researchers across the globe are exploring the potential of using diethyl ether and dimethyl ether as an alternate for diesel fuel to meet the strict emission norms. Due to the variation in the fuel properties the internal flow characteristics in injectors for ether fuels are expected to be different from that of the diesel fuel. In this paper computational technique is used to study and compare the internal flow characteristics of diethyl ether, dimethyl ether and diesel fuel. The two phase flow model considering the fuel as a mixture of liquid and vapor is adopted for the simulation study. The injection pressure is varied from 100 to 400 bar and the flow characteristics of all three fuels are simulated and compared. Results indicate that all three fuels have distinct cavitating patterns owing to different property values. The dimethyl ether is found to be more cavitating than diesel and diethyl ether fuels as expected. The mass of fuel injected are found to be decreasing for the ether fuels when compared with diesel fuel at all injection pressures.

Multiple steady states detection in a packed-bed reactive distillation column using bifurcation analysis

DEFF Research Database (Denmark)

Ramzan, Naveed; Faheem, Muhammad; Gani, Rafiqul

2010-01-01

A packed reactive distillation column producing ethyl tert-butyl ether from tert-butyl alcohol and ethanol was simulated for detection of multiple steady states using Aspen Plus®. A rate-based approach was used to make the simulation model more realistic. A base-case was first developed and fine...

Effects of a Squalene Epoxidase Inhibitor, Terbinafine, on Ether Lipid Biosyntheses in a Thermoacidophilic Archaeon, Thermoplasma acidophilum

Science.gov (United States)

Kon, Takahide; Nemoto, Naoki; Oshima, Tairo; Yamagishi, Akihiko

2002-01-01

The archaeal plasma membrane consists mainly of diether lipids and tetraether lipids instead of the usual ester lipids found in other organisms. Although a molecule of tetraether lipid is thought to be synthesized from two molecules of diether lipids, there is no direct information about the biosynthetic pathway(s) or intermediates of tetraether lipid biosynthesis. In this study, we examined the effects of the fungal squalene epoxidase inhibitor terbinafine on the growth and ether lipid biosyntheses in the thermoacidophilic archaeon Thermoplasma acidophilum. Terbinafine was found to inhibit the growth of T. acidophilum in a concentration-dependent manner. When growing T. acidophilum cells were pulse-labeled with [2-14C]mevalonic acid in the presence of terbinafine, incorporation of radioactivity into the tetraether lipid fraction was strongly suppressed, while accumulation of radioactivity was noted at the position corresponding to diether lipids, depending on the concentration of terbinafine. After the cells were washed with fresh medium and incubated further without the radiolabeled substrate and the inhibitor, the accumulated radioactivity in the diether lipid fraction decreased quickly while that in the tetraether lipids increased simultaneously, without significant changes in the total radioactivity of ether lipids. These results strongly suggest that terbinafine inhibits the biosynthesis of tetraether lipids from a diether-type precursor lipid(s). The terbinafine treatment will be a tool for dissecting tetraether lipid biosynthesis in T. acidophilum. PMID:11844769

Health assessment of gasoline and fuel oxygenate vapors: developmental toxicity in rats.

Science.gov (United States)

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.

AIRBORNE POLYBROMINATED DIPHENYL ETHERS IN A COMPUTER CLASSROOM OF COLLEGE IN TAIWAN

Directory of Open Access Journals (Sweden)

F. H. Chang ، C. R. Yang ، C. Y. Tsai ، W. C. Lin

2009-04-01

Full Text Available This study characterized the airborne exposure of students to thirty polybrominated diphenyl ether congeners inside and outside a computer classroom in a southern Taiwan college. Arithmetic mean values of total indoor and outdoor polybrominated diphenyl ether concentrations were 125.0 pg/m3 (89.8 to 203.9 pg/m3 and 110.3 pg/m3 (83.5 to 157.0 pg/m3, respectively. Total indoor polybrominated diphenyl ether concentrations were one order of magnitude lower than those detected in homes in Birmingham, United Kingdom and in Ottawa, Canada but were several times higher than those measured in the ambient air in Ottawa, Canada and from the Bohai Sea to the Arctic. The five highest indoor concentrations of polybrominated diphenyl ether congeners were decabromodiphenyl ether (23.0 pg/m3, 4,4’-dibromodiphenyl ether (15.9 pg/m3, 2,2’,3,4,4’,5,5’,6-octabromodiphenyl ether (10.6 pg/m3, 2,4-dibromodiphenyl ether (10.3 pg/m3 and 2,2’,3,4,4’,5’,6-heptabromodiphenyl ether (10.0 pg/m3. Although indoor and outdoor total polybrominated diphenyl ether concentrations did not significantly differ, the indoor concentrations of 2,4-dibromodiphenyl ether, 2,2’,4-tribromodiphenyl ether, 2,4,4’-tribromodiphenyl ether, 2,2’,4,5’-tetrabromodiphenyl ether and 2,3’,4’,6-tetrabromodiphenyl ether were significantly higher than their outdoor concentrations. This study suggests the following measures: 1 to increase the air exchange rate and open classroom doors and windows for several minutes before classes to reduce indoor PBDE concentrations; 2 to reduce polybrominated diphenyl ether emissions from new devices, it’s better to use computer-related products that meet the Restriction of Hazardous Substances Directive adopted by the European Union.

Thermally reversible cross-linked poly(ether-urethanes

Directory of Open Access Journals (Sweden)

V. Gaina

2013-07-01

Full Text Available Cross-linked poly(ether-urethanes were prepared by Diels-Alder (DA reaction of the furan-containing poly(ether-urethane to bismaleimides and showed thermal reversibility evidenced by differential scanning calorimetry and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR-FTIR. The furan-containing poly(ether-urethanes were synthesized by the polyaddition reaction of 1,6-hexamethylene diisocyanate (HMDI or 4,4'- dibenzyl diisocyanate (DBDI to poly(tetramethylene ether glycol (PTMEG having Mn = 250, 650, 1000, 1500 and 2000 and 2-[N,N-bis(2-methyl-2-hydroxyethylamino]furfuryl as chain extender by the solution prepolymer method. The molar ratio of isocyanate: PTMEG:chain extender varied from 2:1:1 to 4:1:3, which produces a molar concentration of furyl group ranging between 3.65•10–4 and 1.25•10–3 mol/g.

Rearrangement of beta,gamma-unsaturated esters with thallium trinitrate: synthesis of indans bearing a beta-keto ester moiety

Directory of Open Access Journals (Sweden)

Silva Jr. Luiz F.

2006-01-01

Full Text Available The rearrangement of beta,gamma-unsaturated esters, such as 2-(3,4-dihydronaphthalen-1-yl-propionic acid ethyl ester, with thallium trinitrate (TTN in acetic acid leads to 3-indan-1-yl-2-methyl-3-oxo-propionic acid ethyl ester in good yield, through a ring contraction reaction. The new indans thus obtained feature a beta-keto ester moiety, which would be useful for further functionalization.

Natural and synthetic antioxidants: Influence on the oxidative stability of biodiesel synthesized from non-edible oil

Energy Technology Data Exchange (ETDEWEB)

Sarin, Amit [Department of Applied Sciences, Amritsar College of Engineering and Technology, Manawala, Amritsar-143001, Punjab (India); Singh, N.P. [Punjab Technical University, Jalandhar (India); Sarin, Rakesh; Malhotra, R.K. [Indian Oil Corporation Ltd., R and D Centre, Sector-13, Faridabad-121007 (India)

2010-12-15

According to the proposed National Mission on Biodiesel in India, we have undertaken studies on the oxidative stability of biodiesel synthesized from tree borne non-edible oil seeds jatropha. Neat jatropha biodiesel exhibited oxidation stability of 3.95 h and research was conducted to investigate the influence of natural and synthetic antioxidants on the oxidation stability of jatropha methyl ester. Antioxidants namely {alpha}-tocopherol, tert-butylated hydroxytoluene, tert-butylated phenol derivative, octylated butylated diphenyl amine, and tert-butylhydroxquinone were doped to improve the oxidation stability. It was found that both types of antioxidants showed beneficial effects in increasing the oxidation stability of jatropha methyl ester, but comparatively, the synthetic antioxidants were found to be more effective. (author)

Thermal Stability of Sulfonated Poly(Ether Ether Ketone) Films: on the Role of Protodesulfonation

OpenAIRE

Koziara, Beata; Kappert, Emiel; Ogieglo, Wojciech; Nijmeijer, Dorothea C.; Hempenius, Mark A.; Benes, Nieck Edwin

2016-01-01

Thin film and bulk, sulfonated poly(ether ether ketone) (SPEEK) have been subjected to a thermal treatment at 160–250 °C for up to 15 h. Exposing the films to 160 °C already causes partial desulfonation, and heating to temperatures exceeding 200 °C results in increased conjugation in the material, most likely via a slight cross-linking by H-substitution. It is well-known that the sulfonate proton plays a major role in the desulfonation reactions, and exchanging the protons with other cations ...

α-Diazo oxime ethers for N-heterocycle synthesis.

Science.gov (United States)

Choi, Subin; Ha, Sujin; Park, Cheol-Min

2017-06-01

This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

Regioselective Synthesis of Cellulose Ester Homopolymers

Science.gov (United States)

Daiqiang Xu; Kristen Voiges; Thomas Elder; Petra Mischnick; Kevin J. Edgar

2012-01-01

Regioselective synthesis of cellulose esters is extremely difficult due to the small reactivity differences between cellulose hydroxyl groups, small differences in steric demand between acyl moieties of interest, and the difficulty of attaching and detaching many protecting groups in the presence of cellulose ester moieties without removing the ester groups. Yet the...

Triblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers

KAUST Repository

Bouchekif, Hassen; Sulhami, A. I.; AlGhamdi, Rayed D.; Gnanou, Yves; Hadjichristidis, Nikolaos

2015-01-01

A series of novel, well-defined triblock (PnBVE-b-PCEVE-b-PSiDEGVE) and pentablock (PSiDEGVE-b-PCEVE-b-PnBVE-b-PCEVE-b-PSiDEGVE) terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization. The living character of the homopolymerization of the three VE monomers and the crossover reaction resulting in the formation of well-defined block copolymers were investigated in various solvents (toluene, dichloromethane and n-hexane) using either a monofunctional [nBVE-acetic acid adduct (nBEA), CEVE-acetic acid adduct (CEEA) and SiDEGVE-acetic acid adduct (SiDEGEA)] or a difunctional [1,4-cyclohexane-1,4-diyl bis(2-methoxyethyl acetate) (cHDMEA)] initiator. All initiators are structurally equivalent to the dormant species of the corresponding monomers in order to achieve fast initiation. The optimal conditions of polymerization were achieved in n-hexane at -20 °C, in the presence of 1 M AcOEt (base). Good control over the number average molecular weight (Mn) and the polydispersity index (PDI) was obtained only at [Et3Al2Cl3]0 = [Chain-end]0 ≤ 10 mM. 2,6-Di-tert-butylpyridine (DtBP) was used as a non-nucleophilic proton trap to suppress any protonic initiation from moisture (i.e., Et3Al2Cl3·H2O). Well-defined PnBVEn-b-PCEVEp-b-PSiDEGVEq and PSiDEGVEq-b-PCEVEp-b-PnBVEn-b-PCEVEp-b-PSiDEGVEq terpolymers with a high crossover efficiency, no PCEVE-induced physical gelation, and predictable Mn and PDI < 1.15 were synthesized successfully provided that the targeted DPCEVE/DPnBVE ratio (i.e., p/n) did not exceed 2 and 0.2, respectively. The quantitative desilylation of the PSiEGVE by n-Bu4N+F- in THF at 0 °C led to triblock and pentablock terpolymers in which the PCEVE is the central block and the polyalcohol is the outer block. The thermal properties of the synthesized materials were examined by differential scanning

Dimethyl ether as a drift-chamber gas

International Nuclear Information System (INIS)

Bari, G.; Basile, M.; Bonvicini, G.; Cara Romeo, G.; Casaccia, R.; Cifarelli, L.; Cindolo, F.; Contin, A.; D'Ali, G.; Del Papa, C.; Focardi, S.; Iacobucci, G.; Maccarrone, G.; Massam, T.; Motta, F.; Nania, R.; Palmonari, F.; Prisco, G.; Sartorelli, G.; Susinno, G.; Votano, L.; Zichichi, A.; Istituto Nazionale di Fisica Nucleare, Bologna; European Organization for Nuclear Research, Geneva; Istituto Nazionale di Fisica Nucleare, Frascati; Michigan Univ., Ann Arbor; Palermo Univ.

1986-01-01

We have continued the testing of dimethyl ether as a drift-chamber gas in order to improve the understanding of its properties. In particular, we report on measurement accuracy, on systematic effects, and some preliminary data on the ageing of a detector filled with dimethyl ether. (orig.)

Correlation and prediction of mixing thermodynamic properties of ester-containing systems: Ester + alkane and ester + ester binary systems and the ternary dodecane + ethyl pentanoate + ethyl ethanoate

International Nuclear Information System (INIS)

Pérez, Noelia; Fernández, Luís; Ortega, Juan; Toledo, Francisco J.; Wisniak, Jaime

2012-01-01

Highlights: ► Excess enthalpies and volumes were measured for ester–ester–alkane. ► Mixing behaviour for ester–ester, ester–alkane and ester–ester–alkane are analyzed. ► Correlations with a new polynomial model reproduce well the mixing properties. ► UNIFAC predictions for h E result acceptable excluding the ester–ester mixtures. - Abstract: Excess thermodynamic properties V m E and H m E , have been measured for the ternary mixture dodecane + ethyl pentanoate + ethyl ethanoate and for the corresponding binaries dodecane + ethyl pentanoate, dodecane + ethyl ethanoate, ethyl pentanoate + ethyl ethanoate at 298.15 K. All mixtures show endothermic and expansive effects. Experimental results are correlated with a suitable equation whose final form for the excess ternary quantity M E contains the particular contributions of the three binaries (i–j) and a last term corresponding to the ternary, all of them obtained considering fourth-order interactions. The fit goodness for all mixtures is good and comparable to others equations taken from the literature. In this work the dissolution model for the binaries and ternary is analyzed with a special attention to ester–ester binaries whose behaviour is discussed. The application of the UNIFAC group contribution model to estimate the H m E yields acceptable results for the binaries (with the exception of ester–ester) and for the ternary mixture.

Process for making propenyl ethers and photopolymerizable compositions containing them

Science.gov (United States)

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.

Selective crystallization of cations with crown ethers

International Nuclear Information System (INIS)

Heffels, Dennis Egidius

2014-01-01

The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

Effect of antioxidants on the performance and emission characteristics of a diesel engine fuelled by waste cooking sunflower methyl ester

Science.gov (United States)

Reddy, V. Puneeth Kumar; Senthil Kumar, D.; Thirumalini, S.

2018-02-01

Biodiesel is a renewable, biodegradable fuel produced from vegetable oils and animal fats. Nonetheless, its extensive utilization is impeded by the auto-oxidation resulting in degradation of the fuel. Adding antioxidants to the biodiesel is a potential solution, but it might have an effect on the clean-burning characteristics of the fuel. This paper investigates the effect of antioxidants on the performance and emission characteristics of a diesel engine fuelled by the waste cooking sunflower methyl ester. The fuel samples tested include B10, B20, B30 and B40, among which B20 produced the best possible results. Antioxidants 2, 6-ditert-butyl-4-methylphenol (BHA) and 2(3)-tert-butyl-4-methoxy phenol (BHT) of two concentrations 1000 ppm, 2000 ppm were added to B20 to evaluate the effectiveness. B20BHA1000 had the best effect with an average decrease of 5.035%, 2.02% in brake specific fuel consumption (BSFC) and exhaust gas temperature (EGT) compared to B20. Regarding the emission characteristics it was observed that B20BHA1000 had produced an increase of 7.21%, 27.79% in NOx and smoke emissions and a decrease of 33.33% in HC emissions when compared to B20. On the whole, without any requirement of alteration in the diesel engines, B20 blends with antioxidant can be utilized as fuel.

Phthalates and polybrominated diphenyl ethers in retail stores

Science.gov (United States)

Xu, Ying; Liang, Yirui; Urquidi, Jorge R.; Siegel, Jeffrey A.

2014-04-01

Retail stores contain a wide range of products that can emit a variety of indoor pollutants. Among these chemicals, phthalate esters and polybrominated diphenyl ethers (PBDEs) are two important categories, because they are extensively used as additives in consumer products and associated with serious health concerns. This study measured six phthalate and 14 PBDE compounds inside of 12 retail stores in Texas and Pennsylvania, U.S. Phthalates and PBDEs were widely found in the retail environment, indicating that they are ubiquitous indoor air pollutants. DEP, DnBP, and DEHP were the most abundant phthalates, with DnBP showing the highest concentration (0.23 ± 0.36 μg m-3). PBDEs were dominated by BDE-28, -99, and -209, having concentrations as high as 0.85 ± 1.99 ng m-3 (BDE-99). The levels of phthalates and PBDEs measured in this study are comparable to concentrations found in previous investigations of residential buildings, with phthalates showing lower concentrations and PBDEs exhibiting higher concentrations in retail stores. The potential co-occurrence of phthalates was not as strong as that of PBDEs, suggesting that phthalates might have more diverse sources. Whole building emission rates were calculated and showed similar patterns of variations as indoor air concentrations, suggestion the diversity of indoor sources of phthalates and PBDEs in retail environments.

Radiation-induced transformations of cellulose ethers

International Nuclear Information System (INIS)

Nud'ga, L.A.; Petropavlovskii, G.S.; Plisko, E.A.; Isakova, O.V.; Ershov, B.G.

1988-01-01

The purpose of this investigation was to study the transformation which take place under the action of γ-radiation in a number of cellulose ethers containing both saturated (carboxymethyl, hydroxyethyl) and unsaturated (allyl, methacryloyl) groups. Irradiation was carried out on a 60 Co unit in air at 77 and 300 K; the dose rate was 37 and 50 kGy/h respectively. The EPR spectra of γ-irradiated hydroxyethyl- and allylhydroxyethylcelluloses are identical. Under the action of γ-radiation extensive changes took place in cellulose ethers which are exhibited in degradation or the formation of three-dimensional structures and are accompanied by a change in the functional composition. The efficiency in the formation of radicals and their localization are determined by the nature and number of substituents in the cellulose ethers

Synthesis of 11C labelled methyl esters: transesterification of enol esters versus BF3 catalysed esterification-a comparative study

International Nuclear Information System (INIS)

Ackermann, Uwe; Blanc, Paul; Falzon, Cheryl L.; Issa, William; White, Jonathan; Tochon-Danguy, Henri J.; Sachinidis, John I.; Scott, Andrew M.

2006-01-01

C-11 labelled methyl esters have been synthesized via the transesterification of enol esters in the presence of C-11 methanol and 1,3 dichlorodibutylstannoxane as catalyst. This method leaves functional groups intact and allows access to a wider variety of C-11 labelled methyl esters compared to the BF 3 catalysed ester formation, which uses carboxylic acids and C-11 methanol as starting materials

Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

Energy Technology Data Exchange (ETDEWEB)

T.A. Semelsberger

2004-10-01

The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

Preparation and characterization of emulsifier-free polyphenylsilsesquioxane-poly (styrene–butyl acrylate) hybrid particles

Energy Technology Data Exchange (ETDEWEB)

Bai, Ruiqin; Qiu, Teng, E-mail: qiuteng@mail.buct.edu.cn; Han, Feng; He, Lifan; Li, Xiaoyu, E-mail: lixy@mail.buct.edu.cn

2013-10-01

The core–shell polyphenylsilsesquioxane-poly (styrene–butyl acrylate) hybrid latex paticles with polyphenylsilsesquioxane as core and poly (styrene–butyl acrylate) as shell were successfully synthesized by seeded emulsion polymerization using polyphenylsisesquioxane (PPSQ) latex particles as seeds. X-ray diffraction (XRD) indicated that the polyphenylsilsesquioxane (PPSQ) had ladder structure, and PPSQ had incorporated into the hybrid latex particles. Transmission electron microscopy (TEM) confirmed that the resultant hybrid latex particles had the core–shell structure. TEM and dynamic light scattering (DLS) analysis indicated that the polyphenylsisesquioxane latex particles and obtained core–shell hybrid latex particles were uniform and possessed narrow size distributions. X-ray photoelectron spectroscopy (XPS) analysis also indicated that the PPSQ core particles were enwrapped by the polymer shell. In addition, compared with pure poly (styrene–butyl acrylate) latex film, the polyphenylsilsesquioxane-poly (styrene–butyl acrylate) hybrid latex film exhibited lower water uptake, higher pencil hardness and better thermal stability.

Ester Tuiksoo / Ester Tuiksoo ; interv. Piret Tali

Index Scriptorium Estoniae

Tuiksoo, Ester, 1965-

2007-01-01

Juhan Partsi valitsuse (05.04.2004-13.04.2005) ja Andrus Ansipi valitsuse (13.04.2005-) põllumajandusminister Ester Tuiksoo oma lapsepõlvest ja elukutsevalikust, poliitilise karjääri algusest ja erakonna valikust, ministritöö kogemustest, naistest poliitikas

Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

International Nuclear Information System (INIS)

Tewatia, Arya; Hendrix, Justin; Dong, Zhizhong; Taghon, Meredith; Tse, Stephen; Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas; Lynch, Jennifer

2017-01-01

Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

2017-02-15

Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

Thermodynamic study of (alkyl esters + α,ω-alkyl dihalides) VI. HmE and VmE for 20 binary mixtures {xCu-1H2u-1CO2(CH2)3CH3 + (1 - x)α,ω-BrCH2(CH2)v-2CH2Br}, where u = 1 to 5, α = 1, and v = ω = 2 to 6

International Nuclear Information System (INIS)

Navas, A.; Ortega, J.; Nuez, I. de la

2009-01-01

This work shows the experimental values obtained for H m E and V m E at the temperature of 298.15 K and atmospheric pressure, for a set of 20 binary mixtures comprised of the first four butyl esters (methanoate to butanoate) with five α,ω-dibromoalkanes (1,2-dibromoethane to 1,6-dibromohexane). The H m E are endothermic for mixtures with butyl methanoate, while for the other esters the H m E adopt a sigmoidal shape. The V m E are positive for mixtures with low molecular weight dibromoalkanes, becoming negative with contractive effects in the final mixture, as the dihalide chain increases. The results indicate that the mixtures present specific interactions, with simultaneous expansion/contraction and exothermic/endothermic effects, and an explanation is given for the different types of interaction taking place. Experimental data are correlated with a polynomial equation used in previous works with satisfactory results. Modelling of the experimental results of the mixtures is carried out on the H m E values, giving rise to an adequate definition of the different interactions taking place. Two versions of the UNIFAC method were used, and for Dang and Tassios' version different possibilities were considered for the interaction parameters of the ester (G)/dibromide (G'). The best estimations were obtained when the pair of interaction parameters, type a G/G ' , depended on the number of carbon atoms in the compounds constituting the mixture.

On the ether-like Lorentz-breaking actions

International Nuclear Information System (INIS)

Petrov, A.Yu; Nascimento, J.R.; Gomes, M.; Silva, A. J. da

2011-01-01

We demonstrate the generation of the CPT-even, ether-like Lorentz-breaking actions for the scalar and electro-magnetic fields via their appropriate Lorentz-breaking coupling to spinor fields in three, four and five space-time dimensions. Besides, we show that the ether-like terms for the spinor field also can be generated as a consequence of the same couplings. The key result which will be presented here is the finiteness of the ether-like term for the electromagnetic field not only in three and five space-time dimensions where it is natural due to known effects of the dimensional regularization but also in four space-time dimensions. Moreover, we present the calculation of the last result within different calculational schemes and conclude that the result for the four-dimensional ether-like term for the electromagnetic field essentially depending on the calculation scheme, similarly to the result for the Carroll-Field-Jackiw (CFJ) term which probably signalizes a possibility for arising of a new anomaly. Also we discuss the dispersion relations in the theories with ether-like Lorentz-breaking terms which allows to discuss the consistency of the Lorentz-breaking modified theories for different (space-like or time-like) Lorentz-breaking vectors and find the tree-level effective (Breit) potential for fermion scattering and the one-loop effective potential corresponding to the action of the scalar field. (author)

Anticholinesterase activity of fluorochloronitroacetic acid esters

Energy Technology Data Exchange (ETDEWEB)

Ivanov, Yu.Ya.; Brel, V.K. Martynov, I.V.

1984-11-01

Results are presented from pharmacologic and biochemical experiments leading to the conclusion that fluorochloronitroacetic acid esters have anticholinesterase activity. Since the esters caused muscular weakness in mice, experiments were performed on isolated tissue preparation. The biochemical experiments consisted of finding the biomolecular constants of irreversible inhibition of acetylcholinesterase by the esters, using acetylcholinesterase from human erythrocytes, as well as horse serum cholinesterase. The ethyl and n-propyl esters of halogen nitroacetic acid were used in all experiments. It was found that the propyl ester caused an increase in the force of individual contractions in the isolated muscle specimens, plus an inability of the muscle to retain tetanus. The substances were determined to have an anticholinesterase effect. The mechanism of cholinesterase inhibition is not yet known. It is probable that the substances acylate the serine hydroxyl of the esterase center of the cholinestersase. 7 references, 1 figure.

Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

Science.gov (United States)

Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

2016-06-01

Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

Foliar application of amino acids modulates aroma components of 'FUJI' apple (malus domestica L.)

International Nuclear Information System (INIS)

Gou, W.; Zhang, L.; Chen, F.; Cui, Z.; Zhao, Y.; Zheng, P.; Tian, L.; Zhang, L.; Zhang, C.

2015-01-01

Volatile flavor compounds play a key role in determining the perception and acceptability as well as enhancing market competitiveness of apple (Malus domestica L.). In our study, we evaluated the effects of foliar-applied four different amino acids, i.e. leucine (Leu), isoleucine (Ile), valine (Val) and alanine (Ala), on aroma components and two key enzymes activities involved in aroma metabolism of Fuji apple. The total amount of aromatic components under Ala treatment was significantly higher than those under other treatments. There was a considerable increase in total aroma content, including hexanal, 2-methyl-butanol, nonanal, (E)-2-hexenal, methyleugenol, ethyl acetate, butanoic acid-pentyl ester, butanoic acid-hexyl ester, butyric acid ethyl ester, acetic acid-2-methyl-butyl ester, treated with spraying amino acids compared with the control. More specifically, hexanal, 2-methyl-butanol, methyleugenol and acetic acid-2-methyl-butyl ester exhibited a greater substantial increase of their contents than those of in other ingredients. However, butanoic acid-2-methyl-2-methyl butyl ester maintained a highest level among all aroma components regardless of different amino acids application. Furthermore, the activities of alcohol dehydrogenase (ADH) and alcohol acyltransferase (AAT) were much higher under Ala treatment than those under other treatments. We concluded that foliar-applied organic nitrogen (N), especially for Ala, can improve aroma metabolism and it could be used in production to enhance fruit quality on a commercial scale. (author)

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Science.gov (United States)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

Health assessment of gasoline and fuel oxygenate vapors: neurotoxicity evaluation.

Science.gov (United States)

O'Callaghan, James P; Daughtrey, Wayne C; Clark, Charles R; Schreiner, Ceinwen A; White, Russell

2014-11-01

Sprague-Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess potential neurotoxicity of evaporative emissions. Test articles included vapor condensates prepared from "baseline gasoline" (BGVC), or gasoline combined with methyl tertiary 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). Target concentrations were 0, 2000, 10,000 or 20,000mg/mg(3) and exposures were for 6h/day, 5days/week for 13weeks. The functional observation battery (FOB) with the addition of motor activity (MA) testing, hematoxylin and eosin staining of brain tissue sections, and brain regional analysis of glial fibrillary acidic protein (GFAP) were used to assess behavioral changes, traditional neuropathology and astrogliosis, respectively. FOB and MA data for all agents, except G/TBA, were negative. G/TBA behavioral effects resolved during recovery. Neuropathology was negative for all groups. Analyses of GFAP revealed increases in multiplebrain regions largely limited to males of the G/EtOH group, findings indicative of minor gliosis, most significantly in the cerebellum. Small changes (both increases and decreases) in GFAP were observed for other test agents but effects were not consistent across sex, brain region or exposure concentration. Copyright © 2014 Elsevier Inc. All rights reserved.

Thermogravimetric analysis of the polymer acrylate-vinyl ether mixture cured by radiation

International Nuclear Information System (INIS)

Danu, Sugiarto

1998-01-01

An experiment on thermal stability of the polymer acrylate-vinyl ether mixture cured by radiation have been done using thermogravimetric analysis. Three kinds of acrylic oligomers i.e., epoxy acrylate, urethane acrylate, and polypropylene glycol diacrylate, and vinyl ether monomers i.e., triethylene glycol divinyl ether (DVE-3), 1,4-cyclohexane dimethanol divinyl ether (CHVE), and butanediol monovinyl ether (HBVE) were used in the experiment. Reaction was taken via radical and cationic polymerisation. In case of cationic polymerisation, diphenyliodonium hexafluorophosphate fotoinisiator was used in the formulation. Thermogravimetric analysis was conducted in a nitrogen atmosphere at a flow rate of 40 ml/minute with a constant heating rate 10 o C and evaluation range were done from 25 to 500 o C. The results of thermogravimetric analysis showed that acrylate and DVE-3 mixture produced the polymer films with higher thermal stability than the mixture of acrylate with CHVE or HBVE. The composition of acrylate-vinyl ether mixture and degree of unsaturation of vinyl ether monomers influenced the thermal stability of polymer. The mixture of epoxy acrylate-vinyl ether and polypropylene glycol diacrylate-vinyl ether have 1 initial decomposition temperature whereas the urethane acrylate-vinyl ether mixture has 2 initial decomposition temperatures. (authors)

COMBUSTION ANALYSIS OF ALGAL OIL METHYL ESTER IN A DIRECT INJECTION COMPRESSION IGNITION ENGINE

Directory of Open Access Journals (Sweden)

HARIRAM V.

2013-02-01

Full Text Available Algal oil methyl ester was derived from microalgae (Spirulina sp. The microalga was cultivated in BG 11 media composition in a photobioreactor. Upon harvesting, the biomass was filtered and dried. The algal oil was obtained by a two step solvent extraction method using hexane and ether solvent. Cyclohexane was added to biomass to expel the remaining algal oil. By this method 92% of algal oil is obtained. Transesterification process was carried out to produce AOME by adding sodium hydroxide and methanol. The AOME was blended with straight diesel in 5%, 10% and 15% blend ratio. Combustion parameters were analyzed on a Kirloskar single cylinder direct injection compression ignition engine. The cylinder pressure characteristics, the rate of pressure rise, heat release analysis, performance and emissions were studied for straight diesel and the blends of AOME’s. AOME 15% blend exhibits significant variation in cylinder pressure and rate of heat release.

Method of making a cyanate ester foam

Science.gov (United States)

Celina, Mathias C.; Giron, Nicholas Henry

2014-08-05

A cyanate ester resin mixture with at least one cyanate ester resin, an isocyanate foaming resin, other co-curatives such as polyol or epoxy compounds, a surfactant, and a catalyst/water can react to form a foaming resin that can be cured at a temperature greater than 50.degree. C. to form a cyanate ester foam. The cyanate ester foam can be heated to a temperature greater than 400.degree. C. in a non-oxidative atmosphere to provide a carbonaceous char foam.

Final report of the addendum to the safety assessment of n-butyl alcohol as used in cosmetics.

Science.gov (United States)

McLain, Valerie C

2008-01-01

n-Butyl Alcohol is a primary aliphatic alcohol historically used as a solvent in nail care cosmetic products, but new concentration of use data indicate that it also is being used at low concentrations in eye makeup, personal hygiene, and shaving cosmetic products. n-Butyl Alcohol has been generally recognized as safe for use as a flavoring substance in food and appears on the 1982 Food and Drug Administration (FDA) list of inactive ingredients for approved prescription drug products. n-Butyl Alcohol can be absorbed through the skin, lungs, and gastrointestinal tract. n-Butyl Alcohol may be formed by hydrolysis of butyl acetate in the blood, but is rapidly oxidized. The single oral dose LD(50) of n-Butyl Alcohol for rats was 0.79 to 4.36 g/kg. The dermal LD(50) for rabbits was 4.2 g/kg. Inhalation toxicity studies in humans demonstrate sensory irritation of the upper respiratory tract, but only at levels above 3000 mg/m(3). Animal studies demonstrate intoxication, restlessness, ataxia, prostration, and narcosis. Exposures of rats to levels up to 4000 ppm failed to produce hearing defects. High concentrations of n-Butyl Alcohol vapors can be fatal. Ocular irritation was observed for n-Butyl alcohol at 0.005 ml of a 40% solution. The behavioral no-effect dose for n-Butyl Alcohol injected subcutaneously (s.c.) was 120 mg/kg. Fetotoxicity has been demonstrated, but only at maternally toxic levels (1000 mg/kg). No significant behavioral or neurochemical effects were seen in offspring following either maternal or paternal exposure to 3000 or 6000 ppm. n-Butyl Alcohol was not mutagenic in Ames tests, did not induce sister-chromatid exchange or chromosome breakage in chick embryos or Chinese hamster ovary cells, did not induce micronuclei formation in V79 Chinese hamster cells, did not have any chromosome-damaging effects in a mouse micronucleus test, and did not impair chromosome distribution in the course of mitosis. Clinical testing of n-Butyl Alcohol for

Liquid-chromatographic analysis for cyclosporine with use of a microbore column and small sample volume.

Science.gov (United States)

Annesley, T; Matz, K; Balogh, L; Clayton, L; Giacherio, D

1986-07-01

This liquid-chromatographic assay requires 0.2 to 0.5 mL of whole blood, avoids the use of diethyl ether, and consumes only 10 to 20% of the solvents used in prior methods. Sample preparation involves an acidic extraction with methyl-t-butyl ether, performed in a 13 X 100 mm disposable glass tube, then a short second extraction of the organic phase with sodium hydroxide. After evaporation of the methyl-t-butyl ether, chromatography is performed on an "Astec" 2.0-mm (i.d.) octyl column. We compared results by this procedure with those by use of earlier larger-scale extractions and their respective 4.6-mm (i.d.) columns; analytical recoveries of cyclosporins A and D were comparable with previous findings and results for patients' specimens were equivalent, but the microbore columns provided greatly increased resolution and sensitivity.

Thermodynamic properties of 4-tert-butyl-diphenyl oxide

International Nuclear Information System (INIS)

Druzhinina, A.I.; Pimenova, S.M.; Tarazanov, S.V.; Nesterova, T.N.; Varushchenko, R.M.

2015-01-01

Highlights: • The sample of the 4-tert-butyl-diphenyl oxide was synthesized and purified. • Heat capacities, energy of combustion, saturation vapor pressures were measured. • The temperature, the enthalpy and the entropy of fusion were determined. • The enthalpy of sublimation at T = 298.15 K was derived. • The main thermodynamic functions and functions of formation were computed. - Abstract: The main thermodynamic functions (changes of the entropy, enthalpy, and Gibbs free energy) and functions of formation at T = 298.15 K of 4-tert-butyl-diphenyl oxide in condensed and ideal gas states were computed on the basis of experimental results obtained. The heat capacities of 4-tert-butyl-diphenyl oxide was measured by vacuum adiabatic calorimetry over the temperature range (8 to 371) K. The temperature, the enthalpy and the entropy of fusion were determined. The energy of combustion of the sample was determined by static-bomb combustion calorimetry. The saturation vapor pressures of the substance were measured by dynamic transpiration method over the temperature and pressure intervals (298 to 325) K and (0.05 to 1.2) Pa. The enthalpy of sublimation at T = 298.15 K was derived. The contribution of O-(2C b ) group (where C b is the carbon atom in a benzene ring) into the absolute entropies of diphenyl oxide derivatives was assessed

Exogenous ether lipids predominantly target mitochondria

DEFF Research Database (Denmark)

Kuerschner, Lars; Richter, Doris; Hannibal-Bach, Hans Kristian

2012-01-01

Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high......, accumulated to mitochondria and induced morphological changes and cellular apoptosis. These data indicate that edelfosine could exert its pro-apoptotic power by targeting and damaging mitochondria and thereby inducing cellular apoptosis. In general, this study implies an important role of mitochondria...

Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

International Nuclear Information System (INIS)

Silva, V.S.; Ruffmann, B.; Vetter, S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M.; Nunes, S.P.

2006-01-01

Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion[reg] 112 was used as reference material. DMFC tests were also performed at 50 deg. C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion[reg] 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion[reg] 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%

Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

Energy Technology Data Exchange (ETDEWEB)

Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

2011-01-01

Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

Analysis of electron-irradiated poly-ether ether ketone by X-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Oyabu, Matashige; Kobayashi, Yoshinori; Seguchi, Tadao; Sasuga, Tsuneo; Kudoh, Hisaaki.

1995-01-01

Organic polymers used in atomic power plants or space are damaged by ionizing irradiation. Radicals produced by irradiation cause oxidation, chain scission and crosslinking, all of which lead to degradation of the material. In this paper, the surface of electron-irradiated poly-ether ether ketone (PEEK) was studied by X-ray photoelectron spectroscopy (XPS). The irradiation in air was found to oxidize the PEEK surface producing carboxyl groups, the content of which dependant on the dose. Carboxyl groups were not produced in helium gas. Quantitative spectral analysis indicated that the aromatic structure might be decomposed. Some comparison was made between the semicrystalline and amorphous samples. The oxygen content resulting from irradiation, of semicrystalline PEEK increased more than that of amorphous PEEK. (author)

Solvent free lipase catalyzed synthesis of butyl caprylate

Indian Academy of Sciences (India)

MEERA T SOSE

2017-11-10

Nov 10, 2017 ... Department of Chemical Engineering, Institute of Chemical Technology, Matunga (E), ... study for the synthesis of butyl caprylate in presence of bio-catalyst. ..... −1 with Thermomyces lanuginosus lipase.26 The relation.

Application of simplified PC-SAFT to glycol ethers

DEFF Research Database (Denmark)

Avlund, Ane Søgaard; Kontogeorgis, Georgios; Michelsen, Michael Locht

2012-01-01

The simplified PC-SAFT (sPC-SAFT) equation of state is applied for binary glycol ether-containing mixtures, and it is investigated how the results are influenced by inclusion of intramolecular association in the association theory. Three different glycol ethers are examined: 2-methoxyethanol, 2...

Synthetic phenolic antioxidants, including butylated hydroxytoluene (BHT), in resin-based dental sealants

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei; Kannan, Pranav; Xue, Jingchuan [Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, P.O. Box 509, Albany, NY 12201-0509 (United States); Kannan, Kurunthachalam, E-mail: Kurunthachalam.kannan@health.ny.gov [Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, P.O. Box 509, Albany, NY 12201-0509 (United States); Biochemistry Department, Faculty of Science, Experimental Biochemistry Unit, King Fahd Medical Research Center, King Abdulaziz University, Jeddah (Saudi Arabia)

2016-11-15

Resin-based dental sealants (also referred to as pit-and-fissure sealants) have been studied for their contribution to bisphenol A (BPA) exposure in children. Nevertheless, little attention has been paid to the occurrence of other potentially toxic chemicals in dental sealants. In this study, the occurrence of six synthetic phenolic antioxidants (SPAs), including 2,6-di-tert-butyl-4-hydroxytoluene (BHT), 2,6-di-tert-butyl-4-(hydroxyethyl)phenol (BHT-OH), 3,5-di-tert-butyl-4-hydroxy-benzaldehyde (BHT-CHO), 2,6-di-tert-butylcyclohexa-2,5-diene-1,4-dione (BHT-Q), 3,5-di-tert-butyl-4-hydroxybenzoic acid (BHT-COOH) and 2-tert-butyl-4-methoxyphenol (BHA), was examined in 63 dental sealant products purchased from the U.S. market. BHT was found in all dental sealants at median and maximum concentrations of 56.8 and 1020 µg/g, respectively. The metabolites of BHT and BHA were detected in 39–67% of samples, at concentration ranges of butyl-4-hydroxytoluene (BHT) concentration of up to 1020 µg/g was found. • Estimated daily intake of BHT after sealant placement was up to 9.52 µg/kg bw/d. • Daily intake of BHT through dental sealant application was below the acceptable daily intake.

Synthetic phenolic antioxidants, including butylated hydroxytoluene (BHT), in resin-based dental sealants

International Nuclear Information System (INIS)

Wang, Wei; Kannan, Pranav; Xue, Jingchuan; Kannan, Kurunthachalam

2016-01-01

Resin-based dental sealants (also referred to as pit-and-fissure sealants) have been studied for their contribution to bisphenol A (BPA) exposure in children. Nevertheless, little attention has been paid to the occurrence of other potentially toxic chemicals in dental sealants. In this study, the occurrence of six synthetic phenolic antioxidants (SPAs), including 2,6-di-tert-butyl-4-hydroxytoluene (BHT), 2,6-di-tert-butyl-4-(hydroxyethyl)phenol (BHT-OH), 3,5-di-tert-butyl-4-hydroxy-benzaldehyde (BHT-CHO), 2,6-di-tert-butylcyclohexa-2,5-diene-1,4-dione (BHT-Q), 3,5-di-tert-butyl-4-hydroxybenzoic acid (BHT-COOH) and 2-tert-butyl-4-methoxyphenol (BHA), was examined in 63 dental sealant products purchased from the U.S. market. BHT was found in all dental sealants at median and maximum concentrations of 56.8 and 1020 µg/g, respectively. The metabolites of BHT and BHA were detected in 39–67% of samples, at concentration ranges of butyl-4-hydroxytoluene (BHT) concentration of up to 1020 µg/g was found. • Estimated daily intake of BHT after sealant placement was up to 9.52 µg/kg bw/d. • Daily intake of BHT through dental sealant application was below the acceptable daily intake.

High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

Science.gov (United States)

Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

2015-03-01

Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

International Nuclear Information System (INIS)

Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

2014-01-01

Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

Energy Technology Data Exchange (ETDEWEB)

Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang, E-mail: wolfgang.bacsa@cemes.fr [CEMES-CNRS and University of Toulouse, 29 Jeanne Marvig, 31055 Toulouse (France); Boyer, François; Olivier, Philippe [Université de Toulouse, Institut Clément Ader, I.U.T. Université Paul Sabatier - 133C Avenue de Rangueil - B.P. 67701, 31077 Toulouse CEDEX 4 (France); Sapelkin, Andrei [School of Physics and Astronomy, Queen Mary, University of London, Mile End Road, E1 4NS London (United Kingdom); King, Stephen; Heenan, Richard [ISIS Facility, Rutherford Appleton Laboratory, Chilton, OX11 0QX Didcot (United Kingdom); Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri [AIRBUS FRANCE (B.E. M and P Toulouse), 316 Route de Bayonne, 31060 Toulouse (France)

2014-06-21

Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

Agricultural transportation fuels

International Nuclear Information System (INIS)

Anon.

1993-01-01

The recommendations on the title subject are focused on the question whether advantages and disadvantages of agricultural fuels compared to fossil fuels justify the Dutch policy promotion of the use of agricultural products as basic materials for agricultural fuels. Attention is paid to energetic, environmental and economical aspects of both fuel types. Four options to apply agricultural transportation fuels are discussed: (1) 10% bio-ethanol in euro-unleaded gasoline for engines of passenger cars, equipped with a three-way catalyst; (2) the substitution of 15% methyl tertiair butyl ether (MTBE) by ethyl tertiair butyl ether (ETBE) as a substituent for lead in unleaded super plus gasoline (Sp 98) for engines of passenger cars, equipped with a three-way catalyst; (3) 50% KME (rapeseed oil ester) in low-sulfur diesel (0.05%S D) for engines of vans without a catalyst; and (4) the substitution of 0.05% S D by bio-ethanol or KME for buses with fuel-adjusted engines, equipped with a catalyst. Also the substitution by liquefied petroleum gas (LPG), compressed natural gas (CNG) or E 95 was investigated in option four. Each of the options investigated can contribute to a reduction of the use of fossil energy and the environmental effects of the use of fossil fuels, although some environmental effects from agricultural fuels must be taken into consideration. It is recommended to seriously pay attention to the promotion of agricultural fuels, not only in the Netherlands, but also in an international context. Policy instruments to be used in the stimulation of the use of such fuels are the existing European Community subsidies on fallow lands, exemption of the European Community energy levy, and the use of tax differentiation. Large-scale demonstration projects must be started to quantify hazardous emissions and to solve still existing technical problems. 8 figs., 3 tabs., refs., 4 appendices

Diethyl Ether Production as a Substitute for Gasoline

Directory of Open Access Journals (Sweden)

Alviany Riza

2018-01-01

Full Text Available Diethyl ether is one of alternative fuel that could be used as a significant component of a blend or as a complete replacement for transportation fuel. The aim of this research is to produce diethyl ether through dehydration reaction of ethanol with fixed bed reactor using nanocrystalline γ-Al2O3 catalyst. Nanocrystalline γ-Al2O3 catalyst was synthesized by precipitation method using Al(NO33.9H2O as precursors and NH4OH as the precipitating agent. Dehydration reaction was performed at temperature range of 125 to 225°C. The result shows that synthesized γ-Al2O3 catalyst gave higher ethanol conversion and diethyl ether yield than that of commercial Al2O3 catalyst. The use of synthesized γ-Al2O3 catalyst could reach ethanol conversion as high as 94.71% and diethyl ether yield as high as 11,29%.

Allied, MGC link on cyanate esters

International Nuclear Information System (INIS)

Wood, A.

1993-01-01

In the latest of a line of joint ventures in its plastics business, Allied Signal has reached agreement with Mitsubishi Gas Chemical (MGC) to jointly develop thermoset cyanate ester resins and blends. The deal will involve further development of Allied Signal's Primaset phenol-formaldehyde cyanate ester resins, a new entrant in the thermoset arena. Although the Primaset resins were discovered in the 1960s, this would be the first time they are available commercially. The deal will marry Primaset technology with MGC's Skylex bisphenol A cyanate ester resins, says Fred DiAntonis, director/advanced materials at Allied Signal. The two firms are looking at marketing blends of the two materials. The potential market for these resins, used commercially by the electronics industry in printed circuit boards and by the aerospace industry in composites, is significant, says Robert P. Viarengo, Allied Signal president/performance materials. By aligning ourselves with MGC, the world leader in cyanate ester resin, we anticipate moving forward aggressively. The main competitor is Ciba, which acquired bisphenol A cyanate ester resins with its purchase of Rhone-Poulenc's high temperature resins business. DiAntonis estimates the market for cyanate ester resins could be worth $150 million by the end of the decade, although development costs have been in the tens of millions of dollars range

40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

Science.gov (United States)

2010-07-01

... Neopentyl glycol (dimethylpropane) 126-30-7 Niacinamide 98-92-0 o-Nitroaniline 88-74-4 Nitroglycerin 55-63-0... Diethanolamine 111-42-2 N,N-Diethylaniline 91-66-7 Diethylene glycol 111-46-6 Diethylene glycol dimethyl ether (dimethyl Carbitol) 111-96-6 Diethylene glycol monobutyl ether (butyl Carbitol) 112-34-5 Diethylene glycol...

Synthesis of a new energetic nitrate ester

Energy Technology Data Exchange (ETDEWEB)

Chavez, David E [Los Alamos National Laboratory

2008-01-01

Nitrate esters have been known as useful energetic materials since the discovery of nitroglycerin by Ascanio Sobrero in 1846. The development of methods to increase the safety and utility of nitroglycerin by Alfred Nobel led to the revolutionary improvement in the utility of nitroglycerin in explosive applications in the form of dynamite. Since then, many nitrate esters have been prepared and incorporated into military applications such as double-based propellants, detonators and as energetic plasticizers. Nitrate esters have also been shown to have vasodilatory effects in humans and thus have been studied and used for treatments of ailments such as angina. The mechanism of the biological response towards nitrate esters has been elucidated recently. Interestingly, many of the nitrate esters used for military purposes are liquids (ethylene glycol dinitrate, propylene glycol dinitrate, etc). Pentaerythritol tetranitrate (PETN) is one of the only solid nitrate esters, besides nitrocellulose, that is used in any application. Unfortunately, PETN melting point is above 100 {sup o}C, and thus must be pressed as a solid for detonator applications. A more practical material would be a melt-castable explosive, for potential simplification of manufacturing processes. Herein we describe the synthesis of a new energetic nitrate ester (1) that is a solid at ambient temperatures, has a melting point of 85-86 {sup o}C and has the highest density of any known nitrate ester composed only of carbon, hydrogen, nitrogen and oxygen. We also describe the chemical, thermal and sensitivity properties of 1 as well as some preliminary explosive performance data.

Degradation of methyl-tert-butyl ether (MTBE)

Czech Academy of Sciences Publication Activity Database

Cajthaml, Tomáš; Baldrian, Petr; Stoychev, I.; Nerud, František

2004-01-01

Roč. 53, - (2004), s. 208-209 ISSN 0964-8305. [International Bideterioration and Biodegradation Symposium /12./. Praha, 14.07.2002-18.07.2002] R&D Projects: GA MŠk LN00B030 Institutional research plan: CEZ:AV0Z5020903 Keywords : mtbe Subject RIV: EE - Microbiology, Virology Impact factor: 0.835, year: 2004

A highly sensitive and selective dimethyl ether sensor based on cataluminescence.

Science.gov (United States)

Zhang, Runkun; Cao, Xiaoan; Liu, Yonghui; Peng, Yan

2010-07-15

A sensor for detecting dimethyl ether was designed based on the cataluminescence phenomenon when dimethyl ether vapors were passing through the surface of the ceramic heater. The proposed sensor showed high sensitivity and selectivity to dimethyl ether at an optimal temperature of 279 degrees C. Quantitative analysis were performed at a wavelength of 425 nm, the flow rate of carrier air is around 300 mL/min. The linear range of the cataluminescence intensity versus concentration of dimethyl ether is 100-6.0x10(3) ppm with a detection limit of 80 ppm. The sensor response time is 2.5 s. Under the optimized conditions, none or only very low levels of interference were observed while the foreign substances such as benzene, formaldehyde, ammonia, methanol, ethanol, acetaldehyde, acetic acid, acrolein, isopropyl ether, ethyl acetate, glycol ether and 2-methoxyethanol were passing through the sensor. Since the sensor does not need to prepare and fix up the granular catalyst, the simple technology reduces cost, improves stability and extends life span. The method can be applied to facilitate detection of dimethyl ether in the air. The possible mechanism of cataluminescence from the oxidation of dimethyl ether on the surface of ceramic heater was discussed based on the reaction products. Copyright 2010 Elsevier B.V. All rights reserved.

Crosslinked superhydrophobic films fabricated by simply casting poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-poly(perfluorohexylethyl methacrylate) solution

Science.gov (United States)

Wen, Xiufang; Ye, Chao; Cai, Zhiqi; Xu, Shouping; Pi, Pihui; Cheng, Jiang; Zhang, Lijuan; Qian, Yu

2015-06-01

This study focuses on the preparation of superhydrophobic films by crosslinkable polymer material-Poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-Poly(perfluorohexylethyl methacrylate) (P (MMA-BA-HEMA)-b-PFMA) with a simple one-step casting process. Nanoscale micelle particles with core-shell structure was obtained by dissolving the polymer and curing agent in the mixture of acetone and 1H, 1H, 5H octafluoropentyl-1,1,2,2 tetrafluoroethyl ether (FHT). Superhydrophobic films were fabricated by casting the micelle solution on the glass slides. By controlling the polymer concentration and acetone/FHT volume ratio, superhydrophobic polymer film with water contact angle of 153.2 ± 2.1° and sliding angle of 4° was obtained. By introducing a curing agent into the micelle solution, mechanical properties of the films can be improved. The adhension grade and hardness of the crosslinked superhydrophobic films reached 2 grade and 3H, respectively. The hydrophobicity is attributed to the synergistic effect of micro-submicro-nano-meter scale roughness by nanoscale micelle particles and low surface energy of fluoropolymer. This procedure makes it possible for widespread applications of superhydrophobic film due to its simplicity and practicability.

Unitary information ether and its possible applications

International Nuclear Information System (INIS)

Horodecki, R.

1991-01-01

The idea of information ether as the unitary information field is developed. It rests on the assumption that the notion of information is a fundamental category in the description of reality and that it can be defined independently from the notion of probability itself. It is shown that the information ether provides a deterministic background for the nonlinear wave hypothesis and quantum cybernetics. (orig.)

The Ether Wind and the Global Positioning System.

Science.gov (United States)

Muller, Rainer

2000-01-01

Explains how students can perform a refutation of the ether theory using information from the Global Positioning System (GPS). Discusses the functioning of the GPS, qualitatively describes how position determination would be affected by an ether wind, and illustrates the pertinent ideas with a simple quantitative model. (WRM)

The breakdown of vinyl ethers as a two-center synchronous reaction

Science.gov (United States)

Pokidova, T. S.; Shestakov, A. F.

2009-11-01

The experimental data on the molecular decomposition of vinyl ethers of various structures to alkanes and the corresponding aldehydes or ketones in the gas phase were analyzed using the method of intersecting parabolas. The enthalpies and kinetic parameters of decomposition were calculated for 17 reactions. The breakdown of ethers is a two-center concerted reaction characterized by a very high classical potential barrier to the thermally neutral reaction (180-190 kJ/mol). The kinetic parameters (activation energies and rate constants) of back reactions of the formation of vinyl ethers in the addition of aldehydes or ketones to alkanes were calculated using the method of intersecting parabolas. The factors that influenced the activation energy of the decomposition and formation of ethers were discussed. Quantum-chemical calculations of several vinyl ether decomposition reactions were performed. Ether formation reactions were compared with the formation of unsaturated alcohols as competitive reactions, which can occur in the interaction of carbonyl compounds with alkenes.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

The ester, butyl caprylate has wide applications in commercial market and it also possesses characteristic fruity flavor. The work exhibits the effect of various reaction parameters and the optimization study for the synthesis of butyl caprylate in presence of bio-catalyst. To achieve maximum conversion theoptimum parameters ...

Total Costs and Benefits of Biomass in Selected regions of the European Union

DEFF Research Database (Denmark)

Almeida, A. de; Bauen, A.; Costa, F.B.

1998-01-01

biomass for combined heat and power generation in Vaernamo, Sweden, and Eggborough, UK, versus the use of coal in the Naessjoe plant mentioned above and a UK power plant;- production of cold-pressed rape-seed oil and its use in a cogeneration plant at Weissenburg, Germany, versus the use of diesel fuel...... and power production in Mangualde, Portugal, versus the use of fuel oil in an engine generating heat and power;- production of biogas from animal slurry for municipal combined heat an power generation at Hashoej, Denmark, versus the use fo Danish natural gas in the same engine;- gasification of woody...... in a similar engine;- production of rape-seed oil methyl ester (RME) and its use for goods transport in Germay, versus the use of diesel fuel in the same fleet of trucks;- production of ethyl tertiary butyl ether (ETBE) from sugar beets and sweet sorghum for transport applications in France, versus the use...

A fast isocratic liquid chromatography method for the quantification of xanthophylls and their stereoisomers.

Science.gov (United States)

Nimalaratne, Chamila; Lopes-Lutz, Daise; Schieber, Andreas; Wu, Jianping

2015-12-01

A fast isocratic liquid chromatography method was developed for the simultaneous quantification of eight xanthophylls (13-Z-lutein, 13'-Z-lutein, 13-Z-zeaxanthin, all-E-lutein, all-E-zeaxanthin, all-E-canthaxanthin, all-E-β-apo-8'-carotenoic acid ethyl ester and all-E-β-apo-8'-carotenal) within 12 min, compared to 90 min by the conventional high-performance liquid chromatography method. The separation was achieved on a YMC C30 reversed-phase column (100 mm x 2.0 mm; 3 μm) operated at 20°C using a methanol/tert-butyl methyl ether/water solvent system at a flow rate of 0.8 mL/min. The method was successfully applied to quantify lutein and zeaxanthin stereoisomers in egg yolk, raw and cooked spinach, and a dietary supplement. The method can be used for the rapid analysis of xanthophyll isomers in different food products and for quality control purposes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Double-Balloon-Assisted n-Butyl-2-Cyanoacrylate Embolization of Intrahepatic Arterioportal Shunt Prior to Chemoembolization of Hepatocellular Carcinoma

Energy Technology Data Exchange (ETDEWEB)

Takao, Hidemasa, E-mail: takaoh-tky@umin.ac.jp; Shibata, Eisuke; Ohtomo, Kuni [University of Tokyo, Department of Radiology, Graduate School of Medicine (Japan)

2016-10-15

A case of multiple hepatocellular carcinomas with a severe intrahepatic arterioportal shunt that was successfully embolized with n-butyl-2-cyanoacrylate with coaxial double-balloon occlusion prior to transcatheter arterial chemoembolization is presented. A proximal balloon positioned at the proper hepatic artery was used for flow control, and a coaxial microballoon, positioned in the closest of three arterial feeding branches to the arterioportal shunt, was used to control the delivery of n-butyl-2-cyanoacrylate. This coaxial double-balloon technique can prevent proximal embolization and distal migration of n-butyl-2-cyanoacrylate and enable precise control of the distribution of n-butyl-2-cyanoacrylate. It could also be applicable to n-butyl-2-cyanoacrylate embolization for other than intrahepatic arterioportal shunt.

Stereosequence distributions of poly(t-butyl methacrylate)s prepared with butyllithium

International Nuclear Information System (INIS)

Suzuki, Toshimitsu; Yamada, Osamu; Watanabe, Yoshihisa; Takegami, Yoshinobu

1982-01-01

13 C NMR spectra of poly(t-butyl methacrylate)s (PBMA) prepared with butyl-lithium (n-BuLi) were studied. Methylene carbon resonances appeared as five overlapped peaks, which were interpreted as a combination of hexad stereosequence distributions. The stereosequence distribution of PBMA prepared with n-BuLi at -78 0 C obeyed the first order Markov chain model even polymerized in tetrahydrofuran (THF). Syndiotactic PBMA was obtained with azobisisobutyronitrile (AIBN) as the initiator, and the stereosequence distribution of this polymer agreed well with Bernoullian statistics. (author)

Fast liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their derivatives in canned food and beverages.

Science.gov (United States)

Gallart-Ayala, H; Moyano, E; Galceran, M T

2011-03-25

In this work a fast liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method using a C18 Fused Core™ column, was developed for the simultaneous analysis of bisphenol A diglycidyl ether (BADGE), bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE·H(2)O), bisphenol A bis(2,3-dihydroxypropyl) ether (BADGE·2H(2)O), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE·HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE·2HCl) and bisphenol A (3-chloro-2-hydroxypropyl)(2,3-dihydroxypropyl ether) (BADGE·HCl·H(2)O) and bisphenol F diglycidyl ether (BFDGE), bisphenol F bis(2,3-dihydroxypropyl) ether (BFDGE·2H(2)O), bisphenol F bis(3-chloro-2-hydroxypropyl) ether (BFDGE·2HCl). The LC method was coupled with a triple quadrupole mass spectrometer, using an ESI source in positive mode and using the [M+NH(4)](+) adduct as precursor ion for tandem mass spectrometry experiments. The method developed was applied to the determination of these compounds in canned soft drinks and canned food. OASIS HLB solid phase extraction (SPE) cartridges were used for the analysis of soft drinks, while solid canned food was extracted with ethyl acetate. Method limits of quantitation ranged from 0.13 μgL(-1) to 1.6 μgL(-1) in soft drinks and 1.0 μgkg(-1) to 4.0 μgkg(-1) in food samples. BADGE·2H(2)O was detected in all the analyzed samples, while other BADGEs such as BADGE·H(2)O, BADGE·HCl·H(2)O, BADGE·HCl and BADGE·2HCl were also detected in canned foods. Copyright © 2011 Elsevier B.V. All rights reserved.

Technetium and rhenium tracers with metabolizable ester functions

International Nuclear Information System (INIS)

Syhre, R.; Seifert, S.; Schneider, F.; Pietzsch, H.J.; Spies, H.; Johannsen, B.

1993-01-01

Re-DMSA (dimercaptosuccinic acid) ester complexes were prepored by ligand exchange reactions. To determine whether the ester band in Re-DMSA ester complexes is susceptible to cleavage by esterases, incubation experiments with tissue homogenates and plasma were carried out. (BBR)

27 CFR 21.101 - tert-Butyl alcohol.

Science.gov (United States)

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false tert-Butyl alcohol. 21.101 Section 21.101 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS FORMULAS FOR DENATURED ALCOHOL AND RUM Specifications for Denaturants § 21...

27 CFR 21.100 - n-Butyl alcohol.

Science.gov (United States)

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false n-Butyl alcohol. 21.100 Section 21.100 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS FORMULAS FOR DENATURED ALCOHOL AND RUM Specifications for Denaturants § 21...

Effect of p-amino-diphenyl ethers on hepatic microsomal cytochrome P450.

Science.gov (United States)

Jiang, Huidi; Xuan, Guida

2003-09-01

The present paper aims to investigate whether p-amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether are inhibitors as well as inducers of P450. Mice were given daily intraperitoneal (ip) injections of p-amino-2',4'-dichlorodiphenyl ether (0.25 mmol/kg) or p-amino-4'-methyldiphenyl ether (0.25 mmol/kg) for 4 days and tested at 24 h and 48 h after the last dose injection. The results showed the mice pentobarbital sleeping time was shorter and the P450 content of hepatic microsome increased significantly in the group pretreated with p-amino-4'-methyldiphenyl ether when compared with the control group, while in mice pretreated with p-amino-2',4'-dichlorodiphenyl ether the hepatic microsome P450 content increased but the pentobarbital sleeping time was extended in clear contrast to the control group. The sleeping time of the phenobarbital group (80 mg/kg daily ip injection for 4 days) was shortened at 24 h after the last injection with increased P450 content of hepatic microsome, but it showed no difference at 48 h. The zoxazolamine-paralysis times of mice treated with p-amino-2',4'-dichlorodiphenyl ether were longer than those of the control mice, while the same dose of zoxazolamine did not lead to paralysis in mice pretreated with BNF. p-Amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether inhibited the activity of 7-ethoxyresorufin O-deethylase from rat hepatic microsome induced by BNF in vitro by 70.0% and 50.1% respectively. These results suggest that p-amino-2',4'-dichlorodiphenyl ether and p-amino-4'-methyldiphenyl ether are inhibitors as well as inducers of P450.

(Liquid + liquid) equilibria of binary systems containing hyperbranched polymer Boltorn (registered) H2004 - Experimental study and modelling in terms of lattice-cluster theory

International Nuclear Information System (INIS)

Domanska, Urszula; Paduszynski, Kamil; Zolek-Tryznowska, Zuzanna

2011-01-01

(Liquid + liquid) phase equilibria (LLE) of binary mixtures containing hyperbranched polymer Boltorn (registered) H2004 and n-alkanes (n-hexane, n-heptane, n-octane, and n-decane) were studied over the temperature range from about (260 up to 360) K. The polymer is partially miscible with n-alkanes and the solubility decreases with an increase of the chain length of the solvent. Corresponding LLE phase diagrams including spinodal and binodal (liquid + liquid) coexistence curves were calculated in terms of the statistical mechanics - based on the lattice-cluster theory, based only on the upper critical solution temperature, and the polymer chain architecture. The results show semi-qualitative agreement of predicted and experimental equilibrium compositions and temperatures. Boltorn (registered) H2004 reveals complete miscibility in the liquid phase with alcohols (C 1 -C 8 ), aromatic hydrocarbons (benzene, toluene, and thiophene), and ethers (methyl tetra-butyl ether, ethyl tetra-butyl ether, and tetrahydrofurane).

21 CFR 172.854 - Polyglycerol esters of fatty acids.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyglycerol esters of fatty acids. 172.854 Section... HUMAN CONSUMPTION Multipurpose Additives § 172.854 Polyglycerol esters of fatty acids. Polyglycerol esters of fatty acids, up to and including the decaglycerol esters, may be safely used in food in...

Stability of a metabolizable ester bond in radioimmunoconjugates

International Nuclear Information System (INIS)

Arano, Yasushi; Wakisaka, Kouji; Mukai, Takahiro; Uezono, Takashi; Motonari, Hiroshi; Akizawa, Hiromichi; Kairiyama, Claudia; Ohmomo, Yoshiro; Tanaka, Chiaki; Ishiyama, Munetaka; Sakahara, Harumi; Konishi, Junji; Yokoyama, Akira

1996-01-01

Ester bonds have been used as metabolizable linkages to reduce radioactivity levels in non-target tissues following the administration of antibodies labeled with metallic radionuclides. In this radiochemical design of antibodies, while the ester bonds should be cleaved rapidly in non-target tissues, high stability of the ester bonds in plasma is also required to preserve target radioactivity levels. To assess the structural requirements to stabilize the ester bond, a new benzyl-EDTA-derived bifunctional chelating agent with an ester bond, (1-[4-[4-(2-maleimidoethoxy)succinamido]benzyl]ethylenediamine-N,N,N',N'- tetraacetic acid; MESS-Bz-EDTA), was developed. MESS-Bz-EDTA was coupled with a thiolated monoclonal antibody (OST7, IgG 1 ) prepared by reducing its disulfide bonds to introduce the ester bond close and proximal to the antibody molecule. For comparison, 1-[4-(5-maleimidopentyl)aminobenzyl]ethylenediamine-N,N,N',N'-tetraacetic acid (EMCS-Bz-EDTA) and meleimidoethyl 3-[ 131 I]iodohippurate (MIH) was coupled to OST7 under the same conjunction chemistry. When incubated in 50% murine plasma or a buffered-solution of neutral pH, OST7-MESS-Bz-EDTA- 111 In rapidly released the radioactivity, and more than 95% of the initial radioactivity was liberated after a 24 h incubation in both solutions, due to a cleavage of the ester bond. On the other hand, only about 20% of the radioactivity was released from OST7-MIH- 131 I in both solutions during the same incubation period. In mice biodistribution studies, while a slightly faster radioactivity clearance from the blood with less radioactivity levels in the liver and kidneys was observed with OST7-MIH- 131 I than with OST7-EMCS-Bz-EDTA- 111 In, OST7-MESS-Bz-EDTA- 111 In indicated radioactivity clearance from the blood much faster than and almost comparable to that of OST7-MIH- 131 I and succinamidobenzyl-EDTA- 111 In, respectively. These findings as well as previous findings on radiolabeled antibodies with ester bonds

rett produc Congo ted cas ced in to: Nsam ssava two tra m

African Journals Online (AJOL)

sunny

2-Nonanone. 1.0451. Linalol GIVAUDAN. 2.4808. CIS-ROSE OXIDE. 0.5274. Ocimene « Neo-allo ». 0.7592. Camphor. 0.5182. 2-Methyl butyl angelate. 0.2858. Menthone. 2.4612. Iso-menthone. 1.1662. Terpinene-4-ol. 1.1721. Methyl salicylate. 0.7165. Estragol. 33.8179. Methyl thymol ether. 0.7945. Methyl carvacrol ether.

Polymerization behavior of butyl bis(hydroxymethyl)phosphine oxide ...

Indian Academy of Sciences (India)

lenovo

Polymerization behavior of butyl bis(hydroxymethyl)phosphine oxide: Phosphorus containing polyethers for. Li‒ion conductivities. Heeralal Vignesh Babu, Billakanti Srinivas and Krishnamurthi Muralidharan*. School of Chemistry, University of Hyderabad, Hyderabad - 500046, India. Table of Contents. TGA plots of SPE2.

Health assessment of gasoline and fuel oxygenate vapors: reproductive toxicity assessment.

Science.gov (United States)

Gray, Thomas M; Steup, David; Roberts, Linda G; O'Callaghan, James P; Hoffman, Gary; Schreiner, Ceinwen A; Clark, Charles R

2014-11-01

Vapor condensates of baseline gasoline (BGVC), or gasoline-blended with methyl tertiary 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 reproductive toxicity in rats at target concentrations of 2000, 10,000, or 20,000mg/m(3), 6h/day, 7days/week. BGVC and G/MTBE were assessed over two generations, the others for one generation. BGVC and G/MTBE F1 offspring were evaluated for neuropathology and changes in regional brain glial fibrillary acidic protein content. No neurotoxicity was observed. Male kidney weight was increased consistent with light hydrocarbon nephropathy. In adult rats, decreased body weight gain and increased liver weight were seen. Spleen weight decreased in adults and pups exposed to G/TBA. No pathological changes to reproductive organs occurred in any study. Decreased food consumption was seen in G/TAME lactating females. Transient decreases in G/TAME offspring weights were observed during lactation. Except for a minor increase in time to mating in G/TBA which did not affect other reproductive parameters, there were no adverse reproductive findings. The NOAEL for reproductive and offspring parameters was 20,000mg/m(3) for all vapor condensates except for lower offspring NOAELs of 10,000mg/m(3) for G/TBA and 2000mg/m(3) for G/TAME. Copyright © 2014 Elsevier Inc. All rights reserved.

Health assessment of gasoline and fuel oxygenate vapors: micronucleus and sister chromatid exchange evaluations.

Science.gov (United States)

Schreiner, Ceinwen A; Hoffman, Gary M; Gudi, Ramadevi; Clark, Charles R

2014-11-01

Micronucleus and sister chromatid exchange (SCE) tests were performed for vapor condensate of baseline gasoline (BGVC), or gasoline with oxygenates, methyl tert-butyl ether (G/MTBE), ethyl tert butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), t-butyl alcohol (TBA), or ethanol (G/EtOH). Sprague Dawley rats (the same 5/sex/group for both endpoints) were exposed to 0, 2000, 10,000, or 20,000mg/m(3) of each condensate, 6h/day, 5days/week over 4weeks. Positive controls (5/sex/test) were given cyclophosphamide IP, 24h prior to sacrifice at 5mg/kg (SCE test) and 40mg/kg (micronucleus test). Blood was collected from the abdominal aorta for the SCE test and femurs removed for the micronucleus test. Blood cell cultures were treated with 5μg/ml bromodeoxyuridine (BrdU) for SCE evaluation. No significant increases in micronucleated immature erythrocytes were observed for any test material. Statistically significant increases in SCE were observed in rats given BGVC alone or in female rats given G/MTBE. G/TAME induced increased SCE in both sexes at the highest dose only. Although DNA perturbation was observed for several samples, DNA damage was not expressed as increased micronuclei in bone marrow cells. Inclusion of oxygenates in gasoline did not increase the effects of gasoline alone or produce a cytogenetic hazard. Copyright © 2014 Elsevier Inc. All rights reserved.

Health assessment of gasoline and fuel oxygenate vapors: subchronic inhalation toxicity.

Science.gov (United States)

Clark, Charles R; Schreiner, Ceinwen A; Parker, Craig M; Gray, Thomas M; Hoffman, Gary M

2014-11-01

Sprague Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess whether their use in gasoline influences the hazard of evaporative emissions. Test substances included vapor condensates prepared from an EPA described "baseline gasoline" (BGVC), or gasoline combined with methyl tertiary 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). Target concentrations were 0, 2000, 10,000 or 20,000mg/m(3) and exposures were for 6h/day, 5days/week for 13weeks. A portion of the animals were maintained for a four week recovery period to determine the reversibility of potential adverse effects. Increased kidney weight and light hydrocarbon nephropathy (LHN) were observed in treated male rats in all studies which were reversible or nearly reversible after 4weeks recovery. LHN is unique to male rats and is not relevant to human toxicity. The no observed effect level (NOAEL) in all studies was 10,000mg/m(3), except for G/MTBE (<2000) and G/TBA (2000). The results provide evidence that use of the studied oxygenates are unlikely to increase the hazard of evaporative emissions during refueling, compared to those from gasoline alone. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Measurements of activity coefficients at infinite dilution for organic solutes and water in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide

International Nuclear Information System (INIS)

Domańska, Urszula; Lukoshko, Elena Vadimovna

2013-01-01

Highlights: • Measurements of activity coefficients at infinite dilution using GLC. • 62 organic solvents and water in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide. • High capacity for thiophene, 1.37 at T = 328.15 K. • Possible entrainer for extraction of sulfur, or nitrogen compounds from fuels. • The excess thermodynamic functions and the gas–liquid partition coefficients were calculated. -- Abstract: The activity coefficients at infinite dilution, γ 13 ∞ , for 62 solutes, including alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, water, thiophene, ethers, ketones, acetonitrile, pyridine and 1-nitropropane in the ionic liquid 1-butyl-1-methylpyrrolidinium tricyanomethanide, [BMPYR][TCM] were determined by gas–liquid chromatography at six temperatures over the range of (318.15 to 368.15) K. The partial molar excess Gibbs free energy, ΔG 1 E ∞, enthalpy ΔH 1 E ∞, and entropy term T ref ΔS 1 E ,∞ at infinite dilution were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The densities of [BMPYR][TCM] were measured within temperature range from 318.15 K to 368.15 K. The gas–liquid partition coefficients, K L were calculated for all solutes. The values of selectivity for few separation problems as hexane/benzene, cyclohexane/benzene, heptane/thiophene were calculated from γ 13 ∞ and compared to literature values for N-methyl-2-pyrrolidinone (NMP), sulfolane, and other ionic liquids based on [BMPYR] + cation. In comparison with the former measured ILs, [BMPYR][TCM] present quite high selectivity for the separation of aromatic hydrocarbons and aliphatics hydrocarbons, an average capacity for benzene. The data presented here shows that [BMPYR][TCM] ionic liquid can be used as an alternative solvent for the separation of thiophene from the aliphatic hydrocarbons

Poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers with Various Molecular Weights as Phase Change Materials

Directory of Open Access Journals (Sweden)

Dongfang Pei

2018-02-01

Full Text Available At present, research on the relationship of comb-like polymer phase change material structures and their heat storage performance is scarce. Therefore, this relationship from both micro and macro perspectives will be studied in this paper. In order to achieve a high phase change enthalpy, ethylene glycol segments were introduced between the vinyl and the alkyl side chains. A series of poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers (PC14EnVEs (n = 1, 2 with various molecular weights were polymerized by living cationic polymerization. The results of PC14E1VE and PC14E2VE showed that the minimum number of carbon atoms required for side-chain crystallization were 7.7 and 7.2, which were lower than that reported in the literature. The phase change enthalpy 89 J/g (for poly(mono ethylene glycol n-tetradecyl ether vinyl ethers and 86 J/g (for poly(hexadecyl acrylate were approximately equal. With the increase of molecular weight, the melting temperature, the melting enthalpy, and the initial thermal decomposition temperature of PC14E1VE changed from 27.0 to 28.0 °C, from 95 to 89 J/g, and from 264 to 287 °C, respectively. When the number average molar mass of PC14EnVEs exceeded 20,000, the enthalpy values remained basically unchanged. The introduction of the ethylene glycol chain was conducive to the crystallization of alkyl side chains.

Phytochemical composition and effects of commercial enzymes on the hydrolysis of gallic acid glycosides in mango (Mangifera indica L. cv. 'Keitt') pulp.

Science.gov (United States)

Krenek, Kimberly A; Barnes, Ryan C; Talcott, Stephen T

2014-10-01

A detailed characterization of mango pulp polyphenols and other minor phytochemicals was accomplished for the first time in the cultivar 'Keitt' whereby the identification and semiquantification of five hydroxybenzoic acids, four cinnamic acids, two flavonoids, and six apocarotenoids was accomplished. Among the most abundant compounds were two monogalloyl glucosides (MGG) identified as having an ester- or ether-linked glucose, with the ester-linked moiety present in the highest concentration among nontannin polyphenolics. Additionally, the impact of side activities of three commercial cell-wall degrading enzymes during 'Keitt' mango pulp processing was evaluated to determine their role on the hydrolysis of ester- and ether-linked phenolic acids. The use of Crystalzyme 200XL reduced the concentration of ester-linked MGG by 66%, and the use of Rapidase AR 2000 and Validase TRL completely hydrolyzed ether-linked MGG after 4 h of treatment at 50 °C. Fruit quality, in vivo absorption rate, and bioactivity of mango phytochemicals rely on their chemical characterization, and characterizing changes in composition is critical for a complete understanding of in vivo mechanisms.

Sulfonated polyphenyl ether by electropolymerization

International Nuclear Information System (INIS)

Hou Hongying; Vacandio, Florence; Di Vona, Maria Luisa; Knauth, Philippe

2012-01-01

Highlights: ► Sulfonated polyphenyl ether was for the first time electropolymerized. ► This technique allows the economical preparation of ionomeric membranes for electrochemical energy technologies. ► The mechanism of electropolymerization was discussed in detail. - Abstract: Electropolymerization of sulfonated phenol was for the first time achieved and studied by cyclic voltammetry (CV) and chronoamperometry on stainless steel substrates. The obtained sulfonated polyphenyl ether was characterized in terms of impedance spectroscopy, nuclear magnetic resonance (NMR), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and Fourier-Transform Infrared (FTIR) spectroscopy. Dense films of micrometer thickness can be obtained; the proton conductivity is about 3 mS/cm at room temperature.

Diethyl Ether Production Process with Various Catalyst Type

Directory of Open Access Journals (Sweden)

Widayat Widayat

2012-12-01

Full Text Available Several H-zeolite and HZSM-5 catalysts was preparated and their characters have also been investigated. H-zeolit Catalyst was preparated from Natural Zeolite that obtained from Malang District and Gunung Kidul District. Diethyl ether was produced by Ethanol with concentration of 95%. This research use fixed bed reactor that 1 gram of catalyst as bed catalyst, atmospheric pressure and temperature 140oC as the operating condition. Ethanol vapor from vaporization tank was driven by 200 ml/min Nitrogen stream. The responds in this research is liquid product concentration; diethyl ether, ethanol, methanol and water concentration. The results showed that the largest ethanol conversion was produced by the use of 56.44% HZSM-5 and the largest yield of diethyl ether diethyl was produced by the use of alumina and H-zeolite catalyst. The larger ratio between natural zeolite with HCl solvent will produce the larger surface area of catalyst and ethanol conversion. The largest ethanol conversion was produced at reactan ratio 1:20. [Keywords:  catalyst; ethanol conversion; dehydration process; yield of diethyl ether; natural zeolite].

Estereótipos e mulheres na cultura marroquina

OpenAIRE

Sadiqi,Fatima

2008-01-01

Estereótipos sobre as mulheres no Marrocos podem ser caracterizados como crenças culturais incompletas e inexatas mantidas por algumas pessoas e que se encontram inscritos em expressões lingüísticas ou em discursos subliminares. A cultura popular marroquina emprega representações poderosas para transmitir e sustentar tais estereótipos. Embora existam alguns estereótipos positivos, a maioria dos estereótipos sobre as mulheres no Marrocos é negativa e reflete ditames patriarcais subliminares qu...

1-Butyl-3-methylimidazolium hydrogen sulfate catalyzed in-situ transesterification of Nannochloropsis to fatty acid methyl esters

International Nuclear Information System (INIS)

Sun, Yingqiang; Cooke, Peter; Reddy, Harvind K.; Muppaneni, Tapaswy; Wang, Jun; Zeng, Zheling; Deng, Shuguang

2017-01-01

Highlights: • [Bmim][HSO_4] catalyzed in-situ transesterification of wet algae. • [Bmim][HSO_4] served as both effective solvent and excellent acid catalyst. • Proposed a mechanism for [Bmim][HSO_4] catalyzed in-situ transesterification. • Identified cell walls and lipid droplets in algae using confocal imaging tests. • Obtained crude biodiesel yield about 95% in 30 min at 200 °C. - Abstract: 1-Butyl-3-methylimidazolium hydrogen sulfate ([Bmim][HSO_4]) is used as a solvent and an acid catalyst for in-situ extractive transesterification of wet Nannochloropsis with methanol. The reaction is supposed to be a five-step process: (1) wet algae cell wall dissolves in ionic liquid at reaction temperatures; (2) hydrogen ions and sulfate ions release from the ionization of HSO_4"−. The hydrogen ions (H"+) act as catalysts for accelerating the reactive extraction of triglyceride from wet Nannochloropsis; (3) hydrogen ions and methanol molecules transfer from bulk to active site of cells without passing through cell wall that is dissolved by ionic liquid; (4) in-situ transesterification of lipid (mainly triglycerides) with methanol; and (5) products transfer from inside of algae cells to outside of cells. The crude biodiesel yield of [Bmim][HSO_4] catalyzed in-situ transesterification is about 95.28% at reaction temperature of 200 °C, reaction time of 30 min, mass ratio of [Bmim][HSO_4] to wet Nannochloropsis of 0.9:1, and a mass ratio of methanol to wet algae of 3:1. It decreases to 81.23% after [Bmim][HSO_4] is recycled for 4 times, which indicates that [Bmim][HSO_4] catalyzed in-situ transesterification is an economic approach for biodiesel production from wet algae.

Methyl esters from vegetable oils with hydroxy fatty acids: Comparison of lesquerella and castor methyl esters

Science.gov (United States)

The search for alternative feedstocks for biodiesel as partial replacement for petrodiesel has recently extended to castor oil. In this work, the castor oil methyl esters were prepared and their properties determined in comparison to the methyl esters of lesquerella oil, which in turn is seen as alt...

Subchronic toxicity studies of t-butyl alcohol in rats and mice.

Science.gov (United States)

Lindamood, C; Farnell, D R; Giles, H D; Prejean, J D; Collins, J J; Takahashi, K; Maronpot, R R

1992-07-01

The purpose of this study was to evaluate the toxicity of t-butyl alcohol, an important commodity chemical, an additive to unleaded gasoline, and a contaminant of drinking water. Ninety-day toxicity studies were conducted in B6C3F1 mice and Fischer 344 (F344) rats of both sexes using dosed water. Dose levels of t-butyl alcohol were 0, 0.25, 0.5, 1, 2, and 4% (w/v). Lethality was observed at the 4% level of both sexes and species. Weight-gain depression was present in all dose levels of male rats; 4% female rats; 1, 2, and 4% male mice; and 2 and 4% female mice. Water consumption was increased at lower dose levels in male rats and decreased in the higher dose levels of both sexes of rats and female mice. Clinical signs in rats were ataxia in both sexes and hypoactivity in males. Clinical signs in mice were ataxia, abnormal posture, and hypoactivity. In rats, urine volumes were reduced, in association with crystalluria. Gross lesions at necropsy were urinary tract calculi, renal pelvic and ureteral dilatation, and thickening of the urinary bladder mucosa. Microscopic lesions were hyperplasia of transitional epithelia and inflammation of the urinary bladder. In male rats treated with t-butyl alcohol, microscopic renal changes were suggestive of alpha-2 mu-globulin nephropathy. No-effect levels for the urinary tract lesions were 1% in male rats and mice (803.7 mg/kg/day for the male rats and 1565.8 mg/kg/day for the male mice) and 2% in female rats and mice (1451.5 mg/kg/day for the female rats and 4362.9 mg/kg/day for the female mice). The results indicate that in rodents the urinary tract is the target organ for t-butyl alcohol toxicity, and males are more sensitive to t-butyl alcohol toxicity than females.

Environmentally friendly properties of vegetable oil methyl esters

Directory of Open Access Journals (Sweden)

Gateau Paul

2005-07-01

Full Text Available Measurements were carried out on Vegetable Oil Methyl Esters (VOME or FAME answering the most recent specifications. The products tested are RME (Rapeseed oil Methyl Ester, ERME (Erucic Rapeseed oil Methyl Esters, SME (Sunflower oil Methyl Esters, and HOSME (High Oleic Sunflower oil Methyl Esters. They contain more than 99.5% of fatty acid mono esters. The compositions are given. VOME are not volatile and they are not easily flammable. They are not soluble in water and they are biodegradable. According to the methods implemented for the determination of the German classification of substances hazardous to waters WGK, they are not toxic on mammals and unlike diesel fuel they are not toxic on fish, daphnia, algae and bacteria. The RME is not either toxic for shrimps. According to tests on rabbits, RME and SME are not irritating for the skin and the eyes. VOME display particularly attractive environmental properties.